Novel and specific source identification of PAH in urban soils: Alk-PAH-BPCA index and "V"-shape distribution pattern

Soils in urban and industrial areas, especially in larger metropolitan areas such as the Ruhr area, Germany, are commonly characterized by severe anthropogenic overprinting due to urbanization processes including land development measures. Such urban soils often contain various anthropogenic substrate admixtures, like ash, coal, tailings, building rubble, industrial waste materials, as well as urban dust, soot, fly ash, and others. These admixtures often carry higher contents of pollutants such as polycyclic aromatic hydrocarbons (PAH). Whereas elevated PAH concentrations are commonly attributed to non-point pyrogenic carbon sources like soot and particulate matter, petrogenic PAH sources are still largely neglected in this context. In this study, an extended sample set of 62 samples of PAH source materials and urban soils containing anthropogenic substrate components was investigated by combining extended PAH analysis of 59 PAH, alkylated PAH distributions and benzene polycarboxylic acid (BPCA) analysis with regard to petrogenic and pyrogenic PAH source identification. For more reliability of source apportionment by a more integrative signal, the alkylated PAH distributions of different PAH groups were combined according to their degrees of alkylation. Based on this combination, a new PAH alkylation index (ΣC0/(ΣC0+ΣC2)) was derived, which considers, in contrast to commonly used single PAH ratios, a series of non-alkylated and alkylated PAH. By comparison of this PAH alkylation index with the degree of aromatic condensation a new robust and economic method for identifying petrogenic, pyrogenic and mixed PAH sources within soil samples and sediments was developed. It is shown that coal and coal ash particles are a not negligible PAH source in urban soils of mining-dominated regions and can make up a large proportion of the anthropogenic substrate components encountered. Further analyses of samples with defined levels of petrogenic and pyrogenic PAH are necessary to finally evaluate the usefulness of this proposed new PAH-BPCA approach.