We provide a comprehensive description of the high-resolution version of the TM5-MP global chemistry transport model, which is to be employed for deriving highly resolved vertical profiles of nitrogen dioxide (NO₂), formaldehyde (CH₂O), and sulfur dioxide (SO₂) for use in satellite retrievals from platforms such as the Ozone Monitoring Instrument (OMI) and the Sentinel-5 Precursor, and the TROPOspheric Monitoring Instrument (tropOMI). Comparing simulations conducted at horizontal resolutions of 3° × 2° and 1° × 1° reveals differences of ±20 % exist in the global seasonal distribution of ²²²Rn, being larger near specific coastal locations and tropical oceans. For tropospheric ozone (O₃), analysis of the chemical budget terms shows that the impact on globally integrated photolysis rates is rather low, in spite of the higher spatial variability of meteorological data fields from ERA-Interim at 1° × 1°. Surface concentrations of O₃ in high-NO_x regions decrease between 5 and 10 % at 1° × 1° due to a reduction in NO_x recycling terms and an increase in the associated titration term of O₃ by NO. At 1° × 1°, the net global stratosphere–troposphere exchange of O₃ decreases by ∼ 7 %, with an associated shift in the hemispheric gradient. By comparing NO, NO₂, HNO₃ and peroxy-acetyl-nitrate (PAN) profiles against measurement composites, we show that TM5-MP captures the vertical distribution of NO_x and long-lived NO_x reservoirs at background locations, again with modest changes at 1° × 1°. Comparing monthly mean distributions in lightning NO_x and applying ERA-Interim convective mass fluxes, we show that the vertical re-distribution of lightning NO_x changes with enhanced release of NO_x in the upper troposphere. We show that surface mixing ratios in both NO and NO₂ are generally underestimated in both low- and high-NO_x scenarios. For Europe, a negative bias exists for [NO] at the surface across the whole domain, with lower biases at 1° × 1° at only ∼ 20 % of sites. For NO₂, biases are more variable, with lower (higher) biases at 1° × 1° occurring at ∼ 35 % ( ∼ 20 %) of sites, with the remainder showing little change. For CH₂O, the impact of higher resolution on the chemical budget terms is rather modest, with changes of less than 5 %. The simulated vertical distribution of CH₂O agrees reasonably well with measurements in pristine locations, although column-integrated values are generally underestimated relative to satellite measurements in polluted regions. For SO₂, the performance at 1° × 1° is principally governed by the quality of the emission inventory, with limited improvements in the site-specific biases, with most showing no significant improvement. For the vertical column, improvements near strong source regions occur which reduce the biases in the integrated column. For remote regions missing biogenic source terms are inferred.

The emission of organic compounds from biogenic processes acts as an important source of trace gases in remote regions away from urban conurbations, and is likely to become more important in future decades due to the further mitigation of anthropogenic emissions that affect air quality and climate forcing. In this study we examine the contribution of biogenic volatile organic compounds (BVOCs) towards global tropospheric composition using the global 3-D chemistry transport model TM5 and the recently developed modified CB05 chemical mechanism. By comparing regional BVOC emission estimates we show that biogenic processes act as dominant sources for many regions and exhibit a large variability in the annually and seasonally integrated emission fluxes. By performing sensitivity studies we find that the contribution of BVOC species containing between 1 to 3 carbon atoms has an impact on the resident mixing ratios of tropospheric O₃ and CO, accounting for ~2.5% and ~10.8% of the simulated global distribution, respectively. This is approximately a third of the cumulative effect introduced by isoprene and the monoterpenes. By examining an ensemble of 3-D global chemistry transport simulations which adopt different global BVOC emission inventories we determine the associated uncertainty introduced towards simulating the composition of the troposphere for the year 2000. By comparing the model ensemble values against a composite of atmospheric measurements we show that the effects on tropospheric O₃ are limited to the lower troposphere (with an uncertainty between −2% to 10%), whereas that for tropospheric CO extends up to the upper troposphere (with an uncertainty of between 10 to 45%). Comparing the mixing ratios for low molecular weight alkenes in TM5 against surface measurements taken in Europe implies that the cumulative emission estimates are too low, regardless of the chosen BVOC inventory. This variability in the global distribution of CO due to BVOC emissions introduces an associated uncertainty in the tropospheric CO burden of 11.4%, which impacts strongly on the oxidative capacity of the troposphere, introducing an uncertainty in the atmospheric lifetime of the greenhouse gas CH₄ of ~3.3%. This study thus identifies the necessity of placing further constraints on non-CH₄ global biogenic emission estimates in large-scale global atmospheric chemistry models.

The chemical composition of the troposphere in the tropics and Southern Hemisphere (SH) is significantly influenced by gaseous emissions released from African biomass burning (BB). Here we investigate how various emission estimates given in bottom-up BB inventories (GFEDv2, GFEDv3, AMMABB) affect simulations of global tropospheric composition using the TM4 chemistry transport model. The application of various model parameterizations for introducing such emissions is also investigated. There are perturbations in near-surface ozone (O₃) and carbon monoxide (CO) of ~60–90% in the tropics and ~5–10% in the SH between different inventories. Increasing the update frequency of the temporal distribution to eight days generally results in decreases of between ~5 and 10% in near-surface mixing ratios throughout the tropics, which is larger than the influence of increasing the injection heights at which BB emissions are introduced. There are also associated differences in the long range transport of pollutants throughout the SH, where the composition of the free troposphere in the SH is sensitive to the chosen BB inventory. Analysis of the chemical budget terms reveals that the influence of increasing the tropospheric CO burden due to BB on oxidative capacity of the troposphere is mitigated by the associated increase in NO_x emissions (and thus O₃) with the variations in the CO/N ratio between inventories being low. For all inventories there is a decrease in the tropospheric chemical lifetime of methane of between 0.4 and 0.8% regardless of the CO emitted from African BB. This has implications for assessing the effect of inter-annual variability in BB on the annual growth rate of methane.

Here we present an efficient and accurate method for the online calculation of photolysis rates relevant to both the stratosphere and troposphere for use in global Chemistry Transport Models and General Circulation Models. The method is a modified version of the band model introduced by Landgraf and Crutzen (1998) which has been updated to improve the performance of the approach for solar zenith angles >72° without the use of any implicit parameterisations. For this purpose, additional sets of band parameters have been defined for instances where the incident angle of the light beam is between 72–93°, in conjunction with a scaling component for the far UV region of the spectrum (λ=178.6–202.0 nm). For incident angles between 85–93° we introduce a modification for pseudo-sphericity that improves the accuracy of the 2-stream approximation. We show that this modified version of the Practical Improved Flux Method (PIFM) is accurate for angles <93° by comparing the resulting height resolved actinic fluxes with a recently developed full spherical reference model. We also show that the modified band method is more accurate than the original, with errors generally being less than ±10% throughout the atmospheric column for a diverse range of chemical species. Moreover, we perform certain sensitivity studies that indicate it is robust and performs well over a wide range of conditions relevant to the atmosphere.

Biomass burning (BB) in southern Africa is the largest emission source of CO and O₃ precursors within Africa during the West African Monsoon (WAM) between June and August. The long range transport and chemical processing of such emissions thus has the potential to exert a dominant influence on the composition of the tropical troposphere over Equatorial Africa (EA) and the Tropical Atlantic Ocean (TAO). We have performed simulations using a three-dimensional global chemistry-transport model (CTM) to quantify the effect that continental transport of such BB plumes has on the EA region. BB emissions from southern Africa were found to exert a significant influence over the TAO and EA between 10° S–20° N. The maximum concentrations in CO and O₃ occur between 0–5° S near the position of the African Easterly Jet – South as placed by the European Centre for Medium range Weather Forecasts (ECMWF) meteorological analysis data. By comparing co-located model output with in-situ measurements we show that the CTM fails to capture the tropospheric profile of CO in southern Africa near the main source region of the BB emissions, as well as the "extreme" concentrations of both CO and O₃ seen between 600–700 hPa over EA around 6° N. For more northerly locations the model exhibits high background concentrations in both CO and O₃ related to BB emissions from southern Africa. By altering both the temporal resolution and the vertical distribution of BB emissions in the model we show that changes in temporal resolution have the largest influence on the transport of trace gases near the source regions, EA, and in the outflow towards the west of Central Africa. Using a set of trajectory calculations we show that the performance of the CTM is heavily constrained by the ECMWF meteorological fields used to drive the CTM, which transport biomass burning plumes from southern Africa into the lower troposphere of the TAO rather than up towards the middle troposphere at 650 hPa. Similar trajectory simulations repeated using an updated meteorological dataset, which assimilates additional measurement data taken around EA, show markedly different origins for pollution events and highlight the current limitations in modelling this tropical region.

The authors present results obtained during the chemistry-transport modeling (CTM) component of the African Monsoon Multidisciplinary Analysis Multimodel Intercomparison Project (AMMAMIP) using the recently developed L3JRCv2 emission dataset for Africa, where emphasis is placed on the summer of 2006. With the use of passive tracers, the authors show that the application of different parameterizations to describe advection, vertical diffusion, and convective mixing in a suite of state-of-the-art global CTMs results in significantly different transport mechanisms westward of the African continent. Moreover, the authors identify that the atmospheric composition over the southern Atlantic is governed by air masses originating from southern Africa for this period, resulting in maximal concentrations around 5°S. Comparisons with ozonesonde measurements at Cotonou (6.2°N, 2.2°E) indicate that the models generally overpredict surface ozone and underpredict ozone in the upper troposphere. Moreover, using recent ai... The authors present results obtained during the chemistry-transport modeling (CTM) component of the African Monsoon Multidisciplinary Analysis Multimodel Intercomparison Project (AMMAMIP) using the recently developed L3JRCv2 emission dataset for Africa, where emphasis is placed on the summer of 2006. With the use of passive tracers, the authors show that the application of different parameterizations to describe advection, vertical diffusion, and convective mixing in a suite of state-of-the-art global CTMs results in significantly different transport mechanisms westward of the African continent. Moreover, the authors identify that the atmospheric composition over the southern Atlantic is governed by air masses originating from southern Africa for this period, resulting in maximal concentrations around 5°S. Comparisons with ozonesonde measurements at Cotonou (6.2°N, 2.2°E) indicate that the models generally overpredict surface ozone and underpredict ozone in the upper troposphere. Moreover, using recent ai...