No abstract

Non‐aqueous phase liquids (NAPLs), such as toluene, often contaminate the subsurface. In this study, we focus on the transformation of toluene NAPL trapped in a single glass replica of a rock fracture via in situ chemical oxidation (ISCO) with ferrous activated persulfate. The trapped toluene consisted of a main trapped blob surrounded by smaller blobs. Over 53 days, successive persulfate injections into the fracture were interspersed with periods of water flushing. During persulfate injections, effluent toluene concentrations were below 0.04 mM. The rebound toluene concentrations during intervening water flushing periods decreased from 0.9 to 0.3 mM over the study. The smaller toluene blobs were removed by dissolution and partial oxidation. The main toluene blob was reduced in area by 35.5% and in volume by 37.3% due to dissolution and partial oxidation. The main blob changed in shape with reduction in size and there was also formation of an oxidation by‐product zone around the blob. The reduction in toluene effluent concentrations with time over successive persulfate injections and periods of water flushing was attributed to reductions in the NAPL‐water interfacial area of the blob and the formation of the by‐product zone surrounding the blob, which resulted in limited toluene dissolution. Analysis of by‐products of toluene oxidation by ferrous activated persulfate suggests that oligomers were part of the by‐product zone formed in the fracture. Gas bubbles were also observed in the fracture and may have formed from toluene oxidation and persulfate decomposition.