Metals surface complexation models

In order to test the reversibility of metal-bacteria interactions, Fowle and Fein (2000) compared the extent of desorption estimated from surface complexation modeling with that obtained from sorption-desorption experiments. Using B. subtilis these workers found that both sorption and desorption of Cd occurred rapidly, and the desorption kinetics were independent of sorption contact time. Steady-state conditions were attained within 2 h for all sorption reactions, and within 1 h for all desorption reactions. The extent of sorption or desorption remained constant for at least 24 h and up to 80 h for Cd. The observed extent of desorption in the experimental systems was in accordance with the amount estimated from a surface complexation model based on independently conducted adsorption experiments. 

The data of Loukidou et al. (2004) for the equilibrium biosorption of chromium (VI) by Aeromonas caviae particles were well described by the Langmuir and Freundlich isotherms. Sorption rates estimated from pseudo second-order kinetics were in satisfactory agreement with experimental data. The results of XAFS study on the sorption of Cd by B. subtilis were generally in accord with existing surface complexation models (Boyanov et al. 2003). Intrinsic metal sorption constants were obtained by correcting the apparent sorption constants by the Boltzmann factor. A 1 2 metal-ligand stoichiometry provides the best fit to the experimental data with log K values of 6.0 0.2 for Sr(II) and 6.2 0.2 for Ba(II). 

Molecular simulation methods can be a complement to surface complexation modeling on metal-bacteria adsorption reactions, which provides a more detailed and atomistic information of how metal cations interact with specific functional groups within bacterial cell wall. Johnson et al., (2006) applied molecular dynamics (MD) simulations to analyze equilibrium structures, coordination bond distances of metal-ligand complexes. 

It is useful to compare the capacity for each metal to be sorbed (the amount of each that could sorb if it occupied every surface site) with the metal concentrations in solution. To calculate the capacities, we take into account the amount of ferric precipitate formed in the calculation (0.89 mmol), the number of moles of strongly and weakly binding surface sites per mole of precipitate (0.005 and 0.2, respectively, according to the surface complexation model), and the site types that accept each metal [As(OH)4 and ASO4 sorb on weak sites only, whereas Pb++, Cu++, and Zn++ sorb on both strong and weak]. 

Fig. 32.4. Chromatographic separation of metal contaminants in a groundwater flow at 25 °C, due to differential sorption. According to the surface complexation model used, Hg++ in the simulation sorbs more strongly to the ferric surface in the aquifer than Pb++, which sorbs more strongly than Zn++. Plot at top shows concentrations of the metal ions in groundwater, and bottom plot shows sorbed metal concentrations.

Surface complexation models attempt to represent on a molecular level realistic surface complexes e.g., models attempt to distinguish between inner- or outer-sphere surface complexes, i.e., those that lose portions of or retain their primary hydration sheath, respectively, in forming surface complexes. The type of bonding is also used to characterize different types of surface complexes e.g., a distinction between coordinative (sharing of electrons) or ionic bonding is often made. While surface coordination complexes are always inner-sphere, ion-pair complexes can be either inner- or outer-sphere. Representing model analogues to surface complexes has two parts stoichiometry and closeness of approach of metal ion to... 

In surface-complexation models, the relationship between the proton and metal/surface-site complexes is explicitly defined in the formulation of the proposed (but hypothetical) microscopic subreactions. In contrast, in macroscopic models, the relationship between solute adsorption and the overall proton activity is chemically less direct there is no information given about the source of the proton other than a generic relationship between adsorption and changes in proton activity. The macroscopic solute adsorption/pH relationships correspond to the net proton release or consumption from all chemical interactions involved in proton tranfer. Since it is not possible to account for all of these contributions directly for many heterogeneous systems of interest, the objective of the macroscopic models is to establish and calibrate overall partitioning coefficients with respect to observed system variables. 

Chemical relaxation methods can be used to determine mechanisms of reactions of ions at the mineral/water interface. In this paper, a review of chemical relaxation studies of adsorption/desorption kinetics of inorganic ions at the metal oxide/aqueous interface is presented. Plausible mechanisms based on the triple layer surface complexation model are discussed. Relaxation kinetic studies of the intercalation/ deintercalation of organic and inorganic ions in layered, cage-structured, and channel-structured minerals are also reviewed. In the intercalation studies, plausible mechanisms based on ion-exchange and adsorption/desorption reactions are presented steric and chemical properties of the solute and interlayered compounds are shown to influence the reaction rates. We also discuss the elementary reaction steps which are important in the stereoselective and reactive properties of interlayered compounds. 

Prediction of adsorption of divalent heavy metals at the goethite/water interface by surface complexation models. Environ. Toxicol. 

Hayes, K. F. Katz, L. E. 1996. Application of X-ray absorption spectroscopy for surface complexation modelling of metal ion sorption. In Brady, P. V. (ed) Physics and Chemistry of Mineral Surfaces. CRC Press, Boca Raton, 147-223. 

Payne, T. E Lumpkin, G. R. Waite, T. D. 1998. Uranium(VI) adsorption on model minerals controlling factors and surface complexation modeling. In Jenne, E. (ed) Adsorption of Metals by Geomedia. Academic Press, San Diego, 75-97. 

This example illustrates the qualitative nature of information that can be gleaned from macroscopic uptake studies. Consideration of adsorption isotherms alone cannot provide mechanistic information about sorption reactions because such isotherms can be fit equally well with a variety of surface complexation models assuming different reaction stoichiometries. More quantitative, molecular-scale information about such reactions is needed if we are to develop a fundamental understanding of molecular processes at environmental interfaces. Over the past 20 years in situ XAFS spectroscopy studies have provided quantitative information on the products of sorption reactions at metal oxide-aqueous solution interfaces (e.g., [39,40,129-138]. One... 

The site binding model based on reactions (1), (2), (14) and (15), often called surface complexation model (SCM), was, beside the simple site binding models (for example two layer model or constant capacitance model) readily applied to a description of the edl on the metal oxide-electrolyte solution interface. Reactions (14) and (15) describe the adsorption of so-called back-... 

Deposition-precipitation is often practised with silica as the support. Especially suitable is aerosil silica, which consists of very small non-porous spheres, so that the precipitation process is not affected in any way by diffusion processes. It is well known that most hydrolysed metal species have a high affinity for the silica surface, thus fulfilling the condition for obtaining surface precipitation only. In the colloid-chemical literature, the initial adsorption of the (partially) hydrolysed metal ions with a silica surface is often described in terms of a surface-complexation model, involving negatively charged surface sites, which exist on silica at pH above 2 (= pzc of silica), and positively charged metal species ... 

Here, the adsorption of valine on different cation-exchanged montmorillonites is described (Nagy and Konya 2004). A discussion of the kinds of interactions that are possible in the ternary system of montmorillonite/valine/metal ions will be presented, and a description how the metal ions can affect these interactions. The interlayer cations (calcium, zinc, copper ions) were chosen on the basis of the stability constants of their complexes with valine. The adsorption of valine on montmorillonite is interpreted using a surface-complexation model. 

Faur-Brasquet C, Reddad Z, Kadirvelu K, Le Cloirec P, Modelling the adsorption of metal ions (Cu, Ni, Pb onto activated carbon cloths using surface complexation models, Applied Surface Science, 196 (2002) pp. 356-365. 

In the surface complexation model, Stumm and co-workers (Furrer and Stumm, 1983, 1986 Stumm and Furrer, 1987 Stumm and Wieland, 1990) suggested that adsorption or desorption of protons on an oxide surface polarizes the metal-oxygen bonds, weakening the bonding between the cation and the underlying lattice and explaining the pH-dependence of rates. Surface complexation reactions for an oxide mineral can be written as follows (Schindler, 1981) ... 

More recently, Brennsteiner et al. [ 175] noted that the electrochemical removal efficiency for nickel is dependent on the pH of the contaminant solution. Maximum efficiency was achieved at pH = 7.0, but only when the carbon electrode was preplated with a layer of copper the role of surface chemistry was not investigated. Seco et al. [172] did characterize the surface chemistry of a commercial activated carbon (pHp r = 6.1) and studied its uptake of heavy metals (Ni, Cu, Cd, Zn), as well as of some binary systems. They interpreted the monotonic uptake increase with pH to be consistent with the surface complexation model a decrease in competition between proton and metal species for the surface sites and a decrease in positive surface charge, which results in a lower cou-lombic repulsion of the sorbing metal. In the binary uptake studies, they concluded that Ni (as well as Cd and Zn) is not as strongly attracted to the. sorbent as Cu. 

The preceding discussion relies on an analogy between complexation in solution and complexation at the mineral surface, a fundamental tenet of the surface complexation model (27). Strong complexation of metals in solution by humic substances is well-documented (16, 42-44). Thus surface complex formation is a likely mechanism for the adsorption of humic substances on oxide surfaces. 

Metal mobility in soils is governed by interfacial processes, such as dissolution. The role of DOM in such processes will be determined by the nature t organic matter-surface associations. The surface complexation model pro-odes a conceptual framework for estimating the contributions of specific DOM components, particularly LMW organic ligands, to the mobilization f metals in soils. With this framework, the effects of humic substances on mineral dissolution can be interpreted to provide some insight into hu--mate-surface interactions. 

In the area of interfacial charging at the solid/liquid interface of metal oxide aqueous suspensions, the "surface complexation or site binding concept is commonly used [3-20]. This concept is characterised by consideration of specific ionic reactions with surface groups, rather than assuming simple binding of ions to the surface or their accumulation at the interface (adsorption). In the past decade several different models were introduced on the basis of the surface complexation model (SCM) they differ in the assumed structure of the electrical interfacial layer (EIL) and in the proposed mechanisms and stoichiometries of surface reactions leading to surface charge. 

In this respect the solution chemistry of common anions is very different. For example with phosphate (Fig. 4.4), HP04 and H2P04 are the dominating solution species over the typically studied pH range, and fully dissociated anions occur only at extremely high pH values, which are of limited interest in adsorption studies, e.g. many common adsorbents are unstable at such a high pH (dissolution). On the other hand, the final products of hydrolysis on anions, i.e. fully protonated acid molecules are usually water soluble, thus, the applicability of surface complexation model is not limited by surface precipitation as it was discussed above for metal cations. 

Various chemical surface complexation models have been developed to describe potentiometric titration and metal adsorption data at the oxide—mineral solution interface. Surface complexation models provide molecular descriptions of metal adsorption using an equilibrium approach that defines surface species, chemical reactions, mass balances, and charge balances. Thermodynamic properties such as solid-phase activity coefficients and equilibrium constants are calculated mathematically. The major advancement of the chemical surface complexation models is consideration of charge on both the adsorbate metal ion and the adsorbent surface. In addition, these models can provide insight into the stoichiometry and reactivity of adsorbed species. Application of these models to reference oxide minerals has been extensive, but their use in describing ion adsorption by clay minerals, organic materials, and soils has been more limited. 

The intrinsic equilibrium constants for the diffuse layer model are similar to those for the constant capacitance model where P is replaced by Equations (6.10) and (6.11) describe surface protonation and dissociation, respectively. Metal surface complexation is described by two constants similar to tliat defined in Eq. (6.12) for strong and weak sites ... 

In the triple layer model one of the o-plane metal surface complexes is represented as bidentate, Eq. (6.9), while one of the P-plane metal surface complexes is represented as a hydroxy-metal surface species, Eq. (6.30). Davis and Leckie (1978) considered the hydroxy-metal complexation reaction to be more consistent with their experimental data. Often, an additional metal surface complex containing the background electrolyte anion is postulated to form in the P-plane ... 

In the diffuse layer model, all intrinsic metal surface complexation constants were optimized with the FITEQL program for both the strong and weak sites using the best estimates of the protonation constant, log X +(int) = 7.29, and the dissociation constant log K-(int) = —8.93 obtained with Eq. (6.61) (Dzombak and Morel, 1990). Thus, individual values of log A . (int) and log A . (int) and best estimates of log (int) and log A j (int) are unique in that they represent a self-consistent thermodynamic database for metal adsorption on hydrous ferric oxide. 

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