Fractionation of polycyclic aromatic hydrocarbon residues in soils

Understanding the forms and availabilities of polycylic aromatic hydrocarbons (PAHs) would have considerable benefits for their risk assessment, and is of crucial importance for food security and remediation strategies in contaminated sites. In this work, the forms of six PAHs (fluorene, phenanthrene, fluoranthene, pyrene, benzo[a]anthracene, and benzo[a]pyrene) in soils were separated into three fractions including a desorbing fraction, a non-desorbing fraction, and a bound residual fraction using a sequential extraction mass balance approach. The desorbing and non-desorbing fractions were extracted with hydroxypropyl-beta-cyclodextrin (HPCD) and dichloromethane:acetone (1:1, vol/vol), respectively. The desorbing and non-desorbing fractions always dominated the total PAH content in soils. The proportion of bound PAH residue in nonsterilized soils was small (<16%), and even smaller (4.5%) in sterilized soils. The concentrations of the desorbing fraction of PAHs as well as the percentage of this fraction to the total PAH content in soils clearly decreased in 0-16 weeks, which may be due to microbial biodegradation and its transfer to other fractions in soils. The concentrations of the non-desorbing PAH fractions increased in sterilized soils, while remaining nearly constant or decreasing to some extent in nonsterilized soils after 16 weeks. The proportion of non-desorbing PAH fractions significantly increased in 16 week-incubation, and this proportion was positively correlated with the molecular weights of the PAHs tested, indicating that larger PAHs are more likely to be present in non-desorbing fractions. The bound PAH residue tended to increase at first and decrease thereafter over the 0-16-week period, and microbes played an important role in the formation of bound residue.