Mechanochemically enhanced degradation of pyrene and phenanthrene loaded on magnetite

The enhancement of the degradation of polycyclic aromatic hydrocarbons (PAHs), exemplified by pyrene and phenanthrene, using mild grinding in the presence of common minerals was investigated. Magnetite, birnessite, and Na- and Cu-montmorillonite samples were loaded with pyrene or phenanthrene and ground manually or in a ball mill for short periods of time. The ground samples were analyzed for PAHs and for their metabolites, using high-performance liquid chromatography and liquid chromatography-mass spectrometry. No degradation of pyrene occurred when it was in contact with Na-montmorillonite or birnessite. Sorption of pyrene on Cu-montmorillonite enhanced its degradation, but grinding of the loaded clay actually inhibited pyrene's degradation. Phenanthrene hardly degraded on Cu-montmorillonite. Grinding magnetite loaded with either PAH resulted in a significant degradation of both (∼50% after grinding for 5 min), while in the nonground samples, negligible degradation was detected. The extent of degradation increased with the duration of grinding. The degradation of either PAH loaded on magnetite yielded oxidized products. In soil samples contaminated with PAHs and mixed with magnetite, a similar grinding-induced degradation pattern was observed, but with a lower rate. A liquid phase was required to initiate degradation in the soil. The liquid phase apparently served as the medium through which the pollutants reached the surface of the degradation-enhancing mineral.