<p>The interplay between hydraulic and chemical processes in streams and adjacent storage zones, e.g. streambed sediments, is of crucial importance for the large-scale transport of released contaminants. This thesis presents a methodology for tracer experiments and the development of mechanistic transport models. </p><p>We conducted four field tracer experiments with the reactive tracer chromium, ⁵¹Cr(III) and/or the conservative tracers potassium iodide (KI) and tritium (³H₂O), along 11 km of the Lanna Stream in Skara County, Sweden, and along a 30 km reach of the Säva Stream in Uppland County, Sweden. The field monitoring included sampling of tracer in the surface water as well as in the streambed sediments. A simultaneous injection of tritium and chromium facilitated an independent evaluation of the hydraulic transport into and out of the sub-surface storage zones. The difference in transport behaviour between the two tracers, were attributed to chemical reactivity.</p><p>In terms of idealised transport models we found that the reactivity of chromium could be characterised by simple chemical concepts. The local equilibrium assumption (LEA), the irreversible kinetics assumption (IKA) and the reversible kinetics assumption (RKA) were applied in the experimental evaluations. An independent evaluation of the streambed transport revealed that the impact of reaction kinetics was substantial. Model calculations and results from a chemical extraction procedure indicated that the chemical reactions affecting the chromium transport were to some extent irreversible.</p><p>This thesis presents a number of exact analytical solutions to the governing partial differential equations. The main theoretical contribution is the incorporation of variable coefficients for stream discharge and sediment porosity, which were measured in field.</p>

The interplay between hydraulic and chemical processes in streams and adjacent storage zones, e.g. streambed sediments, is of crucial importance for the large-scale transport of released contaminants. This thesis presents a methodology for tracer experiments and the development of mechanistic transport models. We conducted four field tracer experiments with the reactive tracer chromium, 51Cr(III) and/or the conservative tracers potassium iodide (KI) and tritium (3H2O), along 11 km of the Lanna Stream in Skara County, Sweden, and along a 30 km reach of the Säva Stream in Uppland County, Sweden. The field monitoring included sampling of tracer in the surface water as well as in the streambed sediments. A simultaneous injection of tritium and chromium facilitated an independent evaluation of the hydraulic transport into and out of the sub-surface storage zones. The difference in transport behaviour between the two tracers, were attributed to chemical reactivity. In terms of idealised transport models we found that the reactivity of chromium could be characterised by simple chemical concepts. The local equilibrium assumption (LEA), the irreversible kinetics assumption (IKA) and the reversible kinetics assumption (RKA) were applied in the experimental evaluations. An independent evaluation of the streambed transport revealed that the impact of reaction kinetics was substantial. Model calculations and results from a chemical extraction procedure indicated that the chemical reactions affecting the chromium transport were to some extent irreversible. This thesis presents a number of exact analytical solutions to the governing partial differential equations. The main theoretical contribution is the incorporation of variable coefficients for stream discharge and sediment porosity, which were measured in field.