Varying extractability of petrogenic and pyrogenic polycyclic aromatic hydrocarbons (PAH) in urban soils: Evaluation of sample preparation and extraction of 71 PAH and alkylated PAH

Abstract

PAH extraction methods have been widely studied over the last decades. However, there is still no consistent method for contaminated soils. Here, for the first time, PAH source characteristics in soils were considered for the investigation of different pretreatment methods, extraction techniques and solvents in nine petrogenic to primarily pyrogenic urban soils. Sources were identified by macroscopic identification of source substrates and analysis of 71 PAH and alkylation patterns.The comparison of extraction solvents revealed that a combined sequential extraction using dichloromethane (for petrogenic PAH) and toluene:methanol (6:1) led to the highest extraction efficiencies for all samples and is therefore best suited for PAH analysis of unknown samples. Acetone:n-hexane led to the lowest extraction efficiencies for all samples and is not recommended as extraction solvent. The comparison of extraction techniques showed that Pressurized Solvent Extraction is more efficient than ultrasonic extraction especially for petrogenic PAH, but also for pyrogenic PAH. Grinding increased PAH extractability considerably but mainly for petrogenic PAH from bituminous coal particles. In mixed to primarily pyrogenic samples with a smaller proportion of coal, the enhanced extractability of coal leads to a more petrogenic PAH distribution and consequently a decrease in the source identifying PAH Alkylation Index.It is concluded that PAH contents in unknown (urban) soils, where pyrogenic and petrogenic PAH can be present, cannot generally be compared if different extraction techniques, different extraction solvents and grinding or no grinding are applied. As extraction efficiency increases with more effective methods and solvents for bituminous coals, it is recommended to define a specific extraction technique and solvent mixture for improved comparability in future PAH analyses.