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- ItemMultiphase MCM-CAPRAM modeling of the formation and processing of secondary aerosol constituents observed during the Mt. Tai summer campaign in 2014(Katlenburg-Lindau : EGU, 2020) Zhu, Yanhong; Tilgner, Andreas; Hoffmann, Erik Hans; Herrmann, Hartmut; Kawamura, Kimitaka; Yang, Lingxiao; Xue, Likun; Wang, WenxingDespite the high abundance of secondary aerosols in the atmosphere, their formation mechanisms remain poorly understood. In this study, the Master Chemical Mechanism (MCM) and the Chemical Aqueous-Phase Radical Mechanism (CAPRAM) are used to investigate the multiphase formation and processing of secondary aerosol constituents during the advection of air masses towards the measurement site of Mt. Tai in northern China. Trajectories with and without chemical–cloud interaction are modeled. Modeled radical and non-radical concentrations demonstrate that the summit of Mt. Tai, with an altitude of ∼1.5 km a.m.s.l., is characterized by a suburban oxidants budget. The modeled maximum gas-phase concentrations of the OH radical are 3.2×106 and 3.5×106 molec. cm−3 in simulations with and without cloud passages in the air parcel, respectively. In contrast with previous studies at Mt. Tai, this study has modeled chemical formation processes of secondary aerosol constituents under day vs. night and cloud vs. non-cloud cases along the trajectories towards Mt. Tai in detail. The model studies show that sulfate is mainly produced in simulations where the air parcel is influenced by cloud chemistry. Under the simulated conditions, the aqueous reaction of HSO−3 with H2O2 is the major contributor to sulfate formation, contributing 67 % and 60 % in the simulations with cloud and non-cloud passages, respectively. The modeled nitrate formation is higher at nighttime than during daytime. The major pathway is aqueous-phase N2O5 hydrolysis, with a contribution of 72 % when cloud passages are considered and 70 % when they are not. Secondary organic aerosol (SOA) compounds, e.g., glyoxylic, oxalic, pyruvic and malonic acid, are found to be mostly produced from the aqueous oxidations of hydrated glyoxal, hydrated glyoxylic acid, nitro-2-oxopropanoate and hydrated 3-oxopropanoic acid, respectively. Sensitivity studies reveal that gaseous volatile organic compound (VOC) emissions have a huge impact on the concentrations of modeled secondary aerosol compounds. Increasing the VOC emissions by a factor of 2 leads to linearly increased concentrations of the corresponding SOA compounds. Studies using the relative incremental reactivity (RIR) method have identified isoprene, 1,3-butadiene and toluene as the key precursors for glyoxylic and oxalic acid, but only isoprene is found to be a key precursor for pyruvic acid. Additionally, the model investigations demonstrate that an increased aerosol partitioning of glyoxal can play an important role in the aqueous-phase formation of glyoxylic and oxalic acid. Overall, the present study is the first that provides more detailed insights in the formation pathways of secondary aerosol constituents at Mt. Tai and clearly emphasizes the importance of aqueous-phase chemical processes on the production of multifunctional carboxylic acids.
- ItemSimulation of atmospheric organic aerosol using its volatility-oxygen-content distribution during the PEGASOS 2012 campaign(Katlenburg-Lindau : EGU, 2018) Karnezi, Eleni; Murphy, Benjamin N.; Poulain, Laurent; Herrmann, Hartmut; Wiedensohler, Alfred; Rubach, Florian; Kiendler-Scharr, Astrid; Mentel, Thomas F.; Pandis, Spyros N.A lot of effort has been made to understand and constrain the atmospheric aging of the organic aerosol (OA). Different parameterizations of the organic aerosol formation and evolution in the two-dimensional volatility basis set (2D-VBS) framework are evaluated using ground and airborne measurements collected in the 2012 Pan-European Gas AeroSOls-climate interaction Study (PEGASOS) field campaign in the Po Valley (Italy). A number of chemical aging schemes are examined, taking into account various functionalization and fragmentation pathways for biogenic and anthropogenic OA components. Model predictions and measurements, both at the ground and aloft, indicate a relatively oxidized OA with little average diurnal variation. Total OA concentration and O: C ratios are reproduced within experimental error by a number of chemical aging schemes. Anthropogenic secondary OA (SOA) is predicted to contribute 15-25% of the total OA, while SOA from intermediate volatility compound oxidation contributes another 20-35%. Biogenic SOA (bSOA) contributions varied from 15 to 45% depending on the modeling scheme. Primary OA contributed around 5% for all schemes and was comparable to the hydrocarbon-like OA (HOA) concentrations derived from the positive matrix factorization of the aerosol mass spectrometer (PMF-AMS) ground measurements. The average OA and O: C diurnal variation and their vertical profiles showed a surprisingly modest sensitivity to the assumed vaporization enthalpy for all aging schemes. This can be explained by the interplay between the partitioning of the semi-volatile compounds and their gas-phase chemical aging reactions.
- ItemDevelopment of a protocol for the auto-generation of explicit aqueous-phase oxidation schemes of organic compounds(Katlenburg-Lindau : EGU, 2019) Bräuer, Peter; Mouchel-Vallon, Camille; Tilgner, Andreas; Mutzel, Anke; Böge, Olaf; Rodigast, Maria; Poulain, Laurent; van Pinxteren, Dominik; Wolke, Ralf; Aumont, Bernard; Herrmann, HartmutThis paper presents a new CAPRAM-GECKOA protocol for mechanism auto-generation of aqueous-phase organic processes. For the development, kinetic data in the literature were reviewed and a database with 464 aqueousphase reactions of the hydroxyl radical with organic compounds and 130 nitrate radical reactions with organic compounds has been compiled and evaluated. Five different methods to predict aqueous-phase rate constants have been evaluated with the help of the kinetics database: gas-aqueous phase correlations, homologous series of various compound classes, radical reactivity comparisons, Evans-Polanyi-type correlations, and structure-activity relationships (SARs). The quality of these prediction methods was tested as well as their suitability for automated mechanism construction. Based on this evaluation, SARs form the basis of the new CAPRAM-GECKO-A protocol. Evans-Polanyi-type correlations have been advanced to consider all available H atoms in a molecule besides the H atoms with only the weakest bond dissociation enthalpies (BDEs). The improved Evans- Polanyi-type correlations are used to predict rate constants for aqueous-phase NO3 and organic compounds reactions. Extensive tests have been performed on essential parameters and on highly uncertain parameters with limited experimental data. These sensitivity studies led to further improvements in the new CAPRAM-GECKO-A protocol but also showed current limitations. Biggest uncertainties were observed in uptake processes and the estimation of Henry's law coefficients as well as radical chemistry, in particular the degradation of alkoxy radicals. Previous estimation methods showed several deficits, which impacted particle growth. For further evaluation, a 1,3,5-trimethylbenzene oxidation experiment has been performed in the aerosol chamber "Leipziger Aerosolkammer" (LEAK) at high relative humidity conditions and compared to a multiphase mechanism using the Master Chemical Mechanism (MCMv3.2) in the gas phase and using a methylglyoxal oxidation scheme of about 600 reactions generated with the new CAPRAM-GECKO-A protocol in the aqueous phase. While it was difficult to evaluate single particle constituents due to concentrations close to the detection limits of the instruments applied, the model studies showed the importance of aqueous-phase chemistry in respect to secondary organic aerosol (SOA) formation and particle growth. The new protocol forms the basis for further CAPRAM mechanism development towards a new version 4.0. Moreover, it can be used as a supplementary tool for aerosol chambers to design and analyse experiments of chemical complexity and help to understand them on a molecular level. © 2019 Author(s).
- ItemSource apportionment of the organic aerosol over the Atlantic Ocean from 53° N to 53° S: Significant contributions from marine emissions and long-range transport(Katlenburg-Lindau : EGU, 2018) Huang, Shan; Wu, Zhijun; Poulain, Laurent; van Pinxteren, Manuela; Merkel, Maik; Assmann, Denise; Herrmann, Hartmut; Wiedensohler, AlfredMarine aerosol particles are an important part of the natural aerosol systems and might have a significant impact on the global climate and biological cycle. It is widely accepted that truly pristine marine conditions are difficult to find over the ocean. However, the influence of continental and anthropogenic emissions on the marine boundary layer (MBL) aerosol is still less understood and non-quantitative, causing uncertainties in the estimation of the climate effect of marine aerosols. This study presents a detailed chemical characterization of the MBL aerosol as well as the source apportionment of the organic aerosol (OA) composition. The data set covers the Atlantic Ocean from 53∘ N to 53∘ S, based on four open-ocean cruises in 2011 and 2012. The aerosol particle composition was measured with a high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS), which indicated that sub-micrometer aerosol particles over the Atlantic Ocean are mainly composed of sulfates (50 % of the particle mass concentration), organics (21 %) and sea salt (12 %). OA has been apportioned into five factors, including three factors linked to marine sources and two with continental and/or anthropogenic origins. The marine oxygenated OA (MOOA, 16 % of the total OA mass) and marine nitrogen-containing OA (MNOA, 16 %) are identified as marine secondary products with gaseous biogenic precursors dimethyl sulfide (DMS) or amines. Marine hydrocarbon-like OA (MHOA, 19 %) was attributed to the primary emissions from the Atlantic Ocean. The factor for the anthropogenic oxygenated OA (Anth-OOA, 19 %) is related to continental long-range transport. Represented by the combustion oxygenated OA (Comb-OOA), aged combustion emissions from maritime traffic and wild fires in Africa contributed, on average, a large fraction to the total OA mass (30 %). This study provides the important finding that long-range transport was found to contribute averagely 49 % of the submicron OA mass over the Atlantic Ocean. This is almost equal to that from marine sources (51 %). Furthermore, a detailed latitudinal distribution of OA source contributions showed that DMS oxidation contributed markedly to the OA over the South Atlantic during spring, while continental-related long-range transport largely influenced the marine atmosphere near Europe and western and central Africa (15∘ N to 15∘ S). In addition, supported by a solid correlation between marine tracer methanesulfonic acid (MSA) and the DMS-oxidation OA (MOOA, R2>0.85), this study suggests that the DMS-related secondary organic aerosol (SOA) over the Atlantic Ocean could be estimated by MSA and a scaling factor of 1.79, especially in spring.
- ItemTreatment of non-ideality in the SPACCIM multiphase model-Part 2: Impacts on the multiphase chemical processing in deliquesced aerosol particles(Katlenburg-Lindau : EGU, 2020) Jhony Rusumdar, Ahmad; Tilgner, Andreas; Wolke, Ralf; Herrmann, HartmutTropospheric deliquesced particles are characterised by concentrated non-ideal solutions ("aerosol liquid water" or ALW) that can affect the occurring multiphase chemistry. However, such non-ideal solution effects have generally not yet been considered in and investigated by current complex multiphase chemistry models in an adequate way. Therefore, the present study aims at accessing the impact of non-ideality on multiphase chemical processing in concentrated aqueous aerosols. Simulations with the multiphase chemistry model (SPACCIM-SpactMod) are performed under different environmental and microphysical conditions with and without a treatment of non-ideal solutions in order to assess its impact on aqueous-phase chemical processing. The present study shows that activity coefficients of inorganic ions are often below unity under 90% RH-deliquesced aerosol conditions and that most uncharged organic compounds exhibit activity coefficient values of around or even above unity. Due to this behaviour, model studies have revealed that the inclusion of non-ideality considerably affects the multiphase chemical processing of transition metal ions (TMIs), oxidants, and related chemical subsystems such as organic chemistry. In detail, both the chemical formation and oxidation rates of Fe(II) are substantially lowered by a factor of 2.8 in the non-ideal base case compared to the ideal case. The reduced Fe(II) processing in the non-ideal base case, including lowered chemical rates of the Fenton reaction (70 %), leads to a reduced processing of HOx=HOy under deliquesced aerosol conditions. Consequently, higher multiphase H2O2 concentrations (larger by a factor of 3.1) and lower aqueous-phase OH concentrations (lower by a factor of 4) are modelled during non-cloud periods. For H2O2, a comparison of the chemical reaction rates reveals that the most important sink, the reaction with HSO3 , contributes with a 40% higher rate in the non-ideal base case than in the ideal case, leading to more efficient sulfate formation. On the other hand, the chemical formation rates of the OH radical are about 50% lower in the non-ideal base case than in the ideal case, leading to lower degradation rates of organic aerosol components. Thus, considering non-ideality influences the chemical processing and the concentrations of organic compounds under deliquesced particle conditions in a compound-specific manner. For example, the reduced oxidation budget under deliquesced particle conditions leads to both increased and decreased concentration levels, e.g. of important C2=C3 carboxylic acids. For oxalic acid, the present study demonstrates that the non-ideality treatment enables more realistic predictions of high oxalate concentrations than observed under ambient highly polluted conditions. Furthermore, the simulations imply that lower humidity conditions, i.e. more concentrated solutions, might promote higher oxalic acid concentration levels in aqueous aerosols due to differently affected formation and degradation processes. © 2020 Copernicus GmbH. All rights reserved.
- ItemThe Importance of the Representation of DMS Oxidation in Global Chemistry‐Climate Simulations(Hoboken, NJ : Wiley, 2021) Hoffmann, Erik Hans; Heinold, Bernd; Kubin, Anne; Tegen, Ina; Herrmann, HartmutThe oxidation of dimethyl sulfide (DMS) is key for the natural sulfate aerosol formation and its climate impact. Multiphase chemistry is an important oxidation pathway but neglected in current chemistry-climate models. Here, the DMS chemistry in the aerosol-chemistry-climate model ECHAM-HAMMOZ is extended to include multiphase methane sulfonic acid (MSA) formation in deliquesced aerosol particles, parameterized by reactive uptake. First simulations agree well with observed gas-phase MSA concentrations. The implemented formation pathways are quantified to contribute up to 60% to the sulfate aerosol burden over the Southern Ocean and Arctic/Antarctic regions. While globally the impact on the aerosol radiative forcing almost levels off, a significantly more positive solar radiative forcing of up to +0.1 W m−2 is computed in the Arctic (>60°N). The findings imply the need of both further laboratory and model studies on the atmospheric multiphase oxidation of DMS.