Chemistry And Transport Model Research Articles

Evaluation of modelled versus observed non-methane volatile organic compounds at European Monitoring and Evaluation Programme sites in Europe

Abstract. Atmospheric volatile organic compounds (VOCs) constitute a wide range of species, acting as precursors to ozone and aerosol formation. Atmospheric chemistry and transport models (CTMs) are crucial to understanding the emissions, distribution, and impacts of VOCs. Given the uncertainties in VOC emissions, lack of evaluation studies, and recent changes in emissions, this work adapts the European Monitoring and Evaluation Programme Meteorological Synthesizing Centre – West (EMEP MSC-W) CTM to evaluate emission inventories in Europe. Here we undertake the first intensive model–measurement comparison of VOCs in 2 decades. The modelled surface concentrations are evaluated both spatially and temporally, using measurements from the regular EMEP monitoring network in 2018 and 2019, as well as a 2022 campaign. To achieve this, we utilised the UK National Atmospheric Emissions Inventory to derive explicit emission profiles for individual species and employed a tracer method to produce pure concentrations that are directly comparable to observations. The degree to which the modelled and measured VOCs agree varies depending on the specific species. The model successfully captures the overall spatial and temporal variations of major alkanes (e.g. ethane, n-butane) and unsaturated species (e.g. ethene, benzene) but less so for propane, i-butane, and ethyne. This discrepancy underscores potential issues in the boundary conditions for the latter species and in their primary emissions from, in particular, the solvent and road transport sectors. Specifically, potential missing propane emissions and issues with its boundary conditions are highlighted by large model underestimations and smaller propane-to-ethane ratios compared to the measurement. Meanwhile, both the model and measurements show strong linear correlations among butane isomers and among pentane isomers, indicating common sources for these pairs of isomers. However, modelled ratios of i-butane to n-butane and i-pentane to n-pentane are approximately one-third of the measured ratios, which is largely driven by significant emissions of n-butane and n-pentane from the solvent sector. This suggests issues with the speciation profile of the solvent sector, underrepresented contributions from transport and fuel evaporation sectors in current inventories, or both. Furthermore, the modelled ethene-to-ethyne and benzene-to-ethyne ratios differ significantly from measured ratios. The different model performance strongly points to shortcomings in the spatial and temporal patterns and magnitudes of ethyne emissions, especially during winter. For OVOCs, the modelled and measured concentrations of methanal and methylglyoxal show a good agreement, despite a moderate underestimation by the model in summer. This discrepancy could be attributed to an underestimation of contributions from biogenic sources or possibly a model overestimation of their photolytic loss in summer. However, the insufficiency of suitable measurements limits the evaluation of other OVOCs. Finally, model simulations employing the CAMS inventory show slightly better agreements with measurements than those using the Centre on Emission Inventories and Projections (CEIP) inventory. This enhancement is likely due to the CAMS inventory's detailed segmentation of the road transport sector, including its associated sub-sector-specific emission profiles. Given this improvement, alongside the previously mentioned concerns about the model's biased estimations of various VOC ratios, future efforts should focus on a more detailed breakdown of dominant emission sectors (e.g. solvents) and the refinement of their speciation profiles to improve model accuracy.

SIMBAD: a simplified emission-concentration model for a computationally efficient assessment of energy policies impact on air quality

The reconstruction of airborne pollutant concentration fields based on emission reduction scenarios is a complex task. Simulations with chemistry and transport models (CTM) are computationally expensive and not suited for iterative optimisation that could require the evaluation of a great number of scenarios. To address this, data-driven surrogate models have been used to approximate the relationship between emission and ambient air concentrations. In this study, a different approach is presented. SIMBAD is a simplified model based on CAMx (Comprehensive Air Quality Model with Extensions) and the Direct Decoupled Method (DDM) algorithm that estimates concentration changes due to variations in emission fields. SIMBAD was validated by comparing PM10 and NO2 concentrations with CAMx simulations implementing the same emission variations. The testing scenarios involved different emission reductions and precursor species to assess SIMBAD’s performance in both simple and complex cases. The model’s performance in reproducing the non-linear nature of atmospheric processes was satisfactory, showing an average Root Mean Square Error (RMSE) always lower than 0.2 μg/m3 and a normalised bias below 2%. Slightly lower accuracy was found in more complex scenarios involving multiple pollutants and sectors modified simultaneously. Overall, SIMBAD proved to be an efficient and accurate tool for evaluating the impacts of energy policies on air quality, providing valuable insights for policymakers and researchers alike.

Observation and modeling of high-<sup>7</sup>Be concentration events at the surface in northern Europe associated with the instability of the Arctic polar vortex in early 2003

Abstract. Events of very high concentrations of 7Be cosmogenic radionuclide have been recorded at low-elevation surface stations in the subpolar regions of Europe during the cold season. With an aim to investigate the mechanisms responsible for those peak 7Be events, and in particular to verify if they are associated with the fast descent of stratospheric air masses occurring during sudden stratospheric warming (SSW) events, we analyze 7Be observations at six sampling sites in Fennoscandia during January–March 2003 when very high 7Be concentrations were observed and the Arctic vortex was relatively unstable as a consequence of several SSW events. We use the GEOS-Chem chemistry and transport model driven by the MERRA-2 meteorological reanalysis to simulate tropospheric 7Be over northern Europe. We show that the model reasonably reproduces the temporal evolution of surface 7Be concentrations observed at the six sampling sites. Our analysis of model simulations, surface 7Be observations, atmospheric soundings of ozone and temperature and surface ozone measurements indicates that the 7Be peak observed in late February 2003 (between 20 and 28 February 2003) at the six sampling sites in Fennoscandia was associated with downward transport of stratospheric vortex air that originated during an SSW that occurred a few days earlier (between 18 and 21 February 2003).

Evaluation of global EMEP MSC-W (rv4.34) WRF (v3.9.1.1) model surface concentrations and wet deposition of reactive N and S with measurements

Abstract. Atmospheric pollution has many profound effects on human health, ecosystems, and the climate. Of concern are high concentrations and deposition of reactive nitrogen (Nr) species, especially of reduced N (gaseous NH3, particulate NH4+). Atmospheric chemistry and transport models (ACTMs) are crucial to understanding sources and impacts of Nr chemistry and its potential mitigation. Here we undertake the first evaluation of the global version of the EMEP MSC-W ACTM driven by WRF meteorology (1∘×1∘ resolution), with a focus on surface concentrations and wet deposition of N and S species relevant to investigation of atmospheric Nr and secondary inorganic aerosol (SIA). The model–measurement comparison is conducted both spatially and temporally, covering 10 monitoring networks worldwide. Model simulations for 2010 compared use of both HTAP and ECLIPSEE (ECLIPSE annual total with EDGAR monthly profile) emissions inventories; those for 2015 used ECLIPSEE only. Simulations of primary pollutants are somewhat sensitive to the choice of inventory in places where regional differences in primary emissions between the two inventories are apparent (e.g. China) but are much less sensitive for secondary components. For example, the difference in modelled global annual mean surface NH3 concentration using the two 2010 inventories is 18 % (HTAP: 0.26 µg m−3; ECLIPSEE: 0.31 µg m−3) but is only 3.5 % for NH4+ (HTAP: 0.316 µg m−3; ECLIPSEE: 0.305 µg m−3). Comparisons of 2010 and 2015 surface concentrations between the model and measurements demonstrate that the model captures the overall spatial and seasonal variations well for the major inorganic pollutants NH3, NO2, SO2, HNO3, NH4+, NO3-, and SO42- and their wet deposition in East Asia, Southeast Asia, Europe, and North America. The model shows better correlations with annual average measurements for networks in Southeast Asia (mean R for seven species: R7‾=0.73), Europe (R7‾=0.67), and North America (R7‾=0.63) than in East Asia (R5‾=0.35) (data for 2015), which suggests potential issues with the measurements in the latter network. Temporally, both model and measurements agree on higher NH3 concentrations in spring and summer and lower concentrations in winter. The model slightly underestimates annual total precipitation measurements (by 13 %–45 %) but agrees well with the spatial variations in precipitation in all four world regions (0.65–0.94 R range). High correlations between measured and modelled NH4+ precipitation concentrations are also observed in all regions except East Asia. For annual total wet deposition of reduced N, the greatest consistency is in North America (0.75–0.82 R range), followed by Southeast Asia (R=0.68) and Europe (R=0.61). Model–measurement bias varies between species in different networks; for example, bias for NH4+ and NO3- is largest in Europe and North America and smallest in East Asia and Southeast Asia. The greater uniformity in spatial correlations than in biases suggests that the major driver of model–measurement discrepancies (aside from differing spatial representativeness and uncertainties and biases in measurements) are shortcomings in absolute emissions rather than in modelling the atmospheric processes. The comprehensive evaluations presented in this study support the application of this model framework for global analysis of current and potential future budgets and deposition of Nr and SIA.

Present-day radiative effect from radiation-absorbing aerosols in snow

Abstract. Black carbon (BC), brown carbon (BrC), and soil dust are the most important radiation-absorbing aerosols (RAAs). When RAAs are deposited on the snowpack, they lower the snow albedo, causing an increase in the solar radiation absorption. The climatic impact associated with the snow darkening induced by RAAs is highly uncertain. The Intergovernmental Panel on Climate Change (IPCC) Special Report on the Ocean and Cryosphere in a Changing Climate (SROCC) attributes low and medium confidence to radiative forcing (RF) from BrC and dust in snow, respectively. Therefore, the contribution of anthropogenic sources and carbonaceous aerosols to RAA RF in snow is not clear. Moreover, the snow albedo perturbation induced by a single RAA species depends on the presence of other light-absorbing impurities contained in the snowpack. In this work, we calculated the present-day RF of RAAs in snow starting from the deposition fields from a 5-year simulation with the GEOS-Chem global chemistry and transport model. RF was estimated taking into account the presence of BC, BrC, and mineral soil dust in snow, simultaneously. Modeled BC and black carbon equivalent (BCE) mixing ratios in snow and the fraction of light absorption due to non-BC compounds (fnon-BC) were compared with worldwide observations. We showed that BC, BCE, and fnon-BC, obtained from deposition and precipitation fluxes, reproduce the regional variability and order of magnitude of the observations. Global-average all-sky total RAA-, BC-, BrC-, and dust-snow RF were 0.068, 0.033, 0.0066, and 0.012 W m−2, respectively. At a global scale, non-BC compounds accounted for 40 % of RAA-snow RF, while anthropogenic RAAs contributed to the forcing for 56 %. With regard to non-BC compounds, the largest impact of BrC has been found during summer in the Arctic (+0.13 W m−2). In the middle latitudes of Asia, the forcing from dust in spring accounted for 50 % (+0.24 W m−2) of the total RAA RF. Uncertainties in absorbing optical properties, RAA mixing ratio in snow, snow grain dimension, and snow cover fraction resulted in an overall uncertainty of −50 %/+61 %, −57 %/+183 %, −63 %/+112 %, and −49 %/+77 % in BC-, BrC-, dust-, and total RAA-snow RF, respectively. Uncertainty upper bounds of BrC and dust were about 2 and 3 times larger than the upper bounds associated with BC. Higher BrC and dust uncertainties were mainly due to the presence of multiple absorbing impurities in the snow. Our results highlight that an improvement of the representation of RAAs in snow is desirable, given the potential high efficacy of this forcing.

Sources of gaseous NH3 in urban Beijing from parallel sampling of NH3 and NH4+, their nitrogen isotope measurement and modeling

Atmospheric gaseous ammonia (NH3) is the most abundant alkaline gas in the atmosphere while aerosol ammonium (NH4+) constitutes a majority of the inorganic cation concentration in total PM2.5 mass and plays a vital role in severe haze formation. This study tried to shed some light on sources of gaseous NH3 through integrating the parallel measurements of δ15N values in NH4+ and ambient NH3, NH3 source signature measurement, IsoSource model, and chemistry and transport model (CTM). As a result, predicted initial δ15N (NH3) values ranging from −42.0‰ to −4.9‰ were derived from daily δ15N(NH4+) values of fine particulate NH4+, and δ15N(NH3) values ranging from −26.8‰ to −17.2‰ were obtained from weekday/weekend δ15N(NH3) values, respectively. During summer, non-agricultural sources (e.g. fossil fuel sources, urban waste) contributed 63% to ambient NH3 in urban Beijing, derived from δ15N(NH3) values whereas 64% to ambient NH3, derived from δ15N(NH4+) values. These results suggested that non-agricultural sources were main contributors to gaseous NH3 even during summer and agricultural sources were not likely the main source of gaseous NH3 in urban Beijing. To further reduce the uncertainty of isotope-based source apportionment results, more laboratory and field studies are necessary to refine the δ15N(NH3) source profile of NH3 using validated collection technique as overlapping exist between δ15N(NH3) values in agricultural sources such as livestock breeding waste (−42.5‰ to −29.1‰) and fertilizer application (−51.5‰ to −35.0‰).

Effects of elevated ozone concentration and nitrogen addition on ammonia stomatal compensation point in a poplar clone

The stomatal compensation point of ammonia (χs) is a key factor controlling plant-atmosphere NH3 exchange, which is dependent on the nitrogen (N) supply and varies among plant species. However, knowledge gaps remain concerning the effects of elevated atmospheric N deposition and ozone (O3) on χs for forest species, resulting in large uncertainties in the parameterizations of NH3 incorporated into atmospheric chemistry and transport models (CTMs). Here, we present leaf-scale measurements of χs for hybrid poplar clone ‘546’ (Populusdeltoides cv. 55/56 x P. deltoides cv. Imperial) growing in two N treatments (N0, no N added; N50, 50 kg N ha−1 yr−1 urea fertilizer added) and two O3 treatments (CF, charcoal-filtered air; E-O3, non-filtered air plus 40 ppb) for 105 days. Our results showed that χs was significantly reduced by E-O3 (41%) and elevated N (19%). The interaction of N and O3 was significant, and N can mitigate the negative effects of O3 on χs. Elevated O3 significantly reduced the light-saturated photosynthetic rate (Asat) and chlorophyll (Chl) content and significantly increased intercellular CO2 concentrations (Ci), but had no significant effect on stomatal conductance (gs). By contrast, elevated N did not significantly affect all measured photosynthetic parameters. Overall, χs was significantly and positively correlated with Asat, gs and Chl, whereas a significant and negative relationship was observed between χs and Ci. Our results suggest that O3-induced changes in Asat, Ci and Chl may affect χs. Our findings provide a scientific basis for optimizing parameterizations of χs in CTMs in response to environmental change factors (i.e., elevated N deposition and/or O3) in the future.

Influence of anthropogenic emissions and boundary conditions on multi-model simulations of major air pollutants over Europe and North America in the framework of AQMEII3.

In the framework of the third phase of the Air Quality Model Evaluation International Initiative (AQMEII3), and as contribution to the second phase of the Hemispheric Transport of Air Pollution (HTAP2) activities for Europe and North America, the impacts of a 20 % decrease of global and regional anthropogenic emissions on surface air pollutant levels in 2010 are simulated by an international community of regional-scale air quality modeling groups, using different state-of-the-art chemistry and transport models (CTMs). The emission perturbations at the global level, as well as over the HTAP2-defined regions of Europe, North America and East Asia, are first simulated by the global Composition Integrated Forecasting System (C-IFS) model from European Centre for Medium-Range Weather Forecasts (ECMWF), which provides boundary conditions to the various regional CTMs participating in AQMEII3. On top of the perturbed boundary conditions, the regional CTMs used the same set of perturbed emissions within the regional domain for the different perturbation scenarios that introduce a 20 % reduction of anthropogenic emissions globally as well as over the HTAP2-defined regions of Europe, North America and East Asia.Results show that the largest impacts over both domains are simulated in response to the global emission perturbation, mainly due to the impact of domestic emission reductions. The responses of NO2, SO2 and PM concentrations to a 20 % anthropogenic emission reduction are almost linear (~ 20 % decrease) within the global perturbation scenario with, however, large differences in the geographical distribution of the effect. NO2, CO and SO2 levels are strongly affected over the emission hot spots. O3 levels generally decrease in all scenarios by up to ~ 1 % over Europe, with increases over the hot spot regions, in particular in the Benelux region, by an increase up to ~ 6 % due to the reduced effect of NOx titration. O3 daily maximum of 8 h running average decreases in all scenarios over Europe, by up to ~ 1 %. Over the North American domain, the central-to-eastern part and the western coast of the US experience the largest response to emission perturbations. Similar but slightly smaller responses are found when domestic emissions are reduced. The impact of intercontinental transport is relatively small over both domains, however, still noticeable particularly close to the boundaries. The impact is noticeable up to a few percent, for the western parts of the North American domain in response to the emission reductions over East Asia. O3 daily maximum of 8 h running average decreases in all scenarios over north Europe by up to ~ 5 %. Much larger reductions are calculated over North America compared to Europe.In addition, values of the Response to Extra-Regional Emission Reductions (RERER) metric have been calculated in order to quantify the differences in the strengths of nonlocal source contributions to different species among the different models. We found large RERER values for O3 (~ 0.8) over both Europe and North America, indicating a large contribution from non-local sources, while for other pollutants including particles, low RERER values reflect a predominant control by local sources. A distinct seasonal variation in the local vs. non-local contributions has been found for both O3 and PM2.5, particularly reflecting the springtime long-range transport to both continents.

A quantitative analysis of the reactions involved in stratospheric ozone depletion in the polar vortex core

Abstract. We present a quantitative analysis of the chemical reactions involved in polar ozone depletion in the stratosphere and of the relevant reaction pathways and cycles. While the reactions involved in polar ozone depletion are well known, quantitative estimates of the importance of individual reactions or reaction cycles are rare. In particular, there is no comprehensive and quantitative study of the reaction rates and cycles averaged over the polar vortex under conditions of heterogeneous chemistry so far. We show time series of reaction rates averaged over the core of the polar vortex in winter and spring for all relevant reactions and indicate which reaction pathways and cycles are responsible for the vortex-averaged net change of the key species involved in ozone depletion, i.e., ozone, chlorine species (ClOx, HCl, ClONO2), bromine species, nitrogen species (HNO3, NOx) and hydrogen species (HOx). For clarity, we focus on one Arctic winter (2004–2005) and one Antarctic winter (2006) in a layer in the lower stratosphere around 54 hPa and show results for additional pressure levels and winters in the Supplement. Mixing ratios and reaction rates are obtained from runs of the ATLAS Lagrangian chemistry and transport model (CTM) driven by the European Centre for Medium-Range Weather Forecasts (ECMWF) ERA-Interim reanalysis data. An emphasis is put on the partitioning of the relevant chemical families (nitrogen, hydrogen, chlorine, bromine and odd oxygen) and activation and deactivation of chlorine.

Sensitivity of tropospheric loads and lifetimes of short lived pollutants to fire emissions

Abstract. The capability of global chemistry and transport models (CTMs) to simulate atmospheric composition and its spatial and temporal changes highly relies on the input data used by the models, in particular the emission inventories. Biomass burning emissions show large spatial, diurnal, seasonal and year-to-year variability. In the present study, we applied a global 3-D CTM to evaluate uncertainties in the computed atmospheric composition associated with the use of different biomass burning emissions and identify areas where observational data can help to reduce these uncertainties. We find the emission inventory choice to lead to regional differences in the calculated load of aerosols up to a factor of 4. Assumptions on the injection height of the biomass burning emissions are found to produce regionally up to 30% differences in the calculated tropospheric lifetimes of pollutants. Computed changes in lifetimes point to a strong chemical feedback mechanism between emissions from biomass burning and isoprene emissions from vegetation that are linked via NOx-driven oxidant chemistry, NOx-dependent changes in isoprene oxidation products, aerosol emissions and atmospheric transport. These interactions reduce isoprene load in the presence of biomass burning emissions by 15%, calculated for the same amount of isoprene emitted into the troposphere. Thus, isoprene load and lifetime are inversely related to the quantities of pollutants emitted by biomass burning. These interactions are shown to be able to increase the global annual secondary aerosol yield from isoprene emissions, defined as the ratio of tropospheric loads of secondary aerosol from isoprene oxidation to isoprene emissions, by up to 18%.

U.S. NO2 trends (2005–2013): EPA Air Quality System (AQS) data versus improved observations from the Ozone Monitoring Instrument (OMI)

Emissions of nitrogen oxides (NOx) and, subsequently, atmospheric levels of nitrogen dioxide (NO2) have decreased over the U.S. due to a combination of environmental policies and technological change. Consequently, NO2 levels have decreased by 30–40% in the last decade. We quantify NO2 trends (2005–2013) over the U.S. using surface measurements from the U.S. Environmental Protection Agency (EPA) Air Quality System (AQS) and an improved tropospheric NO2 vertical column density (VCD) data product from the Ozone Monitoring Instrument (OMI) on the Aura satellite. We demonstrate that the current OMI NO2 algorithm is of sufficient maturity to allow a favorable correspondence of trends and variations in OMI and AQS data. Our trend model accounts for the non-linear dependence of NO2 concentration on emissions associated with the seasonal variation of the chemical lifetime, including the change in the amplitude of the seasonal cycle associated with the significant change in NOx emissions that occurred over the last decade. The direct relationship between observations and emissions becomes more robust when one accounts for these non-linear dependencies. We improve the OMI NO2 standard retrieval algorithm and, subsequently, the data product by using monthly vertical concentration profiles, a required algorithm input, from a high-resolution chemistry and transport model (CTM) simulation with varying emissions (2005–2013). The impact of neglecting the time-dependence of the profiles leads to errors in trend estimation, particularly in regions where emissions have changed substantially. For example, trends calculated from retrievals based on time-dependent profiles offer 18% more instances of significant trends and up to 15% larger total NO2 reduction versus the results based on profiles for 2005. Using a CTM, we explore the theoretical relation of the trends estimated from NO2 VCDs to those estimated from ground-level concentrations. The model-simulated trends in VCDs strongly correlate with those estimated from surface concentrations (r = 0.83, N = 355). We then explore the observed correspondence of trends estimated from OMI and AQS data. We find a significant, but slightly weaker, correspondence (i.e., r = 0.68, N = 208) than predicted by the model and discuss some of the important factors affecting the relationship, including known problems (e.g., NOz interferents) associated with the AQS data. This significant correspondence gives confidence in trend and surface concentration estimates from OMI VCDs for locations, such as the majority of the U.S. and globe, that are not covered by surface monitoring networks. Using our improved trend model and our enhanced OMI data product, we find that both OMI and AQS data show substantial downward trends from 2005 to 2013, with an average reduction of 38% for each over the U.S. The annual reduction rates inferred from OMI and AQS measurements are larger (−4.8 ± 1.9%/yr, −3.7 ± 1.5%/yr) from 2005 to 2008 than 2010 to 2013 (−1.2 ± 1.2%/yr, −2.1 ± 1.4%/yr). We quantify NO2 trends for major U.S. cities and power plants; the latter suggest larger negative trend (−4.0 ± 1.5%/yr) between 2005 and 2008 and smaller or insignificant changes (−0.5 ± 1.2%/yr) during 2010–2013.

A tropical West Pacific OH minimum and implications for stratospheric composition

Abstract. Most of the short-lived biogenic and anthropogenic chemical species that are emitted into the atmosphere break down efficiently by reaction with OH and do not reach the stratosphere. Here we show the existence of a pronounced minimum in the tropospheric column of ozone over the West Pacific, the main source region for stratospheric air, and suggest a corresponding minimum of the tropospheric column of OH. This has the potential to amplify the impact of surface emissions on the stratospheric composition compared to the impact when assuming globally uniform OH conditions. Specifically, the role of emissions of biogenic halogenated species for the stratospheric halogen budget and the role of increasing emissions of SO2 in Southeast Asia or from minor volcanic eruptions for the increasing stratospheric aerosol loading need to be reassessed in light of these findings. This is also important since climate change will further modify OH abundances and emissions of halogenated species. Our study is based on ozone sonde measurements carried out during the TransBrom cruise with the RV Sonne roughly along 140–150° E in October 2009 and corroborating ozone and OH measurements from satellites, aircraft campaigns and FTIR instruments. Model calculations with the GEOS-Chem Chemistry and Transport Model (CTM) and the ATLAS CTM are used to simulate the tropospheric OH distribution over the West Pacific and the transport pathways to the stratosphere. The potential effect of the OH minimum on species transported into the stratosphere is shown via modeling the transport and chemistry of CH2Br2 and SO2.

Validation of ozone data from the Superconducting Submillimeter‐Wave Limb‐Emission Sounder (SMILES)

The Superconducting Submillimeter‐Wave Limb‐Emission Sounder (SMILES) onboard the International Space Station provided global measurements of ozone profiles in the middle atmosphere from 12 October 2009 to 21 April 2010. We present validation studies of the SMILES version 2.1 ozone product based on coincidence statistics with satellite observations and outputs of chemistry and transport models (CTMs). Comparisons of the stratospheric ozone with correlative data show agreements that are generally within 10%. In the mesosphere, the agreement is also good and better than 30% even at a high altitude of 73 km, and the SMILES measurements with their local time coverage also capture the diurnal variability very well. The recommended altitude range for scientific use is from 16 to 73 km. We note that the SMILES ozone values for altitude above 26 km are smaller than some of the correlative satellite datasets; conversely the SMILES values in the lower stratosphere tend to be larger than correlative data, particularly in the tropics, with less than 8% difference below ~24 km. The larger values in the lower stratosphere are probably due to departure of retrieval results between two detection bands at altitudes below 28 km; it is ~3% at 24 km and is increasing rapidly down below.

The contributions of chemistry and transport to low arctic ozone in March 2011 derived from Aura MLS observations

Stratospheric and total columns of Arctic O3 (63–90oN) in late March 2011 averaged 320 and 349 DU, respectively, 50–100 DU lower than any of the previous 6 years. We use Aura Microwave Limb Sounder (MLS) O3 observations to quantify the roles of chemistry and transport and find there are two major reasons for low O3 in March 2011: heterogeneous chemical loss and a late final warming that delayed the resupply of O3 until April. Daily vortex‐averaged partial columns in the lowermost stratosphere (p > 133 hPa) and middle stratosphere (p < 29 hPa) are largely unaffected by local heterogeneous chemistry, according to model calculations. Very weak transport into the vortex between late January and late March contributes to the observed low ozone. The lower stratospheric (LS) column (133–29 hPa, ~370–550 K) is affected by both heterogeneous chemistry and transport. Because MLS N2O data show strong isolation of the vortex, we estimate the contribution of vertical transport to LS O3 using the descent of vortex N2O profiles. Simulations with the Global Modeling Initiative (GMI) chemistry and transport model (CTM) with and without heterogeneous chemical reactions show 73 DU vortex averaged O3 loss; the loss derived from MLS O3 is 84 ± 12 DU. The GMI simulation reproduces the observed O3 and N2O with little error and demonstrates credible transport and chemistry. Without heterogeneous chemical loss, March 2011 vortex O3 would have been at least 40 DU lower than climatology due to the late final warming that did not resupply O3 until mid‐April.

Results from a new linear O<sub>3</sub> scheme with embedded heterogeneous chemistry compared with the parent full-chemistry 3-D CTM

Abstract. A detailed full-chemistry 3-D chemistry and transport model (CTM) is used to evaluate the current stratospheric O3 parameterisation in the European Centre for Medium-Range Weather Forecasts (ECMWF) model and to obtain an alternative version of the ozone scheme implicitly including heterogeneous chemistry. The approach avoids the inaccurate treatment currently given to heterogeneous ozone chemistry in the ECMWF model, as well as the uncertainties of a cold-tracer. The new O3 scheme (COPCAT) is evaluated within the same CTM used to calculate it. It is the first time such a comparison has been possible, providing direct information on the validity of the linear parameterisation approach for stratospheric ozone. Simulated total column and O3 profiles are compared against Total Ozone Mapping Spectrometer (TOMS) and Halogen Occultation Experiment (HALOE) observations. COPCAT successfully simulates polar loss and reproduces a realistic Antarctic O3 hole. The new scheme is comparable to the full-chemistry in many regions for multiannual runs. The parameterisation produces less ozone over the tropics around 10 hPa, compared to full-chemistry and observations. However, this problem can be ameliorated by choosing a different ozone climatology for the scheme. The new scheme is compared to the current ECMWF scheme in the same CTM runs. The Antarctic O3 hole with the current ECMWF scheme is weaker and disappears earlier than with the new COPCAT scheme. Differences between the current ECMWF scheme and COPCAT are difficult to explain due to the different approach used for heterogeneous chemistry and differences in the photochemical models used to calculate the scheme coefficients. Results with the new COPCAT scheme presented here show that heterogeneous and homogeneous ozone chemistry can be included in a consistent way in a linear ozone parameterisation, without any additional tunable parameters, providing a parameterisation scheme in better agreement with the current knowledge of stratospheric O3 chemistry than previous approaches.

The Lagrangian chemistry and transport model ATLAS: simulation and validation of stratospheric chemistry and ozone loss in the winter 1999/2000

Abstract. ATLAS is a new global Lagrangian Chemistry and Transport Model (CTM), which includes a stratospheric chemistry scheme with 46 active species, 171 reactions, heterogeneous chemistry on polar stratospheric clouds and a Lagrangian denitrification module. Lagrangian (trajectory-based) models have several important advantages over conventional Eulerian models, including the absence of spurious numerical diffusion, efficient code parallelization and no limitation of the largest time step by the Courant-Friedrichs-Lewy criterion. This work describes and validates the stratospheric chemistry scheme of the model. Stratospheric chemistry is simulated with ATLAS for the Arctic winter 1999/2000, with a focus on polar ozone depletion and denitrification. The simulations are used to validate the chemistry module in comparison with measurements of the SOLVE/THESEO 2000 campaign. A Lagrangian denitrification module, which is based on the simulation of the nucleation, sedimentation and growth of a large number of polar stratospheric cloud particles, is used to model the substantial denitrification that occured in this winter.

The impact of tropical recirculation on polar composition

Abstract. We derive the tropical modal age of air from an analysis of the water vapor tape recorder. We combine the observationally derived modal age with mean age of air from CO2 and SF6 to create diagnostics for the independent evaluation of the vertical transport rate and horizontal recirculation into the tropics between 16–32 km. These diagnostics are applied to two Global Modeling Initiative (GMI) chemistry and transport model (CTM) age tracer simulations to give new insights into the tropical transport characteristics of the meteorological fields from the GEOS4-GCM and the GEOS4-DAS. Both simulations are found to have modal ages that are in reasonable agreement with the empirically derived age (i.e., transit times) over the entire altitude range. Both simulations show too little horizontal recirculation into the tropics above 22 km, with the GEOS4-DAS fields having greater recirculation. Using CH4 as a proxy for mean age, comparisons between HALOE and model CH4 in the Antarctic demonstrate how the strength of tropical recirculation affects polar composition in both CTM experiments. Better tropical recirculation tends to improve the CH4 simulation in the Antarctic. However, mean age in the Antarctic lower stratosphere can be compromised by poor representation of tropical ascent, tropical recirculation, or vortex barrier strength. The connection between polar and tropical composition shown in this study demonstrates the importance of diagnosing each of these processes separately in order to verify the adequate representation of the processes contributing to polar composition in models.

Simulation of upper tropospheric CO2 from chemistry and transport models

The California Institute of Technology/Jet Propulsion Laboratory two‐dimensional (2‐D), three‐dimensional (3‐D) GEOS‐Chem, and 3‐D MOZART‐2 chemistry and transport models (CTMs), driven respectively by NCEP2, GEOS‐4, and NCEP1 reanalysis data, have been used to simulate upper tropospheric CO2 from 2000 to 2004. Model results of CO2 mixing ratios agree well with monthly mean aircraft observations at altitudes between 8 and 13 km (Matsueda et al., 2002) in the tropics. The upper tropospheric CO2 seasonal cycle phases are well captured by the CTMs. Model results have smaller seasonal cycle amplitudes in the Southern Hemisphere compared with those in the Northern Hemisphere, which are consistent with the aircraft data. Some discrepancies are evident between the model and aircraft data in the midlatitudes, where models tend to underestimate the amplitude of CO2 seasonal cycle. Comparison of the simulated vertical profiles of CO2 between the different models reveals that the convection in the 3‐D models is likely too weak in boreal winter and spring. Model sensitivity studies suggest that convection mass flux is important for the correct simulation of upper tropospheric CO2.

Contribution of stratospheric ozone to the interannual variability of tropospheric ozone in the northern extratropics

We examined the role of variability in the input of stratospheric ozone on the interannual variability of tropospheric ozone in the northern extratropics using correlations of monthly ozone anomalies for the lower stratosphere and the troposphere. We used output from a multiyear simulation of the NASA Goddard Space Flight Center (GSFC) Chemistry and Transport Model (CTM), and evaluated model results using ozonesonde data. The GSFC CTM explicitly calculates stratospheric ozone and simulates separate tracers of stratospheric and tropospheric ozone (O3‐strat and O3‐trop, respectively). The climatological seasonal cycle of ozone shows that O3‐strat contributes significantly to the spring maximum of ozone at 500 hPa, ∼40% at high latitudes and ∼30% at midlatitudes. We find large regional differences in the correlation of ozone in the lower stratosphere and troposphere in the model that are supported by the ozonesonde data. Highest correlations are found from the eastern Atlantic to Europe, from the eastern Pacific to the western United States, and over the polar regions, in winter‐spring. This spatial pattern is due to the input of O3‐strat into the troposphere. The distribution and time lag of the correlations (highest with no lag for midlatitudes and a 1–2 month lag for polar regions) are consistent with the dynamical indicators of stratosphere‐troposphere exchange (STE), such as storm tracks in the midlatitudes and slow descending motion in the polar region. Our simple approach can be widely applied to diagnose the effect of STE on tropospheric ozone.

Global isoprene emissions estimated using MEGAN, ECMWF analyses and a detailed canopy environment model

Abstract. The global emissions of isoprene are calculated at 0.5° resolution for each year between 1995 and 2006, based on the MEGAN (Model of Emissions of Gases and Aerosols from Nature) version 2 model (Guenther et al., 2006) and a detailed multi-layer canopy environment model for the calculation of leaf temperature and visible radiation fluxes. The calculation is driven by meteorological fields – air temperature, cloud cover, downward solar irradiance, windspeed, volumetric soil moisture in 4 soil layers – provided by analyses of the European Centre for Medium-Range Weather Forecasts (ECMWF). The estimated annual global isoprene emission ranges between 374 Tg (in 1996) and 449 Tg (in 1998 and 2005), for an average of ca. 410 Tg/year over the whole period, i.e. about 30% less than the standard MEGAN estimate (Guenther et al., 2006). This difference is due, to a large extent, to the impact of the soil moisture stress factor, which is found here to decrease the global emissions by more than 20%. In qualitative agreement with past studies, high annual emissions are found to be generally associated with El Niño events. The emission inventory is evaluated against flux measurement campaigns at Harvard forest (Massachussets) and Tapajós in Amazonia, showing that the model can capture quite well the short-term variability of emissions, but that it fails to reproduce the observed seasonal variation at the tropical rainforest site, with largely overestimated wet season fluxes. The comparison of the HCHO vertical columns calculated by a chemistry and transport model (CTM) with HCHO distributions retrieved from space provides useful insights on tropical isoprene emissions. For example, the relatively low emissions calculated over Western Amazonia (compared to the corresponding estimates in the inventory of Guenther et al., 1995) are validated by the excellent agreement found between the CTM and HCHO data over this region. The parameterized impact of the soil moisture stress on isoprene emissions is found to reduce the model/data bias over Australia, but it leads to underestimated emissions near the end of the dry season over subtropical Africa.