USGS2004
Two experimental permeable reactive barriers (PRBs) of granular zero-valent iron were emplaced in the path of a tetrachloroethene plume (the Chemical Spill-10 plume) at the Massachusetts Military Reservation, Cape Cod, Massachusetts, in June 1998. The goal of the field experiment was to achieve emplacement of a granular-iron PRB deeper than attempted before. The PRBs were expected to create a reducing environment and degrade the tetrachloroethene by reductive dechlorination. The goal of the work presented in this report was to observe temporary and sustained changes to the ground-water chemistry downgradient from the PRBs. A hydraulic-fracturing method involving injection of the granular iron with a guar-biopolymer and enzyme slurry was used to install the parallel 30- to 33-foot-wide wall-shaped barriers at a depth of 82 to 113 feet below land surface. An acetic acid and enzyme mixture was subsequently injected in wells near the barriers to degrade the guar biopolymer. Prior to the emplacement, tetrachloroethene concentrations in the Chemical Spill-10 plume at the study area were as high as 250 micrograms per liter. Other water properties in the plume generally were similar to the properties of uncontaminated ground water in the area, which typically has dissolved oxygen concentrations of 250 to 375 micromoles per liter, pH of 5.5 to 6.0, and specific conductance of 60 to 90 microsiemens per centimeter. Water-quality samples were collected periodically from monitoring wells near the PRBs to determine how the emplacement of the granular-iron walls altered the ground-water quality. In addition, an automated well-sampling device measured temperature, specific conductance, pH, and dissolved oxygen every 1–4 days for 16 months in a well downgradient from the two parallel PRBs. Temporary increases (lasting about 5 to 6 months) in specific conductance were observed downgradient from the PRBs as a result of the sodium chloride, potassium carbonate, and other salts included in the slurry and the acetic acid and enzyme mixture that was subsequently injected to degrade the guar biopolymer. Temporary increases in the concentrations of major cations (sodium, potassium, magnesium, and calcium) were observed downgradient from the PRBs, as were temporary but substantial increases in the dissolved and total organic carbon concentrations. Methane was detected, sulfate concentrations decreased temporarily, and concentrations of dissolved inorganic carbon increased in samples from wells downgradient from the PRBs. A sustained (longer than 12 months) reducing environment, in which dissolved oxygen concentrations decreased to zero, the pH increased to about 6.8, and dissolved iron concentrations increased substantially, developed as a result of the oxidation (corrosion) of the granular iron; this zone persisted at least 65 feet downgradient from the PRBs. The pH and dissolved iron concentrations increased with distance from the granular-iron walls. Concentrations of arsenic, cobalt, manganese, and phosphorus increased, and nitrate concentrations were reduced to below the detection limit downgradient from the walls. A sustained decrease of tetrachloroethene concentrations was not observed; however, reductive dechlorination products were observed at wells downgradient from the PRBs during several rounds of sampling. The emplacement of zero-valent iron in the aquifer to remove tetrachloroethene from the ground water caused changes in the water chemistry that persisted farther downgradient from the PRBs than has been observed at other sites because of the low chemical reactivity of the quartz-dominated aquifer sediments and the low ambient dissolved chemical concentrations in the ground water. The small transverse dispersion in the aquifer and the probable long-term persistence of the iron indicate that the chemically altered zone probably will extend a substantial distance downgradient from the PRBs for a substantial period of time (years); further investigation would be needed to determine this distance.