We characterised surface-active substances (SASs) in aqueous extract of atmospheric aerosols by using phase sensitive alternating current voltammetry. The electrochemical method has mainly been used for the quantification of surfactants in sea water but has not been applied to atmospheric aerosols yet. The advantage of the method is its simplicity and sensitivity that enables direct analysis of aerosol extracts without the need for sample concentration. Aerosol samples were collected at Middle Adriatic Martinska station influenced by different air masses as well as from urban (Zagreb, Croatia) and rural (K-puszta, Hungary) areas from late spring to early autumn in 2010. The highest SAS concentrations, expressed in equivalents of T-X-100, ranging from 0.34 to 0.91 µg m−3 were detected in urban samples. The SAS concentrations obtained for marine, regional and continental samples ranged from 0.14 to 0.31, 0.18 to 0.42 and 0.07 to 0.28 µg m−3, respectively. The SAS concentrations in K-puszta aerosols ranged from 0.13 to 0.46 µg m−3. Investigation of humic-like substances isolated from K-puszta samples (2008) confirmed their significant surfactant nature. Different SAS chemistry was noticed for urban and non-urban samples. Investigations at different pH revealed anionic character of SASs in aerosol samples
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