Impact of organic matter on transformation during thermal remediation of pyrene-contaminated substrates

Thermal remediation (TR) is a broadly applicable technology that is effective at removing volatile and semivolatile contaminants from soil. However, TR can be costly and inefficient in practice, with underlying removal and transformation mechanisms poorly understood. To better understand the role organic matter plays in removal, a series of experiments was performed with a humic substance, humic modified silica, and a natural soil in the presence of pyrene from 100 to 500 degrees C and compared to prior experiments using pure minerals. Detection of by-products confirmed that pyrene was removed by transformation in addition to volatilization. Oxidation via hydroxyl radical formation and reductive hydrogenation were both indicated as possible reaction mechanisms promoted by organic matter. Because the presence of bulk water did not impact the extent of pyrene degradation or transformation, it is hypothesized that hydroxyl radicals were produced from soil organic matter functional groups, such as carboxyl and phenol groups, and possibly bound water at elevated temperatures in dry experiments. Additionally, the average oxidation state of carbon in detected by-products increased with temperature in experiments with humic modified silica and soil but not humic substance alone, though the extent of degradation did not significantly change. This shift in oxidation state may indicate that attachment of organic matter to another surface may increase interaction between reactive species. The results of this study show that contaminant transformation in soils during TR significantly contributes to removal, even at temperatures lower than those used in traditional treatment. This information will help to guide the design and operation of TR systems, potentially reducing energy requirements and highlighting the necessity of testing for transformation by-products.

Automated summary

Thermal remediation is an effective technology for removing contaminants from soil, but it is costly and inefficient. This study investigates the role of organic matter in the removal process and identifies possible reaction mechanisms. The results show that contaminant transformation contributes significantly to removal even at lower temperatures.