scholarly journals Global stratospheric fluorine inventory for 2004–2009 from Atmospheric Chemistry Experiment Fourier Transform Spectrometer (ACE-FTS) measurements and SLIMCAT model simulations

2014 ◽  
Vol 14 (1) ◽  
pp. 267-282 ◽  
Author(s):  
A. T. Brown ◽  
M. P. Chipperfield ◽  
N. A. D. Richards ◽  
C. Boone ◽  
P. F. Bernath
Keyword(s):  
Atmospheric Chemistry ◽  
Radiative Forcing ◽  
Transport Model ◽  
Similar Rate ◽  
Montreal Protocol ◽  
Negative Slope ◽  
Mixing Ratios ◽  
Inorganic Species ◽  
The Tropics ◽  
The Impact

Abstract. Fluorine-containing species can be extremely effective atmospheric greenhouse gases. We present fluorine budgets using organic and inorganic species retrieved by the ACE-FTS satellite instrument supplemented with output from the SLIMCAT 3-D chemical transport model. The budgets are calculated between 2004 and 2009 for a number of latitude bands: 70–30° N, 30–00° N, 00° N–30° S, and 30–70° S. At lower altitudes total fluorine profiles are dominated by the contribution from CFC-12, up to an altitude of 20 km in the extra-tropics and 29 km in the tropics; above these altitudes the profiles are dominated by hydrogen fluoride (HF). Our data show that total fluorine profiles at all locations have a negative slope with altitude, providing evidence that overall fluorine emissions (measured by their F content) have been increasing with time. Total stratospheric fluorine is increasing at a similar rate in the tropics: 32.5 ± 4.9 ppt yr−1 (1.31 ± 0.20% per year) in the Northern Hemisphere (NH) and 29.8 ± 5.3 ppt yr−1 (1.21 ± 0.22% per year) in the Southern Hemisphere (SH). Extra-tropical total stratospheric fluorine is also increasing at a similar rate in both the NH and SH: 28.3 ± 2.7 ppt per year (1.12 ± 0.11% per year) in the NH and 24.3 ± 3.1 ppt per year (0.96 ± 0.12% per year) in the SH. The calculation of radiative efficiency-weighted total fluorine allows the changes in radiative forcing between 2004 and 2009 to be calculated. These results show an increase in radiative forcing of between 0.23 ± 0.11% per year and 0.45 ± 0.11% per year, due to the increase in fluorine-containing species during this time. The decreasing trends in the mixing ratios of halons and chlorofluorocarbons (CFCs), due to their prohibition under the Montreal Protocol, have suppressed an increase in total fluorine caused by increasing mixing ratios of hydrofluorocarbons (HFCs). This has reduced the impact of fluorine-containing species on global warming.

scholarly journals Global stratospheric fluorine inventories for 2004–2009 from Atmospheric Chemistry Experiment Fourier Transform Spectrometer (ACE-FTS) measurements

2013 ◽  
Vol 13 (6) ◽  
pp. 16885-16924
Author(s):  
A. T. Brown ◽  
M. P. Chipperfield ◽  
N. A. D. Richards ◽  
C. Boone ◽  
P. F. Bernath
Keyword(s):  
Global Warming ◽  
Atmospheric Chemistry ◽  
Similar Rate ◽  
Montreal Protocol ◽  
Negative Slope ◽  
Relative Molecular Mass ◽  
Mixing Ratios ◽  
Inorganic Species ◽  
The Tropics ◽  
The Impact

Abstract. Fluorine-containing species can be extremely effective atmospheric greenhouse gases. We present fluorine budgets using organic and inorganic species retrieved by the ACE-FTS satellite instrument supplemented with output from the SLIMCAT 3D chemical transport model. The budgets are calculated between 2004 and 2009 for a number of latitude bands: 70–30° N, 30–0° N, 0–30° S, and 30–70° S. At lower altitudes total fluorine profiles are dominated by the contribution from CFC-12, up to an altitude of 20 km in the extra-tropics and 29 km in the tropics, above these altitudes the profiles are dominated by HF. Our data show that total fluorine profiles at all locations have a negative slope with altitude, providing evidence that overall fluorine emissions (measured by their F content) have been increasing with time. Total stratospheric fluorine is increasing at a similar rate in the tropics; 32.5 ± 4.9 ppt yr−1 (1.31 ± 0.20% per year) in the Northern Hemisphere (NH) and 29.8 ± 5.3 ppt yr−1 (1.21 ± 0.22% per year) in the Southern Hemisphere (SH). Extra-tropical total stratospheric fluorine is also increasing at a similar rate in both the NH and SH; 28.3 ± 2.7 ppt per year (1.12 ± 0.11% per year) in the NH and 24.3 ± 3.1 ppt per year (0.96 ± 0.12% per year) in the SH. The volume mixing ratio of each species used in this study was weighted by its global warming potential (GWP), relative molecular mass and the atmospheric pressure to produce a GWP-weighted total fluorine trend. These trends show mean changes of 0.02 ± 0.08% per year in the NH, and 0.07 ± 0.05% per year in the SH. Overall, GWP-weighted fluorine remains roughly constant globally. However, the decreasing trends in the mixing ratios of halons and CFCs, due to their prohibition under the Montreal Protocol, have suppressed an increase in total fluorine caused by increasing mixing ratios of HFCs. This has reduced the impact of fluorine containing species on global warming.

scholarly journals Global stratospheric chlorine inventories for 2004–2009 from Atmospheric Chemistry Experiment Fourier Transform Spectrometer (ACE-FTS) measurements

2013 ◽  
Vol 13 (9) ◽  
pp. 23491-23548 ◽  
Author(s):  
A. T. Brown ◽  
M. P. Chipperfield ◽  
S. Dhomse ◽  
C. Boone ◽  
P. F. Bernath
Keyword(s):  
Southern Hemisphere ◽  
Northern Hemisphere ◽  
Atmospheric Chemistry ◽  
Transport Model ◽  
Montreal Protocol ◽  
Chemical Transport Model ◽  
Mixing Ratios ◽  
Ozone Depleting Substances ◽  
The Tropics ◽  
Chemistry Experiment

Abstract. We present chlorine budgets calculated between 2004 and 2009 for four latitude bands (70° N–30° N, 30° N–0° N, 0° N–30° S, and 30° S–70° S). The budgets were calculated using ACE-FTS version 3.0 retrievals of the volume mixing ratios (VMRs) of 9 chlorine-containing species: CCl4, CFC-12 (CCl2F2), CFC-11 (CCl3F), COCl2, COClF, HCFC-22 (CHF2Cl), CH3Cl, HCl and ClONO2. These data were supplemented with calculated VMRs from the SLIMCAT 3-D chemical transport model (CFC-113, CFC-114, CFC-115, H-1211, H-1301, HCFC-141b, HCFC-142b, ClO and HOCl). The total chlorine profiles are dominated by chlorofluorocarbons (CFCs) and halons up to 24 km in the tropics and 19 km in the extra-tropics. In this altitude range CFCs and halons account for 58% of the total chlorine VMR. Above this altitude HCl increasingly dominates the total chlorine profile, reaching a maximum of 95% of total chlorine at 54 km. All total chlorine profiles exhibit a positive slope with altitude, suggesting that the total chlorine VMR is now decreasing with time. This conclusion is supported by the time series of the mean stratospheric total chlorine budgets which show mean decreases in total stratospheric chlorine of 0.38 ± 0.03% per year in the Northern Hemisphere extra-tropics, 0.35 ± 0.07% per year in the Northern Hemisphere tropical stratosphere, 0.54 ± 0.16% per year in the Southern Hemisphere tropics and 0.53 ± 0.12% per year in the Southern Hemisphere extra-tropical stratosphere for 2004–2009. Globally stratospheric chlorine is decreasing by 0.46 ± 0.02% per year. Both global warming potential-weighted chlorine and ozone depletion potential-weighted chlorine are decreasing at all latitudes. These results show that the Montreal Protocol has had a significant effect in reducing emissions of both ozone-depleting substances and greenhouse gases.

scholarly journals Impact of uncertainties in inorganic chemical rate constants on tropospheric composition and ozone radiative forcing

2017 ◽  
Author(s):  
Ben Newsome ◽  
Mat Evans
Keyword(s):  
Rate Constant ◽  
Atmospheric Chemistry ◽  
Rate Constants ◽  
Tropospheric Ozone ◽  
Radiative Forcing ◽  
Transport Model ◽  
Surface Ozone ◽  
Photolysis Rates ◽  
The Impact ◽  
Chemical Rate

Abstract. Chemical rate constants determine the composition of the atmosphere and how this composition has changed over time. They are central to our understanding of climate change and air quality degradation. Atmospheric chemistry models, whether online or offline, box, regional or global use these rate constants. Expert panels synthesise laboratory measurements, making recommendations for the rate constants that should be used. This results in very similar or identical rate constants being used by all models. The inherent uncertainties in these recommendations are, in general, therefore ignored. We explore the impact of these uncertainties on the composition of the troposphere using the GEOS-Chem chemistry transport model. Based on the JPL and IUPAC evaluations we assess 50 mainly inorganic rate constants and 10 photolysis rates, through simulations where we increase the rate of the reactions to the 1σ upper value recommended by the expert panels. We assess the impact on 4 standard metrics: annual mean tropospheric ozone burden, surface ozone and tropospheric OH concentrations, and tropospheric methane lifetime. Uncertainty in the rate constants for NO2 + OH    M →  HNO3, OH + CH4 → CH3O2 + H2O and O3 + NO → NO2 + O2 are the three largest source of uncertainty in these metrics. We investigate two methods of assessing these uncertainties, addition in quadrature and a Monte Carlo approach, and conclude they give similar outcomes. Combining the uncertainties across the 60 reactions, gives overall uncertainties on the annual mean tropospheric ozone burden, surface ozone and tropospheric OH concentrations, and tropospheric methane lifetime of 11, 12, 17 and 17 % respectively. These are larger than the spread between models in recent model inter-comparisons. Remote regions such as the tropics, poles, and upper troposphere are most uncertain. This chemical uncertainty is sufficiently large to suggest that rate constant uncertainty should be considered when model results disagree with measurement. Calculations for the pre-industrial allow a tropospheric ozone radiative forcing to be calculated of 0.412 ± 0.062 Wm−2. This uncertainty (15 %) is comparable to the inter-model spread in ozone radiative forcing found in previous model-model inter-comparison studies where the rate constants used in the models are all identical or very similar. Thus the uncertainty of tropospheric ozone radiative forcing should expanded to include this additional source of uncertainty. These rate constant uncertainties are significant and suggest that refinement of supposedly well known chemical rate constants should be considered alongside other improvements to enhance our understanding of atmospheric processes.

Investigation of strongly enhanced methane Part I: Chemical feedbacks and rapid adjustments.

2020 ◽  
Author(s):  
Franziska Winterstein ◽  
Patrick Jöckel ◽  
Martin Dameris ◽  
Michael Ponater ◽  
Fabian Tanalski ◽  
...  
Keyword(s):  
Atmospheric Chemistry ◽  
Radiative Forcing ◽  
Climate Model ◽  
Numerical Study ◽  
Stratospheric Ozone ◽  
Lower Boundary ◽  
Tropospheric Chemistry ◽  
Substantial Part ◽  
Mixing Ratios ◽  
The Impact

<p>Methane (CH<sub>4</sub>) is the second most important greenhouse gas, which atmospheric concentration is influenced by human activities and currently on a sharp rise. We present a study with numerical simulations using a Chemistry-Climate-Model (CCM), which are performed to assess possible consequences of strongly enhanced CH<sub>4</sub> concentrations in the Earth's atmosphere for the climate.</p><p>Our analysis includes experiments with 2xCH<sub>4</sub> and 5xCH<sub>4</sub> present day (2010) lower boundary mixing ratios using the CCM EMAC. The simulations are conducted with prescribed oceanic conditions, mimicking present day tropospheric temperatures as its changes are largely suppressed. By doing so we are able to investigate the quasi-instantaneous chemical impact on the atmosphere. We find that the massive increase in CH<sub>4</sub> strongly influences the tropospheric chemistry by reducing the OH abundance and thereby extending the tropospheric CH<sub>4</sub> lifetime as well as the residence time of other chemical pollutants. The region above the tropopause is impacted by a substantial rise in stratospheric water vapor (SWV). The stratospheric ozone (O<sub>3</sub>) column increases overall, but SWV induced stratospheric cooling also leads to enhanced ozone depletion in the Antarctic lower stratosphere. Regional  patterns of ozone change are affected by modification of stratospheric dynamics, i.e. increased tropical up-welling and stronger meridional transport  towards the polar regions. We calculate the net radiative impact (RI) of the 2xCH<sub>4</sub> experiment to be 0.69 W m<sup>-2</sup> and for the 5xCH<sub>4</sub> experiment to be 1.79 W m<sup>-2</sup>. A substantial part of the RI is contributed by chemically induced O<sub>3</sub> and SWV changes, in line with previous radiative forcing estimates and is for the first time splitted and spatially asigned to its chemical contributors.</p><p>This numerical study using a CCM with prescibed oceanic conditions shows the rapid responses to significantly enhanced CH<sub>4</sub> mixing ratios, which is the first step towards investigating the impact of possible strong future CH<sub>4</sub> emissions on atmospheric chemistry and its feedback on climate.</p>

scholarly journals Impact of the new HNO<sub>3</sub>-forming channel of the HO<sub>2</sub>+NO reaction on tropospheric HNO<sub>3</sub>, NO<sub>x</sub>, HO<sub>x</sub> and ozone

2008 ◽  
Vol 8 (14) ◽  
pp. 4061-4068 ◽  
Author(s):  
D. Cariolle ◽  
M. J. Evans ◽  
M. P. Chipperfield ◽  
N. Butkovskaya ◽  
A. Kukui ◽  
...  
Keyword(s):  
Southern Hemisphere ◽  
Atmospheric Chemistry ◽  
Tropospheric Ozone ◽  
Transport Model ◽  
Chemical Transport Model ◽  
Temperature Dependent ◽  
Upper Troposphere ◽  
The Mean ◽  
The Tropics ◽  
The Impact

Abstract. We have studied the impact of the recently observed reaction NO+HO2→HNO3 on atmospheric chemistry. A pressure and temperature-dependent parameterisation of this minor channel of the NO+HO2→NO2+OH reaction has been included in both a 2-D stratosphere-troposphere model and a 3-D tropospheric chemical transport model (CTM). Significant effects on the nitrogen species and hydroxyl radical concentrations are found throughout the troposphere, with the largest percentage changes occurring in the tropical upper troposphere (UT). Including the reaction leads to a reduction in NOx everywhere in the troposphere, with the largest decrease of 25% in the tropical and Southern Hemisphere UT. The tropical UT also has a corresponding large increase in HNO3 of 25%. OH decreases throughout the troposphere with the largest reduction of over 20% in the tropical UT. The mean global decrease in OH is around 13%, which is very large compared to the impact that typical photochemical revisions have on this modelled quantity. This OH decrease leads to an increase in CH4 lifetime of 5%. Due to the impact of decreased NOx on the OH:HO2 partitioning, modelled HO2 actually increases in the tropical UT on including the new reaction. The impact on tropospheric ozone is a decrease in the range 5 to 12%, with the largest impact in the tropics and Southern Hemisphere. Comparison with observations shows that in the region of largest changes, i.e. the tropical UT, the inclusion of the new reaction tends to degrade the model agreement. Elsewhere the model comparisons are not able to critically assess the impact of including this reaction. Only small changes are calculated in the minor species distributions in the stratosphere.

scholarly journals Impact of the new HNO<sub>3</sub>-forming channel of the HO<sub>2</sub>+NO reaction on tropospheric HNO<sub>3</sub>, NO<sub>x</sub>, HO<sub>x</sub> and ozone

2008 ◽  
Vol 8 (1) ◽  
pp. 2695-2713 ◽  
Author(s):  
D. Cariolle ◽  
M. J. Evans ◽  
M. P. Chipperfield ◽  
N. Butkovskaya ◽  
A. Kukui ◽  
...  
Keyword(s):  
Southern Hemisphere ◽  
Atmospheric Chemistry ◽  
Tropospheric Ozone ◽  
Transport Model ◽  
Chemical Transport Model ◽  
Temperature Dependent ◽  
Upper Troposphere ◽  
The Tropics ◽  
The Impact ◽  
Model Agreement

Abstract. We have studied the impact of the recently established reaction NO+HO2→HNO3 on atmospheric chemistry. A pressure and temperature-dependent parameterisation of this minor channel of the NO+HO2→NO2+OH reaction has been included in both a 2-D stratosphere-troposphere model and a 3-D tropospheric chemical transport model (CTM). Significant effects on the nitrogen species and hydroxyl radical concentrations are found throughout the troposphere, with the largest percentage changes occurring in the tropical upper troposphere (UT). Including the reaction leads to a reduction in NOx everywhere in the troposphere, with the largest decrease of 25% in the tropical and southern hemisphere UT. The tropical UT also has a corresponding large increase in HNO3 of 25%. OH decreases throughout the troposphere with the largest reduction of over 20% in the tropical UT. Mean global decreases in OH are around 13% which leads to a increase in CH4 lifetime of 5%. Due to the impact of decreased NOx on the OH:HO2 partitioning, modelled HO2 actually increases in the tropical UT on including the new reaction. The impact on tropospheric ozone is a decrease in the range 5 to 12%, with the largest impact in the tropics and southern hemisphere. Comparison with observations shows that in the region of largest changes, i.e. the tropical UT, the inclusion of the new reaction tends to degrade the model agreement. Elsewhere the model comparisons are not able to critically assess the impact of including this reaction. Only small changes are calculated in the minor species distributions in the stratosphere.

scholarly journals Impact of uncertainties in inorganic chemical rate constants on tropospheric composition and ozone radiative forcing

2017 ◽  
Vol 17 (23) ◽  
pp. 14333-14352 ◽  
Author(s):  
Ben Newsome ◽  
Mat Evans
Keyword(s):  
Rate Constant ◽  
Atmospheric Chemistry ◽  
Rate Constants ◽  
Tropospheric Ozone ◽  
Radiative Forcing ◽  
Transport Model ◽  
Surface Ozone ◽  
Chemistry Transport Model ◽  
The Impact ◽  
Chemical Rate

Abstract. Chemical rate constants determine the composition of the atmosphere and how this composition has changed over time. They are central to our understanding of climate change and air quality degradation. Atmospheric chemistry models, whether online or offline, box, regional or global, use these rate constants. Expert panels evaluate laboratory measurements, making recommendations for the rate constants that should be used. This results in very similar or identical rate constants being used by all models. The inherent uncertainties in these recommendations are, in general, therefore ignored. We explore the impact of these uncertainties on the composition of the troposphere using the GEOS-Chem chemistry transport model. Based on the Jet Propulsion Laboratory (JPL) and International Union of Pure and Applied Chemistry (IUPAC) evaluations we assess the influence of 50 mainly inorganic rate constants and 10 photolysis rates on tropospheric composition through the use of the GEOS-Chem chemistry transport model. We assess the impact on four standard metrics: annual mean tropospheric ozone burden, surface ozone and tropospheric OH concentrations, and tropospheric methane lifetime. Uncertainty in the rate constants for NO2 + OH →M  HNO3 and O3 + NO  →  NO2 + O2 are the two largest sources of uncertainty in these metrics. The absolute magnitude of the change in the metrics is similar if rate constants are increased or decreased by their σ values. We investigate two methods of assessing these uncertainties, addition in quadrature and a Monte Carlo approach, and conclude they give similar outcomes. Combining the uncertainties across the 60 reactions gives overall uncertainties on the annual mean tropospheric ozone burden, surface ozone and tropospheric OH concentrations, and tropospheric methane lifetime of 10, 11, 16 and 16 %, respectively. These are larger than the spread between models in recent model intercomparisons. Remote regions such as the tropics, poles and upper troposphere are most uncertain. This chemical uncertainty is sufficiently large to suggest that rate constant uncertainty should be considered alongside other processes when model results disagree with measurement. Calculations for the pre-industrial simulation allow a tropospheric ozone radiative forcing to be calculated of 0.412 ± 0.062 W m−2. This uncertainty (13 %) is comparable to the inter-model spread in ozone radiative forcing found in previous model–model intercomparison studies where the rate constants used in the models are all identical or very similar. Thus, the uncertainty of tropospheric ozone radiative forcing should expanded to include this additional source of uncertainty. These rate constant uncertainties are significant and suggest that refinement of supposedly well-known chemical rate constants should be considered alongside other improvements to enhance our understanding of atmospheric processes.

scholarly journals Importance of reactive halogens in the tropical marine atmosphere: A regional modelling study using WRF-Chem

2017 ◽  
Author(s):  
Alba Badia ◽  
Claire E. Reeves ◽  
Alex R. Baker ◽  
Alfonso Saiz-Lopez ◽  
Rainer Volkamer ◽  
...  
Keyword(s):  
Atmospheric Chemistry ◽  
Marine Boundary Layer ◽  
Transport Model ◽  
Model Performance ◽  
Sea Salt ◽  
Heterogeneous Reactions ◽  
Regional Modelling ◽  
Mixing Ratios ◽  
Inorganic Iodine ◽  
The Impact

Abstract. This study investigates the impact of halogens on atmospheric chemistry in the tropical troposphere and explores the sensitivity of this to uncertainties in the fluxes of halogens to the atmosphere and the chemical processing. To do this the regional chemistry transport model WRF-Chem has been extended, for the first time, to include halogen chemistry (bromine, chlorine and iodine chemistry), including heterogeneous recycling reactions involving sea-salt aerosol and other particles, reactions of Br with volatile organic compounds (VOCs), along with oceanic emissions of halocarbons, VOCs and inorganic iodine. The study focuses on the tropical East Pacific using field observations from the TORERO campaign (January–February 2012) to evaluate the model performance. Including all the new processes, the model does a reasonable job reproducing the observed mixing ratios of BrO and IO, albeit with some discrepancies, some of which can be attributed to difficulties in the model's ability to reproduce the observed halocarbons. This is somewhat expected given the large uncertainties in the air-sea fluxes of the halocarbons in a region where there are few observations of seawater concentrations. We see a considerable impact on the Bry partitioning when heterogeneous chemistry is included, with a greater proportion of the Bry in active forms such as BrO, HOBr and dihalogens. Including debromination of sea-salt increases BrO slightly throughout the free troposphere, but in the tropical marine boundary layer, where the sea-salt particles are plentiful and relatively acidic, debromination leads to overestimation of the observed BrO. However, it should be noted that the modelled BrO was extremely sensitive to the inclusion of reactions between Br and the VOCs, which convert Br to HBr, a far less reactive form of Bry. Excluding these reactions leads to modelled BrO mixing ratios greater than observed. The reactions between Br and aldehydes were found to be particularly important, despite the model underestimating the amount of aldehydes observed in the atmosphere. There are only small changes to Iy partitioning and IO when the heterogeneous reactions, primarly on sea-salt, are included. Our model results show that the tropospheric Ox loss due to halogens is 31 %. This loss is mostly due to I (16 %) and Br (14 %) and it is in good agreement with other estimates from state-of-the-art atmospheric chemistry models.

scholarly journals Global sensitivity of aviation NO<sub>x</sub> effects to the HNO<sub>3</sub>-forming channel of the HO<sub>2</sub>+NO reaction

2012 ◽  
Vol 12 (9) ◽  
pp. 24287-24349
Author(s):  
K. Gottschaldt ◽  
C. Voigt ◽  
P. Jöckel ◽  
M. Righi ◽  
R. Deckert ◽  
...  
Keyword(s):  
Atmospheric Chemistry ◽  
Radiative Forcing ◽  
Climate Model ◽  
Rate Coefficient ◽  
Climate Impact ◽  
Mitigation Strategies ◽  
Global Sensitivity ◽  
Mixing Ratios ◽  
Modelling Studies ◽  
The Impact

Abstract. The impact of a recently proposed HNO3-forming channel of the HO2+NO reaction (Butkovskaya et al., 2005, 2007) on atmospheric mixing ratios of ozone, methane and their precursors is assessed with a global stratosphere-troposphere chemistry-climate model. Previous modelling studies applied a rate coefficient that depends only on pressure and temperature. We additionally considered a possible enhancement of the reaction by humidity, as found by a laboratory study (Butkovskaya et al., 2009). This particularly reduces the oxidation capacity of the atmosphere, increasing methane lifetime significantly. The effects of aircraft NOx emissions on atmospheric chemistry are altered when considering the above reaction, resulting in a negative net radiative forcing relative to an atmosphere without aviation NOx. Uncertainties associated with the inclusion of the HO2+NO → HNO3 reaction and with its corresponding rate coefficient propagate a considerable additional uncertainty on estimates of the climate impact of aviation and on NOx-related mitigation strategies.

scholarly journals Model sensitivity studies of the decrease in atmospheric carbon tetrachloride

2016 ◽  
Vol 16 (24) ◽  
pp. 15741-15754 ◽  
Author(s):  
Martyn P. Chipperfield ◽  
Qing Liang ◽  
Matthew Rigby ◽  
Ryan Hossaini ◽  
Stephen A. Montzka ◽  
...  
Keyword(s):  
Carbon Tetrachloride ◽  
Transport Model ◽  
Three Dimensional ◽  
Montreal Protocol ◽  
Chemical Transport Model ◽  
Uncertainty Range ◽  
The Past ◽  
Systematic Biases ◽  
Lifetime Uncertainty ◽  
The Impact

Abstract. Carbon tetrachloride (CCl4) is an ozone-depleting substance, which is controlled by the Montreal Protocol and for which the atmospheric abundance is decreasing. However, the current observed rate of this decrease is known to be slower than expected based on reported CCl4 emissions and its estimated overall atmospheric lifetime. Here we use a three-dimensional (3-D) chemical transport model to investigate the impact on its predicted decay of uncertainties in the rates at which CCl4 is removed from the atmosphere by photolysis, by ocean uptake and by degradation in soils. The largest sink is atmospheric photolysis (74 % of total), but a reported 10 % uncertainty in its combined photolysis cross section and quantum yield has only a modest impact on the modelled rate of CCl4 decay. This is partly due to the limiting effect of the rate of transport of CCl4 from the main tropospheric reservoir to the stratosphere, where photolytic loss occurs. The model suggests large interannual variability in the magnitude of this stratospheric photolysis sink caused by variations in transport. The impact of uncertainty in the minor soil sink (9 % of total) is also relatively small. In contrast, the model shows that uncertainty in ocean loss (17 % of total) has the largest impact on modelled CCl4 decay due to its sizeable contribution to CCl4 loss and large lifetime uncertainty range (147 to 241 years). With an assumed CCl4 emission rate of 39 Gg year−1, the reference simulation with the best estimate of loss processes still underestimates the observed CCl4 (overestimates the decay) over the past 2 decades but to a smaller extent than previous studies. Changes to the rate of CCl4 loss processes, in line with known uncertainties, could bring the model into agreement with in situ surface and remote-sensing measurements, as could an increase in emissions to around 47 Gg year−1. Further progress in constraining the CCl4 budget is partly limited by systematic biases between observational datasets. For example, surface observations from the National Oceanic and Atmospheric Administration (NOAA) network are larger than from the Advanced Global Atmospheric Gases Experiment (AGAGE) network but have shown a steeper decreasing trend over the past 2 decades. These differences imply a difference in emissions which is significant relative to uncertainties in the magnitudes of the CCl4 sinks.

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