Limitations and potential of commercially available rhodamine WT as a groundwater tracer

We conducted chemical characterization, batch, column, and modeling studies to elucidate the sorption and transport of rhodamine WT (RWT) in the subsurface. The sand-pack material from the Lizzie field site near Greenville, North Carolina, served as our porous media. Our study confirms earlier results that RWT consists of two isomers with different sorption properties. It also shows that the two isomers have distinct emission spectra and are equally distributed in the RWT solution. The presence of the two isomers with different sorption properties and distinct emission spectra introduces an error in measuring the RWT concentration with fluorometers during porous media tracer studies. The two isomers become chromatographically separated during transport and thus arrive in a different concentration ratio than that of the RWT solutions used for fluorometer calibration and test injection. We found that this groundwater tracer chromatographic error could be as high as 7.8%. We fit six different reactive-solute transport models of varying complexity to our four column experiments. A two-solute, two-site sorption transport model that accounts for nonequilibrium sorption accurately describes the breakthrough curves of the shorter-timescale column experiments. However, possibly due to the groundwater tracer chromatographic error we discovered, this model, or a similar one that accounts for a Freundlich isotherm for one of the solutes, fails to describe the RWT transport in the longer-timescale column experiments. The presence of the two RWT isomers may complicate the interpretation of field tracer tests because a shoulder, or any two peaks in a breakthrough curve, could result from either aquifer heterogeneity or the different arrival times of the two isomers. In cases where isomer 2 sorbs to such an extent that its breakthrough is not recorded during a test, only isomer 1 is measured, and therefore only 50% of the injected mass is recorded. Isomer 1 of RWT can be accurately modeled with a one-solute, two-site, nonequilibrium sorption model. This conclusion and the results from our batch studies suggest that RWT isomer 1 is an effective groundwater tracer but that the presence of isomer 2 hampers its effectiveness.