Multisite Surface Complexation Research Articles

Mechanisms of selenate adsorption at the imogolite-water interface

Selenium (Se) can be toxic at high concentrations, mainly through exposure to contaminated groundwater and bioaccumulation in plants. Under oxidizing conditions, Se has preferential inorganic forms, Se oxyanions, which are highly soluble and weakly adsorbed on mineral surfaces. Therefore, retarding the release and migration of Se oxyanions is critical for the protection of groundwater quality. Imogolite is a tubular aluminosilicate with a high adsorptive capacity for anions, including IO3-, TcO4-, and PO43-. However, the potential adsorption of selenate on imogolite has not yet been evaluated to determine potential environmental applications including groundwater remediation. In this study, we synthesized and characterized imogolite using solid-state and electrostatic techniques. The synthesized imogolite was used to evaluate the adsorption of selenate under a range of physiochemical conditions using adsorption isotherms combined with various modeling techniques including the Freundlich model and the charge distribution at multi-site surface complexation (CD-MUSIC) model to decipher surface complexation mechanisms of selenate on imogolite. SynopsisAdsorption affinity and mechanisms of selenate on imogolite are mechanistically evaluated to understand potential environmental applications of imogolite for the protection of groundwater quality.

Adsorption behavior and surface complexation modeling of oxygen anion Sb(V) adsorption on goethite

Simulating the adsorption behavior of Sb(V) on goethite is of great significance for predicting the mobility of Sb(V) in soil. However, there is still a lack of charge distribution and multisite surface complexation (CD-MUSIC) models that conform to the actual adsorption mechanism. Therefore, our research combined the previous EXAFS results with the SCMs and established two CD-MUSIC models (Model I, which introduced bidentate binuclear and bidentate mononuclear complexes, and Model II, which introduced bidentate mononuclear and monodentate mononuclear complexes). It is also one of the rare cases that bidentate edge- and corner-sharing adsorption complexes have been distinguished by introducing different amounts of H+. The results showed that Model I was more suitable for predicting the adsorption behavior of Sb(V) on the goethite surface than Model II. However, at low pH and high Sb(V) loading, the presence of the monodentate complex ≡FeOHSb(OH)50.5- was possible due to the fast and slow two-step mechanism. Using the optimized CD-MUSIC model parameters, the contribution of surface species to the equilibrium adsorption under different conditions was determined. In the adsorption edge and adsorption isotherm simulation process, the edge-sharing bidentate mononuclear complex ≡(FeO)2H2Sb(OH)4 was always the most important product, which was consistent with the results of extended X-ray absorption fine structure (EXAFS) analysis. The applicability of the model parameters was verified by predicting the competitive adsorption between PO43− and Sb(V). The CD-MUSIC model established in the present study could be a useful tool for evaluating the equilibrium distribution behavior and environmental risk of Sb(V) in different types of soils.

Effects of pH and Dissolved Silicate on Phosphate Mineral-Water Partitioning with Goethite

Release of sorbed phosphate from ferric iron oxyhydroxides can contribute to excessive algal growth in surface water bodies. Dissolved silicate has been hypothesized to facilitate phosphate desorption by competing for mineral surface sites. Here, we conducted phosphate and silicate adsorption experiments with goethite under a wide pH range (3–11), both individually (P or Si) and simultaneously (P plus Si). The entire experimental data set was successfully reproduced by the charge distribution multisite surface complexation (CD-MUSIC) model. Phosphate adsorption was highest under acidic conditions and gradually decreased from near-neutral to alkaline pH conditions. Maximum silicate adsorption, in contrast, occurred under alkaline conditions, peaking around pH 10. The competitive effect of silicate on phosphate adsorption was negligible under acidic conditions, becoming more pronounced under alkaline conditions and elevated molar Si:P ratios (>4). In a subsequent experiment, desorption of phosphate with increasing pH was monitored, in the presence or absence of dissolved silicate. While, as expected, desorption of phosphate was observed during the transition from acidic to alkaline conditions, a fraction of phosphate remained irreversibly bound to goethite. Even at high Si:P ratios and alkaline pH, dissolved silicate did not affect phosphate desorption, implying that kinetic factors prevented silicate from displacing phosphate from goethite binding sites.

Exothermic adsorption of chromate by goethite

Goethite is a common Fe oxyhydroxide coating soil particle surfaces, which has a high Cr(VI) adsorption capacity under acidic pH conditions. Batch equilibrium adsorption experiments with chromate concentrations of 0.1, 0.2, and 0.3 mM were performed using solutions with ionic strengths of 0.1, 0.05, and 0.01 M and pH values of 3–11 and at four temperatures between 10 and 75 °C. The results of these experiments show that the amount of chromate adsorbed decreases as the pH increases towards the zero-point-of-surface-charge of goethite (pHPZC 9.1), which is typical for anions. The chromate adsorption efficiency also depends on the ionic strength of the solution. The amount of chromate adsorbed decreases as the ionic strength increases, indicating that outer-sphere surface complexation affects the adsorption process. The data were interpreted using the charge distribution multisite surface complexation (CD-MUSIC) model framework. Variations in the complexation constants with temperature were fitted using the two-term van't Hoff equation to give partial molar enthalpy and entropy constants. The enthalpies were negative, indicating that chromate adsorption is exothermic, whereby outer-sphere binding was found to be less exothermic (ΔrGOS,298 −62.19 kJ mol−1) than inner-sphere binding (ΔrGIS,298 −112.25 kJ mol−1). The adsorption strength, therefore, decreases as the temperature increases because of the exothermic nature of surface complexation.

Effects of aluminum substitution on the surface charge of colloidal goethite particles: experiments and MUSIC modeling.

Proton adsorption behavior on the surface of Al-substituted goethites as a function of pH and ionic strength was investigated and simulated with the multisite surface complexation (MUSIC) model. In addition, X-ray diffraction, X-ray photoelectron spectroscopy, and field emission scanning electron microscope were used to characterize the crystal structure, chemical composition, micromorphology, and surface properties of the Al-substituted goethite. Al substitution was found to affect the crystal structure and micromorphology of goethite. The morphological differences did not result in significant differences in PZC value but largely affected the surface charge values. Goethite surface charge capacity increased progressively with increasing amount of Al substitution, which was attributed to increases in the density of surface coordinated sites due to the increase in (021)/(110) face ratio. The optimization calculations enabled a satisfactory fitting of the titration data of both pure goethite and Al-substituted goethite, and the MUSIC model facilitated a more specific understanding of the charging behavior of Al-substituted goethite. The singly (≡FeOH-0.5 + ≡AlOH-0.5) and triply coordinated (≡Fe3O-0.5 + ≡AlFe2O-0.5) surface groups were most likely responsible for the basic charging behavior of goethite in the pH range of 4-10. All results indicate that the MUSIC model has excellent performance in characterizing Al-substituted goethite, and the model has promising application prospect in other substituted metal (hydr)oxides.

Multi-site surface complexation modelling of Se(IV) sorption on biotite

A surface complexation model of Se(IV) sorption on biotite with one type of strong sorption sites and two types of weak sorption sites were developed based on experimental data obtained from titration, sorption edge and sorption isotherm experiments. Titration data was collected using a batch-wise manner together with backtitration to calibrate the effect of mineral dissolution in 0.01 M KClO4 background electrolytes from pH 3 to 11 in an inert atmosphere glovebox. Further calibrations of the titration curve include proton exchange and cation exchange in which the calculations of cation occupancies on biotite surfaces were taken into account. The sorption edge measurements were determined by measuring the sorption of 10−9 M total Se with a radioactive Se-75 tracer on converted biotite in 0.01 M KClO4 solution from pH 3 to 11. Se sorption was observed to be strongly dependent on pH. Surface complexation modelling was performed by deriving a set of optimized parameters that can fit titration, sorption edge and sorption isotherm (at pH ~7.7) experimental data. A CASTEP code implemented into Materials Studio was used to calculate the site densities and site types on the biotite surfaces. Weak sorption sites with site densities of 3.2 sites/nm2 and 1.4 sites/nm2 were derived from the codes and used in the sorption model. A computer code that coupled PHREEQC with Python was developed for the fitting and optimizing processes. The model was validated by sorption data at pH ~9.5. The results show that the model can provide quantitative predicts of Se(IV) sorption in groundwater conditions of a deep geological repository and help improve the performance assessments by giving more convincing estimates of the release of radionuclides towards aquifers and biosphere.

Simultaneous arsenic and fluoride removal using {201}TiO2-ZrO2: Fabrication, characterization, and mechanism.

The coexistence of arsenic (As) and fluoride (F) in drinking water is an urgent environmental issue that causes increasing public concerns. The need for effective simultaneous removal of As and F has motived great research efforts. Herein, a novel {201}TiO2-ZrO2 composite was synthesized and its application mechanism was explored. Batch adsorption experiments show that the As(III), As(V), and F adsorption followed the pseudo-second-order kinetics with the Langmuir adsorption capacity at 58.5, 21.6, and 13.1 mg/g, respectively. EXAFS and in situ ATR-FTIR results suggested that TiO2 surface sites were occupied by As(III) and As(V) in bidentate binuclear structures, and ZrO2 sites preferentially adsorbed As(III) and F in monodentate mononuclear configurations. This molecular structure obtained in the mono-adsorption system was integrated with the charge distribution multisite surface complexation model to accurately predict the As and F co-existing adsorption behaviors. The results in competitive adsorption, regeneration, and application evidenced that the {201}TiO2-ZrO2 composite is a promising adsorbent for simultaneous As and F removal.

Low-Molecular-Weight Organic Acid Complexation Affects Antimony(III) Adsorption by Granular Ferric Hydroxide.

Antimony(III) mobility in natural aquatic environments is generally enhanced by dissolved organic matter. Tartaric acid is often used to form complexes with and stabilize dissolved Sb(III) in adsorption studies. However, competition between such low-molecular-weight organic acid complexation and adsorption of Sb(III) has received little attention, which prompted us to measure Sb(III) adsorption by iron oxyhydroxide adsorbents commonly used in water treatment plants. Sb K-edge X-ray absorption fine structure (EXAFS) spectra gave Sb-O and Sb-Fe distances and coordinations compatible with a bidentate binuclear inner-sphere complex with trigonal Sb(O,OH)3 polyhedra sharing corners with Fe(O,OH)6 octahedra and a bidentate mononuclear inner-sphere complex but with Sb(O,OH)4 tetrahedra at alkaline pH. Experimental batch titration data were fitted using the charge-distribution multisite surface complexation (CD-MUSIC) model, constrained by the EXAFS molecular level information and taking competitive effects by the organic ligand into consideration. The proportion adsorbed at acid to neutral pH decreased as the Sb(III) concentration increased. The CD-MUSIC adsorption model indicates that this was solely caused by strong competition from tartrate complexation in solution, which leads to adsorption constants higher than those derived without taking this competition into account. The adsorption model results allow for calculating a pe-pH predominance diagram using the USGS PhreePlot code. The study provides consistent surface complexation stability constants, allowing the new database to be used also to reliably model adsorption of toxic oxyanions in anoxic aqueous environments: for example, to accurately simulate competition between Sb(III) and As(III).

Sorption of nickel ontogoethite (α-FeOOH) and desorption kinetics of aged synthetic Ni-goethite: Implication for Ni laterite ore

We have measured the sorption of Ni as a function of surface loading and pH with a series of laboratory experiments. We fit the data using a multisite surface complexation model incorporating the basic Stern model to describe the surface electrostatics. At 0.75 wt% Ni and above, however, we cannot model the sorption data in terms of simple surface complexation but must invoke polynuclear complexes (or surface precipitates) to fit the sorption edges. In addition to surface complexation and surface precipitates, Ni is associated with goethite via structural incorporation. After 21 days of sorption, about 90% of the sample with the highest Ni concentration is reversible while 60% of the sample with the lowest concentration (0.03 wt% Ni) is irreversible. In contrast, after 365 days of sorption about 50–60% of the sorbed Ni is irreversible in all the grades (0.003–2.56 wt% Ni) suggesting almost uniform structural incorporation in the lattice of goethite.

Sorption of Se species on mineral surfaces, part I: Batch sorption and multi-site modelling

The sorption behavior of Se(IV) on Grimsel granodiorite and its main minerals, plagioclase, K-feldspar, quartz and biotite, were investigated in Grimsel groundwater simulant in a large Se concentration range (from 1.66 × 10−10 M to 1 × 10−3 M). Experimental results show that the distribution coefficients (Kd values) of Se(IV) on the rock and mineral samples increased with the decreasing of Se(IV) concentration. The sorption of Se(IV) on biotite has the largest Kd value in low concentration area (<10−7 M) stabilizing between 0.0595 ± 0.0097 m3/Kg and 0.0713 ± 0.0164 m3/Kg. The Kd value of Se(IV) on K-feldspar was the second largest (0.0154 ± 0.0019 m3/Kg in 10−9 M) while the sorption on quartz was negligible. The sorption behavior of Se(IV) on Grimsel granodiorite followed the same trend as plagioclase, the most abundant mineral in Grimsel granodiorite, with Kd values of 0.0078 ± 0.0010 m3/Kg for Grimsel granodiorite and 0.0085 ± 0.0016 m3/Kg for plagioclase, when Se(IV) concentration was 10−9 M. HPLC-ICP-MS results show that all the Se(IV) remained in +IV oxidation state after more than 1 month experimental time and speciation modelling proved that the main species in Grimsel groundwater simulant were HSeO3− and SeO32−. Multi-site surface complexation modelling was performed by PHREEQC with the help of molecular modelling techniques which was performed with the CASTEP code implemented into Materials Studio. The modelling results predict that there are three kinds of sorption sites on the surface of biotite mineral, with sorption site densities differing in three magnitudes.

Surface complexation modeling of Cr(VI) adsorption at the goethite–water interface

In this study, a charge distribution multisite surface complexation model (CD–MUSIC) for adsorption of chromate onto goethite was carefully developed. The adsorption of Cr(VI) on goethite was firstly investigated as a function of pH, ionic strength and Cr(VI) concentration. Results showed that an inner-sphere complexation mechanism was involved because the retention of Cr(VI) was little influenced by ionic strength. Then two surface species: a bidentate complex (Fe2O2CrOOH) and a monodentate complex (FeOCrO3−3/2), which is constrained by prior spectroscopic evidence were proposed to fit the macroscopic adsorption data. Modeling results showed that the bidentate complex was found to be the dominant species at low pH, whereas, with increasing pH, monodentate species became more pronounced. The model was then verified by prediction of competitive adsorption of chromate and phosphate at various ratios and ionic strengths. The model successfully predicted the inhibition of chromate with the presence of phosphate, suggesting phosphate has higher affinity to goethite surface than Cr(VI). Results showed that the model developed in this study for Cr(VI) onto goethite was applicable for various conditions. It is a useful supplement for the surface complexation model database for oxyanions onto goethite surfaces.

Comment on “Citrate adsorption can decrease soluble phosphate concentration in soils: Results of theoretical modelling” by Marek Duputel, Nicolas Devau, Michel Brossard, Benoît Jaillard, Davey L. Jones, Philippe Hinsinger and Frédéric Gérard (2013)

By use of a multi-site surface complexation model, Duputel et al. (2013) showed that citrate can decrease the solubility of phosphorus in soils, in contrast to what is commonly expected. We have identified several major errors in their model, which put the conclusions in doubt. We argue that major re-evaluation of their modelling approach is needed.

Anatase Nanoparticle Surface Reactivity in NaCl Media: A CD–MUSIC Model Interpretation of Combined Experimental and Density Functional Theory Studies

The effect of particle size on the primary charging behavior of a suite of monodisperse nanometer diameter (4, 20, and 40 nm) anatase samples has been quantitatively examined with macroscopic experimental studies. The experimental results were evaluated using surface complexation modeling, which explicitly incorporated corresponding molecular-scale information from density functional theory (DFT) simulation studies. Potentiometric titrations were completed in NaCl media, at five ionic strengths (from 0.005 to 0.3 m), and over a wide pH range (3-11), at a temperature of 25 °C. From the experimental results, the pH of zero net proton charge (pHznpc) for the 4 and 20 nm diameter samples was 6.42, whereas the pHznpc was 6.22 for the 40 nm sample. The slopes of the net proton charge curves increased with an increase in particle size. Multisite surface complexation and charge distribution (CD) models, with a Basic Stern layer description of the electric double layer, were developed to describe all experimental data. Fits to the experimental data included an inner-sphere Na-bidentate species, an outer-sphere Na-monodentate species, and outer-sphere Cl-monodentate species. DFT simulations found the Na-bidentate species to be the most stable species on the (101) anatase surface (the predominant crystal face). The CD value for the Na-bidentate species was calculated using a bond valence interpretation of the DFT-optimized geometry. The Stern layer capacitance value varied systematically with particle size. The collective experimental and modeling studies show that subtle differences exist in the interface reactivity of nanometer diameter anatase samples. These results should help to further elucidate an understanding of the solid-aqueous solution interface reactivity of nanosized particles.

The influence of temperature on selenate adsorption by goethite

Abstract Acid-base batch titration data up to 75 ºC were used to constrain a temperature-dependent 1-pK basic Stern model of the surface protonation reactions of goethite. Experimental data for the temperature dependence of pHPZC (as determined using the two-term Van't Hoff extrapolation) yielded a negative value of −44.9 kJ/mol for the surface protonation enthalpy, and therefore a shift of the zero point of charge towards lower pH values with increasing temperature. Batch titrations at selenate concentrations of between 10 and 100 μM showed an increased degree of adsorption in the acidic pH range, which appeared to be sensitive to the ionic strength of the solution. The selenate adsorption edges shifted towards more acidic pH values with increasing temperature. A 1-pK charge distribution multi-site surface complexation (CD-MUSIC) model was applied, assuming the formation of an outer-spheric surface complex together with an inner-spheric one, in agreement with published spectroscopic information. The temperature behaviour of the intrinsic equilibrium constants were well represented by a linear Van't Hoff log K vs. 1/T plot, from which negative enthalpy values could be derived for both adsorption reactions. The adsorption of the selenate was therefore exothermic and became weaker with increasing temperature. The bidentate inner-spheric complex was more sensitive to rises in temperature (−70 kJ/mol), compared to the outer-spheric complex (−36 kJ/mol). The latter ultimately became the dominating adsorption process at the highest temperature studied.

Reactive transport model and apparent [formula omitted] of Ni in the near field of a HLW repository in granite

Current performance assessment models for radionuclide migration through the near field of high-level radioactive waste repositories often rely on the assumption of a constant Kd for sorption. The validity of such assumption is evaluated here with a reactive transport model for Ni2+ in the near field of a repository in granite. Model results show that Ni2+ sorbs mainly by surface complexation on weak sorption sites. The apparent Kd of Ni2+, Kda, depends on the concentration of dissolved Ni and pH and is constant only when the concentration of dissolved Ni is smaller than 10−6mol/L. The results of the sensitivity runs show that Kda is sensitive to the water flux at the bentonite–granite interface, the effective diffusion of the bentonite and the concentration of weak sorption sites of the bentonite. The competition of other nuclides such as Cs+ on Ni2+ sorption is not important. Corrosion products, however, affect significantly the sorption of Ni2+ on the bentonite. The model with a constant Kd does not reproduce the release rates of Ni2+ from the bentonite into the granite. A model with a variable Kd which depends on the concentration of dissolved Ni2+ and pH may provide an acceptable surrogate of the multicomponent reactive transport model for the conditions of the repository considered in our model. Simulations using the Kd-approach were performed with GoldSim based on the interpolation in the pH and concentration table, while the reactive transport model simulations were performed with CORE2D which incorporates multisite surface complexation.

Arsenic Removal and Recovery from Copper Smelting Wastewater Using TiO2

Removal and recovery of high levels of arsenic (As) in copper smelting wastewater present a great environmental challenge. A novel approach was investigated for the first time using TiO(2) for As adsorptive removal from wastewater and subsequent spent adsorbent regeneration and As recovery using NaOH. EXAFS results demonstrate that As(III), as the only As species present in the raw water, does not form an aqueous complex with other metal ions. An average of 3890 ± 142 mg/L As(III) at pH 1.4 in the wastewater was reduced to 59 ± 79 μg/L in the effluent with final pH at 7 in the 21 successive treatment cycles using regenerated TiO(2). Coexisting heavy metals including Cd, Cu, and Pb with concentrations at 369 mg/L, 24 mg/L, and 5 mg/L, respectively, were reduced to less than 0.02 mg/L. As(III) adsorption followed pseudosecond-order rate kinetics, and the adsorption behavior was described with the charge distribution multisite surface complexation model. Approximately 60% As(III) in the waste solution after the TiO(2) regeneration process was recovered by thermo vaporization and subsequent precipitation of sodium arsenite, as suggested by the EDX and XPS analysis. This "zero" sludge process sheds new light on successful As remediation technology for acidic metallurgical industry wastewater.

Sorption of uranium(VI) at the clay mineral–water interface

Batch experiments were conducted to study the sorption of uranium on selected clay minerals (KGa-1b and KGa-2 reference kaolinite, SWy-2 and STx-1b reference montmorillonite, and IBECO natural bentonite) as a function of pH (4–9) and 0.001, 0.01, and 0.025 M NaCl in equilibrium with the CO2 partial pressure of the atmosphere. Uranium concentrations were kept below 100 μg L−1 to avoid precipitation of amorphous Uranium-hydroxides. Solely PTFE containers and materials were used, because experiments showed significant sorption at higher pH on glass ware. All batch experiments were performed over a period of 24 h, since kinetic experiments proved that the common 10 or 15 min are in many cases by far not sufficient to reach equilibrium. Kaolinite showed much greater uranium sorption than the other clay minerals due to the more aluminol sites available. Sorption on the poorly crystallized KGa-2 was higher than on the well-crystallized KGa-1b. Uranium sorption on STx-1b and IBECO exhibited parabolic behavior with a sorption maximum around pH 6.5. Sorption of uranium on montmorillonites showed a distinct dependency on sodium concentrations because of the effective competition between uranyl and sodium ions, whereas less significant differences in sorption were found for kaolinite. The presence of anatase as impurity in kaolinite enhanced the binding of uranyl-carbonate complexes with surface sites. The kinetic of uranium sorption behavior was primarily dependent on the clay minerals and pH. A multisite surface complexation model without assuming exchange is based on the binding of the most dominant uranium species to aluminol and silanol edge sites of montmorillonite, respectively to aluminol and titanol surface sites of kaolinite. For eight surface species, the log_k was determined from the experimental data using the parameter estimation code PEST together with PHREEQC.

Sorption of Eu(III) onto titanium dioxide: Measurements and modeling

In the present study, the sorption of europium and lutetium onto titanium dioxide from aqueous solutions is presented, as a function of pH, ionic strength and concentration. An acid base model for the titanium dioxide surface was determined from potentiometric titrations and zeta-potential measurements. The common intersection point of potentiometric titrations coincided with the isoelectric point from electrokinetic experiments, resulting in a pristine point of zero charge of about 6.1. The experimental data were in agreement with previously published results and a previously published MUSIC-type model was used as the basis to model the acid–base behavior. Comparison of europium and lutetium showed no difference in the adsorption behavior. Furthermore, no difference was observed both in uptake and spectroscopic studies whether carbonate was absent or present. The absence of a noticeable effect of the ionic strength on the adsorption behavior was indicative of strong binding. EXAFS revealed rough conservation of the coordination with 9–8 water and surface hydroxyl groups upon sorption. EXAFS results suggested the existence of different metal–oxygen distances, more varied than that observed for the respective aquo complex and thus indicative for inner-sphere surface complexation. A clear differentiation of surface complexation denticity was not possible based on spectroscopic data. A multisite surface complexation model approach was applied by assuming monodentate and multidentate binding to describe the trivalent metal uptake data. It is conceivable that mono- and multidentate species contribute to lanthanide sorption to titanium dioxide. In other words a distribution of states occurs in cation surface complexation reactions.

A surface structural model for ferrihydrite I: Sites related to primary charge, molar mass, and mass density

A multisite surface complexation (MUSIC) model for ferrihydrite (Fh) has been developed. The surface structure and composition of Fh nanoparticles are described in relation to ion binding and surface charge development. The site densities of the various reactive surface groups, the molar mass, the mass density, the specific surface area, and the particle size are quantified. As derived theoretically, molecular mass and mass density of nanoparticles will depend on the types of surface groups and the corresponding site densities and will vary with particle size and surface area because of a relatively large contribution of the surface groups in comparison to the mineral core of nanoparticles. The nano-sized (∼2.6 nm) particles of freshly prepared 2-line Fh as a whole have an increased molar mass of M ∼ 101 ± 2 g/mol Fe, a reduced mass density of ∼3.5 ± 0.1 g/cm 3, both relatively to the mineral core. The specific surface area is ∼650 m 2/g. Six-line Fh (5–6 nm) has a molar mass of M ∼ 94 ± 2 g/mol, a mass density of ∼3.9 ± 0.1 g/cm 3, and a surface area of ∼280 ± 30 m 2/g. Data analysis shows that the mineral core of Fh has an average chemical composition very close to FeOOH with M ∼ 89 g/mol. The mineral core has a mass density around ∼4.15 ± 0.1 g/cm 3, which is between that of feroxyhyte, goethite, and lepidocrocite. These results can be used to constrain structural models for Fh. Singly-coordinated surface groups dominate the surface of ferrihydrite (∼6.0 ± 0.5 nm −2). These groups can be present in two structural configurations. In pairs, the groups either form the edge of a single Fe-octahedron (∼2.5 nm −2) or are present at a single corner (∼3.5 nm −2) of two adjacent Fe octahedra. These configurations can form bidentate surface complexes by edge- and double-corner sharing, respectively, and may therefore respond differently to the binding of ions such as uranyl, carbonate, arsenite, phosphate, and others. The relatively low PZC of ferrihydrite can be rationalized based on the estimated proton affinity constant for singly-coordinated surface groups. Nanoparticles have an enhanced surface charge. The charging behavior of Fh nanoparticles can be described satisfactory using the capacitance of a spherical Stern layer condenser in combination with a diffuse double layer for flat plates.

Remediation of organic and inorganic arsenic contaminated groundwater using a nanocrystalline TiO 2-based adsorbent

A nanocrystalline TiO 2-based adsorbent was evaluated for the simultaneous removal of As(V), As(III), monomethylarsonic acid (MMA), and dimethylarsinic acid (DMA) in contaminated groundwater. Batch experimental results show that As adsorption followed pseudo-second order rate kinetics. The competitive adsorption was described with the charge distribution multi-site surface complexation model (CD-MUSIC). The groundwater containing an average of 329 μg L −1 As(III), 246 μg L −1 As(V), 151 μg L −1 MMA, and 202 μg L −1 DMA was continuously passed through a TiO 2 filter at an empty bed contact time of 6 min for 4 months. Approximately 11 000, 14 000, and 9900 bed volumes of water had been treated before the As(III), As(V), and MMA concentration in the effluent increased to 10 μg L −1. However, very little DMA was removed. The EXAFS results demonstrate the existence of a bidentate binuclear As(V) surface complex on spent adsorbent, indicating the oxidation of adsorbed As(III).