Interaction between Eu(III) and graphene oxide nanosheets investigated by batch and extended X-ray absorption fine structure spectroscopy and by modeling techniques

The interaction mechanism between Eu(III) and graphene oxide nanosheets (GONS) was investigated by batch and extended X-ray absorption fine structure (EXAFS) spectroscopy and by modeling techniques. The effects of pH, ionic strength, and temperature on Eu(III) adsorption on GONS were evaluated. The results indicated that ionic strength had no effect on Eu(III) adsorption on GONS. The maximum adsorption capacity of Eu(III) on GONS at pH 6.0 and T = 298 K was calculated to be 175.44 mg·g(-1), much higher than any currently reported. The thermodynamic parameters calculated from temperature-dependent adsorption isotherms suggested that Eu(III) adsorption on GONS was an endothermic and spontaneous process. Results of EXAFS spectral analysis indicated that Eu(III) was bound to ～6-7 O atoms at a bond distance of ～2.44 ? in the first coordination shell. The value of Eu-C bond distance confirmed the formation of inner-sphere surface complexes on GONS. Surface complexation modeling gave an excellent fit with the predominant mononuclear monodentate >SOEu(2+) and binuclear bidentate (>SO)(2)Eu(2)(OH)(2)(2+) complexes. This paper highlights the application of GONS as a suitable material for the preconcentration and removal of trivalent lanthanides and actinides from aqueous solutions in environmental pollution management.     

Binding of iron(III) to organic soils: EXAFS spectroscopy and chemical equilibrium modeling

The complexation of iron(III) to soil organic matter is important for the binding of trace metals in natural environments because of competition effects. In this study, we used extended X-ray absorption fine structure (EXAFS) spectroscopy to characterize the binding mode for iron(III) in two soil samples from organic mor layers, one of which was also treated with iron(III). In most cases the EXAFS spectra had three significant contributions, inner-core Fe-O/N interactions at about 2.02(2) A, Fe-C interactions in the second scattering shell at 3.00(4) A, and a mean Fe-Fe distance at 3.37(3) A. One untreated sample showed features typical for iron (hydr)oxides; however, after treatment of iron(III) the EXAFS spectrum was dominated by organically complexed iron. The presence of a Fe-Fe distance in all samples showed that the major part of the organically complexed iron was hydrolyzed, most likely in a mixture of complexes with an inner core of (O5Fe)2O and (O5Fe)3O. These results were used to constrain a model for metal-humic complexation, the Stockholm Humic Model (SHM). The model was able to describe iron(III) binding verywell at low pH considering only one dimeric iron(III)-humic complex. The competition effect on trace metals was also well described.     

Extended X-ray absorption fine structure spectroscopy evidence for the complexation of cadmium by reduced sulfur groups in natural organic matter

It is widely accepted that the bioavailability, toxicity, and mobility of trace metals are highly dependent on complexation reactions with functional groups in natural organic matter (NOM). In this study, the coordination chemistry of Cd in NOM was investigated by extended X-ray absorption fine structure spectroscopy. Soil organic matter (SOM) from different types of organic soils and dissolved organic matter (DOM) from an organic and a mineral soil horizon of a Spodosol and aquatic DOM from Suwannee River were investigated. In SOM samples (1000-25000 microg of Cd g(-1), pH 4.6-6.6), Cd was coordinated by 1.0-2.5 S atoms at a distance of 2.49-2.55 A and by 3.0-4.5 O/N atoms at a distance of 2.22-2.25 A. In DOM samples (1750-4250 microg of Cd g(-1), pH 5.4-6.3), Cd was coordinated by 0.3-1.8 S atoms at a distance of 2.51-2.56 A and 3.6-4.5 O/N atoms at a distance of 2.23-2.26 A. In both SOM and DOM samples a second coordination shell of 1.7-6.0 carbon atoms was found at an average distance of 3.12 A. This is direct evidence for inner-sphere complexation of Cd by functional groups in NOM. Furthermore, ion activity measurements showed that less than 1% of total Cd was in the form of free Cd2+ in our samples. Bond distances and coordination numbers suggest that Cd complexed in SOM and DOM is a mixture of a 4-coordination with S (thiols) and 4- and 6-coordinations with O/N ligands. Given that Cd-S associations on average are stronger than Cd-O/N associations, our results strongly indicate that reduced S ligands are involved in the complexation of Cd by NOM also at native concentrations of metal in oxidized organic-rich soils and in humic streams.     

Intraparticle reduction of arsenite (As(III)) by nanoscale zerovalent iron (nZVI) investigated with In Situ X-ray absorption spectroscopy

While a high efficiency of contaminant removal by nanoscale zerovalent iron (nZVI) has often been reported for several contaminants of great concern, including aqueous arsenic species, the transformations and translocation of contaminants at and within the nanoparticles are not clearly understood. By analysis using in situ time-dependent X-ray absorption spectroscopy (XAS) of the arsenic core level for nZVI in anoxic As(III) solutions, we have observed that As(III) species underwent two stages of transformation upon adsorption at the nZVI surface. The first stage corresponds to breaking of As-O bonds at the particle surface, and the second stage involves further reduction and diffusion of arsenic across the thin oxide layer enclosing the nanoparticles, which results in arsenic forming an intermetallic phase with the Fe(0) core. Extended X-ray absorption fine-structure (EXAFS) data from experiments conducted at different iron/arsenic ratios indicate that the reduced arsenic species tend to be enriched at the surface of the Fe(0) core region and had limited mobility into the interior of the metal core within the experimental time frame (up to 22 h). Therefore, there was an accumulation of partially reduced arsenic at the Fe(0)/oxide interface when a relatively large arsenic content was present in the solid phase. These results illuminate the role of intraparticle diffusion and reduction in affecting the chemical state and spatial distribution of arsenic in nZVI materials.     

Formation and dissolution of single and mixed Zn and Ni precipitates in soil: evidence from column experiments and extended X-ray absorption fine structure spectroscopy

The stability and the formation and dissolution kinetics of mixed trace metal precipitates in soils are currently unknown. The objective of this study was to investigate slow sorption and release processes of Zn and Ni in a loamy soil using a combination of soil column experiments and extended X-ray absorption fine structure (EXAFS) spectroscopy. To investigate slow sorption processes, the soil material was packed into columns and leached with 5400 pore volumes of 10(-2) M CaCl2 solutions containing either ZnCl2 (5.2 x 10(-5) M) or NiCl2 (5.2 x 10(-5) M) or both ZnCl2 and NiCl2 (5.2 x 10(-5) M each). The Zn and Ni concentrations in the column effluents were monitored. The metal breakthrough curves showed that slow sorption processes lead to metal retention, whereby Zn was more strongly retained than Ni. In the experiment with both Zn and Ni present, amounts of Zn and Ni similar to those in the experiments with either Zn or Ni alone were retained. Analysis of soil samples by EXAFS spectroscopy showed that layered double hydroxide (LDH)-type precipitates had formed in all columns and that a mixed ZnNi-LDH had formed in the presence of both Zn and Ni. The dissolution of those precipitates under acidic conditions was assessed by subsequent leaching of the columns with a 10(-2) M CaCl2 solution at pH 3.0 (approximately 3000 pore volumes). When only Zn was present, 95% of the retained Zn was leached at pH 3. In contrast, only 23% of the retained Ni was leached in experiments with Ni alone. When Zn and Ni were present, 90% of the retained Zn and 87% of the retained Ni were released upon acidification. EXAFS analysis revealed that the LDH phases in the Zn experiment and the Zn-Ni experiment had been completely dissolved, while the LDH phase formed in the Ni experiment was still present. The higher resistance of Ni-LDH against dissolution at low pH could also be shown in dissolution studies with synthetic Zn-LDH, Ni-LDH, and ZnNi-LDH. Our results suggest that the individual rates at which Zn and Ni cations enter into the LDH structure determine the composition of the mixed ZnNi-LDH precipitate, and that the LDH composition determines the rate at which the LDH phase dissolves under acidic conditions.     

Sorption mechanisms of zinc to calcium silicate hydrate: X-ray absorption fine structure (XAFS) investigation

In this study, X-ray absorption fine structure (XAFS) spectroscopy has been used to further elucidate the binding mechanisms of Zn(II) to calcium silicate hydrate (C-S-H), the quantitatively most important cement mineral. Such knowledge is essential for the assessment of the longterm behavior of cement-stabilized waste materials. XAFS spectra of the Zn(II) equilibrated with C-S-H(I) for up to 28 days are best modeled by tetrahedral coordination of Zn(II) by four O atoms in the first atomic shell. Beyond the first coordination shell, data analysis of more highly concentrated samples suggests the presence of two distinct Zn distances and possibly the presence of an Si shell. On the basis of the comparison with a set of reference compounds, this coordination environment can be reasonably related to the structure of hemimorphite, a naturally occurring zinc silicate, and/or the presence of gamma-Zn(OH)2. At the lowest Zn uptake, the above fitting approach failed and data could be described best with a Zn-Si and a Zn-Ca shell. Previous work has been able to show that Zn(II) diffuses into the C-S-H(I) particles and does not form discrete precipitates, so the findings appear to confirm the incorporation of Zn(II) in the interlayer of C-S-H(I).     

Direct determination of oxidation state of gold deposits in metal-reducing bacterium Shewanella algae using X-ray absorption near-edge structure spectroscopy (XANES)

X-ray absorption near-edge structure spectroscopy (XANES) was successfully employed to determine the gold valence in the metal-reducing bacterium Shewanella algae after exposure to a 1 mM aqueous HAuCl4 solution for 10-120 min. XANES spectra revealed the oxidation state of gold in the bacterial cells to be Au(0) without any contribution from Au(III), demonstrating that S. algae cells can reduce AuCl4- ions to elemental gold. Transmission electron microscopy (TEM) and energy dispersive X-ray (EDX) analysis confirmed that gold nanoparticles 5-15 nm in size were deposited in the periplasmic space of the bacterial cells; a preferable, cell surface location for the easy recovery of biogenic nanoparticles.     

Speciation of selenium in stream insects using X-ray absorption spectroscopy

Selenium contamination in the environment is a widespread problem affecting insects and other wildlife. Insects occupy a critical middle link and aid in trophic transfer of selenium in many terrestrial and freshwater food chains, but the mechanisms of selenium uptake through the food chain are poorly understood. In particular, biotransformation of selenium by insects into different chemical forms will greatly influence how toxic or benign the selenium is to that organism or to its predators. We have used X-ray absorption spectroscopy (XAS) to identify the chemical form of selenium in insects inhabiting selenium contaminated streams near Hinton, Alberta (Canada). Selenium K near-edge spectra indicate a variability of selenium speciation among the insects that included mayflies (Ephemeroptera), stoneflies (Plecoptera), caddisflies (Trichoptera), and craneflies (Diptera). Higher percentages of inorganic selenium were observed in primary consumers, detritivores, and filter feeders than in predatory insects. Among the organic forms of selenium, organic selenides constituted a major fraction in most organisms. A species modeled as trimethylselenonium was observed during the pupal stage of caddisflies. These results provide insights into how the insects cope with their toxic cargo, including how the selenium is biotransformed into less toxic forms and how it can be eliminated from the insects. More broadly, this study demonstrates the strengths of XAS to probe the effects of heavy elements at trace levels in insects from the field.     

Mercury speciation by X-ray absorption fine structure spectroscopy and sequential chemical extractions: a comparison of speciation methods

Determining the chemical speciation of mercury in contaminated mining and industrial environments is essential for predicting its solubility, transport behavior, and potential bioavailability as well as for designing effective remediation strategies. In this study, two techniques for determining Hg speciation--X-ray absorption fine structure (XAFS) spectroscopy and sequential chemical extractions (SCE)--are independently applied to a set of samples with Hg concentrations ranging from 132 to 7539 mg/kg to determine if the two techniques provide comparable Hg speciation results. Generally, the proportions of insoluble HgS (cinnabar, metacinnabar) and HgSe identified by XAFS correlate well with the proportion of Hg removed in the aqua regia extraction demonstrated to remove HgS and HgSe. Statistically significant (>10%) differences are observed however in samples containing more soluble Hg-containing phases (HgCl2, HgO, Hg3S2O4). Such differences may be related to matrix, particle size, or crystallinity effects, which could affect the apparent solubility of Hg phases present. In more highly concentrated samples, microscopy techniques can help characterize the Hg-bearing species in complex multiphase natural samples.     

Molybdenum speciation in uranium mine tailings using X-ray absorption spectroscopy

Uranium (U) mill tailings in northern Saskatchewan, Canada, contain elevated concentrations of molybdenum (Mo). The potential for long-term (>10,000 years) mobilization of Mo from the tailings management facilities to regional groundwater systems is an environmental concern. To assist in characterizing long-term stability, X-ray absorption spectroscopy was used to define the chemical (redox and molecular) speciation of Mo in tailings samples from the Deilmann Tailings Management Facility (DTMF) at the Key Lake operations of Cameco Corporation. Comparison of Mo K near-edge X-ray absorption spectra of tailings samples and reference compounds of known oxidation states indicates Mo exists mainly as molybdate (+6 oxidation state). Principal component analysis of tailings samples spectra followed by linear combination fitting using spectra of reference compounds indicates that various proportions of NiMoO(4) and CaMoO(4) complexes, as well as molybdate adsorbed onto ferrihydrite, are the Mo species present in the U mine tailings. Tailings samples with low Fe/Mo (<708) and high Ni/Mo (>113) molar ratios are dominated by NiMoO(4), whereas those with high Fe/Mo (>708) and low Ni/Mo (<113) molar ratios are dominated by molybdate adsorbed onto ferrihydrite. This suggests that the speciation of Mo in the tailings is dependent in part on the chemistry of the original ore.     

Sulfur in wheat gluten: In situ analysis by X-ray absorption near edge structure (XANES) spectroscopy

The sulfur containing gluten proteins largely determine the baking quality of wheat. In order to probe the speciation of sulfur, gluten proteins [gliadin, high molecular weight (HMW) and low molecular weight (LMW) subunits of glutenin], stored glutenin subunits as well as flour were investigated in situ by S K-edge X-ray near edge absorption structure (XANES) spectroscopy. The spectra confirmed the existence of disulfide bonds in oxidised (oxygen stream) glutenin subunits, supporting their significance for the formation of gluten networks. Additionally, glutenin subunits, which were stored under ambient air and temperature conditions, predominantly contained sulfur of higher oxidation states (sulfoxide, sulfonic acid). The disulfide state and also sulfoxide and sulfonic acid states were detected after reoxidation of glutenin subunits with potassium bromate.     

Structural characterization of U(VI) in apatite by X-ray absorption spectroscopy

X-ray absorption spectroscopy was used to determine the local structure of U(VI) within synthetic fluorapatite at a concentration of 2.3 wt %. Extended X-ray absorption fine structure indicates that U(VI) substitutes into the Ca1 site. To accommodate this substitution the apatite structure significantly distorts such that the Ca1 site approximates octahedral coordination, with six uniform U-0 distances of 2.06A. An X-ray adsorption edge structure, with two inflection points, and optical emission spectra are consistent with 6d orbital crystal field splitting. These results indicate that significant amounts of U(VI) can be accommodated in the apatite structure but with an unexpected coordination, which may bear on the ultimate development of apatite-hosted nuclear-waste forms.     

Examination of arsenic speciation in sulfidic solutions using X-ray absorption spectroscopy

Both thioarsenites and thioarsenates have been demonstrated to exist in sulfidic waters, yet there is uncertainty regarding the geochemical conditions that govern the formation of these arsenic species. The purpose of this research was to use advanced spectroscopy techniques, speciation modeling, and chromatography to elucidate the chemical speciation of arsenic in sulfidic solutions initially containing arsenite and sulfide. Results of X-ray absorption spectroscopy (XAS) show that experimental solutions contained mixtures of arsenite and thioarsenites with increasing substitution of sulfur for oxygen on arsenic as the sulfide concentration increased. Experimental samples showed no evidence of polymeric arsenic species, or transformation of thioarsenites to thioarsenates. The arsenic speciation measured using XAS was similar to predictions obtained from a thermodynamic model for arsenic speciation, excluding thioarsenate species in sulfidic systems. Our data cast some doubt on the application of chromatographic methods for determining thioarsenates and thioarsenites (or mixtures) in natural waters in cases where the arsenic oxidation state cannot be independently verified. The same chromatographic peak positions proposed for thioarsenates can be explained bythioarsenite species. Furthermore, sample dilution was shown to change the species distribution and care should be taken to avoid sample dilution prior to chromatographic analysis.     

Speciation of Zn associated with diatoms using X-ray absorption spectroscopy

The long- and short-term interactions between zinc, an essential but also toxic element, and freshwater and marine diatoms are not well understood partly because of a lack of information on Zn speciation on the surface and inside the cells. In this work, interactions of aqueous Zn2+ with marine (Skeletonema costatum) and freshwater (Achnanthidium minutissimum, Navicula minima, and Melosira varians) diatoms were studied using conventional macroscopic techniques, while the local atomic structure of metal ions adsorbed on their surface or incorporated into the cells was characterized by in-situ Zn K-edge X-ray absorption fine structure (XAFS) spectroscopy on both intact and liophylized samples. At the cell surface for all diatom species studied, Zn was tetrahedrally coordinated with oxygen at approximately 2.00 +/- 0.02 A and monodentately bonded to one or two carboxylate groups; these results are consistent with the surface speciation model developed from macroscopic adsorption experiments. The atomic environment of Zn incorporated into freshwater diatoms during long-term growth in normal nutrient media was distinctly differentfrom that of adsorbed Zn: it was dominated by O (and/or N) neighbors in a tetrahedral arrangement at 1.97 +/- 0.02 A in the first atomic shell, with the presence of 1 phosphorus and 2 carbons in the Zn second shell. Contrasting speciation of intracellular zinc was revealed for the marine species Skeletonema costatum in which Zn was coordinated to 2 O/N atoms and 2 sulfur groups in the form of cysteine-histidine complexes and/or zinc thiolate clusters. These new structural data strongly suggest: (i) the predominant > R-COO- ligand binding of Zn atthe diatom surface; (ii) the nonspecific storage of Zn in the form of carboxylate/phosphate groups inside the cell of freshwater species; and (iii) the highly specific thiol-ligand coordination of intracellular zinc for marine S. costatum species.     

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.     

An X-ray absorption spectroscopy study of neptunium(V) reactions with Mackinawite (FeS)

Neptunium is a transuranium element, produced in tonne quantities in nuclear reactors. Because it has access to a range of oxidation states, neptunium may undergo redox transformations in the environment and these can have far-reaching effects on its environmental mobility. Here, the reaction of NpO2+ (the soluble and thermodynamically stable neptunium species in oxic systems) with microcrystalline mackinawite is studied. Uptake of neptunium from solution is relatively low (approximately 10% of the total initially present in solution) and independent of initial solution concentration over the range 0.27-2.74 mM and of equilibration time. X-ray absorption spectroscopy (XAS) of the solid sulfide samples indicates nearest neighbor oxygen atoms at distances around 2.25-2.26 A, sulfur atoms at around 2.61-2.64 A, and two more distant shells fitted with iron, at 3.91-3.95 A and 4.15-4.16 A. These observations suggest that on interaction with the sulfide surface reduction of Np(V) to Np(IV) occurs, accompanied by loss of axial oxygen atoms. Neptunium coordinates directly to surface sulfide atoms, in contrast to the behavior previously observed for uranium under similar conditions. These results demonstrate the importance and variability of the speciation of redox sensitive actinides under anoxic conditions.     

Strategies for detecting organic liquids on soils using mid-infrared reflection spectroscopy

Stand-off monitoring for chemical spills can provide timely information for cleanup efforts, and mid-infrared reflection spectroscopy is one approach being investigated for spill detection. Using laboratory data, anomaly and target detection strategies were examined for the detection of four different low-volatility organic liquids on two different soil types. Several preprocessing and signal-weighting strategies were studied. Anomaly detection for C-H bands was good using second-derivative preprocessing and provided similar performance to that of target detection approaches such as generalized least-squares and partial least-squares, with detections at soil loads of approximately 3-6 microg/cm2 a real dosage. Good performance was also found for the detection of P=O, O-H, and C=O stretching vibrational modes, but the optimal strategy varied. The simplicity and generality of anomaly detection is attractive; however, target detection provides more capability for classification.     

Real-time X-ray absorption spectroscopy of uranium, iron, and manganese in contaminated sediments during bioreduction

The oxidation status of uranium in sediments is important because the solubility of this toxic and radioactive element is much greater for U(VI) than for U(IV) species. Thus, redox manipulation to promote precipitation of UO2 is receiving interest as a method to remediate U-contaminated sediments. Presence of Fe and Mn oxides in sediments at much higher concentrations than U requires an understanding of their redox status as well. This study was conducted to determine changes in oxidation states of U, Fe, and Mn in U-contaminated sediments from Oak Ridge National Laboratory. Oxidation states of these elements were measured in real-time and nondestructively using X-ray absorption spectroscopy on sediment columns supplied with synthetic groundwater containing organic carbon (OC, 0, 3, 10, 30, and 100 mM OC as lactate) for over 400 days. In sediments supplied with OC > or = 30 mM, 80% of the U was reduced to U(IV), with transient reoxidation at about 150 days. Mn(III,IV) oxides were completely reduced to Mn(II) in sediments infused with OC > or = 3 mM. However, Fe remained largely unreduced in all sediment columns, showing that Fe(III) can persist as an electron acceptor in reducing sediments over long times. This result in combination with the complete reduction of all other potential electron acceptors supports the hypothesis that the reactive Fe(III) fraction was responsible for reoxidizing U(IV).     

Speciation and characterization of arsenic in Ketza River mine tailings using X-ray absorption spectroscopy

Ketza River mine tailings deposited underwater and those exposed near the tailings impoundment contain approximately 4 wt % As. Column-leaching tests indicated the potential for high As releases from the tailings. The tailings are composed dominantly of iron oxyhydroxides, quartz, calcite, dolomite, muscovite, ferric arsenates, and calcium-iron arsenates. Arsenopyrite and pyrite are trace constituents. Chemical compositions of iron oxyhydroxide and arsenate minerals are highly variable. The XANES spectra indicate that arsenic occurs as As(V) in tailings, but air-drying prior to analysis may have oxidized lower-valent As. The EXAFS spectra indicate As-Fe distances of 3.35-3.36 A for the exposed tailings and 3.33-3.35 A for the saturated tailings with coordination numbers of 0.96-1.11 and 0.46-0.64, respectively. The As-Ca interatomic distances ranging from 4.15 to 4.18 A and the coordination numbers of 4.12-4.58 confirm the presence of calcium-iron arsenates in the tailings. These results suggest that ferric arsenates and inner-sphere corner sharing or bidentate-binuclear attachment of arsenate tetrahedra onto iron hydroxide octahedra are the dominant form of As in the tailings. EXAFS spectra indicate that the exposed tailings are richer in arsenate minerals whereas the saturated tailings are dominated by the iron oxyhydroxides, which could help explain the greater release of As from the exposed tailings during leaching tests. It is postulated that the dissolution of ferric arsenates during flow-through experiments caused the high As releases from both types of tailings. Arsenic tied to iron oxyhydroxides as adsorbed species are considered stable; however, iron oxyhydroxides having low Fe/As molar ratios may not be as stable. Continued As releases from the tailings are likely due to dissolution of both ferric and calcium-iron arsenates and desorption of As from high-As bearing iron oxyhydroxides during aging.