Bidentate Binuclear Research Articles

Influence of pH on Initial Concentration Effect of Arsenate Adsorption on TiO2 Surfaces: Thermodynamic, DFT, and EXAFS Interpretations

Under the same thermodynamic condition where the total mass of arsenate was fixed, when the initial arsenate was added to TiO2 suspension by multiple batches, adsorption isotherms declined as the multi-batch increased, which was termed initial concentration (C0) effect. The extent of C0 effect decreased gradually as pH decreased from 7.0 to 5.5. Extended X-ray absorption fine structure analysis of 1-batch and 3-batch isotherm samples showed that the relative proportion of bidentate binuclear (BB) and monodentate mononuclear (MM) complex was rarely affected by pH change from 5.5 to 7.0, indicating that the dependence of C0 effect on pH was not due to inner-sphere chemiadsorption. The influence of pH on adsorption was simulated by density functional theory through changing the number of H+ in model clusters. Calculation of adsorption energy showed that BB surface complex was the most thermodynamically favorable mode (−244.5 kJ mol−1) at low pH, but MM surface complex was the most thermodynamically favorable mode (−135.6 to 27.5 kJ mol−1) at intermediate and high pH, which indicated the influence of surface functional groups (−H2O and −OH) on adsorption reaction pathways. As pH decreased, C0 effect weakened gradually because outer-sphere H-bond adsorption became thermodynamically favorable (−203.1 kJ/mol). The dependence of C0 effect on pH showed that traditional equilibrium adsorption constants could not accurately describe the real adsorption equilibrium at solid−liquid interface, because real equilibrium adsorption state is generally a mixture of various outer-sphere and inner-sphere metastable-equilibrium states.

Arsenic sorption on TiO 2 nanoparticles: Size and crystallinity effects

Single solute As (III) and As (V) sorption on nano-sized amorphous and crystalline TiO 2 was investigated to determine: size and crystallinity effects on arsenic sorption capacities, possible As (III) oxidation, and the nature of surface complexes. Amorphous and crystalline nanoparticles were prepared using sol-gel synthesis techniques. For amorphous TiO 2, solute pH in the range of 4–9 had a profound impact on only As (V) sorption. As (III) and As (V) sorption isotherms indicated that sorption capacities of the different TiO 2 polymorphs were dependent on the sorption site density, surface area (particle size) and crystalline structure. When normalized to surface area, As (III) surface coverage on the TiO 2 surface remained almost constant for particles between 5 and 20 nm. However, As (V) surface coverage increased with the degree of crystallinity. X-ray absorption spectroscopic analysis provided evidence of partial As (III) oxidation on amorphous TiO 2 rather than crystalline TiO 2. The data also indicated that As (III) and As (V) form binuclear bidentate inner-sphere complexes with amorphous TiO 2 at neutral pH.

New Hybrid Properties of TiO2 Nanoparticles Surface Modified With Catecholate Type Ligands

Surface modification of nanocrystalline TiO2 particles (45 Å) with bidentate benzene derivatives (catechol, pyrogallol, and gallic acid) was found to alter optical properties of nanoparticles. The formation of the inner-sphere charge–transfer complexes results in a red shift of the semiconductor absorption compared to unmodified nanocrystallites. The binding structures were investigated by using FTIR spectroscopy. The investigated ligands have the optimal geometry for chelating surface Ti atoms, resulting in ring coordination complexes (catecholate type of binuclear bidentate binding–bridging) thus restoring in six-coordinated octahedral geometry of surface Ti atoms. From the Benesi–Hildebrand plot, the stability constants at pH 2 of the order 103 M−1 have been determined.

Evidence for Different Surface Speciation of Arsenite and Arsenate on Green Rust: An EXAFS and XANES Study

The knowledge of arsenic speciation at the surface of green rusts (GRs), [Fe(II)((1-x))Fe(III)(x) (OH)(2)](x+) (CO(3), Cl, SO(4))(x-), is environmentally relevant because arsenic sorption onto GRs could contribute to arsenic retention in anoxic environments (hydromorphic soils, marine sediments, etc.). The nature of arsenic adsorption complexes on hydroxychloride green rust 1 (GR1Cl) at near-neutral pH under anoxic conditions was investigated using extended X-ray absorption fine structure (EXAFS) spectroscopy at the As K-edge. Sorption data indicate that As(V) sorbs more efficiently than As(III) at the studied As loadings (0.27 micromol m(-2) and 2.7 micromol m(-2)). EXAFS results indicate that arsenite [As(III)] and arsenate [As(V)] form inner-sphere complexes on the surface of GR1Cl at arsenic surface coverages of 0.27 and 2.70 micromol m(-2), with distinct types of As(III) and As(V) sorption complexes, which change in relative concentration as a function of arsenic loading. For As(V), the EXAFS-derived As-Fe distances (3.34 +/- 0.02 and 3.49 +/- 0.02 A) suggest the presence of binuclear bidentate double-corner complexes ((2)C) and monodentate mononuclear corner-sharing complexes ((1)V). For As(III), EXAFS-derived As-As distance (3.32 +/- 0.02 A) and As-Fe distances (3.49 +/- 0.02 and 4.72 +/- 0.02 A) are consistent with the presence of dimers of As(III) pyramids binding to the edges of the GR1Cl layers by corner sharing with FeO(6) octahedra. However, (2)C and (1)V As(III) complexes cannot be excluded. These results improve our knowledge of the mode of As(V) and As(III) inner-sphere adsorption on green rusts, which will help to constrain sorption modeling of arsenic in soils, sediments, and aquifers.

Quantitative XANES Studies on Metastable Equilibrium Adsorption of Arsenate on TiO2 Surfaces

Quantitative information on the electronic and geometric structures of adsorption complexes of arsenate on TiO2 surfaces was obtained on the basis of XANES analysis combined with DFT calculation. The density of states (DOS) showed that the As(V) K-absorption edge corresponded to the dipole transition from the As Is electron into the As(4p)-O(2p) antibonding molecular orbital, suggesting that the bonding between arsenate and TiO2 was primarily due to the interaction of As 4p and O 2p orbitals. Previous EXAFS studies indicated that both bidentate binuclear (BB) and monodentate mononuclear (MM) surface complexes coexisted in the As(V)-TiO2 adsorption system. DFT calculation showed that the XANES transition energy of the BB complex was significantly higher than that of the MM complex. Thus, quantitative information on adsorption microstructures call be obtained by measuring the blue-shift of the XANES absorption edge. XANES results of adsorption samples at different kinetic stages indicated that there was a structural evolution from the MM complex to the BB complex as the reaction processed to adsorption equilibrium. Therefore, the final proportion between BB and MM complexes in the real equilibrium state was fundamentally affected by surface coverage and kinetic pathways. This fact implied that the real equilibrium constant, when defined by macroscopic parameters of concentration and adsorption density (mol/m(2)), are generally inconstant in nature and hence cannot describe the real equilibrium properties of adsorption, because different microscopic metastable equilibrium adsorption structures that construct the real adsorption equilibrium cannot be counted for both mass and energy by the macroscopic parameter of surface concentrations (mol/m(2)).

Surface Complexation of Carboxylate Adheres Cryptosporidium parvum Öocysts to the Hematite−Water Interface

The interaction of viable Cryptosporidium parvum oocysts at the hematite (alpha-Fe2O3)-water interface was examined over a wide range in solution chemistry using in situ attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy. Spectra for hematite-sorbed oocysts showed distinct changes in carboxylate group vibrations relative to spectra obtained in the absence of hematite, indicative of direct chemical bonding between carboxylate groups and Fe metal centers of the hematite surface. The data also indicate that complexation modes vary with solution chemistry. InNaCl solution, oocysts are bound to hematite via monodentate and binuclear bidentate complexes. The former predominates at low pH, whereas the latter becomes increasingly prevalent with increasing pH. In a CaCl2 solution, only binuclear bidentate complexes are observed. When solution pH is above the point of zero net proton charge (PZNPC) of hematite, oocyst surface carboxylate groups are bound to the mineral surface via outer-sphere complexes in both electrolyte solutions.

Surface Modification of Colloidal TiO2 Nanoparticles with Bidentate Benzene Derivatives

Surface modification of nanocrystalline TiO2 particles (45 A) with bidentate benzene derivatives, that is, 2-hydroxybenzoic acid, 2,5-dihydroxybenzoic acid, 2,3-dihydroxybenzoic acid, 3,4-dihydroxybenzoic acid, and catechol was found to alter optical properties of nanoparticles. The formation of the inner-sphere charge transfer (CT) complexes results in a red shift of the semiconductor absorption compared to unmodified nanocrystallites. The binding structures were investigated by using FTIR spectroscopy. The investigated ligands have the optimal geometry for chelating surface Ti atoms, resulting in ring coordination complexes (catecholate or salycilate type of binuclear bidentate binding), thus restoring six-coordinated octahedral geometry of surface Ti atoms. From the Benesi−Hildebrand plot, the stability constants at pH 2 of the order 103 M−1 have been determined.

Structural characterization of poorly-crystalline scorodite, iron(III)–arsenate co-precipitates and uranium mill neutralized raffinate solids using X-ray absorption fine structure spectroscopy

X-ray absorption fine structure (XAFS) is used to characterize the mineralogy of the iron(III)–arsenate(V) precipitates produced during the raffinate (aqueous effluent) neutralization process at the McClean Lake uranium mill in northern Saskatchewan, Canada. To facilitate the structural characterization of the precipitated solids derived from the neutralized raffinate, a set of reference compounds were synthesized and analyzed. The reference compounds include crystalline scorodite, poorly-crystalline scorodite, iron(III)–arsenate co-precipitates obtained under different pH conditions, and arsenate-adsorbed on goethite. The poorly-crystalline scorodite (prepared at pH 4 with Fe/As = 1) has similar As local structure as that of crystalline scorodite. Both As and Fe K-edge XAFS of poorly-crystalline scorodite yield consistent results on As–Fe (or Fe–As) shell. From As K-edge analysis the As–Fe shell has an inter-atomic distance of 3.33 ± 0.02 Å and coordination number of 3.2; while from Fe K-edge analysis the Fe–As distance and coordination number are 3.31 ± 0.02 Å and 3.8, respectively. These are in contrast with the typical arsenate adsorption on bidentate binuclear sites on goethite surfaces, where the As–Fe distance is 3.26 ± 0.03 Å and coordination number is close to 2. A similar local structure identified in the poorly-crystalline scorodite is also found in co-precipitation solids (Fe(III)/As(V) = 3) when precipitated at the same pH (pH = 4): As–Fe distance 3.30 ± 0.03 Å and coordination number 3.9; while at pH = 8 the co-precipitate has As–Fe distance of 3.27 ± 0.03 Å and coordination number about 2, resembling more closely the adsorption case. The As local structure in the two neutralized raffinate solid series (precipitated at pH values up to 7) closely resembles that in the poorly-crystalline scorodite. All of the raffinate solids have the same As–Fe inter-atomic distance as that in the poorly-crystalline scorodite, and a systematic decrease in the As–Fe coordination is observed when pH is progressively increased; the basic poorly-crystalline scorodite structural feature remains in the raffinate solid up to pH 7.

Accumulation and mobilization of arsenate by Fe(III) polyions trapped in a Ca-polygalacturonate network

The role of Fe(III) stored at the soil-root interface in the accumulation of arsenate and the influence of citric acid on the As(V) mobility were investigated by using Ca-polygalacturonate networks (PGA). The results indicate that in the 2.5-6.2 pH range Fe(III) interacts with As(V) leading to the sorption of As(V) on Fe(III) precipitates or Fe-As coprecipitates. The FT-IR analysis of these precipitates evidenced that the interaction produces Fe(III)-As(V) inner-sphere complexes with either monodentate or bidentate binuclear attachment of As(V) depending on pH. In the 3.0-6.0 pH range, As(V) diffuses freely through the polysaccharidic matrix that was found to exert a negligible reducing action towards As(V). At pH 6.0 citric acid is able to mobilize arsenate from the As-Fe-PGA network through the complexation of the Fe(III) polyions that leads to the release of As(V).

Silicate adsorption by goethite at elevated temperatures

Batch adsorption experiments with relatively low silica concentrations between 10 µM and 100 µM were conducted at three different ionic strength (0.01 − 0.1 M), and four different temperatures between 10 °C and 75 °C, yielding in a total of 550 experimental data points. The residual concentration of monosilicic acid is controlled by an adsorption equilibrium which is dependent on pH. The % Si adsorbed vs. − log[H +] curves reveal an upward bend with a maximum at about a pH of 9. With acidification below pH 9 the residual Si concentration in the suspensions steadily increases, as well as in the increasingly alkaline pH range. The slope of the latter is becoming steeper with increasing temperature. A basic Stern layer and charge distribution approach was used for modelling surface charge. The − log[H +]-dependent Si adsorption at the goethite surface was modelled involving a single-site approach for both neutral and hydrolyzed silicate inner-sphere surface complexes. For both a binuclear bidentate 2C complex was chosen according to spectroscopic information. Experimental data at all ionic strengths and temperatures are matched equally well by the adsorption model. The model output suggests a decrease in the pH where hydrolysis of the Si surface complex starts, and therefore an increasing importance of the hydrolyzed surface species with increasing temperature. The equilibrium adsorption constants could be well represented by a linear Van't Hoff log K T vs. 1/ T plot, from which thermodynamic Δ r H 298 and Δ r G 298 values of the adsorption reactions were derived. Adsorption of the silicate on the goethite surface is exothermic (Δ r H 298 = − 43.7 kJ mol − 1 for the dominating surface complex), and becomes therefore weaker with increasing temperature.

Competitive Adsorption of 2‐Ketogluconate and Inorganic Ligands onto Gibbsite and Kaolinite

The low‐molecular‐mass organic acid anion 2‐ketogluconate (kG) is produced via microbial activity in rhizosphere soils. One of the mechanisms by which this organic ligand may influence the chemistry of soil systems is through adsorption by constant‐potential minerals. This study examined the adsorption of kG onto gibbsite and kaolinite in the presence or absence of PO4, AsO4, and SO4 as a function of pH and ionic strength. The adsorption edge studies were performed in the pH 3 to 10 range and at ambient (20–22°C) temperatures. The adsorption of kG is a function of solution pH (decreasing with increasing pH) and independent of solution ionic strength, supporting the conclusion that kG is adsorbed by ligand exchange mechanisms. The adsorption of kG was decreased at all pH values in the presence of PO4 and AsO4, and was not significantly affected by the presence of SO4 at pH values >5. The decrease in kG adsorption in the presence of AsO4 and PO4 is further evidence that kG is adsorbed via specific retention mechanisms. The addition of kG to gibbsite containing preadsorbed PO4 did not result in PO4 displacement, regardless of the concentration of kG. Ligand adsorption was modeled using the adsorption edge data and the 1‐pK basic Stern surface complexation model. The kG adsorption data was described by the formation of two inner‐sphere surface species: mononuclear monodentate and binuclear bidentate. The chemical models and associated intrinsic equilibrium constants developed to describe ligand adsorption in single‐adsorbate gibbsite systems were used to predict ligand retention in the kaolinite and binary‐adsorbate systems. In this manner, the competitive adsorption of all ligands as a function of pH was adequately described. The findings of this study indicate that kG is specifically retained by common soil minerals and may impact the availability of PO4 and other specifically retained ligands in the rhizosphere.

Copper and arsenate co-sorption at the mineral–water interfaces of goethite and jarosite

The co-sorption reaction products of arsenate (As(V)) and copper (Cu(II)) on goethite ( α-FeOOH) and natro-jarosite (Na 3Fe 3(SO 4) 2(OH) 6) were investigated with extended X-ray absorption fine structure (EXAFS) spectroscopy to determine if Cu(II) and As(V) would form precipitates or compete with each other for surface sites. The reaction products were prepared by mixing 250 μM Cu(SO 4) with 10, 25, or 50 μM Na 2HAsO 4 at pH 5.65 and allowing the mixture to react in 10 m 2 L −1 goethite or jarosite suspensions for 12 days. In addition, EXAFS data of Cu(SO 4) and As(V) sorbed on goethite and jarosite were collected as control species. All reaction conditions were under-saturated with respect to common copper bearing minerals: tenorite (CuO), brochantite (Cu 4(OH) 6SO 4), and hydrated clinoclase (Cu 3(AsO 4) 2⋅2H 2O). The extents of the As(V) and Cu(II) surface adsorption reactions showed a strong competitive effect from Cu(II) on As(V) adsorption for a nominal Cu:As mole-ratio of 25:1. With increasing nominal As(V) concentration, As(V) sorption on goethite and jarosite increased without diminishing the amount of Cu(II) sorption. In the absence of either co-sorbate, As(V) and Cu(II) formed the expected surface adsorption species, i.e., bidentate binuclear and edge-sharing surface complexes, consistent with previously published results. In each other's presence, the local bonding environments of As(V) and Cu(II) showed that the co-sorbates form a precipitate on the goethite and jarosite surface at nominal concentrations of 10:1 and 5:1. At nominal Cu:As mole-ratios of 25:1, Cu(II) did not form significantly different surface complexes on goethite or jarosite from those in the absence of As(V), however, As K-edge EXAFS results distinctly showed Cu(II) atoms in As(V)'s local bonding environment on the goethite surface. The structures of the two precipitates were different and depended on the anion-layer structure and possibly the presence of structural oxyanions in the case of jarosite. On goethite, the copper–arsenate precipitate was similar to hydrated clinoclase, while on jarosite, a euchroite-like precipitate (Cu 2[AsO 4](OH)⋅3H 2O, P 2(1)2(1)2(1)) had formed. Despite under-saturated solution conditions, the formation of these precipitates may have occurred due to a seed-formation effect from densely surface adsorbed Cu(II) and As(V) for which the “new” saturation index was significantly lower than homogeneous values would otherwise suggest. Synergistic reactions between two co-sorbates of fundamentally different surface adsorption behaviour can thus be achieved if the number of available sites for surface adsorption is limited.

Extended X-ray Absorption Fine Structure Analysis of Arsenite and Arsenate Adsorption on Maghemite

Arsenic sorption onto maghemite potentially contributes to arsenic retention in magnetite-based arsenic removal processes because maghemite is the most common oxidation product of magnetite and may form a coating on magnetite surfaces. Such a sorption reaction could also favor arsenic immobilization at redox boundaries in groundwaters. The nature of arsenic adsorption complexes on maghemite particles, at near-neutral pH under anoxic conditions, was investigated using X-ray absorption fine structure (XAFS) spectroscopy at the As K-edge. X-ray absorption near edge structure spectra indicate that As(III) does notoxidize after 24 h in any of the sorption experiments, as already observed in previous studies of As(III) sorption on ferric (oxyhydr)oxides under anoxic conditions. The absence of oxygen in our sorption experiments also limited Fenton oxidation of As(III). Extended XAFS (EXAFS) results indicate that both As(III) and As(V) form inner-sphere complexes on the surface of maghemite, under high surface coverage conditions (approximately 0.6 to 1.0 monolayer), with distinctly different sorption complexes for As(III) and As(V). For As(V), the EXAFS-derived As-Fe distance (approximately 3.35 +/- 0.03 A) indicates the predominance of single binuclear bidentate double-corner complexes (2C). For As(III), the distribution of the As-Fe distance suggests a coexistence of various types of surface complexes characterized by As-Fe distances of approximately 2.90 (+/-0.03) A and approximately 3.45 (+/-0.03) A. This distribution can be interpreted as being due to a dominant contribution from bidentate binuclear double-corner complexes (2C), with additional contributions from bidentate mononuclear edge-sharing (2E) complexes and monodentate mononuclear corner-sharing complexes (1V). The present results yield useful constraints on As(V) and As(III) adsorption on high surface-area powdered maghemite, which may help in modeling the behavior of arsenic at the maghemite-water interface.

Removal of arsenic from water using granular ferric hydroxide: Macroscopic and microscopic studies

Removal of arsenate from water using granular ferric hydroxide (GFH) was investigated under different pH and As(V) loading conditions, using batch equilibrium adsorption, FTIR, and EXAFS methods. The arsenate adsorption envelopes on GFH exhibited broad adsorption maxima when the initial As(V) concentration was less than 500 mg/L at sorbent concentration of 10 g/L. As the initial As(V) concentration increased to 500, 1000 or 2000 mg/L for the same sorbent concentration, distinct adsorption maxima appeared and shifted to lower pH. Acidimetric–alkalimetric titration and arsenic adsorption isotherm data indicated that the surface of GFH is high heterogeneous. FTIR spectra revealed that complexes of two different structures, bidentate and monodentate, were formed upon the adsorption of arsenate on GFH, and bidentate complexes were only observed at pH values greater than 6. The EXAFS analyses confirmed that arsenate form bidentate binuclear complexes with GFH at pH 7.4 as evidenced by an average Fe-As(V) bond distance of 3.32 Å.

Adsorption and surface oxidation of Fe(II) on metal (hydr)oxides

The Fe(II) adsorption by non-ferric and ferric (hydr)oxides has been analyzed with surface complexation modeling. The CD model has been used to derive the interfacial distribution of charge. The fitted CD coefficients have been linked to the mechanism of adsorption. The Fe(II) adsorption is discussed for TiO 2, γ-AlOOH (boehmite), γ-FeOOH (lepidocrocite), α-FeOOH (goethite) and HFO (ferrihydrite) in relation to the surface structure and surface sites. One type of surface complex is formed at TiO 2 and γ-AlOOH, i.e. a surface-coordinated Fe 2+ ion. At the TiO 2 (Degussa) surface, the Fe 2+ ion is probably bound as a quattro-dentate surface complex. The CD value of Fe 2+ adsorbed to γ-AlOOH points to the formation of a tridentate complex, which might be a double edge surface complex. The adsorption of Fe(II) to ferric (hydr)oxides differs. The charge distribution points to the transfer of electron charge from the adsorbed Fe(II) to the solid and the subsequent hydrolysis of the ligands that coordinate to the adsorbed ion, formerly present as Fe(II). Analysis shows that the hydrolysis corresponds to the hydrolysis of adsorbed Al(III) for γ-FeOOH and α-FeOOH. In both cases, an adsorbed M ( III ) ( OH ) 2 + is found in agreement with structural considerations. For lepidocrocite, the experimental data point to a process with a complete surface oxidation while for goethite and also HFO, data can be explained assuming a combination of Fe(II) adsorption with and without electron transfer. Surface oxidation (electron transfer), leading to adsorbed Fe(III)(OH) 2, is favored at high pH (pH > ∼7.5) promoting the deprotonation of two Fe III-OH 2 ligands. For goethite, the interaction of Fe(II) with As(III) and vice versa has been modeled too. To explain Fe(II)–As(III) dual-sorbate systems, formation of a ternary type of surface complex is included, which is supposed to be a monodentate As(III) surface complex that interacts with an Fe(II) ion, resulting in a binuclear bidentate As(III) surface complex.

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.

Arsenic sequestration by sorption processes in high-iron sediments

High-iron sediments in North Haiwee Reservoir (Olancha, CA), resulting from water treatment for removal of elevated dissolved arsenic in the Los Angeles Aqueduct system, were studied to examine arsenic partitioning between solid phases and porewaters undergoing shallow burial. To reduce arsenic in drinking water supplies, ferric chloride and a cationic polymer coagulant are added to the aqueduct upstream of Haiwee Reservoir, forming an iron-rich floc that scavenges arsenic from the water. Analysis by synchrotron X-ray absorption spectroscopy (XAS) showed that the aqueduct precipitate is an amorphous hydrous ferric oxide (HFO) similar to ferrihydrite, and that arsenic is associated with the floc as adsorbed and/or coprecipitated As(V). Arsenic-rich floc and sediments are deposited along the inlet channel as aqueduct waters enter the reservoir. Sediment core samples were collected in two consecutive years from the edge of the reservoir along the inlet channel using 30- or 90-cm push cores. Cores were analyzed for total and extractable arsenic and iron concentrations. Arsenic and iron speciation and mineralogy in sediments were examined at selected depths by synchrotron XAS and X-ray diffraction (XRD). Sediment–porewater measurements were made adjacent to the core sample sites using polyacrylamide gel probe samplers. Results showed that sediment As(V) is reduced to As(III) in all cores at or near the sediment–water interface (0–4 cm), and only As(III) was observed in deeper sediments. Analyses of EXAFS spectra indicated that arsenic is present in the sediments mostly as a bidentate–binuclear, inner-sphere sorption complex with local atomic geometries similar to those found in laboratory studies. Below about 10 cm depth, XAS indicated that the HFO floc had been reduced to a mixed Fe(II, III) solid with a local structure similar to that of synthetic green rust (GR) but with a slightly contracted average interatomic Fe–Fe distance in the hydroxide layer. There was no evidence from XRD for the formation of a crystalline GR phase. The release of dissolved iron (presumably Fe 2+) and arsenic to solution, as monitored by in situ gel probes, was variable but, in general, occurred at greater depths than arsenic reduction in the sediments by spectroscopic observations and appears to be near or below the depth at which sediment GR was identified. These data point to reductive dissolution of the sorbent iron phase as the primary mechanism of release of sorbed arsenic to solution.

The formation, structure, and ageing of As-rich hydrous ferric oxide at the abandoned Sb deposit Pezinok (Slovakia)

The abandoned Sb deposit Pezinok in Slovakia is a significant source of As and Sb pollution that can be traced in the upper horizons of soils kilometers downstream. The source of the metalloids are two tailing impoundments which hold ∼380,000 m 3 of mining waste. The tailings and the discharged water have circumneutral pH values (7.0 ± 0.6) because the acidity generated by the decomposition of the primary sulfides (pyrite, FeS 2; arsenopyrite, FeAsS; berthierite, FeSb 2S 4) is rapidly neutralized by the abundant carbonates. The weathering rims on the primary sulfides are iron oxides which act as very efficient scavengers of As and Sb (with up to 19.2 wt% As and 23.7 wt% Sb). In-situ μ-XANES experiments indicate that As in the weathering rims is fully oxidized (As 5+). The pore solutions in the impoundment body contain up to 81 ppm As and 2.5 ppm Sb. Once these solutions are discharged from the impoundments, they precipitate or deposit masses of As-rich hydrous ferric oxide (As-HFO) with up to 28.3 wt% As 2O 5 and 2.7 wt% Sb. All As-HFO samples are amorphous to X-rays. They contain Fe and As in their highest oxidation state and in octahedral and tetrahedral coordination, respectively, as suggested by XANES and EXAFS studies on Fe K and As K edges. The iron octahedra in the As-HFO share edges to form short single chains and the chains polymerize by sharing edges or corners with the adjacent units. The arsenate ions attach to the chains in a bidentate–binuclear and monodentate fashion. In addition, hydrogen-bonded complexes may exist to satisfy the bonding requirements of all oxygen atoms in the first coordination sphere of As 5+. Structural changes in the As-HFO samples were traced by chemical analyses and Fe EXAFS spectroscopy during an ageing experiment. As the samples age, As becomes more easily leachable. EXAFS spectra show a discernible trend of increasing number of Fe–Fe pairs at a distance of 3.3–3.5 Å, that is, increasing polymerization of the iron octahedra to form larger units with fewer adsorption sites. Therefore, although ferrihydrite is an excellent material for capturing arsenic, its use as a medium for a long-term storage of As has to be considered with a great caution because it will tend to release arsenic as it ages.

Surface complexes of phthalic acid at the hematite/water interface

The adsorption of o-phthalic acid at the hematite/water interface was investigated experimentally using batch adsorption experiments and attenuated total reflectance–Fourier transform infrared (ATR-FTIR) spectroscopy over a wide range of solution pH, surface loading, and ionic strength conditions. Molecular orbital calculations for several possible surface complexes were also performed to assign atomistic structures to the features observed in the ATR-FTIR spectra. The results of the batch adsorption experiments exhibit typical anionic characteristics with high adsorption at low pH and low adsorption at high pH. The adsorption of phthalic acid also exhibits a strong dependence on ionic strength, which suggests the presence of outer-sphere complexes. ATR-FTIR spectra provide evidence of three fully deprotonated phthalate surface complexes (an outer-sphere complex and two inner-sphere complexes) under variable chemical conditions. A fully deprotonated outer-sphere complex appears to dominate adsorption in the circumneutral pH region, while two fully deprotonated inner-sphere complexes that shift in relative importance with surface coverage increase in importance at low pH. Comparison of experimental and theoretical calculations suggests the two inner-sphere complexes are best described as a mononuclear bidentate (chelating) complex and a binuclear bidentate (bridging) complex. The mononuclear bidentate inner-sphere complex was favored at relatively low surface coverage. With increasing surface coverage, the relative contribution of the binuclear bidentate inner-sphere complex increased in importance.

Bioaccessibility of Arsenic(V) Bound to Ferrihydrite Using a Simulated Gastrointestinal System

The risk posed from incidental ingestion to humans of arsenic-contaminated soil may depend on sorption of arsenate (As(V)) to oxide surfaces in soil. Arsenate sorbed to ferrihydrite, a model soil mineral, was used to simulate possible effects on ingestion of soil contaminated with As-(V) sorbed to Fe oxide surfaces. Arsenate sorbed to ferrihydrite was placed in a simulated gastrointestinal tract (in vitro) to ascertain the bioaccessibility of As(V) and changes in As(V) surface speciation caused by the gastrointestinal system. The speciation of As was determined using extended X-ray absorption fine structure (EXAFS) analysis and X-ray absorption near-edge spectroscopy (XANES). The As(V) adsorption maximum was found to be 93 mmol kg(-1). The bioaccessible As(V) ranged from 0 to 5%, and surface speciation was determined to be binuclear bidentate with no changes in speciation observed post in vitro. Arsenate concentration in the intestine was not constant and varied from 0.001 to 0.53 mM for the 177 mmol kg(-1) As(V) treated sample. These results suggest that the bioaccessibility of As(V) is related to the As(V) concentration, the As(V) adsorption maximum, and that multiple measurements of dissolved As(V) in the intestinal phase may be needed to calculate the bioaccessibility of As(V) adsorbed to ferrihydrite.