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1.
Organic ligands are known to interfere with the polymerization of Fe(III), but the extent of interference has not been systematically studied as a function of structural ligand properties. This study examines how the number and position of phenol groups in hydroxybenzoic acids affect both ferrihydrite formation and its local (<5 Å) Fe coordination. To this end, acid Fe(III) nitrate solutions were neutralized up to pH 6.0 in the presence of 4-hydroxybenzoic acid (4HB), 2,4-dihydroxybenzoic acid (2,4DHB), and the hydroquinone 3,4-dihydroxybenzoic acid (3,4DHB). The initial molar ligand/Fe ratios ranged from 0 to 0.6. The precipitates were dialyzed, lyophilized, and subsequently studied by X-ray absorption spectroscopy and synchrotron X-ray diffraction. The solids contained up to 32 wt.% organic C (4HB ∼ 2,4DHB < 3,4DHB). Only precipitates formed in 3,4DHB solutions comprised considerable amounts of Fe(II) (Fe(II)/Fetot ≤ 6 mol%), implying the abiotic mineralization of the catechol-group bearing ligand during Fe(III) hydrolysis under oxic conditions. Hydroxybenzoic acids decreased ferrihydrite formation in the order 4HB ∼ 2,4DHB ? 3,4DHB, which documents that phenol group position rather than the number of phenol groups controls the ligand’s interaction with Fe(III). The coordination numbers of edge- and double corner-sharing Fe in the precipitates decreased by up to 100%. Linear combination fitting (LCF) of Fe K-edge X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) spectra revealed that this decrease was due to increasing amounts of organic Fe(III) complexes in the precipitates. Although EXAFS derived coordination numbers of Fe in ferrihydrite remained constant within error, all organic ligands decreased the coherently scattering domain (CSD) size of ferrihydrite as indicated by synchrotron X-ray diffraction analysis (4HB < 2,4DHB ? 3,4DHB). With decreasing particle size of ferrihydrite its Fe(O,OH)6 octahedra became progressively distorted as evidenced by an increasing loss of centrosymmetry of the Fe sites. Pre-edge peak analysis of the Fe K-edge XANES spectra in conjunction with LCF results implied that ferrihydrite contains on an average 13 ± 3% tetrahedral Fe(III), which is in very good agreement with the revised single-phase structural model of ferrihydrite (Michel, F. M., Barron, V., Torrent, J., Morales, M. P. et al. (2010) Ordered ferrimagnetic form of ferrihydrite reveals links among structure, composition, and magnetism. Proc. Natl. Acad. Sci. USA107, 2787-2792). The results suggest that hydroxybenzoic acid moieties of natural organic matter (NOM) effectively suppress ferrihydrite precipitation as they kinetically control the availability of inorganic Fe(III) species for nucleation and/or polymerization reactions. As a consequence, NOM can trigger the formation of small ferrihydrite nanoparticles with increased structural strain. These factors may eventually enhance the biogeochemical reactivity of ferrihydrite formed in NOM-rich environments. This study highlights the role of hydroquinone structures of NOM for Fe complexation, polymerization, and redox speciation.  相似文献   

2.
In oxic environments contaminated with arsenate (As(V)), small polyhydroxycarboxylates such as citrate may impact the structure of precipitating ferrihydrite (Fh) and thus the surface speciation of As(V). In this study, ‘2-line’ Fh was precipitated from ferric nitrate solutions that were neutralized to pH 6.5 in the presence of increasing citrate concentrations and in the absence or presence of As(V). The initial citrate/Fe and As/Fe ratios were 0-50 mol% and 5 mol%, respectively. The reaction products, enriched with up to 0.32 mol citrate per mole Fe, were characterized by X-ray diffraction, transmission electron microscopy, and Fe and As K-edge X-ray absorption spectroscopy. Citrate decreased the particle size of Fh by impairing the polymerization of Fe(O,OH)6 octahedra via edge and corner linkages. In the presence of citrate and As(V), coordination numbers of Fe decreased by up to 28% relative to pure Fh. Citrate significantly reduced the static disorder of Fe-O bonds, implying a decreased octahedral distortion in Fh. Mean bond distances in Fh were not affected by citrate and remained constant within error at 1.98 Å for Fe-O, 3.03 Å for Fe-Fe1, and 3.45 Å for Fe-Fe2. Likewise, citrate had no effect on the As-Fe (3.31 Å) bond distance in As(V) coprecipitated with Fh. The As K-edge EXAFS data comply with the formation of (i) only monodentate binuclear (2C) As(V) surface complexes and (ii) combinations of 2C, monodentate mononuclear (1V), and outersphere As(V) surface complexes. Our results suggest that increasing citrate concentrations led to a decreasing 1V/2C ratio and/or that citrate increasingly impaired the formation of outersphere As(V) complexes. Moreover, citrate stabilized colloidal suspensions of Fh (pH 4.3-6.6, I ∼0.45 M) and reduced Fh formation at the expense of soluble Fe(III)-citrate complexes. At initial citrate/Fe ratios ?25 mol%, between 8% and 41% of total Fe was bound in Fe(III)-citrate complexes after Fh formation. Polynuclear Fe(III)-citrate species were found to bind As(V) via surface complexes indistinguishable by EXAFS from those of As(V) adsorbed to or coprecipitated with Fh. Our study implies that low molecular weight polyhydroxycarboxylates may enhance the mobility of As(V) in aqueous systems of high ionic strength (e.g., neutralizing acid mine drainage) by colloidal stabilization of suspended Fh particles and the formation of ternary As(V) complexes.  相似文献   

3.
The Sb speciation in soil samples from Swiss shooting ranges was determined using Sb K-edge X-ray absorption spectroscopy (XAS) and advanced statistical data analysis methods (iterative transformation factor analysis, ITFA). The XAS analysis was supported by a spectral data set of 13 Sb minerals and 4 sorption complexes. In spite of a high variability in geology, soil pH (3.1-7.5), Sb concentrations (1000-17,000 mg/kg) and shooting-range history, only two Sb species were identified. In the first species, Sb is surrounded solely by other Sb atoms at radial distances of 2.90, 3.35, 4.30 and 4.51 Å, indicative of metallic Sb(0). While part of this Sb(0) may be hosted by unweathered bullet fragments consisting of PbSb alloy, Pb LIII-edge XAS of the soil with the highest fraction (0.75) of Sb(0) showed no metallic Pb, but only Pb2+ bound to soil organic matter. This suggests a preferential oxidation of Pb in the alloy, driven by the higher standard reduction potential of Sb. In the second species, Sb is coordinated to 6 O-atoms at a distance of 1.98 Å, indicative of Sb(V). This oxidation state is further supported by an edge energy of 30,496-30,497 eV for the soil samples with <10% Sb(0). Iron atoms at radial distances of 3.10 and 3.56 Å from Sb atoms are in line with edge-sharing and bidentate corner-sharing linkages between Sb(O,OH)6 and Fe(O,OH)6 octahedra. While similar structural units exist in tripuhyite, the absence of Sb neighbors contradicts formation of this Fe antimonate. Hence the second species most likely consists of inner-sphere sorption complexes on Fe oxides, with edge and corner-sharing configuration occurring simultaneously. This pentavalent Sb species was present in all samples, suggesting that it is the prevailing species after weathering of metallic Sb(0) in oxic soils. No indication of Sb(III) was found.  相似文献   

4.
A mixing of metal-loaded acid mine drainage with shallow groundwater or surface waters usually initiates oxidation and/or hydrolysis of dissolved metals such as iron (Fe) and aluminum (Al). Colloidal particles may appear and agglomerate with increasing pH. Likewise chemical conditions may occur while flooding abandoned uranium mines. Here, the risk assessment of hazards requires reliable knowledge on the mobility of uranium (U). A flooding process was simulated at mesocosm scale by mixing U-contaminated acid mine water with near-neutral groundwater under oxic conditions. The mechanism of U-uptake by fresh precipitates and the molecular structure of U bonding were determined to estimate the mobility of U(VI). Analytical and spectroscopic methods such as Extended X-ray Absorption Fine-Structure (EXAFS) spectroscopy at the Fe K-edge and the U LIII-edge, and Attenuated Total Reflectance Fourier Transform Infrared (ATR-FTIR) spectroscopy were employed. The freshly formed precipitate was identified as colloidal two-line ferrihydrite. It removed U(VI) from solution by sorption processes, while surface precipitation or structural incorporation of U was not observed. EXAFS data suggest a mononuclear inner-sphere, edge-sharing complex of U(VI) with ferrihydrite in the absence of dissolved carbonate. By employing a novel EXAFS analysis method, Monte Carlo Target Transformation Factor Analysis, we could for the first time ascertain a 3-D configuration of this sorption complex without the necessity to invoke formation of a ternary complex. The configuration suggests a slightly tilted position of the adsorbed unit relative to the edge-sharing Fe(O, OH)6 octahedra. In the presence of dissolved carbonate and at pH ∼8.0, a distal carbonate O-atom at ∼4.3 Å supports formation of ternary U(VI)-carbonato surface complexes. The occurrence of these complexes was also confirmed by ATR-FTIR. However, in slightly acidic conditions (pH 5-6) in equilibrium with atmospheric CO2, the U(VI) sorption on ferrihydrite was dominated by the binary complex species Fe(O)2UO2, whereas ternary U(VI)-carbonato surface complexes were of minor relevance. While sulfate and silicate were also present in the mine water, they had no detectable influence on U(VI) surface complexation. Our experiments demonstrate that U(VI) forms stable inner-sphere sorption complexes even in the presence of carbonate and at slightly alkaline pH, conditions which previously have been assumed to greatly accelerate the mobility of U(VI) in aqueous environments. Depending on the concentrations of U(VI) and carbonate, the type of surface complexes may change from binary uranyl-ferrihydrite to ternary carbonato-uranyl-ferrihydrite complexes. These different binding mechanisms are likely to influence the binding stability and retention of U(VI) at the macroscopic level.  相似文献   

5.
The mineralogy of natural ferromanganese coatings on quartz grains and the crystal chemistry of associated trace elements Ni, Zn, Ba, and As were characterized by X-ray microfluorescence, X-ray diffraction, and EXAFS spectroscopy. Fe is speciated as ferrihydrite and Mn as vernadite. The two oxides form alternating Fe- and Mn-rich layers that are irregularly distributed and not always continuous. Unlike naturally abundant Fe-vernadite, in which Fe and Mn are mixed at the nanoscale, the ferrihydrite and vernadite are physically segregated and the trace elements clearly partitioned at the microscopic scale. Vernadite consists of two populations of interstratified one-water layer (7 Å phyllomanganate) and two-water layer (10 Å phyllomanganate) crystallites. In one population, 7 Å layers dominate, and in the other 10 Å layers dominate. The three trace metals Ni, Zn, and Ba are associated with vernadite and the metalloid As with ferrihydrite. In vernadite, nickel is both substituted isomorphically for Mn in the manganese layer and sorbed at vacant Mn layer sites in the interlayer. The partitioning of Ni is pH-dependent, with a strong preference for the first site at circumneutral pH and for the second at acidic pH. Thus, the site occupancy of Ni in vernadite may be an indicator of marine vs. continental origin, and in the latter, of the acidity of streams, lakes, or soil pore waters in which the vernadite formed. Zinc is sorbed only in the interlayer at vacant Mn layer sites. It is fully tetrahedral at a Zn/Mn molar ratio of 0.0138, and partly octahedral at a Zn/Mn ratio of 0.1036 consistent with experimental studies showing that the VIZn/IVZn ratio increases with Zn loading. Barium is sorbed in a slightly offset position above empty tetrahedral cavities in the interlayer. Arsenic tetrahedra are retained at the ferrihydrite surface by a bidentate-binuclear attachment to two adjacent iron octahedra, as commonly observed. Trace elements in ferromanganese precipitates are partitioned at a few, well-defined, crystallographic sites that have some elemental specificity, and thus selectivity. The relative diversity of sorption sites contrasts with the simplicity of the layer structure of vernadite, in which charge deficit arises only from Mn4+ vacancies (i.e., no Mn3+ for Mn4+ substitution). Therefore, sorption mechanisms primarily depend on physical and chemical properties of the sorbate and competition with other ions in solution, such as protons at low pH for Ni sorption.  相似文献   

6.
X-ray absorption near-edge spectroscopy (XANES) analysis of sorption complexes has the advantages of high sensitivity (10- to 20-fold greater than extended X-ray absorption fine structure [EXAFS] analysis) and relative ease and speed of data collection (because of the short k-space range). It is thus a potentially powerful tool for characterization of environmentally significant surface complexes and precipitates at very low surface coverages. However, quantitative analysis has been limited largely to “fingerprint” comparison with model spectra because of the difficulty of obtaining accurate multiple-scattering amplitudes for small clusters with high confidence.In the present work, calculations of the XANES for 50- to 200-atom clusters of structure from Zn model compounds using the full multiple-scattering code Feff 8.0 accurately replicate experimental spectra and display features characteristic of specific first-neighbor anion coordination geometry and second-neighbor cation geometry and number. Analogous calculations of the XANES for small molecular clusters indicative of precipitation and sorption geometries for aqueous Zn on ferrihydrite, and suggested by EXAFS analysis, are in good agreement with observed spectral trends with sample composition, with Zn-oxygen coordination and with changes in second-neighbor cation coordination as a function of sorption coverage. Empirical analysis of experimental XANES features further verifies the validity of the calculations. The findings agree well with a complete EXAFS analysis previously reported for the same sample set, namely, that octahedrally coordinated aqueous Zn2+ species sorb as a tetrahedral complex on ferrihydrite with varying local geometry depending on sorption density. At significantly higher densities but below those at which Zn hydroxide is expected to precipitate, a mainly octahedral coordinated Zn2+ precipitate is observed. An analysis of the multiple scattering paths contributing to the XANES demonstrates the importance of scattering paths involving the anion sublattice. We also describe the specific advantages of complementary quantitative XANES and EXAFS analysis and estimate limits on the extent of structural information obtainable from XANES analysis.  相似文献   

7.
Arsenic(V), as the arsenate (AsO4 3?) ion and its conjugate acids, has a strong affinity on Fe, Mn, and Al (oxyhydr)oxides and clay minerals. Removal of arsenate from aqueous solution by poorly crystalline ferrihydrite (hydrous ferric oxide) via a combination of macroscopic (equilibria and kinetics of sorption) and X-ray absorption spectroscopic studies was investigated. The removal of arsenate significantly decreased with increasing pH and sorption maxima of approximately 1.994 mmol/g (0.192 molAs/molFe) were achieved at pH 2.0. The Langmuir isotherm is most appropriate for arsenate sorption over the wide range of pH, indicating that arsenate sorption preferentially takes place at relatively homogenous and monolayer sites rather than heterogeneous and multilayer surfaces. The kinetic study demonstrated that arsenate sorption onto 2-line ferrihydrite is considerably fast, and sorption equilibrium was achieved within the reaction time of 2 h. X-ray absorption near-edge structure spectroscopy indicates no change in oxidation state of arsenate following interaction with the ferrihydrite surfaces. Extended X-ray absorption fine structure spectroscopy supports the efficient removal of arsenate by the 2-line ferrihydrite through the formation of highly stable inner-sphere surface complexes, such as bidentate binuclear corner-sharing (2C) and bidentate mononuclear edge-sharing (2E) complexes.  相似文献   

8.
The surface reactivity of biogenic, nanoparticulate UO2 with respect to sorption of aqueous Zn(II) and particle annealing is different from that of bulk uraninite because of the presence of surface-associated organic matter on the biogenic UO2. Synthesis of biogenic UO2 was accomplished by reduction of aqueous uranyl ions, by Shewanella putrefaciens CN32, and the resulting nanoparticles were washed using one of two protocols: (1) to remove surface-associated organic matter and soluble uranyl species (NAUO2), or (2) to remove only soluble uranyl species (BIUO2). A suite of bulk and surface characterization techniques was used to examine bulk and biogenic, nanoparticulate UO2 as a function of particle size and surface-associated organic matter. The N2-BET surface areas of the two biogenic UO2 samples following the washing procedures are 128.63 m2 g−1 (NAUO2) and 92.56 m2 g−1 (BIUO2), and the average particle sizes range from 5-10 nm based on TEM imaging. Electrophoretic mobility measurements indicate that the surface charge behavior of biogenic, nanoparticulate UO2 (both NAUO2 and BIUO2) over the pH range 3-9 is the same as that of bulk. The U LIII-edge EXAFS spectra for biogenic UO2 (both NAUO2 and BIUO2) were best fit with half the number of second-shell uranium neighbors compared to bulk uraninite, and no oxygen neighbors were detected beyond the first shell around U(IV) in the biogenic UO2. At pH 7, sorption of Zn(II) onto both bulk uraninite and biogenic, nanoparticulate UO2 is independent of electrolyte concentration, suggesting that Zn(II) sorption complexes are dominantly inner-sphere. The maximum surface area-normalized Zn(II) sorption loadings for the three substrates were 3.00 ± 0.20 μmol m−2 UO2 (bulk uraninite), 2.34 ± 0.12 μmol m−2 UO2 (NAUO2), and 2.57 ± 0.10 μmol m−2 UO2 (BIUO2). Fits of Zn K-edge EXAFS spectra for biogenic, nanoparticulate UO2 indicate that Zn(II) sorption is dependent on the washing protocol. Zn-U pair correlations were observed at 2.8 ± 0.1 Å for NAUO2 and bulk uraninite; however, they were not observed for sample BIUO2. The derived Zn-U distance, coupled with an average Zn-O distance of 2.09 ± 0.02 Å, indicates that Zn(O,OH)6 sorbs as bidentate, edge-sharing complexes to UO8 polyhedra at the surface of NAUO2 nanoparticles and bulk uraninite, which is consistent with a Pauling bond-valence analysis. The absence of Zn-U pair correlations in sample BIUO2 suggests that Zn(II) binds preferentially to the organic matter coating rather than the UO2 surface. Surface-associated organic matter on the biogenic UO2 particles also inhibited particle annealing at 90 °C under anaerobic conditions. These results suggest that surface-associated organic matter decreases the reactivity of biogenic, nanoparticulate UO2 surfaces relative to aqueous Zn(II) and possibly other environmental contaminants.  相似文献   

9.
Pb(II) sorption experiments with calcite powders were conducted in suspensions equilibrated at atmospheric PCO2(g) and ambient temperature at pH 7.3, 8.2 and 9.4. Pb fractional sorption was low at pH 7.3 and 9.4 relative to pH 8.2, and correlated well with PbCO30(aq) speciation. Desorption experiments conducted for initial sorption times ranging from 0.5 h to 12 d reveal an almost completely reversible process at pH 8.2, attributed to the dominance of an adsorption mechanism, with slight and pronounced irreversibility at pH 7.3 and 9.4 respectively. Similarities in X-ray absorption near edge spectra (XANES) for 24 h and 12 d pH 7.3 and 9.4 sorption samples indicate no effect of initial sorption time. Results from linear combination (LC) fits of XANES spectra for samples sorbed at pH 9.4 confirm ∼75% adsorbed and ∼25% coprecipitated components. The coprecipitated fraction was attributed to the non-exchangeable metal observed in desorption experiments. At pH 7.3, ∼95% adsorbed and ∼5% coprecipitated components were obtained. A comparison of results from desorption experiments and LC-XANES alludes to an irreversibly bound adsorbed component for the pH 9.4 12 d sorption sample. Extended X-ray absorption fine structure spectroscopy (EXAFS) analysis of pH 7.3 and 9.4 12 d sorption samples confirms the presence of both adsorbed and coprecipitated metal. At pH 7.3 a first-shell Pb-O bond length of 2.38 Å is intermediate between that of adsorbed (2.34 Å) and coprecipitated (2.51 Å) Pb. At pH 9.4, two first-shell Pb-O distances at 2.35 Å and 2.51 Å were obtained, indicative of the occurrence of both adsorption and coprecipitation and a larger coprecipitated fraction relative to that at pH 7.3, consistent with LC-XANES results. We propose that the disparity in the fraction of coprecipitated metal with pH may be linked to the ability of sorbed Pb to inhibit near-surface dynamic exchange of Ca and CO3 species, which dictates step advance and retreat. Less effective inhibition of step motion at pH 9.4, due to lower fractional sorption, combined with highest rates of dynamic exchange results in a significant fraction of coprecipitated Pb at this pH. At low pH, though fractional sorption is also low, lower rates of exchange prohibit significant coprecipitation. At pH 8.2, effective inhibition of surface processes due to higher fractional sorption and lower rates of exchange compared to pH 7.3 and 9.4 preclude detectable coprecipitation. Other factors such as changes in surface speciation and solubility of the Pb-Ca solid solution with pH may also come into play. Overall, this study presents evidence for the influence of pH on Pb sorption mechanisms, and addresses the efficiency of Pb immobilization in calcitic systems.  相似文献   

10.
We investigated the structure of uranyl sorption complexes on gibbsite (pH 5.6-9.7) by two independent methods, density functional theory (DFT) calculations and extended X-ray absorption fine structure (EXAFS) spectroscopy at the U-LIII edge. To model the gibbsite surface with DFT, we tested two Al (hydr)oxide clusters, a dimer and a hexamer. Based on polarization, structure, and relaxation energies during geometry optimization, the hexamer cluster was found to be the more appropriate model. An additional advantage of the hexamer model is that it represents both edges and basal faces of gibbsite. The DFT calculations of (monomeric) uranyl sorption complexes show an energetic preference for the corner-sharing versus the edge-sharing configuration on gibbsite edges. The energy difference is so small, however, that possibly both surface species may coexist. In contrast to the edge sites, sorption to basal sites was energetically not favorable. EXAFS spectroscopy revealed in all investigated samples the same interatomic distances of the uranyl coordination environment (RU-Oax ≈ 1.80 Å, RU-Oeq ≈ 2.40 Å), and towards the gibbsite surface (RU-O ≈ 2.87 Å, RU-Al ≈ 3.38 Å). In addition, two U-U distances were observed, 3.92 Å at pH 9.7 and 4.30 Å at pH 5.6, both with coordination numbers of ∼1. The short U-U distance is close to that of the aqueous uranyl hydroxo dimer, UO2(OH)2, reported as 3.875 Å in the literature, but significantly longer than that of aqueous trimers (3.81-3.82 Å), suggesting sorption of uranyl dimers at alkaline pH. The longer U-U distance (4.30 Å) at acidic pH, however, is not in line with known aqueous uranyl polymer complexes. Based on the EXAFS findings we further refined dimeric surface complexes with DFT. We propose two structural models: in the acidic region, the observed long U-U distance can be explained with a distortion of the uranyl dimer to form both a corner-sharing and an edge-sharing linkage to neighboring Al octahedra, leading to RU-U = 4.150 Å. In the alkaline region, a corner-sharing uranyl dimer complex is the most favorable. The U-O path at ∼2.87 Å in the EXAFS spectra arises from the oxygen atom linking two Al cations in corner-sharing arrangement. The adsorption structures obtained by DFT calculations are in good agreement with the structural parameters from EXAFS analysis: U-Al (3.394 Å), U-U (3.949 Å), and U-O (2.823 Å) for the alkaline pH model, and U-Al (3.279 Å), U-U (4.150 Å), and U-O (2.743 Å) for the acidic pH model. This work shows that by combining EXAFS and DFT, consistent structural models for uranyl sorption complexes can be obtained, which are relevant to predict the migration behavior of uranium at nuclear facilities.  相似文献   

11.
《Applied Geochemistry》2002,17(5):569-581
This study examined the sorption of trace metals to precipitates formed by neutralization of 3 natural waters contaminated with acid mine drainage (AMD) in the former Ducktown Mining District, Tennessee. The 3 water samples were strongly acidic (pH 2.2 to 3.4) but had distinctively different chemical signatures based on the mole fractions of dissolved Fe, Al and Mn. One sample was Fe-rich (Fe=87.5%, Al=11.3%, and Mn=1.3%), another was Al-rich (Al=79.4%, Mn=18.0%, and Fe=2.5%), and the other was Mn-rich (Mn=51.4%, Al=25.7%, and Fe=22.9%). In addition, these waters had high concentrations of trace metals including Zn (37,700 to 17,400 μg/l), Cu (13,000 to 270 μg/l), Co (1,500 to 520 μg/l), Ni (360 to 75 μg/l), Pb (30 to 8 μg/l), and Cd (30 to 6 μg/l). Neutralization of the AMD-contaminated waters in the laboratory caused the formation of either schwertmannite at pH<4 or ferrihydrite at pH>4. Both phases were identified by XRD analyses of precipitates from the most Fe-rich water. At higher pH values (∼5) Al-rich precipitates were formed. Manganese compounds were precipitated at pH∼8. The removal of trace metals depended on the precipitation of these compounds, which acted as sorbents. Accordingly, the pH for 50% sorption (pH50) ranged from 5.6 to 7.5 for Zn, 4.6 to 6.1 for Cu, 5.4 to 7.7 for Ni, 5.9 to 7.9 for Co, 3.1 to 4.3 for Pb, and 5.5 to 7.7 for Cd. The pH dependence of sorption arose not only because of changes in the sorption coefficients of the trace metals but also because the formation and composition of the sorbent was controlled by the pH, the chemical composition of the water, and the solubilities of the oxyhydroxide-sulfate complexes of Fe, Al, and Mn.  相似文献   

12.
Zinc uptake in suspensions (?3.7 g L−1) of MX80 montmorillonite was investigated at pH 4.0 and 7.3, a total Zn concentration ([Zn]total) of 500 μM, and dissolved Si concentrations ([Si]aq) of ∼70 and ∼500 μM in 0.5 M NaCl, by kinetics experiments and polarized extended X-ray absorption fine structure (P-EXAFS) spectroscopy. Differential thermogravimetric analysis verified the cis-vacant character of the montmorillonite. No Zn uptake occurred at pH 4.0, confirming that cation exchange was hampered by the high ionic strength of the suspension. At pH 7.3 and low [Si]aq (∼70 μM), Zn uptake occurred rapidly during the first hour of reaction, and then leveled off to 50 μmol/g montmorillonite at 168 h. The uptake rate is consistent with Zn sorption on pH-dependent edge sites. At pH 7.3 and high [Si]aq (∼500 μM), the initial sorption rate was similar, but Zn sorption continued, reaching 130 μmol/g at 168 h, and was paralleled by Si uptake with a Si/Zn uptake ratio of 1.51(10), suggesting formation of a Zn (hydrous) silicate. P-EXAFS data indicated that the first oxygen coordination shell of sorbed Zn is split into two subshells at 1.97(2) and 2.08(3)-2.12(2) Å for all EXAFS samples. These two distances are assigned to a mixture of tetrahedral (IVZn) and octahedral (VIZn) Zn complexes. The proportion of IVZn was lower in the high [Si]aq samples and decreased with reaction time. Al low [Si]aq and 216 h of reaction, nearest cationic shells of 0.6(4) Al in the film plane and 0.5(4) Si out of the film plane were detected at 3.00(2) and 3.21(2) Å, respectively, and were interpreted as the formation of IVZn and VIZn mononuclear complexes at the edges of montmorillonite platelets, in structural continuity to the (Al, Mg) octahedral sheets. At high [Si]aq, in-plane Zn and Al and out-of-plane Si neighbors were detected at 4 h, indicating the formation of Zn phyllosilicate nuclei at the layer edges. At 313 h, Zn-Al pairs were no longer detected, and Zn atoms were surrounded on average by 3.4(5) in-plane Zn at 3.10(1) Å and 1.7(9) out-of-plane Si at 3.30(2) Å, supporting the precipitation of a Zn phyllosilicate. Thus, dioctahedral Al phyllosilicate may act as a nucleating surface for the heterogeneous formation of trioctahedral Zn phyllosilicate at [Si]aq relevant to natural systems.  相似文献   

13.
The competitive adsorption of arsenate and arsenite with silicic acid at the ferrihydrite–water interface was investigated over a wide pH range using batch sorption experiments, attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy, extended X-ray absorption fine structure (EXAFS) spectroscopy, and density functional theory (DFT) modeling. Batch sorption results indicate that the adsorption of arsenate and arsenite on the 6-L ferrihydrite surface exhibits a strong pH-dependence, and the effect of pH on arsenic sorption differs between arsenate and arsenite. Arsenate adsorption decreases consistently with increasing pH; whereas arsenite adsorption initially increases with pH to a sorption maximum at pH 7–9, where after sorption decreases with further increases in pH. Results indicate that competitive adsorption between silicic acid and arsenate is negligible under the experimental conditions; whereas strong competitive adsorption was observed between silicic acid and arsenite, particularly at low and high pH. In situ, flow-through ATR-FTIR data reveal that in the absence of silicic acid, arsenate forms inner-sphere, binuclear bidentate, complexes at the ferrihydrite surface across the entire pH range. Silicic acid also forms inner-sphere complexes at ferrihydrite surfaces throughout the entire pH range probed by this study (pH 2.8–9.0). The ATR-FTIR data also reveal that silicic acid undergoes polymerization at the ferrihydrite surface under the environmentally-relevant concentrations studied (e.g., 1.0 mM). According to ATR-FTIR data, arsenate complexation mode was not affected by the presence of silicic acid. EXAFS analyses and DFT modeling confirmed that arsenate tetrahedra were bonded to Fe metal centers via binuclear bidentate complexation with average As(V)-Fe bond distance of 3.27 Å. The EXAFS data indicate that arsenite forms both mononuclear bidentate and binuclear bidentate complexes with 6-L ferrihydrite as indicated by two As(III)–Fe bond distances of ∼2.92–2.94 and 3.41–3.44 Å, respectively. The As–Fe bond distances in both arsenate and arsenite EXAFS spectra remained unchanged in the presence of Si, suggesting that whereas Si diminishes arsenite adsorption preferentially, it has a negligible effect on As–Fe bonding mechanisms.  相似文献   

14.
The nature of surface complexes formed on Ni uptake onto montmorillonite (a dioctahedral smectite) has been investigated over an extended time period by polarized extended X-ray absorption fine structure (P-EXAFS) spectroscopy. Self-supporting films of Ni-sorbed montmorillonite were prepared by contacting Ni and montmorillonite at pH 7.2, high ionic strength (0.3 M NaClO4), and low Ni concentration ([Ni]initial = 19.9 μM) for 14- and 360-d reaction time. The resulting Ni concentration on the clay varied from 4 to 7 μmol/g. Quantitative texture analysis indicates that the montmorillonite particles were well orientated with respect to the plane of the film. The full width at half maximum of the orientation distribution of the c* axes of individual clay platelets about the normal to the film plane was 44.3° (14-d reaction time) and 47.1° (360-d reaction time). These values were used to correct the coordination numbers determined by P-EXAFS for texture effects. Ni K-edge P-EXAFS spectra were recorded at angles between the incident beam and the film normal equal to 10, 35, 55, and 80°. Spectral analysis led to the identification of three nearest cationic subshells containing 2.0 ± 0.5 Al at 3.0 Å and 2.0 ± 0.5 Si at 3.12 Å and 4.0 ± 0.5 Si at 3.26 Å. These distances are characteristic of edge-sharing linkages between Al and Ni octahedra and of corner-sharing linkages between Ni octahedra and Si tetrahedra, as in clay structures. The angular dependence of the Ni-Al and Ni-Si contributions indicates that Ni-Al pairs are oriented parallel to the film plane, whereas Ni-Si pairs are not. The study reveals the formation of Ni inner-sphere mononuclear surface complexes located at the edges of montmorillonite platelets and thus that heavy metals binding to edge sites is a possible sorption mechanism for dioctahedral smectites. Data analysis further suggests that either the number of neighboring Al atoms slightly increases from 1.6 to 2 or that the structural order of the observed surface complexes increases from 0.01 Å2 to 0.005 Å2 with increasing reaction time. On the basis of the low Ni-Al coordination numbers, it appears that over an extended reaction time period of 1 yr the diffusion of Ni atoms in the octahedral layer is not the major uptake mechanism of Ni onto montmorillonite.  相似文献   

15.
The speciation of Mn, Fe, As, and Zn in a fast-growing (0.02mm/yr), shallow-marine, ferromanganese nodule has been examined by micro X-ray fluorescence, micro X-ray diffraction, and micro X-ray absorption spectroscopy. This nodule exhibits alternating Fe-rich and Mn-rich layers reflecting redox variations in water chemistry. Fe occurs as two-line ferrihydrite. The As is strictly associated with Fe and is mostly pentavalent, with an environment similar to that of As sorbed on or coprecipitated with synthetic ferrihydrite. The Mn is in the form of turbostratic birnessite with ∼10% trivalent manganese in the layers and probably ∼8% corner-sharing metal octahedra in the interlayers. The Zn is enriched on the rim of the nodule, associated with Mn. The Zn is completely (>90%) tetrahedrally coordinated and sorbed in the interlayers of birnessite on vacant layer Mn sites. The Zn and Mn species are similar to ones found in soils, suggesting common structural principles despite the differing formation conditions in these systems.  相似文献   

16.
Natural ferrihydrites (Fh) often contain impurities such as aluminum, especially in acid mine drainage, and these impurities can potentially impact the chemical reactivity of Fh with respect to metal (loid) adsorption. In the present study, we have investigated the influence of aluminum on the sorption properties of ferrihydrite with respect to environmentally relevant aqueous arsenic species, arsenite and arsenate. We have conducted sorption experiments by reacting aqueous As(III) and As(V) with synthetic Al-free and Al-bearing ferrihydrite at pH 6.5. Our results reveal that, when increasing the Al:Fe molar ratio in Fh, the sorption density dramatically decreased for As(III), whereas it increased for As(V). Extended X-ray Absorption Fine Structure (EXAFS) spectroscopy analysis at the As K-edge indicated that the AsIIIO3 pyramid binds to FeO6 octahedra on both Al-free Fh and Al-bearing Fh, by forming bidentate mononuclear edge-sharing (2E) and bidentate binuclear corner-sharing (2C) surface complexes characterized by As–Fe distances of 2.9 Å and 3.4 Å, respectively. The decrease in As(III) sorption density with increasing Al:Fe ratio in Fh could thus be explained by a low affinity of the As(OH)3 molecule for Al surface sites compared to Fe ones. In contrast, on the basis of available literature on As(V) adsorption mechanisms, we suggest that, in addition to inner-sphere 2C arsenate surface complexes, outer-sphere arsenate surface complexes forming hydrogen bonds with both Al–OH and Fe–OH surface sites could explain the enhancement of As(V) sorption onto aluminous Fh relative to Al-free Fh, as observed in the present study. The presence of aluminum in Fh may thus enhance the mobility of arsenite with respect to arsenate in Acid Mine Drainage impacted systems, while mixed Al:Fe systems could present an alternative for arsenic removal from impacted waters, provided that As(III) would be oxidized to As(V).  相似文献   

17.
The local structure of iron in three tektites has been studied by means of Fe K-edge extended X-ray absorption fine structure (EXAFS) and high-resolution X-ray absorption near-edge structure (XANES) spectroscopy in order to provide quantitative data on <Fe-O> distance and Fe coordination number. The samples studied are a moldavite and two australasian tektites. Fe model compounds with known Fe oxidation state and coordination number were used as standards in order to extract structural information from the XANES pre-edge peak. EXAFS-derived grand mean <Fe-O> distances and Fe coordination numbers for the three tektite samples are constant within the estimated error (<Fe-O > =2.00 Å ± 0.02 Å, CN = 4.0 ± 0.4). In contrast to other data from the literature on Fe-bearing silicate glasses, the tektites spectra could not be fitted with a single Fe-O distance, but rather were fit with two independent distances (2 × 1.92 Å and 2 × 2.08 Å). High-resolution XANES spectra of the three tektites display a pre-edge peak whose intensity is intermediate between those of staurolite and grandidierite, thus suggesting a mean coordination number intermediate between 4 and 5. Combining the EXAFS and XANES data for Fe, we infer the mean coordination number to be close to 4.5.Comparison of the tektites XANES spectra with those of a suite of different impact glasses clearly shows that tektites display a relatively narrow range of Fe oxidation state and coordination numbers, whereas impact glasses data span a much wider range of Fe oxidation states (from divalent to trivalent) and coordination numbers (from tetra-coordinated to esa-coordinated). These data suggest that the tektite production process is very similar for all the known strewn fields, whereas impact glasses can experience a wide variety of different temperature-pressure-oxygen fugacity conditions, leading to different Fe local structure in the resulting glasses. These data could be of aid in discriminating between tektite-like impact glasses and impact glasses sensu strictu.  相似文献   

18.
Sorption of contaminants such as arsenic (As) to natural Fe(III) (oxyhydr)oxides is very common and has been demonstrated to occur during abiotic and biotic Fe(II) oxidation. The molecular mechanism of adsorption- and co-precipitation of As has been studied extensively for synthetic Fe(III) (oxyhydr)oxide minerals but is less documented for biogenic ones. In the present study, we used Fe and As K-edge X-ray Absorption Near Edge Structure (XANES), extended X-ray Absorption Fine Structure (EXAFS) spectroscopy, Mössbauer spectroscopy, XRD, and TEM in order to investigate the interactions of As(V) and As(III) with biogenic Fe(III) (oxyhydr)oxide minerals formed by the nitrate-reducing Fe(II)-oxidizing bacterium Acidovorax sp. strain BoFeN1. The present results show the As immobilization potential of strain BoFeN1 as well as the influence of As(III) and As(V) on biogenic Fe(III) (oxyhydr)oxide formation. In the absence of As, and at low As loading (As:Fe ≤ 0.008 mol/mol), goethite (Gt) formed exclusively. In contrast, at higher As/Fe ratios (As:Fe = 0.020-0.067), a ferrihydrite (Fh) phase also formed, and its relative amount systematically increased with increasing As:Fe ratio, this effect being stronger for As(V) than for As(III). Therefore, we conclude that the presence of As influences the type of biogenic Fe(III) (oxyhydr)oxide minerals formed during microbial Fe(II) oxidation. Arsenic-K-edge EXAFS analysis of biogenic As-Fe-mineral co-precipitates indicates that both As(V) and As(III) form inner-sphere surface complexes at the surface of the biogenic Fe(III) (oxyhydr)oxides. Differences observed between As-surface complexes in BoFeN1-produced Fe(III) (oxyhydr)oxide samples and in abiotic model compounds suggest that associated organic exopolymers in our biogenic samples may compete with As oxoanions for sorption on Fe(III) (oxyhydr)oxides surfaces. In addition HRTEM-EDXS analysis suggests that As(V) preferentially binds to poorly crystalline phases, such as ferrihydrite, while As(III) did not show any preferential association regarding Fh or Gt.  相似文献   

19.
X-ray absorption fine structure (XAFS) spectroscopic analysis at the As, Se, and Mn K-edges was used to study arsenate [As(V)O43−] and selenite [Se(IV)O32−] sorption complexes on the synthetic hydrous manganese oxides (HMOs) vernadite (δ-MnO2) and K-birnessite (nominal composition: K4Mn14O27 · 9H2O). No significant changes were observed in sorption complex structure as a function of sorbent, pH (5 to 8), surface coverage (0.04 to 0.73 μmol/m2), or reaction time (5 to 22 h) in the arsenate or selenite systems. In the arsenate/HMO system, extended XAFS parameters indicate an average second-neighbor As(V) coordination of 2.0 ± 0.4 Mn at an average distance of 3.16 ± 0.01 Å, which is consistent with formation of As(V)O4 sorption complexes sharing corners with two adjacent Mn(IV)O6 surface species (i.e., bidentate, binuclear). In the selenite/HMO system, selenite surface complexes are surrounded by two shells of Mn atoms, which could represent two different adsorption complexes or a precipitate. The first shell consists of 1.6 ± 0.4 Mn at 3.07 ± 0.01 Å, which is consistent with the selenite anion forming bidentate (mononuclear) edge-sharing complexes with Mn(II)O6 or Mn(III)O6 octahedra. The second shell consists of 1.4 ± 0.4 Mn at 3.49 ± 0.03 Å, consistent with selenite forming monodentate, corner-sharing complexes with Mn(II)O6 or Mn(III)O6 octahedra. Pauling bond valence analysis that uses the extended XAFS-derived bond lengths for As(V)-O, Se(IV)-O, and Mn-O bonds indicates that the proposed surface complexes of selenite and arsenate on HMOs should be stable. Although a nearly identical Se(IV) coordination environment is found in a crystalline Mn(II)-Se(IV) precipitate (which has a structure similar to that of MnSeO3 · H2O), there are significant differences in the X-ray absorption near-edge structure and extended XAFS spectra of this precipitate and the selenite/HMO sorption samples. These differences coupled with transmission electron microscopy results suggest that if a precipitate is present it lacks long-range order characteristic of crystalline MnSeO3 · H2O.  相似文献   

20.
In northern Saskatchewan, Canada, high-grade U ores and the resulting tailings can contain high levels of As. An environmental concern in the U mining industry is the long-term stability of As within tailings management facilities (TMFs) and its potential transfer to the surrounding groundwater. To mitigate this problem, U mill effluents are neutralized with lime to reduce the aqueous concentration of As. This results in the formation of predominantly Fe3+–As5+ secondary mineral phases, which act as solubility controls on the As in the tailings discharged to the TMF. Because the speciation of As in natural systems is critical for determining its long-term environmental fate, characterization of As-bearing mineral phases and complexes within the deposited tailings is required to evaluate its potential transformation, solubility, and long-term stability within the tailings mass. In this study, synchrotron-based bulk X-ray absorption spectroscopy (XAS) was used to study the speciation of As and Fe in mine tailings samples obtained from the Deilmann TMF at Key Lake, Saskatchewan. Comparisons of K-edge X-ray absorption spectra of tailings samples and reference compounds indicate the dominant oxidation states of As and Fe in the mine tailings samples are +5 and +3, respectively, largely reflecting their generation in a highly oxic mill process, deposition in an oxidized environment, and complexation within stable oxic phases. Linear combination fit analyses of the K-edges for the Fe X-ray absorption near edge spectra (XANES) to reference compounds suggest Fe is predominantly present as ferrihydrite with some amount of the primary minerals pyrite (8–15% in some samples) and chalcopyrite (5–15% in some samples). Extended X-ray absorption fine structure (EXAFS) analysis of As K-edge spectra indicates that As5+ (arsenate) present in tailings samples is adsorbed to the ferrihydrite though an inner-sphere bidentate linkage.  相似文献   

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