Fate of pyrene on mineral surfaces during thermal remediation as a function of temperature

There is evidence that contaminants can transform at the elevated temperatures of thermal remediation; however, the contribution of redox active minerals to transformation has not been investigated. Three redox active minerals (i.e., birnessite (MnO2), magnetite (Fe3O4), and hematite (Fe2O3)) and one redox inactive mineral (Ottawa sand (SiO2)) were spiked with pyrene and thermally treated. Under dry, anoxic conditions, 100%, 75% +/- 3%, 70% +/- 15%, and 14% +/- 28% of the initial pyrene mass was removed with birnessite, magnetite, hematite, and Ottawa sand, respectively, after treatment at 250 degrees C for 30 min. Under wet, oxic conditions, 92% +/- 8%, 86% +/- 12%, 79% +/- 4%, and 42% +/- 7% was removed for the same minerals, respectively, after treatment at only 150 degrees C for 30 min. Baseline studies with Ottawa sand resulted in volatilization alone of pyrene with no transformation observed. Increased pyrene loading was used to evaluate potential transformation pathways based on identified by-products, demonstrating that both oxidative and reductive pathways were operative depending on the conditions. Reaction products in the presence of redox active minerals indicate transformation was dominated by reduction via hydrogenation in dry experiments, and by oxidation via hydroxyl radicals in wet experiments. The latter was unexpected, because only low hydroxyl radical concentrations have been detected in mineral-water systems at ambient temperature. These results indicate that understanding dominant reaction pathways and products is advantageous for the design of efficient and safe thermally enhanced treatment systems.

Automated summary

The study found that redox active minerals play a significant role in transforming contaminants like pyrene during thermal treatment, with transformation pathways depending on experimental conditions. Understanding dominant reaction pathways and products is crucial for the design of efficient and safe thermally enhanced treatment systems.