Electrolyte Anion Affinity and Its Effect on Oxyanion Adsorption on Goethite.

The influence of various types of background electrolytes (NaCl, NaNO(3), and NaClO(4)) on the proton adsorption and on the adsorption of sulfate and phosphate on goethite have been studied. Below the PZC the proton adsorption on goethite decreases in the order Cl>NO(3)>ClO(4). The decreasing proton adsorption affects the adsorption of oxyanions on goethite. Anion adsorption of strongly binding polyvalent anions is lower in the studied electrolytes in the order Cl

Fluoride Adsorption on Goethite in Relation to Different Types of Surface Sites.

Metal (hydr)oxides have different types of surface groups. Fluoride ions have been used as a probe to assess the number of surface sites. We have studied the F(-) adsorption on goethite by measuring the F(-) and H(+) interaction and F(-) adsorption isotherms. Fluoride ions exchange against singly coordinated surface hydroxyls at low F(-) concentrations. At higher concentrations also the doubly coordinated OH groups are involved. The replacement of a surface OH(-) by F(-) suggests that all F charge (-1) is located at the surface in contrast to oxyanions which have a charge distribution in the interface due to the binding structure in which the anion only partially coordinates with the surface. Analysis of our F(-) data with the CD-MUSIC approach shows that the formation of the fluoride surface complex is accompanied by a redistribution of charge. This is supposed to be due to a net switch in the H bonding as a result of the change of the type of surface complex from donating (FeOH, FeOH(2)) to proton accepting (FeF). The modeled redistribution of charge is approximately equivalent with the change of a donating H bond into an accepting H bond. At high F(-) concentrations precipitation of F(-), as for instance FeF(3)(s), may occur. The rate of formation is catalyzed by the presence of high electrolyte concentrations. Copyright 2000 Academic Press.

Sulfate Adsorption on Goethite.

Recent spectroscopic work has suggested that only one surface species of sulfate is dominant on hematite. Sulfate is therefore a very suitable anion to test and develop adsorption models for variable charge minerals. We have studied sulfate adsorption on goethite covering a large range of sulfate concentrations, surface coverages, pH values, and electrolyte concentrations. Four different techniques were used to cover the entire range of conditions. For characterization at low sulfate concentrations, below the detection limit of sulfate with ICP-AES, we used proton-sulfate titrations at constant pH. Adsorption isotherms were studied for the intermediate sulfate concentration range. Acid-base titrations in sodium sulfate and electromobility were used for high sulfate concentrations. All the data can be modeled with one adsorbed species if it is assumed that the charge of adsorbed sulfate is spatially distributed in the interface. The charge distribution of sulfate follows directly from modeling the proton-sulfate adsorption stoichiometry since this stoichiometry is independent of the intrinsic affinity constant of sulfate. The charge distribution can be related to the structure of the surface complex by use of the Pauling bond valence concept and is in accordance with the microscopic structure found by spectroscopy. The intrinsic affinity constant follows from the other measurements. Modeling of the proton-ion stoichiometry with the commonly used 2-pK models, where adsorbed ions are treated as point charges, is possible only if at least two surface species for sulfate are used. Copyright 1999 Academic Press.

Proton Binding to Humic Acids: Electrostatic and Intrinsic Interactions.

The proton adsorption behavior of eight humic acids (HA) and a fulvic acid (FA) was studied as a function of pH and KNO(3) concentration. The emphasis is on the comparison of the different humics with respect to their ion binding properties and on the comparison of two different models to describe the electrostatic interactions: the Donnan model and the impermeable sphere (IS) model. Viscosimetric data were used to estimate the hydrodynamic volumes and radii of the HA molecules. These data were incorporated in the electrostatic models and calculations could be carried out without any adjustable parameter. The Donnan model in combination with hydrodynamic volumes obtained by viscometry cannot adequately describe the electrostatic effects related to changes of the electrolyte concentration. This model leads to good prediction of the HA behavior if unrealistically large volumes are used for fulvics and unrealistically large volume-salt concentration dependencies are used for humics. The IS model can successfully reproduce experimental proton adsorption data with physically realistic radii. The good performance of the IS model and the poor performance of the Donnan model is directly related to the fact that the hydrodynamic volumes of the molecules are too small to allow for charge compensation within the molecular limits. The combination of viscometry with the IS model leads to a consistent description of the electrostatic in humics and to a consistent way of positioning the master curves. Therefore, the electrostatic potentials and the intrinsic affinity distributions of the different samples can be compared on an equal basis. The similarities in the intrinsic affinity distributions give faith for the possibility to develop a generic model to describe the ion binding to humics. Copyright 1999 Academic Press.

Surface Structural Ion Adsorption Modeling of Competitive Binding of Oxyanions by Metal (Hydr)oxides.

Spectroscopy has provided a progressive flow of information concerning the binding mechanism(s) of ions and their surface-complex structure. An important challenge in surface complexation models (SCM) is to connect the molecular microscopic reality to macroscopic adsorption phenomena. This is important because SCM alone provide insufficient insight in the binding mechanisms, and moreover, it is a priori not obvious that SCM, which describe the pH dependent adsorption correctly in simple systems, will predict the ion interaction under multicomponent conditions. This study elucidates the primary factor controlling the adsorption process by analysing the adsorption and competition of PO4, AsO4, and SeO3. We show that the structure of the surface-complex acting in the dominant electrostatic field can be ascertained as the primary controlling adsorption factor. The surface species of arsenate are identical with those of phosphate and the adsorption behavior is very similar. On the basis of the selenite adsorption, we show that the commonly used 2pK models are incapable to incorporate in the adsorption modeling the correct bidentate binding mechanism found by spectroscopy. The use of the bidentate mechanism leads to a proton-oxyanion ratio and corresponding pH dependency that are too large. The inappropriate intrinsic charge attribution to the primary surface groups and the condensation of the inner sphere surface complex to a point charge are responsible for this behavior of commonly used 2pK models. Both key factors are differently defined in the charge distributed multi site complexation (CD-MUSIC) model and are based in this model on a surface structural approach. The CD-MUSIC model can successfully describe the macroscopic adsorption phenomena using the surface speciation and binding mechanisms as found by spectroscopy. The model is also able to predict the anion competition well. The charge distribution in the interface is in agreement with the observed structure of surface complexes. Copyright 1999 Academic Press.

Interaction of Cadmium with Phosphate on Goethite

Interactions between different ions are of importance in understanding chemical processes in natural systems. In this study simultaneous adsorption of phosphate and cadmium on goethite is studied in detail. The charge distribution (CD)-multisite complexation (MUSIC) model has been successful in describing extended data sets of cadmium adsorption and phosphate adsorption on goethite. In this study, the parameters of this model for these two data sets were combined to describe a new data set of simultaneous adsorption of cadmium and phosphate on goethite. Attention is focused on the surface speciation of cadmium. With the extra information that can be obtained from the interaction experiments, the cadmium adsorption model is refined. For a perfect description of the data, the singly coordinated surface groups at the 110 face of goethite were assumed to form both monodentate and bidentate surface species with cadmium. The CD-MUSIC model is able to describe data sets of both simultaneous and single adsorption of cadmium and phosphate with the same parameters. The model calculations confirmed the idea that only singly coordinated surface groups are reactive for specific ion binding.

Interpretation of Competitive Adsorption Isotherms in Terms of Affinity Distributions

In the present study we evaluate affinity distributions for competitive adsorption isotherms which involve several components. In such a multicomponent situation, the affinity distribution becomes a function of several affinity constants, and already in the case of two components, little is known about their features. In the two-component situation, we have calculated the affinity distributions from the adsorption isotherms with a numerical inversion technique. This technique is based on a constrained least-squares algorithm and uses a regularization function which biases the resulting affinity distribution toward a smooth function. The applicability of the procedure was tested with a newly derived isotherm, which is based on a fully uncorrelated affinity distribution, and with the generalized Langmuir-Freundlich (LF) isotherm, which is known to have a perfectly correlated distribution. The present study demonstrates that the extended Henderson-Hasselbalch (HH) isotherm has an underlying affinity distribution, which displays a partial correlation, while the non-ideal competitive adsorption (NICA) isotherm has an affinity distribution with a varying degree of correlation. In the competitive situation, the affinity distribution thus provides an interesting means to characterize the corresponding isotherms. As an illustration of the present techniques, experimental data of metal ion binding for a humic acid are analyzed in the same context.

Adsorption of Small Weak Organic Acids on Goethite: Modeling of Mechanisms

The adsorption of lactate, oxalate, malonate, phthalate, and citrate has been determined experimentally as a function of concentration, pH, and ionic strength. The data have been described with the CD-MUSIC model of Hiemstra and Van Riemsdijk [J. Colloid Interface Sci. 179, 488-508 (1996)] which allows a distribution of charge of the organic molecule over the surface and the Stern layer. Simultaneously, the concentration, pH, and salt dependency as well as the basic charging behavior of goethite could be described well. On the basis of model calculations, a distinction is made between inner and outer sphere complexation of weak organic acids by goethite. The results indicate that the affinity of the organic acids is dominated by the electrostatic attraction. The intrinsic affinity constants for the exchange reaction of surface water groups and organic acids, expressed per bond, increases with increasing number of reactive groups on the organic molecule. Ion pair formation between noncoordinated carboxylic groups of adsorbed organic acids and cations of the background electrolyte proved to be important for the salt dependency. The knowledge obtained may contribute to the interpretation of the binding of larger organic acids like fulvic and humic acids. Copyright 1997 Academic Press. Copyright 1997Academic Press

Multisite Adsorption of Cadmium on Goethite

Recently a new general ion adsorption model has been developed for ion binding to mineral surfaces (Hiemstra and van Riemsdijk, 1996). The model uses the Pauling concept of charge distribution (CD) and is an extension of the multi-site complexation (MUSIC) approach. In the CD-MUSIC model the charge of an adsorbing ion that forms an inner sphere complex is distributed over its ligands, which are present in two different electrostatic planes. In this paper we have applied the CD-MUSIC model to the adsorption of metal cations, using an extended data set for cadmium adsorbing on goethite. The adsorption of cadmium and the cadmium-proton exchange ratio were measured as function of metal ion concentration, pH, and ionic strength. The data could be described well, taking into account the surface heterogeneity resulting from the presence of two different crystal planes (the dominant 110 face and the minor 021 face). The surface species used in the model are consistent with recent EXAFS data. In accordance with the EXAFS results, high-affinity complexes at the 021 face were used in the model.