Environmentally Persistent Free Radicals in Soils of Past Coking Sites: Distribution and Stabilization

This study presents the existence of environmentally persistent free radicals (EPFRs) in soils of past coking sites, mainly contaminated by polycyclic aromatic hydrocarbons (PAHs). Measurements of EPFRs were conducted by electron paramagnetic resonance (EPR) technique with numerous soil samples, which were collected from different distances (0-1000 m) and different depths (0-30 cm) of three contaminant sources. EPR signals with ∼3 × 10¹⁷ radicals/g of the soil samples were obtained, which are very similar to that generated in PAHs contaminated clays, that is, g = 2.0028-2.0036. Concentrations of PAHs and soil components were determined to understand their role in producing EPFRs. PAHs, clay, and iron predominately contributed to generating EPRFs. Meanwhile, organic matter negatively influenced the production of EPRFs. The effects of environmental factors (moisture and oxic/anoxic) were also studied to probe the persistency of EPFRs under various simulated conditions. The EPFRs are stable under relatively dry and oxic conditions. Under anoxic conditions without O₂ and H₂O, the spin densities decrease initially, followed by gradual increase before attaining constant values in two months period time. The present work implies that continuous formation of EPFRs induced by PAHs is largely responsible for the presence of relatively stable radicals in soils of coking sites.