Integrative approach to delineate natural attenuation of chlorinated benzenes in anoxic aquifers.

Biodegradation of chlorobenzenes was assessed at an anoxic aquifer by combining hydrogeochemistry and stable isotope analyses. In situ microcosm analysis evidenced microbial assimilation of chlorobenzene (MCB) derived carbon and laboratory investigations asserted mineralization of MCB at low rates. Sequential dehalogenation of chlorinated benzenes may affect the isotope signature of single chlorobenzene species due to simultaneous depletion and enrichment of (13)C, which complicates the evaluation of degradation. Therefore, the compound-specific isotope analysis was interpreted based on an isotope balance. The enrichment of the cumulative isotope composition of all chlorobenzenes indicated in situ biodegradation. Additionally, the relationship between hydrogeochemistry and degradation activity was investigated by principal component analysis underlining variable hydrogeochemical conditions associated with degradation activity at the plume scale. Although the complexity of the field site did not allow straightforward assessment of natural attenuation processes, the application of an integrative approach appeared relevant to characterize the in situ biodegradation potential.

Sensitive detection of anaerobic monochlorobenzene degradation using stable isotope tracers.

Microbial degradation of monochlorobenzene (MCB) under anaerobic conditions was investigated using a stable isotope tracer under in and ex situ conditions. In situ microcosms were incubated directly in an anoxic aquifer and carbon derived from [13C6]-MCB was found to be incorporated into the microbial biomass. In laboratory microcosms, amended with [13C6]-MCB, anaerobic mineralization of MCB was indicated by the production of 13CO2. Further, recovery of the 13C-label in the fatty acids confirmed the assimilation of MCB-derived carbon into microbial biomass. The described approach may be applied to various other organic groundwater contaminants of concern using carbon (13C) as well as other stable isotope tracers, such as nitrogen (15N), allowing direct and sensitive detection of biodegradation.

Applicability of stable isotope fractionation analysis for the characterization of benzene biodegradation in a BTEX-contaminated aquifer.

In recent years the analysis of stable isotope fractionation has increasingly been used for characterizing and quantifying biodegradation of contaminants in aquifers. The correlation of carbon and hydrogen isotope signatures of benzene in a BTEX-contaminated aquifer located in the area of a former hydrogenation plant gave indications that biodegradation mainly occurred under anoxic conditions. This finding was consistent with the investigation of hydrogeochemical conditions within the aquifer. Furthermore, the biodegradation of benzene was calculated by changes in carbon isotope signatures using the Rayleigh-equation-streamline approach. Since contaminant concentrations can be also affected by nonisotope-fractionating abiotic processes such as dilution, volatilization, or irreversible sorption to the aquifer matrix, the Rayleigh-equation-streamline approach was adjusted for scenarios assuming that biodegradation and abiotic processes occur either consecutively or simultaneously along a groundwater flow path between contaminant source and sampling well. The results of the scenarios differed significantly, indicating that an abiotic process (typically dilution) causes a decrease in benzene concentration within the investigated aquifer transect. This comparison of results derived from the different scenarios can help to identify whether biodegradation is the predominant process for decrease in contaminant concentration. However, for a proper quantification of biodegradation, the temporal sequence between biodegradation and dilution needs to be known. The uncertainty associated with the quantification of pollutant biodegradation by the Rayleigh-equation-streamline approach increases when nonisotope-fractionating abiotic processes cause a significant decrease in contaminant concentrations.

Assessment of in situ biodegradation of monochlorobenzene in contaminated groundwater treated in a constructed wetland.

The degradation of monochlorobenzene (MCB) was assessed in a constructed wetland treating MCB contaminated groundwater using a detailed geochemical characterisation, stable isotope composition analysis and in situ microcosm experiments. A correlation between ferrous iron mobilisation, decreasing MCB concentration and enrichment in carbon isotope composition was visible at increasing distance from the inflow point, indicating biodegradation of MCB in the wetland. Additionally, in situ microcosm systems loaded with 13C-labelled MCB were deployed for the first time in sediments to investigate the biotransformation of MCB. Incorporation of 13C-labelled carbon derived from the MCB into bacterial fatty acids substantiated in situ degradation of MCB. The detection of 13C-labelled benzene indicated reductive dehalogenation of MCB. This integrated approach indicated the natural attenuation of the MCB in a wetland system. Further investigations are required to document and optimise the in situ biodegradation of MCB in constructed and natural wetland systems treating contaminated groundwater.