scholarly journals Influences of hydroxyl radicals (OH) on top-down estimates of the global and regional methane budgets

2020 ◽  
Author(s):  
Yuanhong Zhao ◽  
Marielle Saunois ◽  
Philippe Bousquet ◽  
Xin Lin ◽  
Antoine Berchet ◽  
...  
Keyword(s):  
Spatial Distribution ◽  
Climate Models ◽  
Transport Model ◽  
Atmospheric Transport ◽  
Temporal Variations ◽  
Oh Radicals ◽  
Chemical Transport Model ◽  
Top Down ◽  
Ch4 Emissions ◽  
The Impact

Abstract. The hydroxyl radical (OH), which is the dominant sink of methane (CH4), plays a key role to close the global methane budget. Previous research that assessed the impact of OH changes on the CH4 budget mostly relied on box modeling inversions with a very simplified atmospheric transport and no representation of the heterogeneous spatial distribution of OH radicals. Here using a variational Bayesian inversion framework and a 3D chemical transport model, LMDz, combined with 10 different OH fields derived from chemistry-climate models (CCMI experiment), we evaluate the influence of OH burden, spatial distribution, and temporal variations on the global CH4 budget. The global tropospheric mean CH4-reaction-weighted [OH] ([OH]GM-CH4) ranges 10.3–16.3 × 105 molec cm−3 across 10 OH fields during the early 2000s, resulting in inversion-based global CH4 emissions between 518 and 757 Tg yr−1. The uncertainties in CH4 inversions induced by the different OH fields are comparable to, or even larger than the uncertainty typically given by bottom-up and top-down estimates. Based on the LMDz inversions, we estimate that a 1 %-increase in OH burden leads to an increase of 4 Tg yr−1 in the estimate of global methane emissions, which is about 25 % smaller than what is estimated by box-models. The uncertainties in emissions induced by OH are largest over South America, corresponding to large inter-model differences of [OH] in this region. From the early to the late 2000s, the optimized CH4 emissions increased by 21.9 ± 5.7 Tg yr−1 (16.6–30.0 Tg yr−1), of which ~ 25 % (on average) is contributed by −0.5 to +1.8 % increase in OH burden. If the CCMI models represent the OH trend properly over the 2000s, our results show that a higher increasing trend of CH4 emissions is needed to match the CH4 observations compared to the CH4 emission trend derived using constant OH. This study strengthens the importance to reach a better representation of OH burden and of OH spatial and temporal distributions to reduce the uncertainties on the global CH4 budget.

scholarly journals Influences of hydroxyl radicals (OH) on top-down estimates of the global and regional methane budgets

2020 ◽  
Vol 20 (15) ◽  
pp. 9525-9546 ◽  
Author(s):  
Yuanhong Zhao ◽  
Marielle Saunois ◽  
Philippe Bousquet ◽  
Xin Lin ◽  
Antoine Berchet ◽  
...  
Keyword(s):  
Climate Models ◽  
Climate Model ◽  
Transport Model ◽  
3D Models ◽  
Temporal Variations ◽  
Ch4 Emission ◽  
Chemical Transport Model ◽  
Top Down ◽  
Ch4 Emissions ◽  
Methane Budget

Abstract. The hydroxyl radical (OH), which is the dominant sink of methane (CH4), plays a key role in closing the global methane budget. Current top-down estimates of the global and regional CH4 budget using 3D models usually apply prescribed OH fields and attribute model–observation mismatches almost exclusively to CH4 emissions, leaving the uncertainties due to prescribed OH fields less quantified. Here, using a variational Bayesian inversion framework and the 3D chemical transport model LMDz, combined with 10 different OH fields derived from chemistry–climate models (Chemistry–Climate Model Initiative, or CCMI, experiment), we evaluate the influence of OH burden, spatial distribution, and temporal variations on the global and regional CH4 budget. The global tropospheric mean CH4-reaction-weighted [OH] ([OH]GM-CH4) ranges 10.3–16.3×105 molec cm−3 across 10 OH fields during the early 2000s, resulting in inversion-based global CH4 emissions between 518 and 757  Tg yr−1. The uncertainties in CH4 inversions induced by the different OH fields are similar to the CH4 emission range estimated by previous bottom-up syntheses and larger than the range reported by the top-down studies. The uncertainties in emissions induced by OH are largest over South America, corresponding to large inter-model differences of [OH] in this region. From the early to the late 2000s, the optimized CH4 emissions increased by 22±6  Tg yr−1 (17–30  Tg yr−1), of which ∼25  % (on average) offsets the 0.7  % (on average) increase in OH burden. If the CCMI models represent the OH trend properly over the 2000s, our results show that a higher increasing trend of CH4 emissions is needed to match the CH4 observations compared to the CH4 emission trend derived using constant OH. This study strengthens the importance of reaching a better representation of OH burden and of OH spatial and temporal distributions to reduce the uncertainties in the global and regional CH4 budgets.

scholarly journals Key chemical NO<sub>x</sub> sink uncertainties and how they influence top-down emissions of nitrogen oxides

2013 ◽  
Vol 13 (17) ◽  
pp. 9057-9082 ◽  
Author(s):  
T. Stavrakou ◽  
J.-F. Müller ◽  
K. F. Boersma ◽  
R. J. van der A ◽  
J. Kurokawa ◽  
...  
Keyword(s):  
South Asia ◽  
Transport Model ◽  
Field Studies ◽  
Anthropogenic Source ◽  
Oh Radicals ◽  
Top Down ◽  
Model Calculations ◽  
Tropical Regions ◽  
Recent Developments ◽  
The Impact

Abstract. Triggered by recent developments from laboratory and field studies regarding major NOx sink pathways in the troposphere, this study evaluates the influence of chemical uncertainties in NOx sinks for global NOx distributions calculated by the IMAGESv2 chemistry-transport model, and quantifies their significance for top-down NOx emission estimates. Our study focuses on five key chemical parameters believed to be of primary importance, more specifically, the rate of the reaction of NO2 with OH radicals, the newly identified HNO3-forming channel in the reaction of NO with HO2, the reactive uptake of N2O5 and HO2 by aerosols, and the regeneration of OH in the oxidation of isoprene. Sensitivity simulations are performed to estimate the impact of each source of uncertainty. The model calculations show that, although the NO2+OH reaction is the largest NOx sink globally accounting for ca. 60% of the total sink, the reactions contributing the most to the overall uncertainty are the formation of HNO3 in NO+HO2, leading to NOx column changes exceeding a factor of two over tropical regions, and the uptake of HO2 by aqueous aerosols, in particular over East and South Asia. Emission inversion experiments are carried out using model settings which either minimise (MINLOSS) or maximise (MAXLOSS) the total NOx sink, both constrained by one year of OMI NO2 column data from the DOMINO v2 KNMI algorithm. The choice of the model setup is found to have a major impact on the top-down flux estimates, with 75% higher emissions for MAXLOSS compared to the MINLOSS inversion globally. Even larger departures are found for soil NO (factor of 2) and lightning (1.8). The global anthropogenic source is better constrained (factor of 1.57) than the natural sources, except over South Asia where the combined uncertainty primarily associated to the NO+HO2 reaction in summer and HO2 uptake by aerosol in winter lead to top-down emission differences exceeding a factor of 2. Evaluation of the emission optimisation is performed against independent satellite observations from the SCIAMACHY sensor, with airborne NO2 measurements of the INTEX-A and INTEX-B campaigns, as well as with two new bottom-up inventories of anthropogenic emissions in Asia (REASv2) and China (MEIC). Neither the MINLOSS nor the MAXLOSS setup succeeds in providing the best possible match with all independent datasets. Whereas the minimum sink assumption leads to better agreement with aircraft NO2 profile measurements, consistent with the results of a previous analysis (Henderson et al., 2012), the same assumption leads to unrealistic features in the inferred distribution of emissions over China. Clearly, although our study addresses an important issue which was largely overlooked in previous inversion exercises, and demonstrates the strong influence of NOx loss uncertainties on top-down emission fluxes, additional processes need to be considered which could also influence the inferred source.

scholarly journals Key chemical NO<sub>x</sub> sink uncertainties and how they influence top-down emissions of nitrogen oxides

2013 ◽  
Vol 13 (3) ◽  
pp. 7871-7929 ◽  
Author(s):  
T. Stavrakou ◽  
J.-F. Müller ◽  
K. F. Boersma ◽  
R. J. van der A ◽  
J. Kurokawa ◽  
...  
Keyword(s):  
Transport Model ◽  
Field Studies ◽  
Anthropogenic Source ◽  
Oh Radicals ◽  
Top Down ◽  
Model Calculations ◽  
Tropical Regions ◽  
Emission Fluxes ◽  
Recent Developments ◽  
The Impact

Abstract. Triggered by recent developments from laboratory and field studies regarding major NOx sink pathways in the troposphere, this study evaluates the influence of chemical uncertainties in NOx sinks for global NOx distributions calculated by the IMAGESv2 chemistry-transport model, and quantifies their significance for top-down NOx emission estimates. Our study focuses on four key chemical parameters believed to be of primary importance, more specifically, the rate of the reaction of NO2 with OH radicals, the newly-identified HNO3-forming channel in the reaction of NO with HO2, the reactive uptake of N2O5 on aerosols, and the regeneration of OH in the oxidation of isoprene. Sensitivity simulations are performed to estimate the impact of each source of uncertainty. The model calculations show that, although the NO2 + OH reaction is the largest NOx sink globally accounting for 50–70% of the total sink, the reaction contributing the most to the overall uncertainty is the formation of HNO3 in NO + HO2, leading to NOx column changes reaching a~factor of two over tropical regions, and to a 35% decrease in the global tropospheric NOx lifetime. Emission inversion experiments are carried out using model settings which either miminize (MINLOSS) or maximize (MAXLOSS) the total NOx sink, both constrained by one year of OMI NO2 column data from the DOMINO v2 KNMI algorithm. The choice of the model setup is found to have a major impact on the top-down flux estimates, with 50% higher emissions for MAXLOSS compared to the MINLOSS inversion globally. Even larger departures are found for soil NO (factor of 2) and lightning (70%), whereas the global anthropogenic source is comparatively better constrained, especially in China. Evaluation of the emission optimization is performed against independent satellite observations from the SCIAMACHY sensor, airborne NO2 measurements, observed NOx lifetimes at megacities, as well as with two new bottom-up inventories of anthropogenic emissions in Asia (REASv2) and China (MEIC). Neither the MINLOSS nor the MAXLOSS setup succeeds in providing the best possible match with all independent datasets. Whereas the minimum sink assumption leads to better agreement with aircraft NO2 profile measurements, comforting the results of a previous analysis (Henderson et al., 2012), the same assumption leads to unrealistic features in the inferred distribution of emissions over China. Clearly, although our study addresses an important issue which was largely overlooked in previous inversion exercises, and demonstrates the strong influence of NOx loss uncertainties on top-down emission fluxes, additional processes need to be considered which could also influence the inferred source.

scholarly journals Top-down estimate of surface flux in the Los Angeles Basin using a mesoscale inverse modeling technique: assessing anthropogenic emissions of CO, NO<sub>x</sub> and CO<sub>2</sub> and their impacts

2013 ◽  
Vol 13 (7) ◽  
pp. 3661-3677 ◽  
Author(s):  
J. Brioude ◽  
W. M. Angevine ◽  
R. Ahmadov ◽  
S.-W. Kim ◽  
S. Evan ◽  
...  
Keyword(s):  
Spatial Distribution ◽  
Los Angeles ◽  
Transport Model ◽  
Chemical Species ◽  
Flux Ratio ◽  
Surface Fluxes ◽  
Lagrangian Model ◽  
Inversion Method ◽  
Chemical Transport Model ◽  
Top Down

Abstract. We present top-down estimates of anthropogenic CO, NOx and CO2 surface fluxes at mesoscale using a Lagrangian model in combination with three different WRF model configurations, driven by data from aircraft flights during the CALNEX campaign in southern California in May–June 2010. The US EPA National Emission Inventory 2005 (NEI 2005) was the prior in the CO and NOx inversion calculations. The flux ratio inversion method, based on linear relationships between chemical species, was used to calculate the CO2 inventory without prior knowledge of CO2 surface fluxes. The inversion was applied to each flight to estimate the variability of single-flight-based flux estimates. In Los Angeles (LA) County, the uncertainties on CO and NOx fluxes were 10% and 15%, respectively. Compared with NEI 2005, the CO posterior emissions were lower by 43% in LA County and by 37% in the South Coast Air Basin (SoCAB). NOx posterior emissions were lower by 32% in LA County and by 27% in the SoCAB. NOx posterior emissions were 40% lower on weekends relative to weekdays. The CO2 posterior estimates were 183 Tg yr−1 in SoCAB. A flight during ITCT (Intercontinental Transport and Chemical Transformation) in 2002 was used to estimate emissions in the LA Basin in 2002. From 2002 to 2010, the CO and NOx posterior emissions decreased by 41% and 37%, respectively, in agreement with previous studies. Over the same time period, CO2 emissions increased by 10% in LA County but decreased by 4% in the SoCAB, a statistically insignificant change. Overall, the posterior estimates were in good agreement with the California Air Resources Board (CARB) inventory, with differences of 15% or less. However, the posterior spatial distribution in the basin was significantly different from CARB for NOx emissions. WRF-Chem mesoscale chemical-transport model simulations allowed an evaluation of differences in chemistry using different inventory assumptions, including NEI 2005, a gridded CARB inventory and the posterior inventories derived in this study. The biases in WRF-Chem ozone were reduced and correlations were increased using the posterior from this study compared with simulations with the two bottom-up inventories, suggesting that improving the spatial distribution of ozone precursor surface emissions is also important in mesoscale chemistry simulations.

scholarly journals Top-down estimate of surface flux in the Los Angeles Basin using a mesoscale inverse modeling technique: assessing anthropogenic emissions of CO, NO<sub>x</sub> and CO<sub>2</sub> and their impacts

2012 ◽  
Vol 12 (12) ◽  
pp. 31439-31481 ◽  
Author(s):  
J. Brioude ◽  
W. M. Angevine ◽  
R. Ahmadov ◽  
S.-W. Kim ◽  
S. Evan ◽  
...  
Keyword(s):  
Spatial Distribution ◽  
Los Angeles ◽  
Transport Model ◽  
Chemical Species ◽  
Flux Ratio ◽  
Surface Fluxes ◽  
Lagrangian Model ◽  
Inversion Method ◽  
Chemical Transport Model ◽  
Top Down

Abstract. We present top-down estimates of anthropogenic CO, NOx and CO2 surface fluxes at mesoscale using a Lagrangian model in combination with three different WRF model configurations, driven by data from aircraft flights during the CALNEX campaign in southern California in May–June 2010. The US EPA National Emission Inventory 2005 (NEI 2005) was the prior in the CO and NOx inversion calculations. The flux ratio inversion method, based on linear relationships between chemical species, was used to calculate the CO2 inventory without prior knowledge of CO2 surface fluxes. The inversion was applied to each flight to estimate the variability of single-flight-based flux estimates. In Los Angeles (LA) County, the uncertainties on CO and NOx fluxes were 10% and 15%, respectively. Compared with NEI 2005, the CO posterior emissions were lower by 43% ± 6% in LA County and by 37% ± 10% in the South Coast Air Basin (SoCAB). NOx posterior emissions were lower by 32% ± 10% in LA County and by 27% ± 15% in the SoCAB. NOx posterior emissions were 40% lower on weekends relative to weekdays. The CO2 posterior estimates were 183 ± 18 Tg yr−1 in SoCAB. A flight during ITCT in 2002 was used to estimate emissions in the LA Basin in 2002. From 2002 to 2010, the CO and NOx posterior emissions decreased by 41% and 37%, respectively, in agreement with previous studies. Over the same time period, CO2 emissions increased by 10% ± 14% in LA County but decreased by 4% ± 10% in the SoCAB, a statistically insignificant change. Overall, the posterior estimates were in good agreement with the California Air Resources Board (CARB) inventory, with differences of 15% or less. However, the posterior spatial distribution in the basin was significantly different from CARB for NOx emissions. WRF-Chem mesoscale chemical-transport model simulations allowed an evaluation of differences in chemistry using different inventory assumptions, including NEI 2005, CARB 2010 and the posterior inventories derived in this study. The biases in WRF-Chem ozone were reduced and correlations were increased using the posterior from this study compared with simulations with the two bottom-up inventories, showing that improving the spatial distribution of ozone precursor surface emissions is also important in mesoscale chemistry forecasts.

scholarly journals Modeling the biogeochemical impact of atmospheric phosphate deposition from desert dust and combustion sources to the Mediterranean Sea

2017 ◽  
Author(s):  
Camille Richon ◽  
Jean-Claude Dutay ◽  
François Dulac ◽  
Rong Wang ◽  
Yves Balkanski
Keyword(s):  
Mediterranean Sea ◽  
Transport Model ◽  
Atmospheric Transport ◽  
Primary Source ◽  
Biogeochemical Model ◽  
Chemical Transport Model ◽  
Chl A ◽  
The North ◽  
The Mediterranean ◽  
The Impact

Abstract. We used phosphate deposition from natural dust, anthropogenic combustion and wildfires simulated for the year 2005 by a global atmospheric chemical transport model (LMDz–INCA) as additional sources of external nutrient for a high resolution regional coupled dynamical–biogeochemical model of the Mediterranean Sea. In general, dust is considered as the main atmospheric source of phosphorus, but the LMDz–INCA model suggests that combustion is dominant over natural dust as an atmospheric source of phosphate (the bioavailable form of phosphorus in seawater) for the Mediterranean Sea. According to the atmospheric transport model, anthropogenic phosphate deposition from combustion (Pcomb) brings on average 40.5 10−6 mol PO4 m−2 year−1 over the entire Mediterranean Sea for the year 2005 and is the primary source over the northern part (101 10−6 mol PO4 m−2 year−1 from combustion deposited in 2005 over the North Adriatic against 12.4 10−6 from dust). Lithogenic dust brings 17.2 10−6 mol PO4 m−2 year−1 on average over the Mediterranean Sea in 2005 and is the primary source of atmospheric phosphate to the southern Mediterranean basin in our simulations (31.8 10−6 mol PO4 m−2 year−1 from dust deposited in 2005 on average over the South Ionian basin against 12.4 10−6 from combustion). We examine separately the different soluble phosphorus (PO4) sources and their respective fluxes variability and evaluate their impacts on marine surface biogeochemistry (phosphate concentrations, Chl a, primary production). The impacts of the different phosphate deposition sources on the biogeochemistry of the Mediterranean are found localized, seasonally varying and small, but yet statistically significant. The impact of the different sources of phosphate on the biogeochemical cycles is remarkably different and should be accounted for in modeling studies.

scholarly journals The Environmental Effects of the April 2020 Wildfires and the Cs-137 Re-Suspension in the Chernobyl Exclusion Zone: A Multi-Hazard Threat

Atmosphere ◽  
2021 ◽  
Vol 12 (4) ◽  
pp. 467
Author(s):  
Rocío Baró ◽  
Christian Maurer ◽  
Jerome Brioude ◽  
Delia Arnold ◽  
Marcus Hirtl
Keyword(s):  
Air Quality ◽  
Nuclear Power ◽  
Transport Model ◽  
Atmospheric Transport ◽  
Point Of View ◽  
Plume Dispersion ◽  
Exclusion Zone ◽  
Fire Plume ◽  
Mean Values ◽  
The Impact

This paper demonstrates the environmental impacts of the wildfires occurring at the beginning of April 2020 in and around the highly contaminated Chernobyl Exclusion Zone (CEZ). Due to the critical fire location, concerns arose about secondary radioactive contamination potentially spreading over Europe. The impact of the fire was assessed through the evaluation of fire plume dispersion and re-suspension of the radionuclide Cs-137, whereas, to assess the smoke plume effect, a WRF-Chem simulation was performed and compared to Tropospheric Monitoring Instrument (TROPOMI) satellite columns. The results show agreement of the simulated black carbon and carbon monoxide plumes with the plumes as observed by TROPOMI, where pollutants were also transported to Belarus. From an air quality and health perspective, the wildfires caused extremely bad air quality over Kiev, where the WRF-Chem model simulated mean values of PM2.5 up to 300 µg/m3 (during the first fire outbreak) over CEZ. The re-suspension of Cs-137 was assessed by a Bayesian inverse modelling approach using FLEXPART as the atmospheric transport model and Ukraine observations, yielding a total release of 600 ± 200 GBq. The increase in both smoke and Cs-137 emissions was only well correlated on the 9 April, likely related to a shift of the focus area of the fires. From a radiological point of view even the highest Cs-137 values (average measured or modelled air concentrations and modelled deposition) at the measurement site closest to the Chernobyl Nuclear Power Plant, i.e., Kiev, posed no health risk.

scholarly journals Extending methane profiles from aircraft into the stratosphere for satellite total column validation using the ECMWF C-IFS and TOMCAT/SLIMCAT 3-D model

2017 ◽  
Vol 17 (11) ◽  
pp. 6663-6678 ◽  
Author(s):  
Shreeya Verma ◽  
Julia Marshall ◽  
Mark Parrington ◽  
Anna Agustí-Panareda ◽  
Sebastien Massart ◽  
...  
Keyword(s):  
Greenhouse Gases ◽  
Transport Model ◽  
A Priori ◽  
Atmospheric Composition ◽  
Random Errors ◽  
Chemical Transport Model ◽  
Spatial Coverage ◽  
Forecasting System ◽  
The Impact ◽  
Total Column

Abstract. Airborne observations of greenhouse gases are a very useful reference for validation of satellite-based column-averaged dry air mole fraction data. However, since the aircraft data are available only up to about 9–13 km altitude, these profiles do not fully represent the depth of the atmosphere observed by satellites and therefore need to be extended synthetically into the stratosphere. In the near future, observations of CO2 and CH4 made from passenger aircraft are expected to be available through the In-Service Aircraft for a Global Observing System (IAGOS) project. In this study, we analyse three different data sources that are available for the stratospheric extension of aircraft profiles by comparing the error introduced by each of them into the total column and provide recommendations regarding the best approach. First, we analyse CH4 fields from two different models of atmospheric composition – the European Centre for Medium-Range Weather Forecasts (ECMWF) Integrated Forecasting System for Composition (C-IFS) and the TOMCAT/SLIMCAT 3-D chemical transport model. Secondly, we consider scenarios that simulate the effect of using CH4 climatologies such as those based on balloons or satellite limb soundings. Thirdly, we assess the impact of using a priori profiles used in the satellite retrievals for the stratospheric part of the total column. We find that the models considered in this study have a better estimation of the stratospheric CH4 as compared to the climatology-based data and the satellite a priori profiles. Both the C-IFS and TOMCAT models have a bias of about −9 ppb at the locations where tropospheric vertical profiles will be measured by IAGOS. The C-IFS model, however, has a lower random error (6.5 ppb) than TOMCAT (12.8 ppb). These values are well within the minimum desired accuracy and precision of satellite total column XCH4 retrievals (10 and 34 ppb, respectively). In comparison, the a priori profile from the University of Leicester Greenhouse Gases Observing Satellite (GOSAT) Proxy XCH4 retrieval and climatology-based data introduce larger random errors in the total column, being limited in spatial coverage and temporal variability. Furthermore, we find that the bias in the models varies with latitude and season. Therefore, applying appropriate bias correction to the model fields before using them for profile extension is expected to further decrease the error contributed by the stratospheric part of the profile to the total column.

scholarly journals Modeling anthropogenically controlled secondary organic aerosols in a megacity: a simplified framework for global and climate models

2011 ◽  
Vol 4 (4) ◽  
pp. 901-917 ◽  
Author(s):  
A. Hodzic ◽  
J. L. Jimenez
Keyword(s):  
Mexico City ◽  
Biomass Burning ◽  
Climate Models ◽  
Transport Model ◽  
Anthropogenic Pollution ◽  
Temporal Variations ◽  
Anthropogenic Sources ◽  
Organic Vapors ◽  
Chemistry Transport Model ◽  
Evolution Of Oxygen

Abstract. A simplified parameterization for secondary organic aerosol (SOA) formation in polluted air and biomass burning smoke is tested and optimized in this work, towards the goal of a computationally inexpensive method to calculate pollution and biomass burning SOA mass and hygroscopicity in global and climate models. A regional chemistry-transport model is used as the testbed for the parameterization, which is compared against observations from the Mexico City metropolitan area during the MILAGRO 2006 field experiment. The empirical parameterization is based on the observed proportionality of SOA concentrations to excess CO and photochemical age of the airmass. The approach consists in emitting an organic gas as lumped SOA precursor surrogate proportional to anthropogenic or biomass burning CO emissions according to the observed ratio between SOA and CO in aged air, and reacting this surrogate with OH into a single non-volatile species that condenses to form SOA. An emission factor of 0.08 g of the lumped SOA precursor per g of CO and a rate constant with OH of 1.25 × 10−11 cm3 molecule−1 s−1 reproduce the observed average SOA mass within 30 % in the urban area and downwind. When a 2.5 times slower rate is used (5 × 10−12 cm3 molecule−1 s−1) the predicted SOA amount and temporal evolution is nearly identical to the results obtained with SOA formation from semi-volatile and intermediate volatility primary organic vapors according to the Robinson et al. (2007) formulation. Our simplified method has the advantage of being much less computationally expensive than Robinson-type methods, and can be used in regions where the emissions of SOA precursors are not yet available. As the aged SOA/ΔCO ratios are rather consistent globally for anthropogenic pollution, this parameterization could be reasonably tested in and applied to other regions. The evolution of oxygen-to-carbon ratio was also empirically modeled and the predicted levels were found to be in reasonable agreement with observations. The potential enhancement of biogenic SOA by anthropogenic pollution, which has been suggested to play a major role in global SOA formation, is also tested using two simple parameterizations. Our results suggest that the pollution enhancement of biogenic SOA could provide additional SOA, but does not however explain the concentrations or the spatial and temporal variations of measured SOA mass in the vicinity of Mexico City, which appears to be controlled by anthropogenic sources. The contribution of the biomass burning to the predicted SOA is less than 10% during the studied period.

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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