Distribution and Abiotic Degradation of Chlorinated Solvents in Heated Field Samples

The objective of this study was to evaluate the abiotic degradation of tetrachloroethylene (PCE) in contaminated soil and groundwater samples obtained from the Camelot Cleaners Superfund site, West Fargo, ND. The field samples were incubated at temperatures of 25, 55, 75, and 95 °C in sealed ampules containing aqueous, gas, and solid phases for periods of up to 75 days to simulate thermal treatment temperatures. Aqueous PCE concentrations increased with incubation temperature but remained constant over time. The degradation of dolomite to form CO2 facilitated the transfer of sorbed-phase PCE from the solid to the aqueous phase in heated ampules. While compounds associated with PCE degradation were detected in the heated ampules, these compounds were also detected in ampules with PCE-free Camelot soil and were attributed to soil diagenesis rather than PCE degradation. Trichloroethylene underwent hydrogenolysis to form cis-DCE at 95 °C, and TCE levels decreased with first-order half-lives of 157 days at 55 °C and 26 days at 95 °C. The relatively small decrease in total PCE levels after 75 days of heating at 95 °C suggests that abiotic degradation of PCE will not result in significant mass reduction during thermal treatment of the Camelot Cleaners Superfund site

Reductions in Contaminant Mass Discharge Following Partial Mass Removal from DNAPL Source Zones

Although in situ remediation technologies have been used to aggressively treat dense nonaqueous phase liquid (DNAPL) source zones, complete contaminant removal or destruction is rarely achieved. To evaluate the effects of partial source zone mass removal on dissolved-phase contaminant flux, four experiments were conducted in a two-dimensional aquifer cell that contained a tetrachloroethene (PCE) source zone and down-gradient plume region. Initial source zone PCE saturation distributions, quantified using a light transmission system, were expressed in terms of a ganglia-to-pool ratio (GTP), which ranged from 0.16 (13.8% ganglia) to 1.6 (61.5% ganglia). The cells were flushed sequentially with a 4% (wt.) Tween 80 surfactant solution to achieve incremental PCE mass removal, followed by water flooding until steady-state mass discharge and plume concentrations were established. In all cases, the GTP ratio decreased with increasing mass removal, consistent with the observed preferential dissolution of PCE ganglia and persistence of high-saturation pools. In the ganglia-dominated system (GTP = 1.6), greater than 70% mass removal was required before measurable reductions in plume concentrations and mass discharge were observed. For pool-dominated source zones (GTP 50%) in mass discharge were realized after only 50% mass removal

Density-Modified Displacement for DNAPL Source Zone Remediation: Density Conversion and Recovery in Heterogeneous Aquifer Cells

Low interfacial tension (IFT) displacement (mobilization) of nonaqueous phase liquids (NAPLs) offers potential as an efficient remediation technology for contaminated aquifer source zones. However, displacement of dense NAPLs (DNAPLs) is problematic due to the tendency for downward migration and redistribution of the mobilized DNAPL. To overcome this limitation, a density-modified displacement method (DMD) was developed, which couples in situ density conversion of DNAPLs via alcohol partitioning with low IFT NAPL displacement and recovery. The objective of this work was to evaluate the DMD method for two representative DNAPLs, chlorobenzene (CB) and trichloroethene (TCE). Laboratory-scale experiments were conducted in a two-dimensional (2-D) cell, configured to represent a heterogeneous unconfined aquifer system containing low permeability lenses. After release and redistribution of either CB- or TCE-NAPL, the 2-D aquifer cells were flushed with a 6% (wt) n-butanol aqueous solution to achieve DNAPL to light NAPL conversion, followed by a low IFT surfactant solution consisting of 4% (4:1) Aerosol MA/Aerosol OT + 20% n-butanol + 500 mg/L CaCl2. Visual observations and experimental measurements demonstrated that in situ density conversion and immiscible displacement of both CB and TCE were successful. Effluent NAPL densities ranged from 0.96 to 0.90 g/mL for CB and from 0.95 to 0.92 g/mL for TCE, while aqueous phase densities remained above 0.96 g/L. Density conversion of CB and TCE was achieved after flushing with 1.2 and 4.9 pore vol of 6% n-butanol solution, respectively. Recoveries of 90% CB and 85% TCE were realized after flushing with 1.2 pore vol of the low IFT surfactant solution, which was followed by a 1 pore vol posttreatment water flood. Surfactant and n-butanol recoveries ranged from 75 to 96% based on effluent concentration data. The observed minimal mobilization during the n-butanol density conversion preflood and near complete mobilization during the low IFT displacement flood were consistent with total trapping number calculations. The results reported herein demonstrate the potential efficiency of the DMD technology as a means of DNAPL source zone restoration

Density-Modified Displacement for DNAPL Source Zone Remediation: Density Conversion and Recovery in Heterogeneous Aquifer Cells

Low interfacial tension (IFT) displacement (mobilization) of nonaqueous phase liquids (NAPLs) offers potential as an efficient remediation technology for contaminated aquifer source zones. However, displacement of dense NAPLs (DNAPLs) is problematic due to the tendency for downward migration and redistribution of the mobilized DNAPL. To overcome this limitation, a density-modified displacement method (DMD) was developed, which couples in situ density conversion of DNAPLs via alcohol partitioning with low IFT NAPL displacement and recovery. The objective of this work was to evaluate the DMD method for two representative DNAPLs, chlorobenzene (CB) and trichloroethene (TCE). Laboratory-scale experiments were conducted in a two-dimensional (2-D) cell, configured to represent a heterogeneous unconfined aquifer system containing low permeability lenses. After release and redistribution of either CB- or TCE-NAPL, the 2-D aquifer cells were flushed with a 6% (wt) n-butanol aqueous solution to achieve DNAPL to light NAPL conversion, followed by a low IFT surfactant solution consisting of 4% (4:1) Aerosol MA/Aerosol OT + 20% n-butanol + 500 mg/L CaCl2. Visual observations and experimental measurements demonstrated that in situ density conversion and immiscible displacement of both CB and TCE were successful. Effluent NAPL densities ranged from 0.96 to 0.90 g/mL for CB and from 0.95 to 0.92 g/mL for TCE, while aqueous phase densities remained above 0.96 g/L. Density conversion of CB and TCE was achieved after flushing with 1.2 and 4.9 pore vol of 6% n-butanol solution, respectively. Recoveries of 90% CB and 85% TCE were realized after flushing with 1.2 pore vol of the low IFT surfactant solution, which was followed by a 1 pore vol posttreatment water flood. Surfactant and n-butanol recoveries ranged from 75 to 96% based on effluent concentration data. The observed minimal mobilization during the n-butanol density conversion preflood and near complete mobilization during the low IFT displacement flood were consistent with total trapping number calculations. The results reported herein demonstrate the potential efficiency of the DMD technology as a means of DNAPL source zone restoration

Density-Modified Displacement for DNAPL Source Zone Remediation: Density Conversion and Recovery in Heterogeneous Aquifer Cells

Low interfacial tension (IFT) displacement (mobilization) of nonaqueous phase liquids (NAPLs) offers potential as an efficient remediation technology for contaminated aquifer source zones. However, displacement of dense NAPLs (DNAPLs) is problematic due to the tendency for downward migration and redistribution of the mobilized DNAPL. To overcome this limitation, a density-modified displacement method (DMD) was developed, which couples in situ density conversion of DNAPLs via alcohol partitioning with low IFT NAPL displacement and recovery. The objective of this work was to evaluate the DMD method for two representative DNAPLs, chlorobenzene (CB) and trichloroethene (TCE). Laboratory-scale experiments were conducted in a two-dimensional (2-D) cell, configured to represent a heterogeneous unconfined aquifer system containing low permeability lenses. After release and redistribution of either CB- or TCE-NAPL, the 2-D aquifer cells were flushed with a 6% (wt) n-butanol aqueous solution to achieve DNAPL to light NAPL conversion, followed by a low IFT surfactant solution consisting of 4% (4:1) Aerosol MA/Aerosol OT + 20% n-butanol + 500 mg/L CaCl2. Visual observations and experimental measurements demonstrated that in situ density conversion and immiscible displacement of both CB and TCE were successful. Effluent NAPL densities ranged from 0.96 to 0.90 g/mL for CB and from 0.95 to 0.92 g/mL for TCE, while aqueous phase densities remained above 0.96 g/L. Density conversion of CB and TCE was achieved after flushing with 1.2 and 4.9 pore vol of 6% n-butanol solution, respectively. Recoveries of 90% CB and 85% TCE were realized after flushing with 1.2 pore vol of the low IFT surfactant solution, which was followed by a 1 pore vol posttreatment water flood. Surfactant and n-butanol recoveries ranged from 75 to 96% based on effluent concentration data. The observed minimal mobilization during the n-butanol density conversion preflood and near complete mobilization during the low IFT displacement flood were consistent with total trapping number calculations. The results reported herein demonstrate the potential efficiency of the DMD technology as a means of DNAPL source zone restoration

Density-Modified Displacement for DNAPL Source Zone Remediation: Density Conversion and Recovery in Heterogeneous Aquifer Cells

Low interfacial tension (IFT) displacement (mobilization) of nonaqueous phase liquids (NAPLs) offers potential as an efficient remediation technology for contaminated aquifer source zones. However, displacement of dense NAPLs (DNAPLs) is problematic due to the tendency for downward migration and redistribution of the mobilized DNAPL. To overcome this limitation, a density-modified displacement method (DMD) was developed, which couples in situ density conversion of DNAPLs via alcohol partitioning with low IFT NAPL displacement and recovery. The objective of this work was to evaluate the DMD method for two representative DNAPLs, chlorobenzene (CB) and trichloroethene (TCE). Laboratory-scale experiments were conducted in a two-dimensional (2-D) cell, configured to represent a heterogeneous unconfined aquifer system containing low permeability lenses. After release and redistribution of either CB- or TCE-NAPL, the 2-D aquifer cells were flushed with a 6% (wt) n-butanol aqueous solution to achieve DNAPL to light NAPL conversion, followed by a low IFT surfactant solution consisting of 4% (4:1) Aerosol MA/Aerosol OT + 20% n-butanol + 500 mg/L CaCl2. Visual observations and experimental measurements demonstrated that in situ density conversion and immiscible displacement of both CB and TCE were successful. Effluent NAPL densities ranged from 0.96 to 0.90 g/mL for CB and from 0.95 to 0.92 g/mL for TCE, while aqueous phase densities remained above 0.96 g/L. Density conversion of CB and TCE was achieved after flushing with 1.2 and 4.9 pore vol of 6% n-butanol solution, respectively. Recoveries of 90% CB and 85% TCE were realized after flushing with 1.2 pore vol of the low IFT surfactant solution, which was followed by a 1 pore vol posttreatment water flood. Surfactant and n-butanol recoveries ranged from 75 to 96% based on effluent concentration data. The observed minimal mobilization during the n-butanol density conversion preflood and near complete mobilization during the low IFT displacement flood were consistent with total trapping number calculations. The results reported herein demonstrate the potential efficiency of the DMD technology as a means of DNAPL source zone restoration

Density-Modified Displacement for DNAPL Source Zone Remediation: Density Conversion and Recovery in Heterogeneous Aquifer Cells

Low interfacial tension (IFT) displacement (mobilization) of nonaqueous phase liquids (NAPLs) offers potential as an efficient remediation technology for contaminated aquifer source zones. However, displacement of dense NAPLs (DNAPLs) is problematic due to the tendency for downward migration and redistribution of the mobilized DNAPL. To overcome this limitation, a density-modified displacement method (DMD) was developed, which couples in situ density conversion of DNAPLs via alcohol partitioning with low IFT NAPL displacement and recovery. The objective of this work was to evaluate the DMD method for two representative DNAPLs, chlorobenzene (CB) and trichloroethene (TCE). Laboratory-scale experiments were conducted in a two-dimensional (2-D) cell, configured to represent a heterogeneous unconfined aquifer system containing low permeability lenses. After release and redistribution of either CB- or TCE-NAPL, the 2-D aquifer cells were flushed with a 6% (wt) n-butanol aqueous solution to achieve DNAPL to light NAPL conversion, followed by a low IFT surfactant solution consisting of 4% (4:1) Aerosol MA/Aerosol OT + 20% n-butanol + 500 mg/L CaCl2. Visual observations and experimental measurements demonstrated that in situ density conversion and immiscible displacement of both CB and TCE were successful. Effluent NAPL densities ranged from 0.96 to 0.90 g/mL for CB and from 0.95 to 0.92 g/mL for TCE, while aqueous phase densities remained above 0.96 g/L. Density conversion of CB and TCE was achieved after flushing with 1.2 and 4.9 pore vol of 6% n-butanol solution, respectively. Recoveries of 90% CB and 85% TCE were realized after flushing with 1.2 pore vol of the low IFT surfactant solution, which was followed by a 1 pore vol posttreatment water flood. Surfactant and n-butanol recoveries ranged from 75 to 96% based on effluent concentration data. The observed minimal mobilization during the n-butanol density conversion preflood and near complete mobilization during the low IFT displacement flood were consistent with total trapping number calculations. The results reported herein demonstrate the potential efficiency of the DMD technology as a means of DNAPL source zone restoration

Density-Modified Displacement for DNAPL Source Zone Remediation: Density Conversion and Recovery in Heterogeneous Aquifer Cells

Low interfacial tension (IFT) displacement (mobilization) of nonaqueous phase liquids (NAPLs) offers potential as an efficient remediation technology for contaminated aquifer source zones. However, displacement of dense NAPLs (DNAPLs) is problematic due to the tendency for downward migration and redistribution of the mobilized DNAPL. To overcome this limitation, a density-modified displacement method (DMD) was developed, which couples in situ density conversion of DNAPLs via alcohol partitioning with low IFT NAPL displacement and recovery. The objective of this work was to evaluate the DMD method for two representative DNAPLs, chlorobenzene (CB) and trichloroethene (TCE). Laboratory-scale experiments were conducted in a two-dimensional (2-D) cell, configured to represent a heterogeneous unconfined aquifer system containing low permeability lenses. After release and redistribution of either CB- or TCE-NAPL, the 2-D aquifer cells were flushed with a 6% (wt) n-butanol aqueous solution to achieve DNAPL to light NAPL conversion, followed by a low IFT surfactant solution consisting of 4% (4:1) Aerosol MA/Aerosol OT + 20% n-butanol + 500 mg/L CaCl2. Visual observations and experimental measurements demonstrated that in situ density conversion and immiscible displacement of both CB and TCE were successful. Effluent NAPL densities ranged from 0.96 to 0.90 g/mL for CB and from 0.95 to 0.92 g/mL for TCE, while aqueous phase densities remained above 0.96 g/L. Density conversion of CB and TCE was achieved after flushing with 1.2 and 4.9 pore vol of 6% n-butanol solution, respectively. Recoveries of 90% CB and 85% TCE were realized after flushing with 1.2 pore vol of the low IFT surfactant solution, which was followed by a 1 pore vol posttreatment water flood. Surfactant and n-butanol recoveries ranged from 75 to 96% based on effluent concentration data. The observed minimal mobilization during the n-butanol density conversion preflood and near complete mobilization during the low IFT displacement flood were consistent with total trapping number calculations. The results reported herein demonstrate the potential efficiency of the DMD technology as a means of DNAPL source zone restoration

Density-Modified Displacement for DNAPL Source Zone Remediation: Density Conversion and Recovery in Heterogeneous Aquifer Cells

Low interfacial tension (IFT) displacement (mobilization) of nonaqueous phase liquids (NAPLs) offers potential as an efficient remediation technology for contaminated aquifer source zones. However, displacement of dense NAPLs (DNAPLs) is problematic due to the tendency for downward migration and redistribution of the mobilized DNAPL. To overcome this limitation, a density-modified displacement method (DMD) was developed, which couples in situ density conversion of DNAPLs via alcohol partitioning with low IFT NAPL displacement and recovery. The objective of this work was to evaluate the DMD method for two representative DNAPLs, chlorobenzene (CB) and trichloroethene (TCE). Laboratory-scale experiments were conducted in a two-dimensional (2-D) cell, configured to represent a heterogeneous unconfined aquifer system containing low permeability lenses. After release and redistribution of either CB- or TCE-NAPL, the 2-D aquifer cells were flushed with a 6% (wt) n-butanol aqueous solution to achieve DNAPL to light NAPL conversion, followed by a low IFT surfactant solution consisting of 4% (4:1) Aerosol MA/Aerosol OT + 20% n-butanol + 500 mg/L CaCl2. Visual observations and experimental measurements demonstrated that in situ density conversion and immiscible displacement of both CB and TCE were successful. Effluent NAPL densities ranged from 0.96 to 0.90 g/mL for CB and from 0.95 to 0.92 g/mL for TCE, while aqueous phase densities remained above 0.96 g/L. Density conversion of CB and TCE was achieved after flushing with 1.2 and 4.9 pore vol of 6% n-butanol solution, respectively. Recoveries of 90% CB and 85% TCE were realized after flushing with 1.2 pore vol of the low IFT surfactant solution, which was followed by a 1 pore vol posttreatment water flood. Surfactant and n-butanol recoveries ranged from 75 to 96% based on effluent concentration data. The observed minimal mobilization during the n-butanol density conversion preflood and near complete mobilization during the low IFT displacement flood were consistent with total trapping number calculations. The results reported herein demonstrate the potential efficiency of the DMD technology as a means of DNAPL source zone restoration

Natural Attenuation Processes during <i>In Situ</i> Capping

Chlorinated solvents are common groundwater contaminants that threaten surface water quality and benthic health when present in groundwater seeps. Aquatic sediments can act as natural biobarriers to detoxify chlorinated solvent plumes via reductive dechlorination. In situ sediment capping, a remedial technique in which clean material is placed at the sediment−water interface, may alter sedimentary natural attenuation processes. This research explores the potential of Anacostia River sediment to naturally attenuate chlorinated solvents under simulated capping conditions. Results of microcosm studies demonstrated that intrinsic dechlorination of dissolved-phase PCE to ethene was possible, with electron donor availability controlling microbial activity. A diverse microbial community was present in the sediment, including multiple Dehalococcoides strains indicated by the amplifica tion of the reductive dehalogenases tceA, vcrA, and bvcA. An upflow column simulating a capped sediment bed subject to PCE-contaminated groundwater seepage lost dechlorination activity with time and only achieved complete dechlorination when microorganisms present in the sediment were provided electron donor. Increases in effluent chloroethene concentrations during the period of biostimulation were attributed to biologically enhanced desorption and the formation of less sorptive dechlorination products. These findings suggest that in situ caps should be designed to account for reductions in natural biobarrier reactivity and for the potential breakthrough of groundwater contaminants