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Chemical mass balance of 300 °c non-volatile particles at the tropospheric research site Melpitz, Germany

2014, Poulain, L., Birmili, W., Canonaco, F., Crippa, M., Wu, Z.J., Nordmann, S., Wiedensohler, A., Held, A., Spindler, G., Prévôt, A.S.H., Wiedensohler, A., Herrmann, H.

In the fine-particle mode (aerodynamic diameter < 1 μm) non-volatile material has been associated with black carbon (BC) and low-volatile organics and, to a lesser extent, with sea salt and mineral dust. This work analyzes non-volatile particles at the tropospheric research station Melpitz (Germany), combining experimental methods such as a mobility particle-size spectrometer (3–800 nm), a thermodenuder operating at 300 °C, a multi-angle absorption photometer (MAAP), and an aerosol mass spectrometer (AMS). The data were collected during two atmospheric field experiments in May–June 2008 as well as February–March 2009. As a basic result, we detected average non-volatile particle–volume fractions of 11 ± 3% (2008) and 17 ± 8% (2009). In both periods, BC was in close linear correlation with the non-volatile fraction, but not sufficient to quantitatively explain the non-volatile particle mass concentration. Based on the assumption that BC is not altered by the heating process, the non-volatile particle mass fraction could be explained by the sum of black carbon (47% in summer, 59% in winter) and a non-volatile organic contribution estimated as part of the low-volatility oxygenated organic aerosol (LV-OOA) (53% in summer, 41% in winter); the latter was identified from AMS data by factor analysis. Our results suggest that LV-OOA was more volatile in summer (May–June 2008) than in winter (February–March 2009) which was linked to a difference in oxidation levels (lower in summer). Although carbonaceous compounds dominated the sub-μm non-volatile particle mass fraction most of the time, a cross-sensitivity to partially volatile aerosol particles of maritime origin could be seen. These marine particles could be distinguished, however from the carbonaceous particles by a characteristic particle volume–size distribution. The paper discusses the uncertainty of the volatility measurements and outlines the possible merits of volatility analysis as part of continuous atmospheric aerosol measurements.

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Hygroscopic properties of the Paris urban aerosol in relation to its chemical composition

2014, Kamilli, K.A., Poulain, L., Held, A., Nowak, A., Birmili, W., Wiedensohler, A.

Aerosol hygroscopic growth factors and chemical properties were measured as part of the MEGAPOLI "Megacities Plume Case Study" at the urban site Laboratoire d'Hygiène de la Ville de Paris (LHVP) in the city center of Paris from June to August 2009, and from January to February 2010. Descriptive hygroscopic growth factors (DGF) were derived in the diameter range from 25 to 350 nm at relative humidities of 30, 55, 75, and 90% by applying the summation method on humidified and dry aerosol size distributions measured simultaneously with a humidified differential mobility particle sizer (HDMPS) and a twin differential mobility particle sizer (TDMPS). For 90% relative humidity, the DGF varied from 1.06 to 1.46 in summer, and from 1.06 to 1.66 in winter. Temporal variations in the observed mean DGF could be well explained with a simple growth model based on the aerosol chemical composition measured by aerosol mass spectrometry (AMS) and black carbon photometry (MAAP). In particular, good agreement was observed when sulfate was the predominant inorganic factor. A clear overestimation of the predicted growth factor was found when the nitrate mass concentration exceeded values of 10 μg m−3, e.g., during winter.