Abstract: | The distribution of volatile organic compounds (VOCs) in fractured shale overlain by thin (< 10 feet) overburden at the Watervliet Arsenal near Albany, New York, was initially determined by sampling water from the fracture network using packer systems in boreholes and also using conventional monitoring wells. Furthermore, short‐term pumping and injection tests were conducted and the boreholes were logged using a variety of geophysical and hydrophysical tools. Tetrachloroethene is the dominant VOC in the groundwater, with lesser concentrations of trichloroethene and degradation products (cis‐1,2‐dichloroethene, trans‐1,2‐dichloroethene, and vinyl chloride). The vertical VOC distributions in the rock matrix were obtained from continuous‐cored holes from which small rock samples, collected at many depths between 18 and 150 feet below ground surface, were analyzed. The rock core VOC concentrations were determined by methanol extraction of crushed rock followed by direct methanol injection onto a gas chromatograph and subsequent estimation of rock porewater VOC concentrations. The rock core data support the concept that diffusion‐driven mass transfer has caused nearly all the VOC mass initially present in the fractures to now reside in the rock matrix, which has a porosity three or four orders of magnitude larger than the bulk fracture porosity. The results of the site characterization indicate that an effective site investigation strategy in fractured shale must include characterization of both the fracture and matrix contaminant distribution. These results also indicate that the most favorable remediation technologies for this fractured shale are those that will destroy VOCs in the rock matrix, particularly contaminants in the sorbed phase, and also destroy the VOC mass in the fractures including both dissolved and immiscible phases. The site characterization resulted in the selection of potassium permanganate for an in situ chemical oxidation pilot study. © 2004 Wiley Periodicals, Inc. |