title: Effect of low temperature thermal treatment on soils contaminated with pentachlorophenol and environmentally persistent free radicals.
abstract: The effect of low temperature thermal treatment on soils from a former Superfund wood-treating site contaminated with pentachlorophenol (PCP) and the environmentally persistent free radical (EPFR), pentachlorophenoxyl, was determined. The pentachlorophenoxyl EPFRs' and the PCP molecules' chemical behavior were simultaneously monitored at temperatures ranging from 25 to 300 °C via electron paramagnetic resonance (EPR) spectroscopy and GC-MS analysis, respectively. Two types of thermal treatment were employed: a closed heating (oxygen-starved condition) where the soil was heated under vacuum and an open heating system (oxygen-rich conditions), where the soil was heated in ambient air. EPR analyses for closed heating indicated the EPFR concentration was 2-12 × 10(18) spins/g of soil, with a g-factor and line width (ΔHp-p) of 2.00311-2.00323 and 4.190-5.472 G, respectively. EPR analyses for the open heating soils revealed a slightly broader and weaker radical signal, with a concentration of 1-10 × 10(18) spins/g of soil, g-factor of 2.00327-2.00341, and ΔHp-p of 5.209-6.721 G. This suggested the open heating resulted in the formation of a more oxygen-centered structure of the pentachlorophenoxyl radical or additional, similar radicals. The EPFR concentration peaked at 10 × 10(18) spins/g of soil at 100 °C for open heating and 12 × 10(18) spins/g at 75 °C for closed heating. The half-lives of the EPFRs were 2-24 days at room temperature in ambient air. These results suggest low temperature treatment of soils contaminated with PCP can convert the PCP to potentially more toxic pentachlorophenoxyl EPFRs, which may persist in the environment long enough for human exposure.
authors.affiliation: Department of Chemistry, Louisiana State University, Baton Rouge, Louisiana 70802, United States.
authors.forename: Albert Leo N
authors.initials: AL
authors.lastname: dela Cruz
authors.forename: Robert L
authors.initials: RL
authors.lastname: Cook
authors.forename: Slawomir M
authors.initials: SM
authors.lastname: Lomnicki
authors.forename: Barry
authors.initials: B
authors.lastname: Dellinger
mesh_terms: D003080:Cold Temperature; D004578:Electron Spin Resonance Spectroscopy; D052918:Environmental Restoration and Remediation; D005609:Free Radicals / Q000737:chemistry*; D006207:Half-Life; D006361:Heating; D006801:Humans; D007700:Kinetics; D010416:Pentachlorophenol / Q000737:chemistry*; D012987:Soil / Q000737:chemistry*; D012989:Soil Pollutants / Q000737:chemistry*
chemical_list: D005609:Free Radicals; D012987:Soil; D012989:Soil Pollutants; D010416:Pentachlorophenol