Secondary organic aerosols (SOA) are a large source of uncertainty in our current understanding of climate change and air pollution. The phase state of SOA is important for quantifying their effects ...on climate and air quality, but its global distribution is poorly characterized. We developed a method to estimate glass transition temperatures based on the molar mass and molecular O:C ratio of SOA components, and we used the global chemistry climate model EMAC with the organic aerosol module ORACLE to predict the phase state of atmospheric SOA. For the planetary boundary layer, global simulations indicate that SOA are mostly liquid in tropical and polar air with high relative humidity, semi-solid in the mid-latitudes and solid over dry lands. We find that in the middle and upper troposphere SOA should be mostly in a glassy solid phase state. Thus, slow diffusion of water, oxidants and organic molecules could kinetically limit gas-particle interactions of SOA in the free and upper troposphere, promote ice nucleation and facilitate long-range transport of reactive and toxic organic pollutants embedded in SOA.
A global chemistry-climate model has been used to study the impacts of pollutants released by agriculture on fine-particulate matter (PM2.5), with a focus on Europe, North America, East and South ...Asia. Simulations reveal that a relatively strong reduction in PM2.5 levels can be achieved by decreasing agricultural emissions, notably of ammonia (NH3) released from fertilizer use and animal husbandry. The absolute impact on PM2.5 reduction is strongest in East Asia, even for small emission decreases. Conversely, over Europe and North America, aerosol formation is not immediately limited by the availability of ammonia. Nevertheless, reduction of NH3 can also substantially decrease PM2.5 concentrations over the latter regions, especially when emissions are abated systematically. Our results document how reduction of agricultural emissions decreases aerosol pH due to the depletion of aerosol ammonium, which affects particle liquid phase and heterogeneous chemistry. Further, it is shown that a 50 % reduction of agricultural emissions could prevent the mortality attributable to air pollution by ∼ 250 000 people yr−1 worldwide, amounting to reductions of 30, 19, 8 and 3 % over North America, Europe, East and South Asia, respectively. A theoretical 100 % reduction could even reduce the number of deaths globally by about 800 000 per year.
The acidity of atmospheric particulate matter regulates its mass, composition, and toxicity and has important consequences for public health, ecosystems and climate. Despite these broad impacts, the ...global distribution and evolution of aerosol particle acidity are unknown. We used the comprehensive atmospheric multiphase chemistry–climate model EMAC (ECHAM5/MESSy Atmospheric Chemistry) to investigate the main factors that control aerosol particle acidity and uncovered remarkable variability and unexpected trends during the past 50 years in different parts of the world. Aerosol particle acidity decreased strongly over Europe and North America during the past decades while at the same time it increased over Asia. Our simulations revealed that these particle acidity trends are strongly related to changes in the phase partitioning of nitric acid, production of sulfate in aqueous aerosols, and the aerosol hygroscopicity. It is remarkable that the aerosol hygroscopicity (κ) has increased in many regions following the particle pH. Overall, we find that alkaline compounds, notably ammonium and to a lesser extent crustal cations, regulate the particle pH on a global scale. Given the importance of aerosol particles for the atmospheric energy budget, cloud formation, pollutant deposition, and public health, alkaline species hold the key to control strategies for air quality and climate change.
An assessment of global particulate nitrate and ammonium aerosol based on simulations from nine models participating in the Aerosol Comparisons between Observations and Models (AeroCom) phase III ...study is presented. A budget analysis was conducted to understand the typical magnitude, distribution, and diversity of the aerosols and their precursors among the models. To gain confidence regarding model performance, the model results were evaluated with various observations globally, including ground station measurements over North America, Europe, and east Asia for tracer concentrations and dry and wet depositions, as well as with aircraft measurements in the Northern Hemisphere mid-to-high latitudes for tracer vertical distributions. Given the unique chemical and physical features of the nitrate occurrence, we further investigated the similarity and differentiation among the models by examining (1) the pH-dependent NH3 wet deposition; (2) the nitrate formation via heterogeneous chemistry on the surface of dust and sea salt particles or thermodynamic equilibrium calculation including dust and sea salt ions; and (3) the nitrate coarse-mode fraction (i.e., coarse/total). It is found that HNO3, which is simulated explicitly based on full O3-HOx-NOx-aerosol chemistry by all models, differs by up to a factor of 9 among the models in its global tropospheric burden. This partially contributes to a large difference in NO3(-), whose atmospheric burden differs by up to a factor of 13. The atmospheric burdens of NH3 and NHC 4 differ by 17 and 4, respectively. Analyses at the process level show that the large diversity in atmospheric burdens of NO3(-), NH3, and NHC4(+) is also related to deposition processes. Wet deposition seems to be the dominant process in determining the diversity in NH3 and NHC 4 lifetimes. It is critical to correctly account for contributions of heterogeneous chemical production of nitrate on dust and sea salt, because this process overwhelmingly controls atmospheric nitrate production (typically greater than 80 %) and determines the coarse- and fine-mode distribution of nitrate aerosol.
The importance of wind-blown mineral dust for cloud droplet formation is studied by considering (i) the adsorption of water on the surface of insoluble particles, (ii) particle coating by soluble ...material (atmospheric aging) which augments cloud condensation nuclei (CCN) activity, and (iii) the effect of dust on inorganic aerosol concentrations through thermodynamic interactions with mineral cations. The ECHAM5/MESSy Atmospheric Chemistry (EMAC) model is used to simulate the composition of global atmospheric aerosol, while the ISORROPIA-II thermodynamic equilibrium model treats the interactions of K+-Ca2+-Mg2+-NH4+-Na+-SO42−-NO3−-Cl−-H2O aerosol with gas-phase inorganic constituents. Dust is considered a mixture of inert material with reactive minerals and its emissions are calculated online by taking into account the soil particle size distribution and chemical composition of different deserts worldwide. The impact of dust on droplet formation is treated through the unified dust activation parameterization that considers the inherent hydrophilicity from adsorption and acquired hygroscopicity from soluble salts during aging. Our simulations suggest that the presence of dust increases cloud droplet number concentration (CDNC) over major deserts (e.g., up to 20 % over the Sahara and the Taklimakan desert) and decreases CDNC over polluted areas (e.g., up to 10 % over southern Europe and 20 % over northeastern Asia). This leads to a global net decrease in CDNC by 11 %. The adsorption activation of insoluble aerosols and the mineral dust chemistry are shown to be equally important for the cloud droplet formation over the main deserts; for example, these effects increase CDNC by 20 % over the Sahara. Remote from deserts the application of adsorption theory is critically important since the increased water uptake by the large aged dust particles (i.e., due to the added hydrophilicity by the soluble coating) reduce the maximum supersaturation and thus cloud droplet formation from the relatively smaller anthropogenic particles (e.g., CDNC decreases by 10 % over southern Europe and 20 % over northeastern Asia by applying adsorption theory). The global average CDNC decreases by 10 % by considering adsorption activation, while changes are negligible when accounting for the mineral dust chemistry. Sensitivity simulations indicate that CDNC is also sensitive to the mineral dust mass and inherent hydrophilicity, and not to the chemical composition of the emitted dust.
The interactions between aeolian dust and anthropogenic air pollution, notably chemical ageing of mineral dust and coagulation of dust and pollution
particles, modify the atmospheric aerosol ...composition and burden. Since the
aerosol particles can act as cloud condensation nuclei, this affects the radiative transfer not only directly via aerosol–radiation interactions, but also indirectly through cloud adjustments. We study both radiative effects using
the global ECHAM/MESSy atmospheric chemistry-climate model (EMAC) which
combines the Modular Earth Submodel System (MESSy) with the European
Centre/Hamburg (ECHAM) climate model. Our simulations show that
dust–pollution–cloud interactions reduce the condensed water path and hence the reflection of solar radiation. The associated climate warming outweighs
the cooling that the dust–pollution interactions exert through the direct radiative effect. In total, this results in a net warming by dust–pollution
interactions which moderates the negative global anthropogenic aerosol forcing
at the top of the atmosphere by (0.2 ± 0.1) W m−2.
The chemical ageing of aeolian dust, through interactions with air
pollution, affects the optical and hygroscopic properties of the mineral
particles and hence their atmospheric residence time and ...climate forcing.
Conversely, the chemical composition of the dust particles and their role as
coagulation partners impact the abundance of particulate air pollution. This
results in a change in the aerosol direct radiative effect that we interpret
as an anthropogenic radiative forcing associated with mineral dust–pollution
interactions. Using the ECHAM/MESSy atmospheric chemistry climate model
(EMAC), which combines the Modular Earth Submodel System (MESSy) with the
European Centre Hamburg (ECHAM) climate model, including a detailed
parametrisation of ageing processes and an emission scheme accounting for the
chemical composition of desert soils, we study the direct radiative forcing
globally and regionally, considering solar and terrestrial radiation. Our
results indicate positive and negative forcings, depending on the region. The
predominantly negative forcing at the top of the atmosphere over large parts
of the dust belt, from West Africa to East Asia, attains a maximum of about
−2 W m−2 south of the Sahel, in
contrast to a positive forcing over India. Globally averaged, these forcings
partially counterbalance, resulting in a net negative forcing of
−0.05 W m−2, which nevertheless represents a considerable fraction
(40 %) of the total dust forcing.
We present version 4.0 of the atmospheric chemistry box model CAABA/MECCA that now includes a number of new features: (i) skeletal mechanism reduction, (ii) the Mainz Organic Mechanism (MOM) chemical ...mechanism for volatile organic compounds, (iii) an option to include reactions from the Master Chemical Mechanism (MCM) and other chemical mechanisms, (iv) updated isotope tagging, and (v) improved and new photolysis modules (JVAL, RADJIMT, DISSOC). Further, when MECCA is connected to a global model, the new feature of coexisting multiple chemistry mechanisms (PolyMECCA/CHEMGLUE) can be used. Additional changes have been implemented to make the code more user-friendly and to facilitate the analysis of the model results. Like earlier versions, CAABA/MECCA-4.0 is a community model published under the GNU General Public License.
Emissions of organic compounds from biomass, biofuel, and fossil fuel combustion strongly influence the global atmospheric aerosol load. Some of the organics are directly released as primary organic ...aerosol (POA). Most are emitted in the gas phase and undergo chemical transformations (i.e., oxidation by hydroxyl radical) and form secondary organic aerosol (SOA). In this work we use the global chemistry climate model ECHAM/MESSy Atmospheric Chemistry (EMAC) with a computationally efficient module for the description of organic aerosol (OA) composition and evolution in the atmosphere (ORACLE). The tropospheric burden of open biomass and anthropogenic (fossil and biofuel) combustion particles is estimated to be 0.59 and 0.63 Tg, respectively, accounting for about 30 and 32 % of the total tropospheric OA load. About 30 % of the open biomass burning and 10 % of the anthropogenic combustion aerosols originate from direct particle emissions, whereas the rest is formed in the atmosphere. A comprehensive data set of aerosol mass spectrometer (AMS) measurements along with factor-analysis results from 84 field campaigns across the Northern Hemisphere are used to evaluate the model results. Both the AMS observations and the model results suggest that over urban areas both POA (25–40 %) and SOA (60–75 %) contribute substantially to the overall OA mass, whereas further downwind and in rural areas the POA concentrations decrease substantially and SOA dominates (80–85 %). EMAC does a reasonable job in reproducing POA and SOA levels during most of the year. However, it tends to underpredict POA and SOA concentrations during winter indicating that the model misses wintertime sources of OA (e.g., residential biofuel use) and SOA formation pathways (e.g., multiphase oxidation).
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