Winter-time pollution in Central European cities shifts the 208Pb/207Pb isotope ratio of atmospheric PM2.5 to higher values: Implications for lead source apportionment

Atmospheric lead pollution has adverse health effects on humans. Identification of anthropogenic Pb sources is thus crucial for understanding of pollution-related risks and for formulation of efficient abatement strategies. We analyzed concentrations and isotope ratios of Pb in fine air-borne particulate matter (PM2.5) in three Central European cities. Aerosol sampling in 12-h intervals was performed during summer and winter in Hradec Králové, Olomouc and Brno, regional centers of highly industrialized Czech Republic, each with a population of more than 90 thousand. Lead analysis was complemented with concentration measurements of Zn, Cu, Cd, As, Sb, and S. Trace element and PM2.5 concentrations were higher in winter than in summer in all studied cities, on average by 47%. The overall mean concentration of PM2.5 in urban air was 21 μg m−3, similar to that in Bern (Switzerland) and Vienna (Austria). Across the sites, 206Pb/207Pb ratios ranged from 1.142 to 1.178 in summer and from 1.143 to 1.173 in winter. The mean 206Pb/207Pb ratios were statistically indistinguishable in all three studied cities (1.165 in Hradec Králové, 1.163 in Olomouc, and 1.160 in Brno). In the 206Pb/207Pb vs. 208Pb/207Pb graph, Pb isotope composition of summer samples formed a straight line, whereas Pb isotope composition of winter samples was shifted toward higher 208Pb/207Pb ratios. A Pb isotope inventory of regional pollution sources indicated that winter-time Pb pollution was not caused solely by household heating and increased electricity production in coal-burning power plants. Recycling of industrial Pb originating from Variscan ores and waste incineration could have shifted the 208Pb/207Pb ratio of PM2.5 to higher values, however, such sources do not emit more Pb in winter than in summer. Remobilization of legacy alkyl-Pb from gasoline additives and Pb emissions from current unleaded gasoline and diesel could have shifted both Pb isotope ratios to lower values.