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    High-molecular-weight esters in α-pinene ozonolysis secondary organic aerosol: Structural characterization and mechanistic proposal for their formation from highly oxygenated molecules
    (Katlenburg-Lindau : EGU, 2018) Kahnt, Ariane; Vermeylen, Reinhilde; Iinuma, Yoshiteru; Safi Shalamzari, Mohammad; Maenhaut, Willy; Claeys, Magda
    Stable high-molecular-weight esters are present in α-pinene ozonolysis secondary organic aerosol (SOA) with the two most abundant ones corresponding to a hydroxypinonyl ester of cis-pinic acid with a molecular weight (MW) of 368 (C19H28O7) and a diaterpenylic ester of cis-pinic acid with a MW of 358 (C17H26O8). However, their molecular structures are not completely elucidated and their relationship with highly oxygenated molecules (HOMs) in the gas phase is still unclear. In this study, liquid chromatography in combination with positive ion electrospray ionization mass spectrometry has been performed on high-molecular-weight esters present in α-pinene ozonolysis SOA with and without derivatization into methyl esters. Unambiguous evidence could be obtained for the molecular structure of the MWg368 ester in that it corresponds to an ester of cis-pinic acid where the carboxyl substituent of the dimethylcyclobutane ring and not the methylcarboxyl substituent is esterified with 7-hydroxypinonic acid. The same linkage was already proposed in previous work for the MWg358 ester (Yasmeen et al., 2010), but could be supported in the present study. Guided by the molecular structures of these stable esters, we propose a formation mechanism from gas-phase HOMs that takes into account the formation of an unstable C19H28O11 product, which is detected as a major species in α-pinene ozonolysis experiments as well as in the pristine forest atmosphere by chemical ionization-atmospheric pressure ionization-time-of-flight mass spectrometry with nitrate clustering (Ehn et al., 2012, 2014). It is suggested that an acyl peroxy radical related to cis-pinic acid (RO2•) and an alkoxy radical related to 7- or 5-hydroxypinonic acid (R′O•) serve as key gas-phase radicals and combine according to a RO2g+gR′O•→ gRO3R′ radical termination reaction. Subsequently, the unstable C19H28O11 HOM species decompose through the loss of oxygen or ketene from the inner part containing a labile trioxide function and the conversion of the unstable acyl hydroperoxide groups to carboxyl groups, resulting in stable esters with a molecular composition of C19H28O7 (MWg368) and C17H26O8 (MWg358), respectively. The proposed mechanism is supported by several observations reported in the literature. On the basis of the indirect evidence presented in this study, we hypothesize that RO2g+gR′O•→ gRO3R′ chemistry is at the underlying molecular basis of high-molecular-weight ester formation upon α-pinene ozonolysis and may thus be of importance for new particle formation and growth in pristine forested environments.
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    Airborne observations of newly formed boundary layer aerosol particles under cloudy conditions
    (Katlenburg-Lindau : EGU, 2018) Altstädter, Barbara; Platis, Andreas; Jähn, Michael; Baars, Holger; Lückerath, Janine; Held, Andreas; Lampert, Astrid; Bange, Jens; Hermann, Markus; Wehner, Birgit
    This study describes the appearance of ultrafine boundary layer aerosol particles under classical “non-favourable” conditions at the research site of TROPOS (Leibniz Institute for Tropospheric Research). Airborne measurements of meteorological and aerosol properties of the atmospheric boundary layer (ABL) were repeatedly performed with the unmanned aerial system ALADINA (Application of Light-weight Aircraft for Detecting IN-situ Aerosol) during three seasons between October 2013 and July 2015. More than 100 measurement flights were conducted on 23 different days with a total flight duration of 53 h. In 26 % of the cases, maxima of ultrafine particles were observed close to the inversion layer at altitudes between 400 and 600 m and the particles were rapidly mixed vertically and mainly transported downwards during short time intervals of cloud gaps. This study focuses on two measurement days affected by low-level stratocumulus clouds, but different wind directions (NE, SW) and minimal concentrations (< 4.6 µg m−3) of SO2, as a common indicator for precursor gases at ground. Taken from vertical profiles, the onset of clouds led to a non-linearity of humidity that resulted in an increased turbulence at the local-scale and caused fast nucleation (e.g. Bigg, 1997; Wehner et al., 2010), but in relation to rapid dilution of surrounding air, seen in sporadic clusters of ground data, so that ultrafine particles disappeared in the verticality. The typical “banana shape” (Heintzenberg et al., 2007) of new particle formation (NPF) and growth was not seen at ground and thus these days might not have been classified as NPF event days by pure surface studies.
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    A European aerosol phenomenology - 6: Scattering properties of atmospheric aerosol particles from 28 ACTRIS sites
    (Katlenburg-Lindau : EGU, 2018) Pandolfi, Marco; Alados-Arboledas, Lucas; Alastuey, Andrés; Andrade, Marcos; Angelov, Christo; Artiñano, Begoña; Backman, John; Baltensperger, Urs; Bonasoni, Paolo; Bukowiecki, Nicolas; Collaud Coen, Martine; Conil, Sébastien; Coz, Esther; Crenn, Vincent; Dudoitis, Vadimas; Ealo, Marina; Eleftheriadis, Kostas; Favez, Olivier; Fetfatzis, Prodromos; Fiebig, Markus; Flentje, Harald; Ginot, Patrick; Gysel, Martin; Henzing, Bas; Hoffer, Andras; Holubova Smejkalova, Adela; Kalapov, Ivo; Kalivitis, Nikos; Kouvarakis, Giorgos; Kristensson, Adam; Kulmala, Markku; Lihavainen, Heikki; Lunder, Chris; Luoma, Krista; Lyamani, Hassan; Marinoni, Angela; Mihalopoulos, Nikos; Moerman, Marcel; Nicolas, José; O'Dowd, Colin; Petäjä, Tuukka; Petit, Jean-Eudes; Pichon, Jean Marc; Prokopciuk, Nina; Putaud, Jean-Philippe; Rodríguez, Sergio; Sciare, Jean; Sellegri, Karine; Swietlicki, Erik; Titos, Gloria; Tuch, Thomas; Tunved, Peter; Ulevicius, Vidmantas; Vaishya, Aditya; Vana, Milan; Virkkula, Aki; Vratolis, Stergios; Weingartner, Ernest; Wiedensohler, Alfred; Laj, Paolo
    This paper presents the light-scattering properties of atmospheric aerosol particles measured over the past decade at 28 ACTRIS observatories, which are located mainly in Europe. The data include particle light scattering (σsp) and hemispheric backscattering (σbsp) coefficients, scattering Ångström exponent (SAE), backscatter fraction (BF) and asymmetry parameter (g). An increasing gradient of σsp is observed when moving from remote environments (arctic/mountain) to regional and to urban environments. At a regional level in Europe, σsp also increases when moving from Nordic and Baltic countries and from western Europe to central/eastern Europe, whereas no clear spatial gradient is observed for other station environments. The SAE does not show a clear gradient as a function of the placement of the station. However, a west-to-east-increasing gradient is observed for both regional and mountain placements, suggesting a lower fraction of fine-mode particle in western/south-western Europe compared to central and eastern Europe, where the fine-mode particles dominate the scattering. The g does not show any clear gradient by station placement or geographical location reflecting the complex relationship of this parameter with the physical properties of the aerosol particles. Both the station placement and the geographical location are important factors affecting the intraannual variability. At mountain sites, higher σsp and SAE values are measured in the summer due to the enhanced boundary layer influence and/or new particle-formation episodes. Conversely, the lower horizontal and vertical dispersion during winter leads to higher σsp values at all low-altitude sites in central and eastern Europe compared to summer. These sites also show SAE maxima in the summer (with corresponding g minima). At all sites, both SAE and g show a strong variation with aerosol particle loading. The lowest values of g are always observed together with low σsp values, indicating a larger contribution from particles in the smaller accumulation mode. During periods of high σsp values, the variation of g is less pronounced, whereas the SAE increases or decreases, suggesting changes mostly in the coarse aerosol particle mode rather than in the fine mode. Statistically significant decreasing trends of σsp are observed at 5 out of the 13 stations included in the trend analyses. The total reductions of σsp are consistent with those reported for PM2.5 and PM10 mass concentrations over similar periods across Europe.