Carbon isotope effects in the sorption of chlorinated ethenes on biochar and activated carbon

As an alternative to activated carbon, biochar is a promising, environmentally friendly sorbent that can be used to remove organic groundwater pollutants, such as chlorinated ethenes (CEs). Stable isotope fractionation in biofilters is used to quantify pollutant degradation and to distinguish degradation from pollutant sorption on e.g. biochar. However, the sorption of CEs on biochar, and the potential abiotic fractionation processes remain to be tested. The sorption process of CEs and ethene on activated carbon and biochar was investigated with regard to the isotope effects for the differentiation from microbial degradation processes. Results from physical and chemical characterization of biochar indicated that biochar feedstock and pyrolysis conditions determined sorption performance depending on the surface chemistry and the pore size distribution of the coarse sorbent particles. The sorption capacity of the activated carbon was significantly higher with highly chlorinated ethenes, but similar to the biochars with low chlorination. Apparent carbon isotope fractionation factors (ε) of +0.1 to -4.4 ‰ were found above measurement uncertainties of GC/IRMS. The extent of isotope enrichment of the ¹³C bearing isotopologues in the residual aqueous phase (ε < 0) was characteristic for individual pairs of pollutant and sorbent material and could be related to pore-filling processes limited by the micropore size distribution of sorbent materials and the chemical properties of sorbed pollutants. Especially the large isotope fractionation during the sorption of ethene led to the assumption that diffusion processes within the pore matrix of the sorbent particles contributed to the observed isotope effects, but should still be considered a property of sorption. Concluding on the results indicated that sorption processes can have a significant contribution to carbon isotope fractionation in CEs and ethene. These should not be neglected in the evaluation of biofilters for groundwater purification, in which CEs are simultaneously degraded by microbes.