Application of the integrating sphere method to separate the contributions of brown and black carbon in atmospheric aerosols.

Until about a decade ago, black carbon (BC) was thought to be the only light absorbing substance in the atmospheric aerosol except for soil or desert dust In more recent years, light absorbing polymeric carbonaceous material was found in atmospheric aerosols. Absorption increases appreciably toward short wavelengths, so this fraction was called brown carbon. Because brown carbon is thermally rather refractory, it influences the split between organic carbon (OC) and elemental carbon (EC) in thermal methods and, through its light absorption characteristics, leads to overestimations of BC concentrations. The goal of the present study was to extend the integrating sphere method to correct the BC signal for the contribution of brown carbon and to obtain an estimate of brown carbon concentrations. Humic acid sodium salt was used as proxy for brown carbon. The extended method is first tested on mixtures of test substances and then applied to atmospheric samples collected during biomass smoke episodes (Easter bonfires) in Austria. The resulting concentrations of black and brown carbon are compared to EC obtained with a widely used thermal method, the Cachier method (Cachier et al. Tellus 1989, 41B, 379-390) and a thermal-optical method (Schmid et al. Atmos. Environ. 2001, 35, 2111-2121), as well as to concentrations of humic like substances (HULIS) and to biomass smoke POM (particulate organic matter). Both the thermal methods were found to overestimate BC on days with large contributions of woodsmoke, which agrees with the findings of the method intercomparison study by Reisinger et at. (Environ. Sci. Technol. 2008, 42, 884-889). During the days of the bonfires, the Cachier method gave EC concentrations that were higher by a factor of 3.8 than the BC concentrations, while the concentrations obtained with the thermal-optical method were higher by a factor of 2.6.

Combined determination of the chemical composition and of health effects of secondary organic aerosols: the POLYSOA project.

Epidemiological studies show a clear link between increased mortality and enhanced concentrations of ambient aerosols. The chemical and physical properties of aerosol particles causing these health effects remain unclear. A major fraction of the ambient aerosol particle mass is composed of secondary organic aerosol (SOA). Recent studies showed that a significant amount of SOA consists of high molecular weight compounds (oligomers), which are chemically not well characterized. Within the POLYSOA project a large variety of state-of-the-art analytical chemical methods were used to characterize the chemical composition of SOA particles with emphasis on the oligomeric mass fraction. Mass spectrometric results showed that SOA oligomers are highly oxidized compounds and that hydroperoxides are formed, which is consistent with NMR results. This high molecular weight fraction accounts for up to 23% of the total organic carbon in SOA particles. These well-characterized SOA particles were deposited on three lung cell culture systems (microdissected respiratory epithelia from porcine tracheae, the human bronchial epithelial cell line BEAS-2B, and porcine lung surface macrophages obtained by bronchoalveolar lavage) in a newly constructed particle deposition chamber with the goal to eventually identify particle components that are responsible for cell responses leading to adverse health effects. In addition, monolayers of the alveolar epithelial cell line A549 were used in an alveolar epithelial repair model. The lung cells were examined for morphological, biochemical, and physiological changes after exposure to SOA. Analyses of the lung cells after exposure to SOA are ongoing. First data give evidence for a moderate increase of necrotic cell death as measured by lactate dehydrogenase release and for effects on the alveolar epithelial wound repair mainly due to alterations of cell spreading and cell migration at the edge of the wound. Thus, these first results indicate that SOA, in concentrations comparable to environmental concentrations, may induce distinct effects in lung cells.

Carbon-specific analysis of humic-like substances in atmospheric aerosol and precipitation samples.

A new approach for the carbon-specific determination of humic-like substances (HULIS) in atmospheric aerosols is presented. The method is based on a two-step isolation procedure of HULIS and the determination of HULIS carbon with a dissolved organic carbon analyzer. In the first step, a C18 solid-phase extraction is performed to separate HULIS from inorganic and hydrophilic organic sample constituents in aqueous sample solutions. The second isolation step is conducted on a strong anion exchanger to separate HULIS from remaining carbonaceous compounds. This ion chromatographic separation step including the subsequent on-line detection of HULIS carbon was performed fully automated to avoid the risk of sample contamination and to enhance the reproducibility of the method. With a 5-mL sample volume, a limit of detection of 1.0 mg C/L was obtained; this corresponds to an absolute amount of 5 microg of HULIS carbon. The reproducibility of the method given as the relative standard deviation was 4.3% (n = 10). The method was applied for the determination of water-soluble HULIS in airborne particulate matter. PM10 concentrations at an urban site in Vienna, Austria, ranged from around 0.1 to 1.8 microg of C/m(3) (n = 49); the fraction of water-soluble HULIS in OC was 12.1 +/- 7.2% (n = 49).