Evidence for multiple removal pathways in low-temperature (200-400 °C) thermal treatment of pentachlorophenol-laden...

Polychlorinated aromatic compounds (PCACs) pose significant remediation challenges, since their high soil affinities preclude mobile-phase partitioning and subsurface extraction. To enhance partitioning and desorption, subsurface temperatures are raised using a technique called thermal conduction heating-soil vapor extraction (TCH-SVE). While this technique improves PCAC partitioning, it can also promote several degradation reactions under temperatures typical of low-temperature TCH-SVE (200-400 °C). While these reactions are labile, the extent to which they occur in flow-through TCH-SVE is unclear. The current research used bench-scale, flow-through TCH-SVE to assess relative importance of three removal pathways: (1) target volatilization, (2) reductive dechlorination, and (3) oxidation via OH-addition. Pentachlorophenol was used as a representative PCAC, and pathway contributions, extents, and regioselectivity were examined as a function of temperature (225-375 °C) and gas-phase oxygen content (air vs. nitrogen). Across treatments, OH-addition and dechlorination occurred in parallel and accounted for significantly more removal than PCP volatilization. OH-addition byproducts had highest yields (regardless of oxygen content) and were consistent with surface-mediated OH production and ring addition. OH-addition increased with temperature while volatilization and dechlorination decreased. Notable exceptions occurred between 225 and 325 °C (where dechlorination dropped 10-fold) and 325 and 375 °C (where OH-addition fell 75%), signifying major mechanism shifts in these intervals.