Adsorption of Pentachlorophenol onto Oxide and Clay Minerals： Surface Reaction Model and Environmental Implications

The adsorption of pentachlorophenol （PCP） onto quartz, kaolinite, illite, montmorillonite and iron oxides has been investigated by batch equilibrium techniques. The pH-dependent isotherms are curves with peak values, the position of which is at about pH = 5-6 depending on the mineral species. Based on distribution of both speciation of surface hydroxyls on minerals and PCP in solution a surface reaction model involving surface complexation and surface electrostatic attraction is presented to fit the pH-dependent isotherms, and both reaction constants are calculated. The results show that on quartz and phyllosilicate minerals the predominant adsorption reaction is surface complexation, meanwhile both of surface electrostatic attraction and surface complexation are involved on the iron oxide minerals. The reaction constants of surface electrostatic adsorption are usually one to three orders in magnitude, larger than that of surface complexation. The concentration-dependent isotherms can be well fitted by Langmnir equation with the correlation coefficient R〉0.93 for kaolinite and iron oxides. The maximum adsorption is found in the order： hematite 〉 lepidocrocite 〉 goethite 〉 kaolinite 〉 quartz 〉 montmorillonite ≈ illite, which can be interpreted by consideration of both reaction mechanism and surface hydroxyl density. The significant adsorption of PCP onto mineral surfaces suggests that clay and iron oxide minerals will play an important role as HIOCs are adsorbed in laterite or latertoid soil, which is widespread in South China.     

Uranyl adsorption and surface speciation at the imogolite-water interface: Self-consistent spectroscopic and surface complexation models

Macro- and molecular-scale knowledge of uranyl (U(VI)) partitioning reactions with soil/sediment mineral components is important in predicting U(VI) transport processes in the vadose zone and aquifers. In this study, U(VI) reactivity and surface speciation on a poorly crystalline aluminosilicate mineral, synthetic imogolite, were investigated using batch adsorption experiments, X-ray absorption spectroscopy (XAS), and surface complexation modeling. U(VI) uptake on imogolite surfaces was greatest at pH ∼7-8 (I = 0.1 M NaNO₃ solution, suspension density = 0.4 g/L [U(VI)]_i = 0.01-30 μM, equilibration with air). Uranyl uptake decreased with increasing sodium nitrate concentration in the range from 0.02 to 0.5 M. XAS analyses show that two U(VI) inner-sphere (bidentate mononuclear coordination on outer-wall aluminol groups) and one outer-sphere surface species are present on the imogolite surface, and the distribution of the surface species is pH dependent. At pH 8.8, bis-carbonato inner-sphere and tris-carbonato outer-sphere surface species are present. At pH 7, bis- and non-carbonato inner-sphere surface species co-exist, and the fraction of bis-carbonato species increases slightly with increasing I (0.1-0.5 M). At pH 5.3, U(VI) non-carbonato bidentate mononuclear surface species predominate (69%). A triple layer surface complexation model was developed with surface species that are consistent with the XAS analyses and macroscopic adsorption data. The proton stoichiometry of surface reactions was determined from both the pH dependence of U(VI) adsorption data in pH regions of surface species predominance and from bond-valence calculations. The bis-carbonato species required a distribution of surface charge between the surface and β charge planes in order to be consistent with both the spectroscopic and macroscopic adsorption data. This research indicates that U(VI)-carbonato ternary species on poorly crystalline aluminosilicate mineral surfaces may be important in controlling U(VI) mobility in low-temperature geochemical environments over a wide pH range (∼5-9), even at the partial pressure of carbon dioxide of ambient air (p_CO2 = 10^−3.45 atm).     

Surface complexation modeling of Co(II) adsorption on mixtures of hydrous ferric oxide, quartz and kaolinite

Co sorption was measured as a function of pH, ionic strength (0.001-0.1 M NaNO₃) and sorbate/sorbent ratio on pure quartz, HFO and kaolinite and on binary and ternary mixtures of the three solids. Sorption data measured for the pure solids were used to derive internally-consistent diffuse layer surface complexation model (DLM) stability constants for Co sorption. Co sorption on HFO could be adequately modeled over a broad range of ionic strengths and sorbate/sorbent ratios with a two variable-charge site model. Fits based on a single variable-charge site model were reasonable, but were improved by using ionic-strength dependent stability constants. A single variable-charge site model with an additional permanent ion exchange site produced the best fit to Co edges measured on kaolinite over a range of ionic strength and sorbate/sorbent ratios. These DLM fits were also improved by using ionic-strength dependent stability constants. The DLM approach could not adequately describe the slope of Co sorption edges on quartz. This study demonstrates that for accurate prediction of Co sorption over wide ranges of ionic strength and sorbate/sorbent ratio, the DLM may require ionic-strength dependent stability constants. DLM stability constants for Co sorption derived for the pure solids were used to predict sorption as a function of pH and solid concentration on binary and ternary mixtures of the three solids. Discrepancies between predictions and measurements were quantitatively similar to those observed for the pure mineral systems. Thus, a simple component additivity approach provides useful predictions of metal sorption in the mixed solid systems.     

Approaches to surface complexation modeling of Uranium(VI) adsorption on aquifer sediments

Uranium(VI) adsorption onto aquifer sediments was studied in batch experiments as a function of pH and U(VI) and dissolved carbonate concentrations in artificial groundwater solutions. The sediments were collected from an alluvial aquifer at a location upgradient of contamination from a former uranium mill operation at Naturita, Colorado (USA). The ranges of aqueous chemical conditions used in the U(VI) adsorption experiments (pH 6.9 to 7.9; U(VI) concentration 2.5 · 10⁻⁸ to 1 · 10⁻⁵ M; partial pressure of carbon dioxide gas 0.05 to 6.8%) were based on the spatial variation in chemical conditions observed in 1999-2000 in the Naturita alluvial aquifer. The major minerals in the sediments were quartz, feldspars, and calcite, with minor amounts of magnetite and clay minerals. Quartz grains commonly exhibited coatings that were greater than 10 nm in thickness and composed of an illite-smectite clay with occluded ferrihydrite and goethite nanoparticles. Chemical extractions of quartz grains removed from the sediments were used to estimate the masses of iron and aluminum present in the coatings. Various surface complexation modeling approaches were compared in terms of the ability to describe the U(VI) experimental data and the data requirements for model application to the sediments. Published models for U(VI) adsorption on reference minerals were applied to predict U(VI) adsorption based on assumptions about the sediment surface composition and physical properties (e.g., surface area and electrical double layer). Predictions from these models were highly variable, with results overpredicting or underpredicting the experimental data, depending on the assumptions used to apply the model. Although the models for reference minerals are supported by detailed experimental studies (and in ideal cases, surface spectroscopy), the results suggest that errors are caused in applying the models directly to the sediments by uncertain knowledge of: 1) the proportion and types of surface functional groups available for adsorption in the surface coatings; 2) the electric field at the mineral-water interface; and 3) surface reactions of major ions in the aqueous phase, such as Ca²⁺, Mg²⁺, HCO₃⁻, SO₄²⁻, H₄SiO₄, and organic acids. In contrast, a semi-empirical surface complexation modeling approach can be used to describe the U(VI) experimental data more precisely as a function of aqueous chemical conditions. This approach is useful as a tool to describe the variation in U(VI) retardation as a function of chemical conditions in field-scale reactive transport simulations, and the approach can be used at other field sites. However, the semi-empirical approach is limited by the site-specific nature of the model parameters.     

Interactions of uranium with bacteria and kaolinite clay

We assessed the accumulation of uranium (VI) by a bacterium, Bacillus subtilis, suspended in a slurry of kaolinite clay, to elucidate the role of microbes on the mobility of U(VI). Various mixtures of bacteria and the koalinite were exposed to solutions of 8 × 10^− 6 M- and 4 × 10^− 4 M-U(VI) in 0.01 M NaCl at pH 4.7. After 48 h, the mixtures were separated from the solutions by centrifugation, and treated with a 1 M CH₃COOK for 24 h to determine the associations of U within the mixture. The mixture exposed to 4 × 10^− 4 M U was analyzed by transmission electron microscope (TEM) equipped with EDS. The accumulation of U by the mixture increased with an increase in the amount of B. subtilis cells present at both U concentrations. Treatment of kaolinite with CH₃COOK, removed approximately 80% of the associated uranium. However, in the presence of B. subtilis the amount of U removed was much less. TEM–EDS analysis confirmed that most of the U removed from solution was associated with B. subtilis. XANES analysis of the oxidation state of uranium associated with B. subtilis, kaolinite, and with the mixture containing both revealed that it was present as U(VI). These results suggest that the bacteria have a higher affinity for U than the kaolinite clay mineral under the experimental conditions tested, and that they can immobilize significant amount of uranium.     

Reduction of uranium(VI) under sulfate-reducing conditions in the presence of Fe(III)-(hydr)oxides

Hexavalent uranium [U(VI)] dissolved in a modified lactate-C medium was treated under anoxic conditions with a mixture of an Fe(III)-(hydr)oxide mineral (hematite, goethite, or ferrihydrite) and quartz. The mass of Fe(III)-(hydr)oxide mineral was varied to give equivalent Fe(III)-mineral surface areas. After equilibration, the U(VI)-mineral suspensions were inoculated with sulfate-reducing bacteria, Desulfovibrio desulfuricans G20. Inoculation of the suspensions containing sulfate-limited medium yielded significant G20 growth, along with concomitant reduction of sulfate and U(VI) from solution. With lactate-limited medium, however, some of the uranium that had been removed from solution was resolubilized in the hematite treatments and, to a lesser extent, in the goethite treatments, once the lactate was depleted. No resolubilization was observed in the lactate-limited ferrihydrite treatment even after a prolonged incubation of 4 months. Uranium resolubilization was attributed to reoxidation of the uraninite by Fe(III) present in the (hydr)oxide phases. Analysis by U L₃-edge XANES spectroscopy of mineral specimens sampled at the end of the experiments yielded spectra similar to that of uraninite, but having distinct features, notably a much more intense and slightly broader white line consistent with precipitation of nanometer-sized particles. The XANES spectra thus provided strong evidence for SRB-promoted removal of U(VI) from solution by reductive precipitation of uraninite. Consequently, our results suggest that SRB mediate reduction of soluble U(VI) to an insoluble U(IV) oxide, so long as a suitable electron donor is available. Depletion of the electron donor may result in partial reoxidation of the U(IV) to soluble U(VI) species when the surfaces of crystalline Fe(III)-(hydr)oxides are incompletely reduced.     

Surface charge evolution of mineral-organic complexes during pedogenesis in Hawaiian basalt

Changes in surface charge of soil particles that accompany mineral transformations during soil formation were measured for a humid tropical chronosequence in Hawaiian basalt ranging in lava flow age from 0.3 to 4100 kiloyears (ky). Parent mineralogy is dominated by glass, olivine, pyroxene, and feldspar, whereas poorly crystalline (PC) weathering products (allophane, microcrystalline gibbsite, ferrihydrite) accumulate in early to intermediate weathering stages (through 400 ky), and crystalline secondary minerals (kaolinite, gibbsite, goethite) are dominant in the oldest (1400 and 4100 ky) soils. Detailed characterization of the solid phase was accomplished with chemical extractions, X-ray diffraction analysis, and molecular spectroscopy (FTIR and ¹³C MAS NMR). Simultaneous proton titration and background ion adsorption measurements were made on LiCl saturated soils over a range in pH (2-9) and ionic strength (0.001 and 0.01 M LiCl). Dependence of variable surface charge on solution composition reflects the changing nature of mineral-organic interactions over the course of pedogenesis. Points of zero net proton charge (PZNPC) ranged from 3.4 to 6.2 and 2.0 to 5.8 at 0.001 and 0.01 M ionic strength (I), respectively. Intermediate-aged soils containing the highest mass concentration of humified soil organic matter (SOM) and its complexes with PC minerals gave rise to the steepest charging curves (largest pH dependence) and highest PZNPC values. Surface charge properties of these soils most closely reflected their weakly acidic Al and Fe hydroxide constituents, which is consistent with metal hydroxide saturation of organic functional groups, rather than organic coating of mineral surfaces. Charging curves were less steep and PZNPC values were lower for the older soils, consistent with SOM coating of more crystalline goethite, kaolinite, and gibbsite surfaces in a soil system less impacted by labile Al and Fe.     

Impact of phosphate on U(VI) immobilization in the presence of goethite

Past mining, processing, and waste disposal activities have left a legacy of uranium-contaminated soil and groundwater. Phosphate addition to subsurface environments can potentially immobilize U(VI) in-situ through interactions with uranium at mineral-water interfaces. Phosphate can induce the precipitation of low solubility U(VI)-phosphates, and it may enhance or inhibit U(VI) adsorption to iron(III) (oxy)hydroxide surfaces. Such surfaces may also facilitate the heterogeneous nucleation of U(VI)-phosphate precipitates. The interactions among phosphate, U(VI), and goethite (α-FeOOH) were investigated in a year-long series of experiments at pH 4. Reaction time, total U(VI), total phosphate, and the presence and absence of goethite were systematically varied to determine their effects on the extent of U(VI) uptake and the dominant uranium immobilization mechanism. Dissolved U(VI) and phosphate concentrations were interpreted within a reaction-based modeling framework that included dissolution-precipitation reactions and a surface complexation model to account for adsorption. The best available thermodynamic data and past surface complexation models were integrated to form an internally consistent framework. Additional evidence for the uptake mechanisms was obtained using scanning electron microscopy and X-ray diffraction. The formation and crystal growth of a U(VI)-phosphate phase, most likely chernikovite, UO₂HPO₄·4H₂O_(s), occurred rapidly for initially supersaturated suspensions both with and without goethite. Nucleation appears to occur homogeneously for almost all conditions, even in the presence of goethite, but heterogeneous nucleation was likely at one condition. The U(VI)-phosphate solids exhibited metastability depending on the TOTU:TOTP ratio. At the highest phosphate concentration studied (130 μM), U(VI) uptake was enhanced due to the likely formation of a ternary surface complex for low (∼1 μM) to intermediate (∼10 μM) TOTU concentrations and to U(VI)-phosphate precipitation for high TOTU (∼100 μM) concentrations. For conditions favoring precipitation, the goethite surface acted as a sink for dissolved phosphate that resulted in higher dissolved U(VI) concentrations relative to goethite-free conditions. Based on the total uranium and available sorption sites, a critical phosphate concentration between 15 μM and 130 μM was required for preferential precipitation of uranium phosphate over U(VI) adsorption.     

Scaling of adsorption reactions: U(VI) experiments and modeling

Iron-coated sands were prepared via two common protocols, a precipitation method, where Fe was precipitated directly onto the sand in a single step, and an adsorption method, where pure goethite was prepared in the first step and then adsorbed onto the sand in a second step. The coated sands from both the systems were characterized using scanning electron microscopy, energy-dispersive spectroscopy, X-ray diffraction, and selective Fe extraction. Although neither of the methods produced a completely crystalline Fe coating, the precipitation method produced sands with larger portions of amorphous Fe than the adsorption method, with the fraction of amorphous Fe decreasing with increasing Fe content. Uranium(VI) adsorption isotherms and pH adsorption edges were measured on three coated sands with Fe contents ranging from 0.04% to 0.3%. Experimentally, the adsorption of U(VI) onto the three sands was more comparable when normalized to surface area than when normalized to Fe content. A surface complexation model, although originally developed for U(VI) adsorption onto amorphous Fe oxide, captured the differences in adsorption when adjusted for the surface area of the coated sand. The findings indicate that surface area is a better scaling parameter than Fe content in predicting U(VI) adsorption to Fe-dominated media. These findings are significant because many common surface complexation models are parameterized on the basis of Fe content rather than specific surface area. Although the interactions of U(VI) and Fe-coated sands were used as representative adsorbate and adsorbent, the general principles may be applicable to other adsorbate–adsorbent systems as well.     

Resupply mechanism to a contaminated aquifer: A laboratory study of U(VI) desorption from capillary fringe sediments

Contaminated capillary fringe sediments are believed to function as long-term source of U(VI) to Hanford’s 300 Area groundwater uranium plume that discharges to the Columbia River. The deep vadose zone at this site experiences seasonal water table elevation and water compositional changes in response to Columbia River stage. Batch and column desorption experiments of U(VI) were performed on two mildly contaminated sediments from this system that vary in hydrologic position to ascertain their U(VI) release behavior and factors controlling it. Solid phase characterization of the sediments was performed to identify mineralogic and chemical factors controlling U(VI) desorption. Low adsorbed U(VI) concentrations prevented spectroscopic analysis. The desorption behavior of U(VI) was different for the two sediments in spite of similar chemical and textural characteristics, and non-carbonate mineralogy. Adsorption strength and sorbed U(VI) lability was higher in the near-river sediment. The inland sediment displayed low sorbed U(VI) lability (∼10%) and measurable solid-phase carbonate content. Kinetic desorption was observed that was attributed to regeneration of labile U(VI) in the near river sediment, and carbonate mineral dissolution in the inland sediment. The desorption reaction was best described as an equilibrium surface complexation reaction. The noted differences in desorption behavior appear to result from U(VI) contamination and hydrologic history, as well as sediment carbonate content. Insights are provided on the dynamic adsorption/desorption behavior of contaminants in linked groundwater-river systems.     

The mechanism of cadmium surface complexation on iron oxyhydroxide minerals

Many sediment and soil systems have become significantly contaminated with cadmium, and earth scientists are now required to make increasingly accurate predictions of the risks that this contamination poses. This necessitates an improved understanding of the processes that control the mobility and bioavailability of cadmium in the environment. With this in mind, we have studied the composition and structure of aqueous cadmium sorption complexes on the iron oxyhydroxide minerals goethite (α-FeOOH), lepidocrocite (γ-FeOOH), akaganeite (β-FeOOH), and schwertmannite (Fe₈O₈(OH)₆SO₄) using extended X-ray adsorption fine structure spectroscopy. The results show that adsorption to all of the studied minerals occurs via inner sphere adsorption over a wide range of pH and cadmium concentrations. The bonding mechanism varies between minerals and appears to be governed by the availability of different types of adsorption site at the mineral surface. The geometry and relative stability of cadmium adsorption complexes on the goethite surface was predicted with ab initio quantum mechanical modelling. The modelling results, used in combination with the extended X-ray adsorption fine structure data, allow an unambiguous determination of the mechanism by which cadmium bonds to goethite.Cadmium adsorbs to goethite by the formation of bidentate surface complexes at corner sharing sites on the predominant (110) crystallographic surface. There is no evidence for significant cadmium adsorption to goethite at the supposedly more reactive edge sharing sites. This is probably because the edge sharing sites are only available on the (021) crystallographic surface, which comprises just ∼2% of the total mineral surface area. Conversely, cadmium adsorption on lepidocrocite occurs predominately by the formation of surface complexes at bi- and/or tridentate edge sharing sites. We explain the difference in extended X-ray adsorption fine structure results for cadmium adsorption on goethite and lepidocrocite by the greater availability of reactive edge sharing sites on lepidocrocite than on goethite. The structures of cadmium adsorption complexes on goethite and lepidocrocite appear to be unaffected by changes in pH and surface loading. There is no support for cadmium sorption to any of the studied minerals via the formation of an ordered precipitate, even at high pH and high cadmium concentration. Cadmium adsorption on akaganeite and schwertmannite also occurs via inner sphere bonding, but the mechanism(s) by which this occurs remains ambiguous.     

Determining individual mineral contributions to U(VI) adsorption in a contaminated aquifer sediment: A fluorescence spectroscopy study

The adsorption and speciation of U(VI) was investigated on contaminated, fine grained sediment materials from the Hanford 300 area (SPP1 GWF) in simulated groundwater using cryogenic laser-induced U(VI) fluorescence spectroscopy combined with chemometric analysis. A series of reference minerals (montmorillonite, illite, Michigan chlorite, North Carolina chlorite, California clinochlore, quartz and synthetic 6-line ferrihydrite) was used for comparison that represents the mineralogical constituents of SPP1 GWF. Surface area-normalized K_d values were measured at U(VI) concentrations of 5 × 10⁻⁷ and 5 × 10⁻⁶ mol L⁻¹ that displayed the following affinity series: 6-line-ferrihydrite > North Carolina chlorite ≈ California clinochlore > quartz ≈ Michigan chlorite > illite > montmorillonite. Both time-resolved spectra and asynchronous two-dimensional (2D) correlation analysis of SPP1 GWF at different delay times indicated that two major adsorbed U(VI) species were present in the sediment that resembled U(VI) adsorbed on quartz and phyllosilicates. Simulations of the normalized fluorescence spectra confirmed that the speciation of SPP1 GWF was best represented by a linear combination of U(VI) adsorbed on quartz (90%) and phyllosilicates (10%). However, the fluorescence quantum yield for U(VI) adsorbed on phyllosilicates was lower than quartz and, consequently, its fractional contribution to speciation may be underestimated. Spectral comparison with literature data suggested that U(VI) exist primarily as inner-sphere complexes with surface silanol groups on quartz and as surface U(VI) tricarbonate complexes on phyllosilicates.     

叙永式埃洛石矿中矿物演化的研究

川、黔、滇交界处的埃洛石矿俗称“叙永石”,产于上二叠乐平统龙潭页岩和下二叠阳新统茅口灰岩的卡斯特侵蚀面间。成矿母岩为上二叠乐平统含黄铁矿的高岭石粘土岩。母岩在风化淋滤期间经历以下变化:(1)黄铁矿氧化成针铁矿;(2)高岭石从有序向无序转化,最终转变成埃洛石;(3)锐钛矿作为稳定相残留富集于剖面上部。形成的矿物组合以10埃洛石为主,包括伊利石、伊利石/蒙脱石混层矿物、三水铝石、三羟铝石、石膏、水铝英石和石英。     

A surface structural model for ferrihydrite II: Adsorption of uranyl and carbonate

The adsorption of uranyl (UO₂²⁺) on ferrihydrite has been evaluated with the charge distribution (CD) model for systems covering a very large range of conditions, i.e. pH, ionic strength, CO₂ pressure, U(VI) concentration, and loading. Modeling suggests that uranyl forms bidentate inner sphere complexes at sites that do not react chemically with carbonate ions. Uranyl is bound by singly-coordinated surface groups present at particular edges of Fe-octahedra of ferrihydrite while another set of singly-coordinated surface groups may form double-corner bidentate complexes with carbonate ions. The uranyl surface speciation strongly changes in the presence of carbonate due to the specific adsorption of carbonate ions as well as the formation of ternary uranyl-carbonate surface complexes. Data analysis with the CD model suggests that a uranyl tris-carbonato surface complex, i.e. (UO₂)(CO₃)₃⁴⁻, is formed. This species is most abundant in systems with a high pH and carbonate concentration. This finding differs significantly from previous interpretations made in the literature. At high pH and low carbonate concentrations, as can be prepared in CO₂-closed systems, the model suggests the additional presence of a ternary uranyl-monocarbonato complex. The binding mode (type A or type B complex) is uncertain. At high uranyl concentrations, uranyl polymerizes at the surface of ferrihydrite giving, for instance, tris-uranyl surface complexes with and without carbonate. The similarities and differences between U(VI) adsorption by goethite and ferrihydrite are discussed from a surface structural point of view.     

Cu2+污染红黏土土性异变现象分析

研究Cu2+污染物对桂林红黏土土性异变的影响。通过开展XRD、XRF及压汞试验,探讨Cu2+污染红黏土中主要矿物成分的异变规律及微观孔隙结构的变化趋势,结果表明:红黏土中主要矿物成分为高岭石、石英和针铁矿,Cu2+污染对这3种主要矿物成分的含量产生显著影响,随着Cu2+浓度的增大,高岭石和针铁矿的含量逐渐减少,石英的含量逐渐增多,其含量变化率大小关系为:高岭石>针铁矿>石英,且在浓度为2%时,高岭石的损失率高达10.69%,针铁矿的损失率达到5.38%;红黏土孔隙分布曲线为双峰分布,双峰分别分布在0.01-0.1 μm和1~10 μm之间,且在0.01~0.1 μm之间的微小孔隙占了绝对优势。随着Cu2+浓度的增加,"双峰"逐渐右移,孔隙变大;"峰宽"逐渐变宽,孔隙变多。通过开展相关力学试验,观察Cu2+污染红黏土的变形强度特性异变规律,试验结果表明:Cu2+污染对红黏土的变形强度特性影响显著。随着Cu2+浓度的增加,土体的无侧限抗压强度、抗剪强度、黏聚力C和内摩擦角φ逐渐减小,初始孔隙比e₀和压缩系数α逐渐增大;当Cu2+浓度从0增大至2%时,土体应力-应变关系曲线由典型的应变软化型转变为弱应变硬化型,无侧限抗压峰值强度减少了76.91%,抗剪强度平均损失率达到69.36%。     

Dholkata Bauxite Deposit on Metavolcanics, Keonjhar District, Orissa, India

Abstract. The Dholkata bauxite deposit of Keonjhar district, Orissa, has developed on the metavolcanics of tholeiitic basalt composition. The weathered profile reveals five distinct altered zones, such as topsoil, laterite, bauxite, lithomarge and altered metavolcanics. The mineralogy of different zones studied in a representative pit shows the association of major mineral constituents like gibbsite, goethite, hematite, kaolinite, limonite and quartz. Gibbsite is the most dominant one followed by goethite and hematite in the bauxite zone. The geochemical study of all weathering zones indicates the geochemical affinity of the elements Ni, Th and U for laterites and Cr, Zr and Hf for bauxites to occur in high quantities. Trend surface maps predict the bauxite zones in the different levels of the deposit. If the zones having A1₂O₃ 35–40 % are blended with high grade ores, the deposit may prove to be a potential one.     

CTR diffraction and grazing-incidence EXAFS study of U(VI) adsorption onto α-Al2O3 and α-Fe2O3 (11?02) surfaces

Evaluation of the long-term health risks of uranium contamination in soils, sediments, and groundwater requires a fundamental understanding of the various processes affecting subsurface transport of uranium, including adsorption processes at mineral/water interfaces. In this study, the sites of binding and surface complexation of U(VI) adsorbed on the (11?02) surfaces of α-Al₂O₃ and α-Fe₂O₃ have been determined using crystal truncation rod (CTR) diffraction and grazing incidence extended X-ray absorption fine structure (GI-EXAFS) spectroscopy. The available binding sites on the (11?02) surfaces were constrained through bond valence and steric analyses. On both surfaces, U(VI) forms uranyl-carbonato ternary complexes to surface oxygens that are singly coordinated to aluminum or iron. On the α-Al₂O₃ (11?02) surface, a monodentate complex results, whereas on the α-Fe₂O₃ (11?02) surface, the binding is bidentate to adjacent singly coordinated oxygen sites (i.e., binuclear). Differences in protonation of the singly coordinated oxygen atoms, surface charging, U(VI) aqueous speciation, substrate structure, or the electronic structure of surface functional groups may be the cause of these differences in adsorption geometry. Both XPS and CTR diffraction reveal higher U(VI) surface coverages on the α-Fe₂O₃ (11?02) surface than on the α-Al₂O₃ (11?02) surface. This difference cannot be the result of differences in defect concentration alone as CTR diffraction is not sensitive to U(VI) sorbed to defect sites, implying that the α-Fe₂O₃ (11?02) surface has an intrinsically higher affinity for U(VI). The surface complexes observed in this study are different from the bidentate, mononuclear complexes typically derived for U(VI) on powdered aluminum- and iron-(oxyhydr)oxides and clay minerals using U L_III-edge EXAFS spectroscopy. However, the presence of monodentate, mononuclear and bidentate, binuclear complexes may have been overlooked in past EXAFS studies on such substrates, as these complexes have U-Al or U-Fe interatomic distances that are too large to be easily detected by EXAFS spectroscopy.     

A study on the adsorption of chromium on laterite from Guizhou Province,China

The adsorption behaviors of Cr(VI) on laterite from Guizhou Province were studied in this paper, and the adsorption mechanism was discussed as well. Results showed that different mineral compositions in the laterite would cause differences in the capacity of laterite to absorb Cr(VI). Gibbsite, iron oxide minerals and non-crystalloids are the main contributors to enhancing the capacity of laterite to absorb Cr(VI). The pH of the solution is an important factor affecting the adsorption of Cr(VI) on laterite. Acidic environment (pH=2–5) is favorable to the adsorption of Cr(VI). The amount of adsorbed Cr(VI) decreases with increasing pH of the solution. With increasing initial concentrations of Cr(VI), the amount of adsorbed Cr(VI) increases first, and then decreases. The optimal adsorption concentration of Cr(VI) on laterite is 250 μg/mL. The adsorption of Cr(VI) on laterite is a rapid process, about 80% Cr(VI) will be adsorbed within 2 hours. And the adsorption of Cr(VI) on kaolinite is a slow process.     

The effect of calcium on aqueous uranium(VI) speciation and adsorption to ferrihydrite and quartz

Recent studies of uranium(VI) geochemistry have focused on the potentially important role of the aqueous species, CaUO₂(CO₃)₃²⁻ and Ca₂UO₂(CO₃)₃⁰(aq), on inhibition of microbial reduction and uranium(VI) aqueous speciation in contaminated groundwater. However, to our knowledge, there have been no direct studies of the effects of these species on U(VI) adsorption by mineral phases. The sorption of U(VI) on quartz and ferrihydrite was investigated in NaNO₃ solutions equilibrated with either ambient air (430 ppm CO₂) or 2% CO₂ in the presence of 0, 1.8, or 8.9 mM Ca²⁺. Under conditions where the Ca₂UO₂(CO₃)₃⁰(aq) species predominates U(VI) aqueous speciation, the presence of Ca in solution lowered U(VI) adsorption on quartz from 77% in the absence of Ca to 42% and 10% at Ca concentrations of 1.8 and 8.9 mM, respectively. U(VI) adsorption to ferrihydrite decreased from 83% in the absence of Ca to 57% in the presence of 1.8 mM Ca. Surface complexation model predictions that included the formation constant for aqueous Ca₂UO₂(CO₃)₃⁰(aq) accurately simulated the effect of Ca²⁺ on U(VI) sorption onto quartz and ferrihydrite within the thermodynamic uncertainty of the stability constant value. This study confirms that Ca²⁺ can have a significant impact on the aqueous speciation of U(VI), and consequently, on the sorption and mobility of U(VI) in aquifers.