title: Uncertainty analysis of the nonideal competitive adsorption-donnan model: effects of dissolved organic matter variability on predicted metal speciation in soil solution.
abstract: Ion binding models such as the nonideal competitive adsorption-Donnan model (NICA-Donnan) and model VI successfully describe laboratory data of proton and metal binding to purified humic substances (HS). In this study model performance was tested in more complex natural systems. The speciation predicted with the NICA-Donnan model and the associated uncertainty were compared with independent measurements in soil solution extracts, including the free metal ion activity and fulvic (FA) and humic acid (HA) fractions of dissolved organic matter (DOM). Potentially important sources of uncertainty are the DOM composition and the variation in binding properties of HS. HS fractions of DOM in soil solution extracts varied between 14 and 63% and consisted mainly of FA. Moreover, binding parameters optimized for individual FA samples show substantial variation. Monte Carlo simulations show that uncertainties in predicted metal speciation, for metals with a high affinity for FA (Cu, Pb), are largely due to the natural variation in binding properties (i.e., the affinity) of FA. Predictions for metals with a lower affinity (Cd) are more prone to uncertainties in the fraction FA in DOM and the maximum site density (i.e., the capacity) of the FA. Based on these findings, suggestions are provided to reduce uncertainties in model predictions.
authors.affiliation: Soil Science Centre, Wageningen University and Research Centre, 6700 AA Wageningen, The Netherlands. bertjan.groenenberg@wur.nl
authors.forename: Jan E
authors.initials: JE
authors.lastname: Groenenberg
authors.forename: Gerwin F
authors.initials: GF
authors.lastname: Koopmans
authors.forename: Rob N J
authors.initials: RN
authors.lastname: Comans
mesh_terms: D000042:Absorption; D001578:Benzopyrans / Q000032:analysis; D006812:Humic Substances / Q000032:analysis; D008670:Metals / Q000032:analysis*; D008962:Models, Theoretical; D009010:Monte Carlo Method; D012987:Soil / Q000032:analysis*
chemical_list: D001578:Benzopyrans; D006812:Humic Substances; D008670:Metals; D012987:Soil; C005023:fulvic acid