Chlorine and Carbon Isotopes Fractionation during Volatilization and Diffusive Transport of Trichloroethene in the Unsaturated Zone

To apply compound-specific isotope methods to the evaluation of the origin and fate of organic contaminants in the unsaturated subsurface, the effect of physicochemical processes on isotope ratios needs to be known. The main objective of this study is to quantify chlorine and carbon isotope fractionation during NAPL–vapor equilibration, air–water partitioning, and diffusion of trichloroethene (TCE) and combinations of these effects during vaporization in porous media. Isotope fractionation is larger during NAPL–vapor equilibration than air–water partitioning. During NAPL–vapor equilibration, carbon, and chlorine isotope ratios evolve in opposite directions although both elements are present in the same bond, with a normal isotope effect for chlorine (ε_Cl = −0.39 ± 0.03‰) and an inverse effect for carbon (ε_C = +0.75 ± 0.04‰). During diffusion-controlled vaporization in a sand column, no significant carbon isotope fractionation is observed (ε_C = +0.10 ± 0.05‰), whereas fairly strong chlorine isotope fractionation occurs (ε_Cl = −1.39 ± 0.06‰) considering the molecular weight of TCE. In case of carbon, the inverse isotope fractionation associated with NAPL–vapor equilibration and normal diffusion isotope fractionation cancel, whereas for chlorine both processes are accompanied by normal isotope fractionation and hence they cumulate. A source of contamination that aged might thus show a shift toward heavier chlorine isotope ratios

Complementing approaches to demonstrate chlorinated solvent biodegradation in a complex pollution plume: Mass balance, PCR and compound-specific stable isotope analysis.

International audienceThis work describes the use of different complementing methods (mass balance, polymerase chain reaction assays and compound-specific stable isotope analysis) to demonstrate the existence and effectiveness of biodegradation of chlorinated solvents in an alluvial aquifer. The solvent-contaminated site is an old chemical factory located in an alluvial plain in France. As most of the chlorinated contaminants currently found in the groundwater at this site were produced by local industries at various times in the past, it is not enough to analyze chlorinated solvent concentrations along a flow path to convincingly demonstrate biodegradation. Moreover, only a few data were initially available to characterize the geochemical conditions at this site, which were apparently complex at the source zone due to (i) the presence of a steady oxygen supply to the groundwater by irrigation canal losses and river infiltration and (ii) an alkaline pH higher than 10 due to former underground lime disposal. A demonstration of the existence of biodegradation processes was however required by the regulatory authority within a timeframe that did not allow a full geochemical characterization of such a complex site. Thus a combination of different fast methods was used to obtain a proof of the biodegradation occurrence. First, a mass balance analysis was performed which revealed the existence of a strong natural attenuation process (biodegradation, volatilization or dilution), despite the huge uncertainty on these calculations. Second, a good agreement was found between carbon isotopic measurements and PCR assays (based on 16S RNA gene sequences and functional genes), which clearly indicated reductive dechlorination of different hydrocarbons (Tetrachloroethene--PCE-, Trichloroethene--TCE-, 1,2-cisDichloroethene--cis-1,2-DCE-, 1,2-transDichloroethene-trans--1,2-DCE-, 1,1-Dichloroethene--1,1-DCE-, and Vinyl Chloride--VC) to ethene. According to these carbon isotope measurements, although TCE biodegradation seems to occur only in the upgradient part of the studied zone, DCE and VC dechlorination (originating from the initial TCE dechlorination) occurs along the entire flowpath. TCE reductase was not detected among the Dehalococcoides bacteria identified by quantitative PCR (qPCR), while DCE and VC reductases were present in the majority of the population. Reverse transcriptase PCR assays (rt-PCR) also indicated that bacteria and their DCE and VC reductases were active. Mass balance calculations showed moreover that 1,1-DCE was the predominant DCE isomer produced by TCE dechlorination in the upgradient part of the site. Consequently, coupling rt-PCR assays with isotope measurements removes the uncertainties inherent in a simple mass balance approach, so that when the three methods are used jointly, they allow the identification and quantification of natural biodegradation, even under apparently complex geochemical and hydraulic conditions