Push–pull partitioning tracer tests using radon-222 to quantify non-aqueous phase liquid contamination

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Naturally occurring radon in groundwater can be used as an in situ partitioning tracer for locating and quantifying non-aqueous phase liquid (NAPL) contamination in the subsurface. When combined with the single-well, push–pull test, this methodology has the potential to provide a low-cost alternative to inter-well partitioning tracer tests. During a push–pull test, a known volume of test solution (radon-free water containing a conservative tracer) is first injected (“pushed”) into a well; flow is then reversed and the test solution/groundwater mixture is extracted (“pulled”) from the same well. In the presence of NAPL radon transport is retarded relative to the conservative tracer. Assuming linear equilibrium partitioning, retardation factors for radon can be used to estimate NAPL saturations. The utility of this methodology was evaluated in laboratory and field settings. Laboratory push–pull tests were conducted in both non-contaminated and trichloroethene NAPL (TCE)-contaminated sediment. The methodology was then applied in wells located in non-contaminated and light non-aqueous phase liquid (LNAPL)-contaminated portions of an aquifer at a former petroleum refinery. The method of temporal moments and an approximate analytical solution to the governing transport equations were used to interpret breakthrough curves and estimate radon retardation factors; estimated retardation factors were then used to calculate TCE saturations. Numerical simulations were used to further investigate the behavior of the breakthrough curves. The laboratory and field push–pull tests demonstrated that radon retardation does occur in the presence of TCE and LNAPL and that radon retardation can be used to calculate TCE saturations. Laboratory injection-phase test results in TCE-contaminated sediment yielded radon retardation factors ranging from 1.1 to 1.5, resulting in calculated TCE saturations ranging from 0.2 to 0.9%. Laboratory extraction-phase test results in the same sediment yielded a radon retardation factor of 5.0, with a calculated TCE saturation of 6.5%. Numerical simulation breakthrough curves provided reasonably good matches to the approximate analytical solution breakthrough curves. However, non-equilibrium radon partitioning and heterogeneous TCE distributions may affect the retardation factors and TCE saturation estimates.