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Monitoring In Situ Biodegradation of MTBE Using Multiple Rounds of Compound‐Specific Stable Carbon Isotope Analysis

At a large industrial facility, methyl tert‐butyl ether (MTBE) was released to the subsurface and dispersed into the light, non‐aqueous phase liquids (LNAPL), in the first aquifer, with the LNAPL serving as a continuous source of MTBE in groundwater. Compound‐specific isotope analysis was conducted on both MTBE and tert‐butyl alcohol (TBA) in groundwater samples collected in 2008, 2011, and 2013 from wells located along and off the center line of the MTBE plume. The study demonstrated the onset and progress of biodegradation of MTBE between 2008 and 2013. The TBA observed in 2008 appears to be derived only in part from MTBE transformation while a significant portion of TBA might be contributed directly from LNAPL sources. In 2011 to 2013, the dominant source of TBA in the mid‐gradient plume was MTBE transformation. A contribution of an offsite LNAPL source, in particular to the down‐gradient area of the plume, is possible but could not be unequivocally confirmed. The time series provided direct evidence for MTBE biodegradation, but also a valuable insight on the sources of TBA.