On the formation of multiple local peaks in breakthrough curves

The analysis of breakthrough curves (BTCs) is of interest in hydrogeology as a way to parameterize and explain processes related to anomalous transport. Classical BTCs assume the presence of a single peak in the curve, where the location and size of the peak and the slope of the receding limb has been of particular interest. As more information is incorporated into BTCs (for example, with high-frequency data collection, supercomputing efforts), it is likely that classical definitions of BTC shapes will no longer be adequate descriptors for contaminant transport problems. We contend that individual BTCs may display multiple local peaks depending on the hydrogeologic conditions and the solute travel distance. In such cases, classical definitions should be reconsidered. In this work, the presence of local peaks in BTCs is quantified from high-resolution numerical simulations in synthetic fields with a particle tracking technique and a kernel density estimator to avoid either overly jagged or smoothed curves that could mask the results. Individual BTCs from three-dimensional heterogeneous hydraulic conductivity fields with varying combinations of statistical anisotropy, heterogeneity models, and local dispersivity are assessed as a function of travel distance. The number of local peaks, their corresponding slopes, and a transport connectivity index are shown to strongly depend on statistical anisotropy and travel distance. Results show that the choice of heterogeneity model also affects the frequency of local peaks, but the slope is less sensitive to model selection. We also discuss how solute shearing and rerouting can be determined from local peak quantification.Peer Reviewe