The demonstration of monitored natural attenuation
(MNA) of chlorinated hydrocarbons in groundwater is
typically conducted through the evaluation of concentration
trends and parent−daughter product relationships along
prevailing groundwater flow paths. Unfortunately, at sites
contaminated by mixtures of chlorinated ethenes, ethanes,
and methanes, the evaluation of MNA by using solely
concentration data and parent−daughter relationships can
result in erroneous conclusions regarding the degradation
mechanisms that are truly active at the site, since
many of the daughter products can be derived from
multiple parent compounds. Stable carbon isotope analysis
was used, in conjunction with concentration data, to
clarify and confirm the active degradation pathways at a
former waste solvent disposal site where at least 14 different
chlorinated hydrocarbons have been detected in the
groundwater. The isotope data indicate that TCE, initially
believed to be present as a disposed product and/or a PCE
dechlorination intermediate, is attributable to dehydrochlorination of 1,1,2,2-PCA. The isotope data further support
that vinyl chloride and ethene in the site groundwater
result from dichloroelimination of 1,1,2-trichlorethane and
1,2-dichloroethane, respectively, rather than from reductive
dechlorination of the chlorinated ethenes PCE, TCE, or
1,2-DCE. The isotope data confirm that the chlorinated
ethanes and chlorinated methanes are undergoing significant
intrinsic degradation, whereas degradation of the
chlorinated ethenes may be limited. In addition to the
classical trend of enriched isotope values of the parent
compounds with increasing distance associated to
biodegradation, shifts of isotope ratios of degradation
byproduct in the opposite direction due to mixing of isotopically
light byproducts of biodegradation with compounds from
the source are shown to be of high diagnostic value. These
data underline the value of stable isotope analysis in
confirming transformation processes at sites with complex
mixtures of chlorinated compounds.