The presence of coal tars in the subsurface associated with former manufactured gas plants (MGPs) offers a remediation challenge due to their complex chemical composition, dissolution behaviour and recalcitrant characteristics. A former MGP site in Clearwater Beach, Florida was characterized and bench-scale analyses were conducted to assess the potential for in situ chemical oxidation (ISCO) using persulfate to treat MGP residuals. Completion of a conceptual site model identified a homogeneous, silty sand aquifer, with an average hydraulic conductivity of approximately 2.3x10-3 cm/s and a groundwater flow rate of 2 cm/day in the direction of S20°E. Six source zones, three near the water table and three in the deep aquifer were estimated to have a total volume of 108 m3. A multi-level well transect was installed to monitor concentrations of dissolved compounds and to estimate mass discharge downgradient of the source zones over time. On average, the morphology of the aqueous concentrations remained consistent with time. A total mass discharge across the transect of 94 mg/day was estimated for site-specific compounds. Bench-scale tests were conducted on aquifer sediments and groundwater samples. The aquifer was determined to have a low buffering capacity, low chemical oxygen demand, and low natural oxidant interaction (NOI) with persulfate. Aqueous batch experiments identified the potential for iron (II) activated persulfate to reduce concentrations of BTEX and PAHs below method detection limits (MDLs). Unactivated persulfate was able to reduce BTEX concentrations to below MDLs after 14 days; however, the concentration of PAH compounds remained above MDLs after 14 days. Higher iron doses within the system were shown to be more effective in reducing BTEX and PAH compounds. Column experiments designed to mimic site conditions were used to evaluate the feasibility of persulfate treatment on impacted sediments from the Clearwater site. Two sets of column experiments were conducted: one using unactivated persulfate followed by alkaline activated persulfate; and one using iron (II) activated persulfate. On average, unactivated persulfate was able to reduce BTEX and PAH aqueous effluent concentrations by > 75% and 40%, respectively, after a total dose of 60 g/g soil. Two additional doses of alkaline activated persulfate (total persulfate dose of ~80g/g soil) in these columns were able to further reduce effluent BTEX and PAH concentrations by > 90% and > 75%, respectively. Iron (II) activated persulfate reduced effluent BTEX concentrations by > 70% and PAHs by > 65% after a total dose of 35 g/g soil. Average reductions in mass for BTEX and PAH compounds were approximately of 48% and 26% respectively in the iron (II) activated persulfate columns, and 24% and 10%, respectively in the alkaline activated persulfate columns. The potential for the ability to use in situ chemical oxidation using persulfate for the remediation of MGP residuals in the subsurface is evaluated using field measurements and bench-scale experimentation. The reductions observed in aqueous phase compounds in MGP groundwater as observed in the laboratory indicate the potential for reductions in groundwater concentrations at this and other contaminated former MGP sites. However, column experiments, indicating the inability for activated persulfate to reduce all identified compounds in the MGP NAPL suggest source treatment with activated persulfate would not reduce concentrations to below Florida Department of Environmental Protection natural attenuation concentrations.

The presence of coal tars in the subsurface associated with former manufactured gas plants (MGPs) offers a remediation challenge due to their complex chemical composition, dissolution behaviour and recalcitrant characteristics. A former MGP site in Clearwater Beach, Florida was characterized and bench-scale analyses were conducted to assess the potential for in situ chemical oxidation (ISCO) using persulfate to treat MGP residuals. Completion of a conceptual site model identified a homogeneous, silty sand aquifer, with an average hydraulic conductivity of approximately 2.3x10-3 cm/s and a groundwater flow rate of 2 cm/day in the direction of S20°E. Six source zones, three near the water table and three in the deep aquifer were estimated to have a total volume of 108 m3. A multi-level well transect was installed to monitor concentrations of dissolved compounds and to estimate mass discharge downgradient of the source zones over time. On average, the morphology of the aqueous concentrations remained consistent with time. A total mass discharge across the transect of 94 mg/day was estimated for site-specific compounds. Bench-scale tests were conducted on aquifer sediments and groundwater samples. The aquifer was determined to have a low buffering capacity, low chemical oxygen demand, and low natural oxidant interaction (NOI) with persulfate. Aqueous batch experiments identified the potential for iron (II) activated persulfate to reduce concentrations of BTEX and PAHs below method detection limits (MDLs). Unactivated persulfate was able to reduce BTEX concentrations to below MDLs after 14 days; however, the concentration of PAH compounds remained above MDLs after 14 days. Higher iron doses within the system were shown to be more effective in reducing BTEX and PAH compounds. Column experiments designed to mimic site conditions were used to evaluate the feasibility of persulfate treatment on impacted sediments from the Clearwater site. Two sets of column experiments were conducted: one using unactivated persulfate followed by alkaline activated persulfate; and one using iron (II) activated persulfate. On average, unactivated persulfate was able to reduce BTEX and PAH aqueous effluent concentrations by > 75% and 40%, respectively, after a total dose of 60 g/g soil. Two additional doses of alkaline activated persulfate (total persulfate dose of ~80g/g soil) in these columns were able to further reduce effluent BTEX and PAH concentrations by > 90% and > 75%, respectively. Iron (II) activated persulfate reduced effluent BTEX concentrations by > 70% and PAHs by > 65% after a total dose of 35 g/g soil. Average reductions in mass for BTEX and PAH compounds were approximately of 48% and 26% respectively in the iron (II) activated persulfate columns, and 24% and 10%, respectively in the alkaline activated persulfate columns. The potential for the ability to use in situ chemical oxidation using persulfate for the remediation of MGP residuals in the subsurface is evaluated using field measurements and bench-scale experimentation. The reductions observed in aqueous phase compounds in MGP groundwater as observed in the laboratory indicate the potential for reductions in groundwater concentrations at this and other contaminated former MGP sites. However, column experiments, indicating the inability for activated persulfate to reduce all identified compounds in the MGP NAPL suggest source treatment with activated persulfate would not reduce concentrations to below Florida Department of Environmental Protection natural attenuation concentrations.