The Spatial Heterogeneity of Polycyclic Aromatic Hydrocarbons in Soil Depends on Their Physico-chemical Properties

The present study investigates the heterogenic distribution of nine polycyclic aromatic hydrocarbons (PAHs) in soil on a microscale. For this purpose, we developed a method allowing for the detailed analysis of PAHs in minute amounts of soil (5 to 25 mg). A certified reference soil with a known PAH content and a diffusely polluted Danish surface soil from central Copenhagen were used in the study. In order to separate soil heterogeneity from analytical variation, we attempted to establish the least amount of soil in which homogeneous and reproducible results could be obtained for the PAHs in question. The results demonstrated that for fluoranthene, analytical results in accordance with the certified reference values could be obtained in quantities of 10 mg of soil or more. For phenanthrene and pyrene, certified reference values could be obtained in quantities of 25 mg of soil or more. Similar results were obtained with the Nyboder soil, using the reference soil for quality and quantity assurance. For quantification of all nine PAHs, a minimum of 100 mg of soil was needed for both soils. In order to obtain an expression for the degree of heterogeneity of PAHs in the soils, a subsample variation was calculated based on overall sample variation and analytical measurements variation. The results demonstrate that the PAHs in the Nyboder soil are much more heterogeneously distributed than the PAHs in the reference soil due to much larger subsample variations. Furthermore, strong relationships between different physico-chemical properties and subsample variation were found. These included molecular weight, water solubility, log octanol/water partition coefficient, and soil–water distribution coefficient of the investigated PAHs, demonstrating that the heterogeneity of PAHs in the Nyboder soil is significantly influenced by such parameters.