Assessing the Reactive Surface Area of Soils and the Association of Soil Organic Carbon with Natural Oxide Nanoparticles Using Ferrihydrite as Proxy.

Assessment of the surface reactivity of natural metal-(hydr)oxide nanoparticles is necessary for predicting ion adsorption phenomena in soils using surface complexation modeling. Here, we describe how the equilibrium concentrations of PO4, obtained with 0.5 M NaHCO3 extractions at different solution-to-soil ratios, can be interpreted with a state-of-the-art ion adsorption model for ferrihydrite to assess the reactive surface area (RSA) of agricultural top soils. Simultaneously, the method reveals the fraction of reversibly adsorbed soil PO4 (R-PO4). The applied ion-probing methodology shows that ferrihydrite is a better proxy than goethite for consistently assessing RSA and R-PO4. The R-PO4 pool agrees well with ammonium oxalate (AO)-extractable phosphorus, but only if measured as orthophosphate. The RSA varied between ∼2 and 20 m2/g soil. The corresponding specific surface area (SSA) of the natural metal-(hydr)oxide fraction is ∼350-1400 m2/g, illustrating that this property is highly variable and cannot be represented by a single value based on the AO-extractable oxide content. The soil organic carbon (SOC) content of our top soils increases linearly not only with the increase in RSA but remarkably also with the increase in mean particle size (1.5-5 nm). To explain these observations, we present a structural model for organo-mineral associations based on the coordination of SOC particles to metal-(hydr)oxide cores.

Size and shape dependency of the surface energy of metallic nanoparticles: unifying the atomic and thermodynamic approaches.

Surface energy is a fundamental property of metallic nanoparticles (MeNPs), which plays a crucial role in nucleation and growth and has strong implications for the application and environmental impact of MeNPs. Surface energy (J m-2) can be size dependent, but experimental data on surface energy trends for MeNPs are inconclusive. Computational chemistry may resolve the issue, but the location and area of the surface used for scaling, which dramatically influences the outcome and interpretation, has not been properly investigated. The size dependency of the surface energy can only be determined by scaling to the thermodynamic surface of tension. To identify this, we have derived a generalized Tolman approach for non-spherical particles, which is used to analyze the thermodynamic consistency of various surface definitions. Only the physical surface, defined here, is consistent with the surface of tension. Scaling of recent computational data for faceted MeNPs to this surface yields a low size dependency of surface energy, in good agreement with the Tolman lengths corresponding to its interfacial position. We find Tolman lengths of -0.03 nm for icosahedra and -0.04 nm for cuboctahedra of gold or silver. With this result, our approach can be used to quantify the twinning energy for icosahedral nanoparticles, being ∼0.06 J per m2 twin area. To understand the unorthodox negative Tolman lengths, we have analyzed the surface energetics of the solid-gas interface of metals in relation to the liquid-vapor interface of water. Surface entropy is found to be imperative in determining the size dependence of surface free energy. At room temperature, the influence of surface entropy on surface enthalpy is much smaller for metals than for water. It explains why these two interfaces have opposite size dependencies of the surface Gibbs free energy and opposite signs of the Tolman length. For water, forming nanodroplets or nanobubbles, the Tolman length is negative (∼-0.014 nm) for the surface enthalpy, but positive (∼+0.06 ± 0.02 nm) for the surface Gibbs free energy. For MeNPs at room temperature, both entities are negative, but at high temperature, the increased surface entropy term may cause the size dependency of surface Gibbs free energy to become reversed.

Surface Structure of Silver Nanoparticles as a Model for Understanding the Oxidative Dissolution of Silver Ions.

The toxicity of silver nanoparticles (AgNPs) has been related to the release of ionic silver. This process is influenced by a large variety of factors and is poorly understood. The key to understanding Ag(+) release by AgNPs is its subvalency. This is a fundamental property of Ag that can be elucidated by analyzing the crystal structures of a specific class of Ag materials as well as MO/DFT (molecular orbital/density functional theory)-optimized Ag13(OH)4 clusters, being precursors of AgNPs. Semimetallic silver at the (111) faces of AgNPs has a subvalency of +(1)/3 v.u., forming ≡Ag3OH(0) surface groups with a maximum site density of 4.7 sites/nm(2). Oxidative dissolution may remove these groups with the simultaneous formation of oxygen radicals that may further interact with the surface via different pathways. Reactive oxygen species (ROS) can create a circular process with the dissolution of ≡Ag3OH(0), exposure of new metallic sites at the underlying lattice, and subsequent oxidation to ≡Ag3OH(0). This regeneration process is interrupted by the penetration of O(•) radicals into the lattice, forming highly stable Ag6O octahedra with subvalent silver that protects the AgNP from further oxidation. A thermodynamic model has been developed that quantitatively describes the equilibrium condition between ≡Ag3OH(0) and ≡Ag6O(0) and explains a large variety of collectively observed phenomena.

A new consistent modeling framework for the competitive adsorption of humic nanoparticles and oxyanions to metal (hydr)oxides: Multiple modes of heterogeneity, fractionation, and conformational change.

HYPOTHESIS: The competitive interaction of oxyanions and humic nanoparticles (HNPs) with metal (hydr)oxide surfaces can be used to trace the ligand and charge distribution of adsorbed HNPs in relation to heterogeneity, fractionation, and conformational change. EXPERIMENTS: Batch adsorption experiments of HNPs on goethite were performed in the absence and presence of phosphate. The size of HNPs was measured with size exclusion chromatography. The Ligand and Charge Distribution (LCD) model framework was further developed to describe the simultaneous interaction of HNPs and phosphate with goethite. FINDINGS: Preferential adsorption decreases the mean molar mass of adsorbed HNPs, independent of the phosphate presence, showing a linear dependency on the adsorbed HNPs fraction. Phosphate ion can be used as a probe to trace the distribution of functional groups and the variation in affinity of HNPs. The spatial distribution of adsorbed HNPs is driven by the potential gradients in the electrical double layer, which changes the conformation of the adsorbed HNPs. At the particle level, the adsorption of heterogeneous HNPs has an affinity distribution, which can be explained by the variation in molar mass (kDa) and density of the functional groups (mol kg-1) of the HNPs. The presented model can simultaneously describe the competitive adsorption of HNPs and phosphate in a consistent manner.

Natural and pyrogenic humic acids at goethite and natural oxide surfaces interacting with phosphate.

Fulvic and humic acids have a large variability in binding to metal (hydr) oxide surfaces and interact differently with oxyanions, as examined here experimentally. Pyrogenic humic acid has been included in our study since it will be released to the environment in the case of large-scale application of biochar, potentially creating Darks Earths or Terra Preta soils. A surface complexation approach has been developed that aims to describe the competitive behavior of natural organic matter (NOM) in soil as well as model systems. Modeling points unexpectedly to a strong change of the molecular conformation of humic acid (HA) with a predominant adsorption in the Stern layer domain at low NOM loading. In soil, mineral oxide surfaces remain efficiently loaded by mineral-protected organic carbon (OC), equivalent with a layer thickness of ≥ ~0.5 nm that represents at least 0.1-1.0% OC, while surface-associated OC may be even three times higher. In natural systems, surface complexation modeling should account for this pervasive NOM coverage. With our charge distribution model for NOM (NOM-CD), the pH-dependent oxyanion competition of the organo-mineral oxide fraction can be described. For pyrogenic HA, a more than 10-fold increase in dissolved phosphate is predicted at long-term applications of biochar or black carbon.

Variable charge and electrical double layer of mineral-water interfaces: silver halides versus metal (hydr)oxides.

Classically, silver (Ag) halides have been used to understand thermodynamic principles of the charging process and the corresponding development of the electrical double layer (EDL). A mechanistic approach to the processes on the molecular level has not yet been carried out using advanced surface complexation modeling (SCM) as applied to metal (hydr)oxide interfaces. Ag halides and metal (hydr)oxides behave quite differently in some respect. The location of charge in the interface of Ag halides is not a priori obvious. For AgI(s), SCM indicates the separation of interfacial charge in which the smaller silver ions are apparently farther away from the surface than iodide. This charge separation can be understood from the surface structure of the relevant crystal faces. Charge separation with positive charge above the surface is due to monodentate surface complex formation of Ag(+) ions binding to I sites located at the surface. Negative surface charge is due to the desorption of Ag(+) ions out of the lattice. These processes can be described with the charge distribution (CD) model. The MO/DFT optimized geometry of the complex is used to estimate the value of the CD. SCM reveals the EDL structure of AgI(s), having two Stern layers in series. The inner Stern layer has a very low capacitance (C(1) = 0.15 ± 0.01 F/m(2)) in comparison to that of metal (hydr)oxides, and this can be attributed to the strong orientation of the (primary) water molecules on the local electrostatic field of the Ag(+) and I(-) ions of the surface (relative dielectric constant ε(r) ≈ 6). Depending on the extent of water ordering, mineral surfaces may in principle develop a second Stern layer. The corresponding capacitance (C(2)) will depend on the degree of water ordering that may decrease in the series AgI (C(2) = 0.57 F/m(2)), goethite (C(2) = 0.74 F/m(2)), and rutile (C(2) = ∞), as discussed. The charging principles of AgI minerals iodargyrite and miersite may also be applied to minerals with the same surface structure (e.g., sphalerite and würtzite (ZnS)).

Factors controlling phosphate interaction with iron oxides.

Factors such as pH, solution ion composition, and the presence of natural organic matter (NOM) play a crucial role in the effectiveness of phosphorous adsorption by iron oxides. The interplay between these factors shows a complicated pattern and can sometimes lead to controversial results. With the help of mechanistic modeling and adsorption experiments, the net macroscopic effect of single and combined factors can be better understood and predicted. In the present work, the relative importance of the above-mentioned factors in the adsorption of phosphate was analyzed using modeling and comparison between the model prediction and experimental data. The results show that, under normal soil conditions, pH, concentration of Ca, and the presence of NOM are the most important factors that control adsorption of phosphate to iron oxides. The presence of Ca not only enhances the amount of phosphate adsorbed but also changes the pH dependency of the adsorption. An increase of dissolved organic carbon from 0.5 to 50 mg L can lead to a >50% decrease in the amount of phosphate adsorbed. Silicic acid may decrease phosphate adsorption, but this effect is only important at a very low phosphate concentration, in particular at high pH.

Key factors in the adsorption of natural organic matter to metal (hydr)oxides: Fractionation and conformational change.

Adsorption of natural organic matter (NOM) to mineral surfaces is an important process determining the environmental fate and biogeochemical cycling of many elements. Natural organic matter consists of a heterogeneous mixture of soft and flexible organic molecules. Upon adsorption, size fractionation may occur, as well as changes in molecular conformation. Although very important, these phenomena have been omitted in existing adsorption models. Filling this gap, a novel framework for NOM adsorption to metal (hydr)oxides is presented. Humic acid (HA) was used as an analog for studying experimentally the NOM adsorption to goethite and its size fractionation as a function of pH, ionic strength, and surface loading. Size fractionation was evaluated for adsorption isotherms collected at pH 4 and 6, showing HA molecules of low molar mass were preferentially adsorbed. This phenomenon was incorporated into the new model. Consistent description of the HA adsorption data over the entire range of pH (3-11), ionic strength (2-100 mM), and surface loading (0.1-3 mg m-2) indicated that the spatial distribution of HA molecules adsorbed in the interface is a trade-off between maximizing the interaction of the HA ligands with the oxide surface and minimizing the electrostatic repulsion between HA particles as a result of interfacial crowding. Our advanced consistent framework is able to quantify changes in molar mass and molecular conformation, thereby significantly contributing to an improved understanding of the competitive power of HA for interacting on oxides with other adsorbed small organic acids as well as environmentally important oxyanions, such as phosphate, arsenate, and others.

Diffusion of neutral and ionic species in charged membranes: boric acid, arsenite, and water.

Dynamic ion speciation using DMT (Donnan membrane technique) requires insight into the physicochemical characteristics of diffusion in charged membranes (tortuosity, local diffusion coefficients) as well as ion accumulation. The latter can be precluded by studying the diffusion of neutral species, such as boric acid, B(OH)3°(aq), arsenite, As(OH)3°(aq), or water. In this study, the diffusion rate of B(OH)3° has been evaluated as a function of the concentration, pH, and ionic strength. The rate is linearly dependent on the concentration of solely the neutral species, without a significant contribution of negatively charged species such as B(OH)4⁻, present at high pH. A striking finding is the very strong effect (factor of ~10) of the type of cation (K(+), Na(+), Ca(2+), Mg(2+), Al(3+), and H(+)) on the diffusion coefficient of B(OH)3° and also As(OH)3°. The decrease of the diffusion coefficient can be rationalized as an enhancement of the mean viscosity of the confined solution in the membrane. The diffusion coefficients can be described by a semiempirical relationship, linking the mean viscosity of the confined solute of the membrane to the viscosity of the free solution. In proton-saturated membranes, as used in fuel cells, viscosity is relatively more enhanced; i.e., a stronger water network is formed. Extraordinarily, our B(OH)3-calibrated model (in HNO3) correctly predicts the reported diffusion coefficient of water (D(H2O)), measured with ¹H NMR and quasi-elastic neutron scattering in H(+)-Nafion membranes. Upon drying these membranes, the local hydronium, H(H2O)(n)(+), concentration and corresponding viscosity increase, resulting in a severe reduction of the diffusion coefficient (D(H2O) ≈ 5-50 times), in agreement with the model. The present study has a second goal, i.e., development of the methodology for measuring the free concentration of neutral species in solution. Our data suggest that the free concentration can be measured with DMT in natural systems if one accounts for the variation in the cation composition of the membrane and corresponding viscosity/diffusion coefficient.

Carbonate Adsorption to Ferrihydrite: Competitive Interaction with Phosphate for Use in Soil Systems.

Carbonate (CO3) interacts with Fe-(hydr)oxide nanoparticles, affecting the availability and geochemical cycle of other important oxyanions in nature. Here, we studied the carbonate-phosphate interaction in closed systems with freshly prepared ferrihydrite (Fh), using batch experiments that cover a wide range of pH values, ionic strength, and CO3 and PO4 concentrations. The surface speciation of CO3 has been assessed by interpreting the ion competition with the Charge Distribution (CD) model, using CD coefficients derived from MO/DTF optimized geometries. Adsorption of CO3 occurs predominately via formation of bidentate inner-sphere complexes, either (≡FeO)2CO or (≡FeO)2CO··Na+. The latter complex is electrostatically promoted at high pH and in the presence of adsorbed PO4. Additionally, a minor complex is present at high CO3 loadings. The CD model, solely parametrized by measuring the pH-dependent PO4 adsorption as a function of the CO3 concentration, successfully predicts the CO3 adsorption to Fh in single-ion systems. The adsorption affinity of CO3 to Fh is higher than to goethite, particularly at high pH and CO3 loadings due to the enhanced formation (≡FeO)2CO··Na+. The PO4 adsorption isotherm in 0.5 M NaHCO3 can be well described, being relevant for assessing the reactive surface area of the natural oxide fraction with soil extractions and CD modeling. Additionally, we have evaluated the enhanced Fh solubility due to Fe(III)-CO3 complex formation and resolved a new species (Fe(CO3)2(OH)2 3-(aq)), which is dominant in closed systems at high pH. The measured solubility of our Fh agrees with the size-dependent solubility predicted using the surface Gibbs free energy of Fh.

Multi-competitive interaction of As(III) and As(V) oxyanions with Ca(2+), Mg(2+), PO(3-)(4), and CO(2-)(3) ions on goethite.

Complex systems, simulating natural conditions like in groundwater, have rarely been studied, since measuring and in particular, modeling of such systems is very challenging. In this paper, the adsorption of the oxyanions of As(III) and As(V) on goethite has been studied in presence of various inorganic macro-elements (Mg(2+), Ca(2+), PO(3-)(4), CO(2-)(3)). We have used 'single-,' 'dual-,' and 'triple-ion' systems. The presence of Ca(2+) and Mg(2+) has no significant effect on As(III) oxyanion (arsenite) adsorption in the pH range relevant for natural groundwater (pH 5-9). In contrast, both Ca(2+) and Mg(2+) promote the adsorption of PO(3-)(4). A similar (electrostatic) effect is expected for the Ca(2+) and Mg(2+) interaction with As(V) oxyanions (arsenate). Phosphate is a major competitor for arsenate as well as arsenite. Although carbonate may act as competitor for both types of As oxyanions, the presence of significant concentrations of phosphate makes the interaction of (bi)carbonate insignificant. The data have been modeled with the charge distribution (CD) model in combination with the extended Stern model option. In the modeling, independently calculated CD values were used for the oxyanions. The CD values for these complexes have been obtained from a bond valence interpretation of MO/DFT (molecular orbital/density functional theory) optimized geometries. The affinity constants (logK) have been found by calibrating the model on data from 'single-ion' systems. The parameters are used to predict the ion adsorption behavior in the multi-component systems. The thus calibrated model is able to predict successfully the ion concentrations in the mixed 2- and 3-component systems as a function of pH and loading. From a practical perspective, data as well as calculations show the dominance of phosphate in regulating the As concentrations. Arsenite (As(OH)(3)) is often less strongly bound than arsenate (AsO(3-)(4)) but arsenite responses less strongly to changes in the phosphate concentration compared to arsenate, i.e., deltalogc(As(III))/deltalogc(PO(4)) approximately 0.4 and deltalogc(As(V))/deltalogc(PO(4)) approximately 0.9 at pH 7. Therefore, the response of As in a sediment on a change in redox conditions will be variable and will depend on the phosphate concentration level.

Carbonate adsorption on goethite in competition with phosphate.

Competitive interaction of carbonate and phosphate on goethite has been studied quantitatively. Both anions are omnipresent in soils, sediments, and other natural systems. The PO4-CO3 interaction has been studied in binary goethite systems containing 0-0.5 M (bi)carbonate, showing the change in the phosphate concentration as a function of pH, goethite concentration, and carbonate loading. In addition, single ion systems have been used to study carbonate adsorption as a function of pH and initial (H)CO3 concentration. The experimental data have been described with the charge distribution (CD) model. The charge distributions of the inner-sphere surface complexes of phosphate and carbonate have been calculated separately using the equilibrium geometries of the surface complexes, which have been optimized with molecular orbital calculations applying density functional theory (MO/DFT). In the CD modeling, we rely for phosphate on recent parameters from the literature. For carbonate, the surface speciation and affinity constants have been found by modeling the competitive effect of CO3 on the phosphate concentration in CO3-PO4 systems. The CO3 constants obtained can also predict the carbonate adsorption in the absence of phosphate very well. A combination of inner- and outer-sphere CO3 complexation is found. The carbonate adsorption is dominated by a bidentate inner-sphere complex, (FeO)2CO. This binuclear bidentate complex can be present in two different geometries that may have a different IR behavior. At a high PO(4) and CO3 loading and a high Na+ concentration, the inner-sphere carbonate complex interacts with a Na+ ion, probably in an outer-sphere fashion. The Na+ binding constant obtained is representative of Na-carbonate complexation in solution. Outer-sphere complex formation is found to be unimportant. The binding constant is comparable with the outer-sphere complexation constants of, e.g., SO(2-)4 and SeO(2-)4.

Interaction of silicic acid with goethite.

The adsorption of Si on goethite (alpha-FeOOH) has been studied in batch experiments that cover the natural range of Si concentrations as found in the environment. The results have been interpreted and quantified with the charge distribution (CD) and multi-site surface complexation (MUSIC) model in combination with an extended Stern (ES) layer model option. This new double layer approach (ES) accounts for ordering of interfacial water molecules leading to stepwise changes in the location of electrolyte ions near the surface [T. Hiemstra, W.H. Van Riemsdijk, J. Colloid Interface Sci. 301 (2006) 1]. The Si adsorption on goethite peaks at a pH of approximately 9 and decreases at lower and higher pH values. Thermodynamically, the pH-dependency of silicic acid adsorption is related to the value of the proton co-adsorption and can also be linked to the Si charge distribution in the interface as is discussed. Based on published EXAFS data, the adsorption of Si on goethite was modeled as the formation of a bidentate surface complex. The ionic charge distribution (CD) of this complex can be calculated from the geometry of this surface complex, optimized with molecular orbital/density functional theory (MO/DFT), and combined with a correction for water dipole orientation. The resulting CD value has been applied successfully in the description of the adsorption data. The use of a theoretical CD value has the practical advantage of a reduction of the number of adjustable parameters with a factor 2. To describe the adsorption at a high Si loading, formation of a Si polymer, e.g. a tetramer, is proposed. Such a species is only contributing to the overall adsorption at solution concentrations above about 10(-4) M, where super saturation with respect to quartz exists. The adsorbed silica polymer hydrolyzes at high pH. The reactive ligand of the polymer is quite acid (logK approximately 6.5-7.1), which is typically for the triple bond SiO(-1) surface groups of polymerized Si, like amorphous SiO(2)(s), and the triple bond SiO(-1) ligand of the aqueous dimer Si(2)O(OH)(5)O(-1)(aq). The applied model correctly predicts the change of particles charge and the shift in IEP due to proton release upon Si adsorption.

Adsorption of humic acids onto goethite: effects of molar mass, pH and ionic strength.

In this paper, the LCD (ligand charge distribution) model is applied to describe the adsorption of (Tongbersven) humic acid (HA) to goethite. The model considers both electrostatic interactions and chemical binding between HA and goethite. The large size of HA particles limits their close access to the surface. Part of the adsorbed HA particles is located in the compact part at the goethite surface (Stern layers) and the rest in the less structured diffuse double layer (DDL). The model can describe the effects of pH, ionic strength, and loading on the adsorption. Compared to fulvic acid (FA), adsorption of HA is stronger and more pH- and ionic-strength-dependent. The larger number of reactive groups on each HA particle than on a FA particle results in the stronger HA adsorption observed. The stronger pH dependency in HA adsorption is related to the larger number of protons that are coadsorbed with HA due to the higher charge carried by a HA particle than by a FA particle. The positive ionic-strength dependency of HA adsorption can be explained by the conformational change of HA particles with ionic strength. At a higher ionic strength, the decrease of the particle size favors closer contact between the particles and the surface, leading to stronger competition with electrolyte ions for surface charge neutralization and therefore leading to more HA adsorption.

On the relationship between charge distribution, surface hydration, and the structure of the interface of metal hydroxides.

The double layer structure of metal (hydr)oxides is discussed. Charge separation may exist between the minimum distance of approach of electrolyte ions and the DDL domain. The corresponding capacitance value of the outer Stern layer is similar to the capacitance value of the inner Stern layer. The extended Stern model implicitly supports a hydration structure at the near-surface with some discrete layering of water and electrolyte ions. The significance of dipole orientation is analyzed theoretically. Dipole theory in combination with a calculated ion charge distribution is compared with the experimental overall charge distribution. Ion charge distribution for various oxyanions has been calculated applying the Brown bond valence concept to the geometry of surface complexes that have been optimized with MO/DFT calculations. The comparison is done in detail for silicic acid adsorption on goethite. In addition, results are discussed for arsenite, carbonate, sulfate, and phosphate, using the same approach. The dipole correction depends on the charge introduced in a neutral surface by ion adsorption, which differs for the various ions studied. The fractional correction factor phi derived for the experimental data agrees with the theoretical value phi(m)=0.17+/-0.02. On an absolute scale, the dipole corrections are usually limited to the range about 0-0.15 v.u. The CD values calculated with MO/DFT are not particularly sensitive (approximately 0.03 v.u.) to the precise Fe-octahedral geometry, which suggests that a calculated CD is a reasonable approximation in ion adsorption modeling for ill-defined Fe-oxides like HFO and natural Fe oxide materials of soils.

Surface speciation of As(III) and As(V) in relation to charge distribution.

The adsorption of As(III) and As(V) on goethite has been studied as a function of pH and loading. The data can be successfully described with the charge distribution (CD) model (extended Stern layer option) using realistic species observed by EXAFS. The CD values have been derived theoretically. Therefore, the Brown bond valence approach has been applied to MO/DFT optimized geometries of a series of hydrated complexes of As(III) and As(V) with Fe(III) (hydr)oxide. The calculated ionic CD values have been corrected for the effect of dipole orientation of interfacial water, resulting in overall interfacial CD coefficients that can be used to describe the surface speciation as a function of pH and loading. For As(III), the main surface species is a bidentate complex and a minor contribution of a monodentate species is found, which is in agreement with EXAFS. The CD values have also been fitted. Such an analysis of the adsorption data resulted in the same surface species. The fitted CD values for the bidentate complex points to the presence of strong AsO bonds with the surface and a weaker AsOH bond with the free OH ligand. This agrees quantitatively with the MO/DFT optimized geometry. Interpretation of free fitted CD values for As(V) binding suggests that the main surface species is a non-protonated bidentate complex (B) with a contribution of a singly protonated surface complex (MH) at sub-neutral pH and high loading. In addition, a protonated bidentate surface complex (BH) may be present. The same species are found if the theoretical CD values are used in the data analysis. The pH dependency of surface speciation is strongly influenced by the charge attribution of adsorbed species to the electrostatic surface plane while the effect of loading is primarily controlled by the amount of charge attributed to the 1-plane, illustrating the different action of the CD value. The MO/DFT geometry optimizations furthermore suggest that for As(V) the B, MH and BH surface complexes may have very similar AsFe distances which may complicate the interpretation of EXAFS data.

A new surface structural approach to ion adsorption: tracing the location of electrolyte ions.

Electrolyte ions differ in size leading to the possibility that the distance of closest approach to a charged surface differs for different ions. So far, ions bound as outersphere complexes have been treated as point charges present at one or two electrostatic plane(s). However, in a multicomponent system, each electrolyte ion may have its own distance of approach and corresponding electrostatic plane with an ion-specific capacitance. It is preferable to make the capacitance of the compact part of the double layer a general characteristic of the solid-solution interface. A new surface structural approach is presented that may account for variation in size of electrolyte ions. In this approach, the location of the charge of the outersphere surface complexes is described using the concept of charge distribution in which the ion charge is allowed to be distributed over two electrostatic planes. It was shown that the concept can successfully describe the pH dependent proton binding and the shift in the isoelectric point (IEP) in the presence of variety of monovalent electrolyte ions, including Li(+), Na(+), K(+), Cs(+), Cl(-), NO(-)(3), and ClO(-)(4) with a common set of parameters. The new concept also sheds more light on the degree of hydration of the ions when present as outersphere complexes. Interpretation of the charge distribution values obtained shows that Cl(-) ions are located relatively close to the surface. The large alkali ions K(+), Cs(+), and Rb(+) are at the largest distance. Li(+), Na(+), NO(-)(3), and ClO(-)(4) are present at intermediate positions.

Inner- and outer-sphere complexation of ions at the goethite-solution interface.

Formation of inner- and outer-sphere complexes of environmentally important divalent ions on the goethite surface was examined by applying the charge distribution CD model for inner- and outer-sphere complexation. The model assumes spatial charge distribution between the surface (0-plane) and the next electrostatic plane (1-plane) for innersphere complexation and between the 1-plane and the head end of the diffuse double layer (2-plane) for the outersphere complexation. The latter approach has been used because the distance of closest approach to a charged surface may differ for different ions. The surface structural approach implies the use of a Three-Plane model for the compact part (Stern layer) of solid-solution interface, which is divided into two layers. The thickness of each layer depends on the capacitance and the local dielectric constant. The new approach has been applied to describe the adsorption of magnesium, calcium, strontium, and sulfate ions. It is shown that the concept can successfully describe the development of surface charge in the presence of Ca(+2), Mg(+2), Sr(+2), and SO4(-2) as a function of loading, pH, and salt level, and also the shift in the isoelectric point (IEP) of goethite. The CD modeling revealed that, for the conditions studied, magnesium is mainly adsorbed as a bidentate innersphere complex, calcium can be a combination of bidentate innersphere and a monodentate inner- or outer-sphere complexes, and strontium is probably adsorbed as an outersphere complex. Sulfate is present as a mixture of inner- and outer-sphere monodentate complexes. Outersphere complexation is less pH dependent than innersphere complexation. The CD model predicts that the outersphere complexation of divalent cations and anions is relatively favorable at respectively low and high pH. Increase of ion loading favors the formation of innersphere complexes.

Ligand and Charge Distribution (LCD) model for the description of fulvic acid adsorption to goethite.

The LCD model (Ligand and Charge Distribution) has recently been proposed to describe the adsorption of humic substances to oxides, in which the CD-MUSIC model and the NICA model for ion binding to respectively oxides and humic substances are integrated. In this paper, the LCD model is improved by applying the ADAPT model (ADsorption and AdaPTation) to calculate the equilibrium distribution of the humic substances based on the change of the average chemical state of the particles. The improved LCD model is applied to calculate the adsorption of fulvic acid (Strichen) to goethite, in which it is assumed that the carboxylic type of groups of fulvic acid can form innersphere complexes with the surface sites. The charge of the carboxylic groups in the innersphere complexes is distributed between the 0- and d-plane, whereas the charge of the other carboxylic and phenolic groups is located in the d-plane. The average distribution of the carboxylic and phenolic groups among their various chemical states (carboxylic groups: innersphere complex, protonated and deprotonated; phenolic groups: protonated and deprotonated) depends on pH, ionic strength and loading, and are the outcome of the model. The calculation shows that the LCD model can describe sufficiently the effects of pH, ionic strength and loading on the adsorption of fulvic acid, using one adjustable parameter (logK (S,1)). The model calculations indicate that the chemical complexation between fulvic acid and goethite is the main driving force of the adsorption, while the electrostatic repulsion between the particles and the surface is the major limiting factor for further adsorption.