Hydrogeochemical and isotopic evaluation of VOC commingled plumes in a weathered fractured bedrock aquifer treated with thermal and bioremediation

Chlorinated ethanes and ethenes isotopic analyses in groundwater and hydrogeochemical results from a former industrial area in Sao Paulo (Brazil) were used to confirm the existence and allow further characterization of source areas and their commingled plumes, both before and after thermal and bioremediation treatments. Prior to full scale remediation, a recently identified off-site source area with unknown history and limited access for further intrusive works presented lower δ13C values (−6.5‰ to −1.8‰ for 1,2-DCA) than the downgradient on-site source area (+8.6‰ to +20.0‰). Intermediate δ13C values for 1,2-DCA were identified further downgradient from the sources, within commingled plumes patterns. The isotope and concentration results show the typical degradation patterns associated with biotic reductive dechlorination for chlorinated ethenes and dihaloelimination for 1,2-DCA. Results following remediation treatments show further levels of isotopic enrichment, for chlorinated ethenes and chlorinated ethanes in the tropically weathered and deeper fractured bedrock (gneisses) groundwater. Hydrogeochemical results, isotopic mass balance and Carbon-Chlorine isotope slopes data are coherent with remediation treatment and a complex commingled plume setting. The results of this study confirmed the Temporal Conceptual Model proposed by Hart et al. (2021) and identified the need for further studies to evaluate isotopic dynamics under thermal remediation, including thermal-induced hydrolysis processes.