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Ambient tropospheric deliquesced particles generally comprise a complex mixture of electrolytes, organic compounds, and water. Dynamic modeling of physical and chemical processes in this complex matrix is challenging. Thus, up-to-date multiphase chemistry models generally do not consider non-ideal solution effects. Therefore, the present study was aimed at presenting further development of the SPACCIM (Spectral Aerosol Cloud Chemistry Interaction Model) through treatment of solution non-ideality, which has not been considered before. The present paper firstly describes the model developments including (i) the implementation of solution non-ideality in aqueous-phase reaction kinetics in the SPACCIM framework, (ii) the advancements in the coupling scheme of microphysics and multiphase chemistry and (iii) the required adjustments of the numerical schemes, especially in the sparse linear solver and the calculation of the Jacobian. Secondly, results of sensitivity investigations are outlined, aiming at the evaluation of different activity coefficient modules and the examination of the contributions of different intermolecular forces to the overall activity coefficients. Finally, first results obtained with the new model framework are presented. The SPACCIM parcel model was developed and, so far, applied for the description of aerosol-cloud interactions. To advance SPACCIM also for modeling physical and chemical processes in deliquesced particles, the solution non-ideality has to be taken into account by utilizing activities in reaction terms instead of aqueous concentrations. The main goal of the extended approach was to provide appropriate activity coefficients for solved species. Therefore, an activity coefficient module was incorporated into the kinetic model framework of SPACCIM. Based on an intercomparison of different activity coefficient models and the comparison with experimental data, the AIOMFAC approach was implemented and extended by additional interaction parameters from the literature for mixed organic-inorganic systems. Moreover, the performance and the capability of the applied activity coefficient module were evaluated by means of water activity measurements, literature data and results of other activity coefficient models. Comprehensive comparison studies showed that the SpactMod (SPACCIM activity coefficient module) is valuable for predicting the thermodynamic behavior of complex mixtures of multicomponent atmospheric aerosol particles. First simulations with a detailed chemical mechanism have demonstrated the applicability of SPACCIM-SpactMod. The simulations indicate that the treatment of solution non-ideality might be needed for modeling multiphase chemistry processes in deliquesced particles. The modeled activity coefficients imply that chemical reaction fluxes of chemical processes in deliquesced particles can be both decreased and increased depending on the particular species involved in the reactions. For key ions, activity coefficients on the order of 0.1-0.8 and a strong dependency on the charge state as well as the RH conditions are modeled, implying a lowered chemical processing of ions in concentrated solutions. In contrast, modeled activity coefficients of organic compounds are in some cases larger than 1 under deliquesced particle conditions and suggest the possibility of an increased chemical processing of organic compounds. Moreover, the model runs have shown noticeable differences in the pH values calculated with and without consideration of solution non-ideality. On average, the predicted pH values of the simulations considering solution non-ideality are -0.27 and -0.44 pH units lower under 90 and 70%RH con- ditions, respectively. More comprehensive results of detailed SPACCIM-SpactMod studies on the multiphase processing in organic-inorganic mixtures of deliquesced particles are described in a companion paper. [ABSTRACT FROM AUTHOR]

Elemental Carbon (EC) has significant impact on human health and climate change. In order to evaluate the size segregation of EC emission and investigation of its influence on atmospheric transport processes in Europe, we used the fully coupled online Weather Research and Forecasting/Chemistry model (WRF-Chem) at a resolution of 2 km focusing on a region in Germany, in conjunction with a high-resolution EC emission inventory. The ground meteorology conditions, vertical structure and wind pattern were well reproduced by the model. The simulations of particle number/mass size distributions were evaluated by observations taken at the central European background site Melpitz. The fine mode aerosol was reasonably well simulated, but the coarse mode was substantially overestimated by the model. We found that it was mainly due to the nearby point source plume emitting a high amount of EC in the coarse mode. The comparisons between simulated EC and Multi-angle Absorption Photometers (MAAP) measurements at Melpitz, Leipzig-TROPOS and Bösel indicated that coarse mode EC (ECc) emission in the nearby point sources might be overestimated by a factor of 2-10. The emission fraction of EC in coarse mode was overestimated by about 10-30% for Russian and 5-10% for Eastern Europe (e.g.: Poland and Belarus), respectively. This overestimation in ECc emission fraction makes EC particles having less opportunity to accumulate in the atmosphere and participate to the long range transport, due to the shorter lifetime of coarse mode aerosol. The deposition concept model showed that the transported EC mass from Warsaw and Moskva to Melpitz may be reduced by 25-35 and 25-55% respectively, due to the overestimation of ECc emission fraction. This may partly explain the underestimation of EC concentrations for Germany under eastern wind pattern in some other modelling research. [ABSTRACT FROM AUTHOR]

Ambient tropospheric deliquesced particles generally comprise a complex mixture of electrolytes, organic compounds, and water. Dynamic modeling of physical and chemical processes in this complex matrix is challenging. Thus, up-to-date multiphase chemistry models do generally not consider non-ideal solution effects. Therefore, the present study was aimed at the further development of the SPACCIM model to treat both complex multiphase chemistry and phase transfer processes considering newly non-ideality properties of concentrated aerosol solutions. The present paper describes firstly, the performed model development including (i) the kinetic implementation of the non ideality in the SPACCIM framework, (ii) the advancements in the coupling scheme of microphysics and multiphase chemistry and (iii) the required adjustments of the numerical schemes, especially in the sparse linear solver and the calculation of the Jacobian. Secondly, results of performed sensitivity investigations are outlined aiming at the evaluation of different activity coeffcient modules and the examination of the contributions of different intermolecular forces to the overall activity coeffcients. Finally, first results obtained with the new model framework are presented. The main product of the performed model development is the new kinetic model approach SPACCIM-SpactMod, which utilizes activities in reaction terms instead of aqueous concentrations. Based on an intercomparison of different activity coeffcient models and the comparison with experimental data, AIOMFAC was selected as base model and extended by additional interaction parameters from literature for mixed organic-inorganic systems. Moreover, the performance and the capability of the applied activity coeffcient module were evaluated by means of water activity measurements, literature data and results of other thermodynamic equilibrium models. Comprehensive comparison studies showed that the SpactMod (SPACCIM activity coeffcient module) is valuable to predict the thermodynamic behavior of complex mixtures of multicomponent atmospheric aerosol particles. First simulations with a detailed chemical mechanism have demonstrated the applicability of SPACCIM-SpactMod. The simulations have implied that the treatment of non-ideality should be mandatory for modeling multiphase chemistry processes in deliquesced particles. The modeled activity coeffcients implicate that turnovers of chemical processes in deliquesced particles can be both decreased and increased depending on the particular species involved in the reactions. For 5 key ions, activity coeffcients on the order of 0.1-0.8 and a strong dependency on the charge state as well as the RH conditions are modeled implicating a lowered chemical ion processing in concentrated solutions. In contrast, modeled activity coeffcients of organic compounds are partly >1 and suggest the possibility of an increased organic processing. Moreover, the model runs have shown noticeable differences in the 10 pH values calculated with and without consideration of non-ideality. On average, the predicted pH values of the simulations considering non-ideality are -0.27 and -0.44 pH units lower under 90 and 70% RH conditions, respectively. More comprehensive results of detailed SPACCIM-SpactMod studies on the multiphase processing in organic-inorganic mixtures of deliquesced particles are described in a companion paper. [ABSTRACT FROM AUTHOR]

This study presents a comprehensive assessment of the meteorological conditions and atmospheric flow during the Lagrangian-type "Hill Cap Cloud Thuringia 2010" experiment (HCCT-2010), which was performed in September and October 2010 at Mt. Schmücke in the Thuringian Forest, Germany and which used observations at three measurement sites (upwind, in-cloud, and downwind) to study physical and chemical aerosol-cloud interactions. A Lagrangian-type hill cap cloud experiment requires not only suitable cloud conditions but also connected airflow conditions (i.e. representative air masses at the different measurement sites). The primary goal of the present study was to identify time periods during the 6-week duration of the experiment in which these conditions were fulfilled and therefore which are suitable for use in further data examinations. The following topics were studied in detail: (i) the general synoptic weather situations, including the mesoscale flow conditions, (ii) local meteorological conditions and (iii) local flow conditions. The latter were investigated by means of statistical analyses using best-available quasi-inert tracers, SF6 tracer experiments in the experiment area, and regional modelling. This study represents the first application of comprehensive analyses using statistical measures such as the coefficient of divergence (COD) and the crosscorrelation in the context of a Lagrangian-type hill cap cloud experiment. This comprehensive examination of local flow connectivity yielded a total of 14 full-cloud events (FCEs), which are defined as periods during which all connected flow and cloud criteria for a suitable Lagrangian-type experiment were fulfilled, and 15 non-cloud events (NCEs), which are defined as periods with connected flow but no cloud at the summit site, and which can be used as reference cases. The overall evaluation of the identified FCEs provides the basis for subsequent investigations of the measured chemical and physical data during HCCT-2010 (see http://www.atmos-chem-phys.net/special_issue287.html). Results obtained from the statistical flow analyses and regional-scale modelling performed in this study indicate the existence of a strong link between the three measurement sites during the FCEs and NCEs, particularly under conditions of constant southwesterly flow, high wind speeds and slightly stable stratification. COD analyses performed using continuous measurements of ozone and particle (49 nm diameter size bin) concentrations at the three sites revealed, particularly for COD values < 0.1, very consistent time series (i.e. close links between air masses at the different sites). The regional-scale model simulations provided support for the findings of the other flow condition analyses. Cross-correlation analyses revealed typical overflow times of ↑15-30 min between the upwind and downwind valley sites under connected flow conditions. The results described here, together with those obtained from the SF6 tracer experiments performed during the experiment, clearly demonstrate that (a) under appropriate meteorological conditions a Lagrangian-type approach is valid and (b) the connected flow validation procedure developed in this work is suitable for identifying such conditions. Overall, it is anticipated that the methods and tools developed and applied in the present study will prove useful in the identification of suitable meteorological and connected airflow conditions during future Lagrangian-type hill cap cloud experiments. [ABSTRACT FROM AUTHOR]

Primary marine aerosol composed of sea salt and organic material is an important contributor to the global aerosol load. By comparing measurements from two EMEP (co-operative programme for monitoring and evaluation of the long-range transmissions of air-pollutants in Europe) intensive campaigns in June 2006 and January 2007 with results from an atmospheric transport model this work shows that accounting for the influence of the sea surface temperature on the emission of primary marine aerosol improves the model results towards the measurements in both months. Different sea surface temperature dependencies were evaluated. Using correction functions based on Sofiev et al. (2011) and Jaeglé et al. (2011) improves the model results for coarse mode particles. In contrast, for the fine mode aerosols no best correction function could be found. The model captures the low sodium concentrations at the marine station Virolahti II (Finland), which is influenced by air masses from the low salinity Baltic Sea, as well as the higher concentrations at Cabauw (Netherlands) and Auchencorth Moss (Scotland). These results indicate a shift towards smaller sizes with lower salinity for the emission of dry sea salt aerosols. Organic material was simulated as part of primary marine aerosol assuming an internal mixture with sea salt. A comparison of the model results for primary organic carbon with measurements by a Berner-impactor at Sao Vincente (Cape Verde) indicated that the model underpredicted the observed organic carbon concentration. This leads to the conclusion that the formation of secondary organic material needs to be included in the model to improve the agreement with the measurements. [ABSTRACT FROM AUTHOR]

The article presents a study regarding the efficient adoption of general splitting approach that uses as multirate-implicit/explicit (IMEX) time integration methods for air pollution modelling. The study uses generate multirate methods known as recursive flux splitting multirate (RFSM). Results show efficiency of implicit solving because of the synergetic effects.

The article presents a study on the enforcement of splitting methods for air pollution models. It mentions the application of such methods for efficient combination of implicit and explicit approaches (IMEX splitting) which lead to competent schemes in terms of assessment. It also notes its effective execution for parallel computation on computer clusters.