ALBERT

Description: We present an oxidation mechanism of intermediate size for isoprene (2-methyl-1,3-butadiene) suitable for simulations in regional and global atmospheric chemistry models, which we call MIM2. It is a reduction of the corresponding detailed mechanism in the Master Chemical Mechanism (MCM v3.1) and intended as the second version of the well-established Mainz Isoprene Mechanism (MIM). Our aim is to improve the representation of tropospheric chemistry in regional and global models under all NOx regimes. We evaluate MIM2 and re-evaluate MIM through comparisons with MCM v3.1. We find that MIM and MIM2 compute similar O3, OH and isoprene mixing ratios. Unlike MIM, MIM2 produces small relative biases for NOx and organic nitrogen-containing species due to a good representation of the alkyl and peroxy acyl nitrates (RONO2 and RC(O)OONO2). Moreover, MIM2 computes only small relative biases with respect to hydrogen peroxide (H2O2), methyl peroxide (CH3OOH), methanol (CH3OH), formaldehyde (HCHO), peroxy acetyl nitrate (PAN), and formic and acetic acids (HCOOH and CH3C(O)OH), being always below ≈6% in all NOx scenarios studied. Most of the isoprene oxidation products are represented explicitly, including methyl vinyl ketone (MVK), methacrolein (MACR), hydroxyacetone and methyl glyoxal. MIM2 is mass-conserving with respect to carbon, including CO2 as well. Therefore, it is suitable for studies assessing carbon monoxide (CO) from biogenic sources, as well as for studies focused on the carbon cycle. Compared to MIM, MIM2 considers new species like acetaldehyde (CH3CHO), propene (CH2=CHCH3) and glyoxal (CHOCHO) with global chemical production rates for the year 2005 of 7.3, 9.5 and 33.8 Tg/yr, respectively. Our new mechanism is expected to substantially improve the results of atmospheric chemistry models by more accurately representing the interplay between atmospheric chemistry, transport and deposition, especially of nitrogen reservoir species. MIM2 allows regional and global models to easily incorporate new experimental results on the chemistry of organic species.

Description: The GABRIEL airborne field measurement campaign, conducted over the Guyanas in October 2005, produced measurements of hydroxyl radical (OH) concentration which are significantly higher than can be simulated using current generation models of atmospheric chemistry. Based on the hypothesis that this "missing OH" is due to an as-yet undiscovered mechanism for recycling OH during the oxidation chain of isoprene, we determine that an OH recycling of about 40–50% (compared with 5–10% in current generation isoprene oxidation mechanisms) is necessary in order for our modelled OH to approach the lower error bounds of the OH observed during GABRIEL. Such a large amount of OH in our model leads to unrealistically low mixing ratios of isoprene. In order for our modelled isoprene mixing ratios to match those observed during the campaign, we also require that the effective rate constant for the reaction of isoprene with OH be reduced by about 50% compared with the lower bound of the range recommended by IUPAC. We show that a reasonable explanation for this lower effective rate constant could be the segregation of isoprene and OH in the mixed layer. Our modelling results are consistent with a global, annual isoprene source of about 500 Tg(C) yr−1, allowing experimentally derived and established isoprene flux rates to be reconciled with global models.

Description: The GABRIEL airborne field measurement campaign, conducted over the Guyanas in October 2005, produced measurements of hydroxyl radical (OH) concentration which are significantly higher than can be simulated using current generation models of atmospheric chemistry. Based on the hypothesis that this "missing OH" is due to an as-yet undiscovered mechanism for recycling OH during the oxidation chain of isoprene, we determine that an OH recycling of about 40–50% (compared with 5–10% in current generation isoprene oxidation mechanisms) is necessary in order for our modelled OH to approach the lower error bounds of the OH observed during GABRIEL. Such a large amount of OH in our model leads to unrealistically low mixing ratios of isoprene. In order for our modelled isoprene mixing ratios to match those observed during the campaign, we also require that the effective rate constant for the reaction of isoprene with OH be reduced by about 50% compared with the lower bound of the range recommended by IUPAC. We show that a reasonable explanation for this lower effective rate constant could be the segregation of isoprene and OH in the mixed layer. Our modelling results are consistent with a global, annual isoprene source of about 500 Tg(C) yr−1, allowing experimentally derived and established isoprene flux rates to be reconciled with global models.

Description: We present an oxidation mechanism of intermediate size for isoprene (2-methyl-1,3-butadiene) suitable for simulations in regional and global atmospheric chemistry models, which we call MIM2. It is a reduction of the corresponding detailed mechanism in the Master Chemical Mechanism (MCM v3.1) and intended as the second version of the well-established Mainz Isoprene Mechanism (MIM). Our aim is to improve the representation of tropospheric chemistry in regional and global models under all NOx regimes. We evaluate MIM2 and re-evaluate MIM through comparisons with MCM v3.1. We find that MIM and MIM2 compute similar O3, OH and isoprene mixing ratios. Unlike MIM, MIM2 produces small relative biases for NOx and organic nitrogen-containing species due to a good representation of the alkyl and peroxy acyl nitrates (RONO2 and RC(O)OONO2). Moreover, MIM2 computes only small relative biases with respect to hydrogen peroxide (H2O2), methyl peroxide (CH3OOH), methanol (CH3OH), formaldehyde (HCHO), peroxy acetyl nitrate (PAN), and formic and acetic acids (HCOOH and CH3C(O)OH), being always below ≈6% in all NOx scenarios studied. Most of the isoprene oxidation products are represented explicitly, including methyl vinyl ketone (MVK), methacrolein (MACR), hydroxyacetone and methyl glyoxal. MIM2 is mass-conserving with respect to carbon, including CO2 as well. Therefore, it is suitable for studies assessing carbon monoxide (CO) from biogenic sources, as well as for studies focused on the carbon cycle. Compared to MIM, MIM2 considers new species like acetaldehyde (CH3CHO), propene (CH2=CHCH3) and glyoxal (CHOCHO) with global chemical production rates for the year 2005 of 7.3, 9.5 and 33.8 Tg/yr, respectively. Our new mechanism is expected to substantially improve the results of atmospheric chemistry models by representing many more intermediates, that are transported and deposited, which allows us to test model results with many more new measurements. MIM2 allows regional and global models to easily incorporate new experimental results on the chemistry of organic species.

Description: We examine the effects of ozone precursor emissions from megacities on present-day air quality using the global chemistry–climate model UM-UKCA (UK Met Office Unified Model coupled to the UK Chemistry and Aerosols model). The sensitivity of megacity and regional ozone to local emissions, both from within the megacity and from surrounding regions, is important for determining air quality across many scales, which in turn is key for reducing human exposure to high levels of pollutants. We use two methods, perturbation and tagging, to quantify the impact of megacity emissions on global ozone. We also completely redistribute the anthropogenic emissions from megacities, to compare changes in local air quality going from centralised, densely populated megacities to decentralised, lower density urban areas. Focus is placed not only on how changes to megacity emissions affect regional and global NOx and O3, but also on changes to NOy deposition and to local chemical environments which are perturbed by the emission changes. The perturbation and tagging methods show broadly similar megacity impacts on total ozone, with the perturbation method underestimating the contribution partially because it perturbs the background chemical environment. The total redistribution of megacity emissions locally shifts the chemical environment towards more NOx-limited conditions in the megacities, which is more conducive to ozone production, and monthly mean surface ozone is found to increase up to 30% in megacities, depending on latitude and season. However, the displacement of emissions has little effect on the global annual ozone burden (0.12% change). Globally, megacity emissions are shown to contribute ~3% of total NOy deposition. The changes in O3, NOx and NOy deposition described here are useful for quantifying megacity impacts and for understanding the sensitivity of megacity regions to local emissions. The small global effects of the 100% redistribution carried out in this study suggest that the distribution of emissions on the local scale is unlikely to have large implications for chemistry–climate processes on the global scale.

Description: The impact of the megacities of the world on global tropospheric ozone, and conversely, the extent to which megacities are influenced by emissions of ozone precursors from outside of the megacities is examined under the four alternative RCP ("Representative Concentration Pathway") emissions scenarios. Despite accounting for about 6% of present-day anthropogenic emissions of ozone precursor species, the contribution of emissions from megacities to global tropospheric ozone is calculated to be 0.84%. By 2100 this contribution falls to between 0.18% and 0.62% depending on the scenario, with the lower value being for the most-polluting of the four future emissions scenarios due to stringent controls on ozone precursor emissions from highly populated areas combined with a stronger tropospheric background ozone field. The higher end of this range is from the least-polluting of the four emissions scenarios, due to lower background tropospheric ozone combined with the use of a simpler downscaling methodology in the construction of the scenario, which results in higher emissions from megacities. Although the absolute impact of megacities on global ozone is small, an important result of this study is that under all future scenarios, future air quality in megacities is expected to be less influenced by local emissions within the cities, but instead more influenced by emission sources outside of the cities, with mixing ratios of background ozone projected to play an increasing role in megacity air quality throughout the 21st century. Assumptions made when downscaling the emissions scenarios onto the grids used in such modelling studies can have a large influence on these results; future generations of emissions scenarios should include spatially explicit representations or urban development suitable for air quality studies using global chemical transport models.

Description: The impact of the megacities of the world on global tropospheric ozone, and conversely, the extent to which megacities are influenced by emissios of ozone precursors from outside of the megacities is examined under the four alternative RCP (''Representative Concentration Pathway'') emissions scenarios. Despite accounting for about 6% of present-day anthropogenic emissions of ozone precursor species, the contribution of emissions from megacities to global tropospheric ozone is calculated to be 0.84%. By 2100 this contribution falls to between 0.18 and 0.62% depending on the scenario, with the lower value being for the most-polluting of the four future emissions scenarios due to stringent controls on ozone precursor emissions from highly populated areas combined with a stronger tropospheric background ozone field. The higher end of this range is from the least-polluting of the four emissions scenarios, due lower background tropospheric ozone combined with the use of a different downscaling methodology in the construction of the scenario. Although the absolute impact of megacities on global ozone is small, an important result of this study is that under all future scenarios, future air quality in megacities is expected to be less influenced by local emissions within the cities, but instead more influenced by emission sources outside of the cities. Air quality trends in the megacities of the developing world are projected to be similar to observed trends in developed world megacities over the last few decades. Assumptions made when downscaling the emissions scenarios onto the grids used in such modelling studies can have a large influence on these results. Future work should concentrate on the creation of spatially explicit scenarios of urban development for use in global chemical transport models.

Description: We examine the effects of ozone precursor emissions from megacities on present-day air quality using the global chemistry-climate model UM-UKCA. The sensitivity of megacity and regional ozone to local emissions, both from within the megacity and from surrounding regions, is important for determining air quality across many scales, which in turn is key for reducing human exposure to high levels of pollutants. We use two methods, perturbation and tagging, to quantify the impact of megacity emissions on global ozone. We also completely redistribute the anthropogenic emissions from megacities, to compare changes in local air quality going from centralised, densely populated megacities to decentralised, lower density urban areas. Focus is placed not only on how changes to megacity emissions affect regional and global NOx and O3, but also on changes to NOy deposition and to local chemical environments which are perturbed by the emission changes. The perturbation and tagging methods show broadly similar megacity impacts on total ozone, with the perturbation method underestimating the contribution partially because it perturbs the background chemical environment. The total redistribution of megacity emissions locally shifts the chemical environment towards more NOx-limited conditions in the megacities, which is more conducive to ozone production, and monthly mean surface ozone is found to increase up to 30% in megacities, depending on latitude and season. However, the displacement of emissions has little effect on the global annual ozone burden at the surface (0.12% change). Globally, megacity emissions are shown to increase total NOy deposition by ~3%. The changes in O3, NOx and NOy deposition described here are useful for quantifying megacity impacts and for understanding the sensitivity of megacity regions to local emissions. The small global effects of the 100% redistribution carried out in this study suggest that the distribution of emissions on the local scale is unlikely to have large implications for chemistry-climate processes on the global scale.

Description: We present the online calculated Earth's surface trace gas and aerosol emissions and dry deposition in the Modular Earth Submodel System (MESSy) submodel EMDEP as well as the currently applied anthropogenic and natural emissions inventories. These inventories, being read-in by the MESSy submodel OFFLEM, include the industrial, fossil fuel, agricultural and biomass burning emissions considering emission height profiles as a function of the source category based on the EDGAR v3.2 fast track 2000 inventory. Terrestrial and marine emissions of a selection of trace gases and aerosols are calculated online in EMDEP using climate model parameters such as wind speed, temperature and land cover and land use parameters. The online dry deposition calculation includes gases and aerosols, where the default selection for the trace gases for the dry deposition scheme can be easily extended using a commonly applied method based on trace gas solubility and reactivity. In general, the simulated global annual emissions agree with previously reported inventories, although differences exist, partly dependent on the applied model resolution. A high sensitivity of the simulated dry deposition to the applied emission height profiles stresses the importance of a realistic and consistent representation of the spatial and temporal variability in surface exchange processes in Earth system models.

Description: Megacities and other major population centers represent important, concentrated sources of anthropogenic pollutants to the atmosphere, with consequences for both local air quality and for regional and global atmospheric chemistry. The tradeoff between the regional buildup of pollutants near their sources versus long-range export depends on meteorological characteristics which vary as a function of geographical location and season. Both horizontal and vertical transport contribute to pollutant export, and the overall degree of export is strongly governed by the chemical lifetimes of pollutants. We provide a first quantification of this tradeoff and the main factors influencing it in terms of "regional pollution potentials", metrics based on simulations of artificial, representative tracers using the 3-D global model MATCH (Model of Atmospheric Transport and Chemistry). The tracers have three different lifetimes (1, 10, and 100 days) and are emitted from 36 continental point sources representing the 30 current largest cities around the world plus 6 additional major population centers. Several key features of the export characteristics emerge: 1) long-range near-surface pollutant export is generally strongest in the middle and high latitudes, especially for source locations in Eurasia; 2) on the other hand, pollutant export to the upper troposphere is greatest in the tropics, due to transport by deep convection; 3) not only are there order of magnitude interregional differences, such as between low and high latitudes, but also often substantial intraregional differences, for instance between the sources in western India and Pakistan versus eastern India and Bangladesh; 4) contrary to what one might initially expect, efficient long-range export does not necessarily correspond with a more significant dilution of pollutants near their source, rather the amount of low-level, long-range export (e.g., below 1 km and beyond 1000 km) is well-correlated with exceedences of surface density thresholds on regional scales near the source (e.g., within ~1000 km), implying that pollutant buildup to high densities in the surface layer of the region surrounding the source location is more strongly influenced by vertical than horizontal transport.