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Microbiological characterizations of contaminant biodegradation in fractured sedimentary rock have primarily focused on the biomass suspended in groundwater samples and disregarded the biomass attached to fractures and in matrix pores. In fractured sedimentary rock, diffusion causes nearly all contaminant mass to reside in porous, low-permeability matrix. Microorganisms capable of contaminant degradation can grow in the matrix pores if the pores and pore throats are sufficiently large. In this study, the presence of dechlorinating microorganisms in rock matrices was investigated at a site where a fractured, flat-lying, sandstone-dolostone sequence has been contaminated with a mixture of chlorinated and aromatic hydrocarbons for over 40 years. The profile of organic contaminants as well as the distribution and characterization of the microbial community spatial variability was obtained through depth-discrete, high-frequency sampling along a 98-m continuous rock core. Dechlorinating microorganisms, such as Dehalococcoides and Dehalobacter, were detected in the rock matrices away from fracture surfaces, indicating that biodegradation within the rock matrix blocks should be considered as an important component of the system when evaluating the potential for natural attenuation or remediation at similar sedimentary rock sites.

This study aims to investigate whether compound-specific carbon isotope analysis (CSIA) can be used to differentiate the degradation pathways of chlorohydrocarbons in saturated low-permeability sediments. For that purpose, a site was selected, where a complex mixture of chlorohydrocarbons contaminated an aquifer-aquitard system. Almost 50 years after contaminant releases, high-resolution concentration, CSIA, and microbial profiles were determined. The CSIA profiles showed that in the aquitard cis-dichloroethene (cDCE), first considered as a degradation product of trichloroethene (TCE), is produced by the dichloroelimination of 1,1,2,2-tetrachloroethane (TeCA). In contrast, TeCA degrades to TCE via dehydrohalogenation in the aquifer, indicating that the aquifer-aquitard interface separates two different degradation pathways for TeCA. Moreover, the CSIA profiles showed that chloroform (CF) is degraded to dichloromethane (DCM) via hydrogenolysis in the aquitard and, to a minor degree, produced by the degradation of carbon tetrachloride (CT). Several microorganisms capable of degrading chlorohydrocarbons were detected in the aquitard, suggesting that aquitard degradation is microbially mediated. Furthermore, numerical simulations reproduced the aquitard concentration and CSIA profiles well, which allowed the determination of degradation rates for each transformation pathway. This improves the prediction of contaminant fate in the aquitard and potential magnitude of impacts on the adjacent aquifer due to back-diffusion.

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