Abstract

Previous investigations indicate that natural attenuation and biodegradation of chlorinated volatile organic compounds (VOCs) are substantial in groundwater beneath the 9-acre former landfill at Operable Unit 1 (OU 1), Naval Undersea Warfare Center, Division Keyport, Washington. Phytoremediation combined with on-going natural attenuation processes was the preferred remedy selected by the Navy, as specified in the Record of Decision for the site. The Navy planted two hybrid poplar plantations on the landfill in spring 1999 to remove and to control the migration of chlorinated VOCs in shallow groundwater. The U.S. Geological Survey (USGS) has continued to monitor groundwater geochemistry to ensure that conditions remain favorable for contaminant biodegradation as specified in the Record of Decision. In this report are groundwater geochemical and selected VOC data collected at OU 1 by the USGS during June 18–21, 2007, and June 16–18, 2008, in support of long-term monitoring for natural attenuation.

For 2007 and 2008, strongly reducing conditions (sulfate reduction and methanogenesis) most favorable for reductive dechlorination of VOCs were inferred for 9 of 16 upper-aquifer wells and piezometers in the northern and southern phytoremediation plantations. Predominant redox conditions in groundwater from the intermediate aquifer just downgradient from the landfill remained mildly reducing and somewhat favorable for reductive dechlorination of VOCs. Dissolved hydrogen (H₂) concentrations measured in the upper aquifer during 2007 and 2008 generally have been lower than H₂ concentrations measured before 2002. However, widespread and relatively high methane and sulfide concentrations indicate that the lower H₂ concentrations measured do not support a trend from strongly to mildly reducing redox conditions because no widespread changes in groundwater redox conditions were identified that should result in less favorable conditions for the reductive dechlorination of the chlorinated VOCs.

For the upper aquifer beneath the northern phytoremediation plantation, chlorinated VOC concentrations in 2007 and 2008 at most piezometers were similar to or slightly less than chlorinated VOC concentrations measured in previous years. The only chlorinated VOC positively detected at piezometers P1-1 and P1-5 was cis-1,2-dichloroethene (cis‑DCE); most chlorinated VOC concentrations at piezometer P1-3 were at the lowest levels since monitoring began in 1999. Most VOC concentrations at piezometer P1-4 were similar to VOC concentrations measured in previous years except that vinyl chloride (VC) concentrations inexplicably increased from 280 micrograms per liter (μg/L) in June 2007 to 750 μg/L in June 2008. In 2008, measurement of the sum of concentrations of ethane and ethene, reductive dechlorination byproducts, was at the highest level at most northern plantation wells and piezometers, which is evidence of reductive dechlorination of chlorinated VOCs.

For the upper aquifer beneath the southern phytoremediation plantation, chlorinated VOC concentrations in 2007 and 2008 at the piezometers were most often extremely high and they continued to vary considerable over space and between years. At piezometer P1-6, the total chlorinated VOC concentration increased from 380 μg/L in 2007 to more than 20,000 μg/L in 2008. At piezometer P1-7 in 2008, the concentrations of trichloroethene, cis-DCE, and VC were the highest to date, but total chlorinated VOC concentrations at piezometers P1-8, P1-9, and P1-10 in 2008 were relatively low compared to historical levels. The magnitude and persistence of chlorinated VOC concentrations indicate that non-aqueous phase liquid chloroethenes likely are beneath the southern plantation, and the temporal variability in concentrations likely is a result of variations in precipitation and groundwater levels interacting with the non-aqueous phase liquid. The reductive dechlorination byproducts ethane and ethene were detected at all wells and piezometers in the southern plantation, which is reliable evidence of reductive dechlorination of dissolved VOCs.

For the intermediate aquifer, total chlorinated VOC concentrations in 2008 at wells MW1-25, MW1-28, and MW1-39 were consistent with concentrations from previous years. However, concentrations of VC at these wells in 2008 were the highest measured to date, as were the sum of concentrations of ethane and ethene measured at wells MW1‑25 and MW1-28. These data suggest that either the rate of reductive dechlorination of cis-DCE to create VC may have increased, or more non-aqueous phase liquid has dissolved into groundwater.