Unbiased Identiication of Nonlinear Sorption Characteristics by Soil Column Breakthrough Experiments Angewandte Mathematik I Universitt at Erlangen-n Urnberg Germany

Accurate identiication of interactions of reactive solutes with porous media constituents is necessary for reliable risk assessment studies and the development of eecient sanitation strategies. Standard parameter estimation procedures bear a number of unsolved problems with respect to uniqueness and identiiability. This paper presents a new approach for the identiication of nonlinear interaction parameters of column outtow experiments. The procedure requires no a priori-assumptions on the shape of the underlying interaction process functions. Employing experimental data sets on cadmium and anthracene breakthrough as case studies, possible applications of the new approach will be shown and its features will be discussed. Error analysis based on singular value decomposition of the sensitivity matrix quantiies the identiication error. Identiication procedures without a priori shape information are superior to xed parametrizations in diagnostic investigations, especially in cases without reliable a priori knowledge on the sorptive interactions.