Bacteria that degrade natural organic matter in groundwater contain oxygenase enzymes that can co‐oxidize trichloroethene (TCE). This degradation pathway is promising for large dilute plumes, but its evaluation is limited because the density of the bacteria with oxygenase enzymes has not been correlated to field scale rates of degradation. A 14C–TCE assay was developed to determine pseudo first‐order rate constants for the aerobic co‐oxidation of TCE in groundwater. The assay involved incubating 14C–TCE in samples of groundwater contained in 160 mL serum bottles, and monitoring the accumulation of radiolabel in degradation products. A first‐order rate constant for co‐oxidation was extracted from the rate of accumulation of 14C in products, accounting for volumetric changes in the serum bottles due to sampling and subsequent changes to the distribution of TCE between the aqueous and gaseous phases. Of the groundwater samples evaluated from 19 wells at five sites, eight samples at three sites had 14C product accumulation rates that exceeded the accumulation rate in filter‐sterilized groundwater controls. First‐order rate constants ranged from 2.65 to 0.0066 year−1, which is equivalent to half‐lives of 0.26 to 105 years. Groundwater samples from a few of the wells in which co‐oxidation occurred had volatile organic contaminants in addition to TCE; their presence may have induced the oxygenase enzymes that are needed for TCE co‐oxidation. 14CO2 represented ~37% to 97% of the 14C products that accumulated; the balance of the products was soluble and non‐volatile.
Monitored natural attenuation (MNA) is commonly used as a remedy for trichloroethene (TCE) in anaerobic groundwater; however, MNA has not been applied to TCE contamination in aerobic groundwater. Under aerobic conditions, bacteria initiate the degradation of many organic substances with oxygenase enzymes. Several of these enzymes are known to degrade TCE through a fortuitous reaction known as cometabolism. There are commercially available qPCR assays that can determine the number of gene copies of these enzymes. If the qPCR assay could be used to predict the first‐order rate constant for cometabolism of TCE, the qPCR assay could be used to screen sites to determine whether MNA was a plausible remedy for TCE contamination. This study reevaluated data from water samples that were collected from 19 wells on five sites in Minnesota, New York, and Utah. Data had previously been published on the rate constant for cometabolism of TCE in the water samples as determined by a 14C‐assay and the abundance of gene copies for five enzymes that cometabolize TCE as determined using a qPCR assay. The Michaelis‐Menten (Haldane) kinetic parameters for cometabolism of TCE and the abundance of DNA for the five oxygenase enzymes were used to predict the rate constant for cometabolism of TCE. The predicted rate constants were evaluated and validated by comparing them to the rate constants derived from the 14C‐assay. For predicted rate constants greater than 0.003 per year, the predicted rate constants agreed with the measured rate constants within a factor of three. The qPCR assay serves as a convenient screening tool to determine whether MNA is a plausible remedy for an aerobic plume of TCE.
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