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- ItemReal-time detection of highly oxidized organosulfates and BSOA marker compounds during the F-BEACh 2014 field study(München : European Geopyhsical Union, 2017) Brüggemann, Martin; Poulain, Laurent; Held, Andreas; Stelzer, Torsten; Zuth, Christoph; Richters, Stefanie; Mutzel, Anke; van Pinxteren, Dominik; Iinuma, Yoshiteru; Katkevica, Sarmite; Rabe, René; Herrmann, Hartmut; Hoffmann, ThorstenThe chemical composition of ambient organic aerosols was analyzed using complementary mass spectrometric techniques during a field study in central Europe in July 2014 (Fichtelgebirge – Biogenic Emission and Aerosol Chemistry, F-BEACh 2014). Among several common biogenic secondary organic aerosol (BSOA) marker compounds, 93 acidic oxygenated hydrocarbons were detected with elevated abundances and were thus attributed to be characteristic for the organic aerosol mass at the site. Monoterpene measurements exhibited median mixing ratios of 1.6 and 0.8 ppbV for in and above canopy levels respectively. Nonetheless, concentrations for early-generation oxidation products were rather low, e.g., pinic acid (c = 4.7 (±2.5) ng m−3). In contrast, high concentrations were found for later-generation photooxidation products such as 3-methyl-1,2,3-butanetricarboxylic acid (MBTCA, c = 13.8 (±9.0) ng m−3) and 3-carboxyheptanedioic acid (c = 10.2 (±6.6) ng m−3), suggesting that aged aerosol masses were present during the campaign period. In agreement, HYSPLIT trajectory calculations indicate that most of the arriving air masses traveled long distances (> 1500 km) over land with high solar radiation. In addition, around 47 % of the detected compounds from filter sample analysis contained sulfur, confirming a rather high anthropogenic impact on biogenic emissions and their oxidation processes. Among the sulfur-containing compounds, several organosulfates, nitrooxy organosulfates, and highly oxidized organosulfates (HOOS) were tentatively identified by high-resolution mass spectrometry. Correlations among HOOS, sulfate, and highly oxidized multifunctional organic compounds (HOMs) support the hypothesis of previous studies that HOOS are formed by reactions of gas-phase HOMs with particulate sulfate. Moreover, periods with high relative humidity indicate that aqueous-phase chemistry might play a major role in HOOS production. However, for dryer periods, coinciding signals for HOOS and gas-phase peroxyradicals (RO2•) were observed, suggesting RO2• to be involved in HOOS formation.
- ItemSize distributions of polycyclic aromatic hydrocarbons in urban atmosphere: Sorption mechanism and source contributions to respiratory deposition(München : European Geopyhsical Union, 2016) Lv, Yan; Li, Xiang; Xu, Ting Ting; Cheng, Tian Tao; Yang, Xin; Chen, Jian Min; Iinuma, Yoshiteru; Herrmann, HartmutIn order to better understand the particle size distribution of polycyclic aromatic hydrocarbons (PAHs) and their source contribution to human respiratory system, size-resolved PAHs have been studied in ambient aerosols at a megacity Shanghai site during a 1-year period (2012–2013). The results showed the PAHs had a bimodal distribution with one mode peak in the fine-particle size range (0.4–2.1 µm) and another mode peak in the coarse-particle size range (3.3–9.0 µm). Along with the increase in ring number of PAHs, the intensity of the fine-mode peak increased, while the coarse-mode peak decreased. Plotting of log(PAH / PM) against log(Dp) showed that all slope values were above −1, suggesting that multiple mechanisms (adsorption and absorption) controlled the particle size distribution of PAHs. The total deposition flux of PAHs in the respiratory tract was calculated as being 8.8 ± 2.0 ng h−1. The highest lifetime cancer risk (LCR) was estimated at 1.5 × 10−6, which exceeded the unit risk of 10−6. The LCR values presented here were mainly influenced by accumulation mode PAHs which came from biomass burning (24 %), coal combustion (25 %), and vehicular emission (27 %). The present study provides us with a mechanistic understanding of the particle size distribution of PAHs and their transport in the human respiratory system, which can help develop better source control strategies.
- ItemNitrate radicals and biogenic volatile organic compounds: Oxidation, mechanisms, and organic aerosol(München : European Geopyhsical Union, 2017) Ng, Nga Lee; Brown, Steven S.; Archibald, Alexander T.; Atlas, Elliot; Cohen, Ronald C.; Crowley, John N.; Day, Douglas A.; Donahue, Neil M.; Fry, Juliane L.; Fuchs, Hendrik; Griffin, Robert J.; Guzman, Marcelo I.; Herrmann, Hartmut; Hodzic, Alma; Iinuma, Yoshiteru; Jimenez, José L.; Kiendler-Scharr, Astrid; Lee, Ben H.; Luecken, Deborah J.; Mao, Jingqiu; McLaren, Robert; Mutzel, Anke; Osthoff, Hans D.; Ouyang, Bin; Picquet-Varrault, Benedicte; Platt, Ulrich; Pye, Havala O.T.; Rudich, Yinon; Schwantes, Rebecca H.; Shiraiwa, Manabu; Stutz, Jochen; Thornton, Joel A.; Tilgner, Andreas; Williams, Brent J.; Zaveri, Rahul A.Oxidation of biogenic volatile organic compounds (BVOC) by the nitrate radical (NO3) represents one of the important interactions between anthropogenic emissions related to combustion and natural emissions from the biosphere. This interaction has been recognized for more than 3 decades, during which time a large body of research has emerged from laboratory, field, and modeling studies. NO3-BVOC reactions influence air quality, climate and visibility through regional and global budgets for reactive nitrogen (particularly organic nitrates), ozone, and organic aerosol. Despite its long history of research and the significance of this topic in atmospheric chemistry, a number of important uncertainties remain. These include an incomplete understanding of the rates, mechanisms, and organic aerosol yields for NO3-BVOC reactions, lack of constraints on the role of heterogeneous oxidative processes associated with the NO3 radical, the difficulty of characterizing the spatial distributions of BVOC and NO3 within the poorly mixed nocturnal atmosphere, and the challenge of constructing appropriate boundary layer schemes and non-photochemical mechanisms for use in state-of-the-art chemical transport and chemistry–climate models. This review is the result of a workshop of the same title held at the Georgia Institute of Technology in June 2015. The first half of the review summarizes the current literature on NO3-BVOC chemistry, with a particular focus on recent advances in instrumentation and models, and in organic nitrate and secondary organic aerosol (SOA) formation chemistry. Building on this current understanding, the second half of the review outlines impacts of NO3-BVOC chemistry on air quality and climate, and suggests critical research needs to better constrain this interaction to improve the predictive capabilities of atmospheric models.
- ItemKinetic modeling studies of SOA formation from α-pinene ozonolysis(München : European Geopyhsical Union, 2017) Gatzsche, Kathrin; Iinuma, Yoshiteru; Tilgner, Andreas; Mutzel, Anke; Berndt, Torsten; Wolke, RalfThis paper describes the implementation of a kinetic gas-particle partitioning approach used for the simulation of secondary organic aerosol (SOA) formation within the SPectral Aerosol Cloud Chemistry Interaction Model (SPACCIM). The kinetic partitioning considers the diffusion of organic compounds into aerosol particles and the subsequent chemical reactions in the particle phase. The basic kinetic partitioning approach is modified by the implementation of chemical backward reaction of the solute within the particle phase as well as a composition-dependent particle-phase bulk diffusion coefficient. The adapted gas-phase chemistry mechanism for α-pinene oxidation has been updated due to the recent findings related to the formation of highly oxidized multifunctional organic compounds (HOMs). Experimental results from a LEAK (Leipziger Aerosolkammer) chamber study for α-pinene ozonolysis were compared with the model results describing this reaction system. The performed model studies reveal that the particle-phase bulk diffusion coefficient and the particle-phase reactivity are key parameters for SOA formation. Using the same particle-phase reactivity for both cases, we find that liquid particles with higher particle-phase bulk diffusion coefficients have 310 times more organic material formed in the particle phase compared to higher viscous semi-solid particles with lower particle-phase bulk diffusion coefficients. The model results demonstrate that, even with a moderate particle-phase reactivity, about 61% of the modeled organic mass consists of reaction products that are formed in the liquid particles. This finding emphasizes the potential role of SOA processing. Moreover, the initial organic aerosol mass concentration and the particle radius are of minor importance for the process of SOA formation in liquid particles. A sensitivity study shows that a 22-fold increase in particle size merely leads to a SOA increase of less than 10%. Due to two additional implementations, allowing backward reactions in the particle phase and considering a composition-dependent particle-phase bulk diffusion coefficient, the potential overprediction of the SOA mass with the basic kinetic approach is reduced by about 40%. HOMs are an important compound group in the early stage of SOA formation because they contribute up to 65% of the total SOA mass at this stage. HOMs also induce further SOA formation by providing an absorptive medium for SVOCs (semi-volatile organic compounds). This process contributes about 27% of the total organic mass. The model results are very similar to the LEAK chamber results. Overall, the sensitivity studies demonstrate that the particle reactivity and the particle-phase bulk diffusion require a better characterization in order to improve the current model implementations and to validate the assumptions made from the chamber simulations. The successful implementation and testing of the current kinetic gas-particle partitioning approach in a box model framework will allow further applications in a 3-D model for regional-scale process investigations.