Adsorption of uranyl onto ferric oxyhydroxides: Application of the surface complexation site-binding model

Uranyl adsorption was measured from aqueous electrolyte solutions onto well-characterized goethite, amorphous ferric oxyhydroxide, and hematite sols at 25°C. Adsorption was studied at a total uranyl concentration of 10^?5 M, (dissolved uranyl 10^?5 to 10^?8 M) as a function of solution pH, ionic strength and electrolyte concentrations, and of competing cations and carbonate complexing. Solution pHs ranged from 3 to 10 in 0.1 M NaNO₃ solutions containing up to 0.01 M NaHCO₃. All the iron oxide materials strongly adsorbed dissolved uranyl species at pHs above 5 to 6 with adsorption greatest onto amorphous ferric oxyhydroxide and least onto well crystallized specular hematite. The presence of Ca or Mg at the 10^?3 M level did not significantly affect uranyl adsorption. However, uranyl carbonate and hydroxy-carbonate complexing severely inhibited adsorption. The uranyl adsorption data measured in carbonate-free solutions was accurately modeled with the surface complexation-site binding model of Davis et al. (1978), assuming adsorption was chiefly of the UO₂OH⁺ and (UO₂)₃(OH)⁺₅, aqueous complexes. In modeling it was assumed that these complexes formed a monodentate UO₂OH⁺ surface complex, and a monodentate, bidentate or tridentate (UO₂)₃(OH)⁺₅surface complex. Of the latter, the bidentate surface complex is the most likely, based on crystallographic arguments. Modeling was less successful predicting uranyl adsorption in the presence of significant uranyl carbonate and hydroxy-carbonate complexing. It was necessary to slightly vary the intrinsic constants for adsorption of the di- and tricarbonate complexes in order to fit the uranyl adsorption data at total carbonate concentrations of 10^?2 and 10^?3 M.     

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.     

Solubility of grossular, Ca3Al2Si3O12, in H2O-NaCl solutions at 800 °C and 10 kbar, and the stability of garnet in the system CaSiO3-Al2O3-H2O-NaCl

The solubility and stability of synthetic grossular were determined at 800 °C and 10 kbar in NaCl-H₂O solutions over a large range of salinity. The measurements were made by evaluating the weight losses of grossular, corundum, and wollastonite crystals equilibrated with fluid for up to one week in Pt capsules and a piston-cylinder apparatus. Grossular dissolves congruently over the entire salinity range and displays a large solubility increase of 0.0053 to 0.132 molal Ca₃Al₂Si₃O₁₂ with increasing NaCl mole fraction (X_NaCl) from 0 to 0.4. There is thus a solubility enhancement 25 times the pure H₂O value over the investigated range, indicating strong solute interaction with NaCl. The Ca₃Al₂Si₃O₁₂ mole fraction versus NaCl mole fraction curve has a broad plateau between X_NaCl = 0.2 and 0.4, indicating that the solute products are hydrous; the enhancement effect of NaCl interaction is eventually overtaken by the destabilizing effect of lowering H₂O activity. In this respect, the solubility behavior of grossular in NaCl solutions is similar to that of corundum and wollastonite. There is a substantial field of stability of grossular at 800 °C and 10 kbar in the system CaSiO₃-Al₂O₃-H₂O-NaCl. At high Al₂O₃/CaSiO₃ bulk compositions the grossular + fluid field is limited by the appearance of corundum. Zoisite appears metastably with corundum in initially pure H₂O, but disappears once grossular is nucleated. At X_NaCl = 0.3, however, zoisite is stable with corundum and fluid; this is the only departure from the quaternary system encountered in this study. Corundum solubility is very high in solutions containing both NaCl and CaSiO₃: Al₂O₃ molality increases from 0.0013 in initially pure H₂O to near 0.15 at X_NaCl = 0.4 in CaSiO₃-saturated solutions, a >100-fold enhancement. In contrast, addition of Al₂O₃ to wollastonite-saturated NaCl solutions increases CaSiO₃ molality by only 12%. This suggests that at high pH (quench pH is 11-12), the stability of solute Ca chloride and Na-Al ± Si complexes account for high Al₂O₃ solubility, and that Ca-Al ± Si complexes are minor. The high solubility and basic dissolution reaction of grossular suggest that Al may be a very mobile component in calcareous rocks in the deep crust and upper mantle when migrating saline solutions are present.     

Thermochemical study of glasses in the system NaAlSi3O8-KAlSi3O8-Si4O8 and the join Na1.6Al1.6Si2.4O8-K1.6Al1.6Si2.4O8

Enthalpies of solution in 2PbO · B₂O₃ at 981 K have been measured for glasses in the system albite-orthoclase-silica and along the join Na_1.6Al_1.6Si_2.4O₈-K_1.6Al_1.6Si_2.4O₈. The join KAlSi₃O₈-Si₄O₈ shows zero heat of mixing similar to that found previously for NaAlSi₃O₈-Si₄O₈ glasses. Albite-orthoclase glasses show negative heats of mixing symmetric about Ab₅₀Or₅₀ (W_n = ? 2.4 ± 0.8 kcal). Negative heats of (Na, K) mixing are also found at $\text{Si}\text{(Si + Al)}\text{= 0.6.}$ Ternary excess enthalpies of mixing in the glassy system Ab-Or-4Q are positive but rarely exceed 1 kcal mol^?1.Using earlier studies of the thermodynamic properties of the crystals, the present calorimetric data and the “two-lattice” entropy model, the albite-orthoclase phase diagram is calculated in good agreement with experimental data. Attempts to calculate albite-silica and orthoclase-silica phase diagrams reveal complexities probably related to significant (but unknown) mutual solid solubility between cristobalite and alkali feldspar and to the very small heat and entropy of fusion of SiO₂.     

Enthalpies of formation at 970 K of compounds in the system MgO-Al2O3-SiO2 from high temperature solution calorimetry

The enthalpies of solution of petrologically important phases in the system MgO-Al₂O₃-SiO ₂ were measured in a melt of composition 2PbO · B₂O₃ at 970 ± 2K. The substances investigated included synthetic and natural (meteoritic) enstatite (MgSiO₃), synthetic aluminous enstatite (MgSiO_30.9Al₂O_30.1), synthetic and natural cordierite (Mg₂Al₄Si₅O₁₈), synthetic and natural sapphirine (approx. 7MgO·9Al₂O₃ · 3SiO₂), synthetic spinel (MgAl₂O₄), natural sillimanite (Al₂SiO₅), synthetic forsterite (Mg₂SiO₄), synthetic pyrope (Mg₃Al₂Si₃O₁₂), natural quartz (SiO₂), synthetic periclase (MgO) and corundum (Al₂O₃). Improvement in standardization of the calorimeter solvent made possible greater precision in this study than obtainable in former work in this laboratory on some of the same substances.The enthalpies of formation of enstatite, synthetic cordierite, forsterite and spinel are in reasonable agreement with values previously determined by solution calorimetry. The enthalpy of formation of enstatite is about 0.7 kcal less negative than the value for clinoenstatite resulting from the HF calorimetry of Torgesen and Sahama (J. Amer. Chem. Soc.70. 2156–2160, 1948), and is in accord with predictions based on analysis of published pyroxene equilibrium work. Aluminous enstatite with 10 wt.% Al₂O₃ shows an enthalpy of solution markedly lower than pure MgSiO₃: the measurements lead to an estimate of the enthalpy of formation at 970 K for MgAl₂SiO₆ (Mg-Tschermak) orthopyroxene of + 9.4 ± 1.5 kcal/mole from MgSiO₃ and Al₂O₃.Comparison of the enthalpies of formation of synthetic cordierite and anhydrous natural low-iron cordierite shows that they are energetically quite similar and that the synthetic cordierite is not likely to have large amounts of (Al, Si) tetrahedral disorder. Comparison of the enthalpies of formation of synthetic sapphirine and natural low-iron sapphirine shows, on the other hand, that the former is not a good stability model for the latter. The lower enthalpy of formation of the high-temperature synthetic sample is undoubtedly a consequence of cation disordering.The enthalpy of formation of natural sillimanite is considerably less negative than given by the tables of Robie andWaldbaum (U.S. Geol. Surv. Bull.1259 1968).The measured enthalpy of formation of synthetic pyrope is consistent with that deduced from published equilibrium diagrams in conjunction with the present measured enthalpy of formation of aluminous enstatite. Calculation of the entropy of synthetic pyrope from the present data yields surprisingly high values and suggests that synthetic pyrope is not a good stability model for natural pyrope-rich garnets. Hence, considerable doubt exists about the direct quantitative application of experimental diagrams involving pyropic garnet to discussions of the garnet stability field in the Earth's outer regions.     

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.     

Shear viscosities of CaO-Al2O3-SiO2 and MgO-Al2O3-SiO2 liquids: Implications for the structural role of aluminium and the degree of polymerisation of synthetic and natural aluminosilicate melts

The shear viscosity of 66 liquids in the systems CaO-Al₂O₃-SiO₂ (CAS) and MgO-Al₂O₃-SiO₂ (MAS) have been measured in the ranges 1-10⁴ Pa s and 10⁸-10¹² Pa s. Liquids belong to series, nominally at 50, 67, and 75 mol.% SiO₂, with atomic M²⁺/(M²⁺+2Al) typically in the range 0.60 to 0.40 for each isopleth. In the system CAS at 1600°C, viscosity passes through a maximum at all silica contents. The maxima are clearly centered in the peraluminous field, but the exact composition at which viscosity is a maximum is poorly defined. Similar features are observed at 900°C. In contrast, data for the system MAS at 1600°C show that viscosity decreases with decreasing Mg/(Mg + 2Al) at all silica contents, but that a maximum in viscosity must occur in the field where Mg/2Al >1. On the other hand, the viscosity at 850°C increases with decreasing Mg/(Mg + 2Al) and shows no sign of reaching a maximum, even for the most peraluminous composition studied. The data from both systems at 1600°C have been analysed assuming that shear viscosity is proportional to average bond strength and considering the equilibrium:

Al^[4]-(Mg,Ca)_0.5⇔(Mg,Ca)_0.5-NBO+Al_XS     

Role of basicity and tetrahedral speciation in controlling the thermodynamic properties of silicate liquids, part 1: the system CaO-MgO-Al2O3-SiO2

Activity coefficients of oxide components in the system CaO-MgO-Al2O3-SiO2 (CMAS) were calculated with the model of Berman (Berman R. G., “A thermodynamic model for multicomponent melts with application to the system CaO-MgO-Al2O3-SiO2,” Ph.D. dissertation, University of British Columbia, 1983) and used to explore large-scale relationships among these variables and between them and the liquid composition. On the basis of Berman’s model, the natural logarithm of the activity coefficient of MgO, ln(γMgOLiq), and ln(γMgOLiq/γSiO2Liq) are nearly linear functions of ln(γCaOLiq). All three of these variables are simple functions of the optical basicity Λ with which they display minima near Λ ∼ 0.54 that are generated by liquids with low ratios of nonbridging to tetrahedral oxygens (NBO/T) (<0.3) and a mole fraction ratio, XSiO2Liq/XAl2O3Liq, in the range 4 to 20. Variations in ln(γCaOLiq) at constant Λ near the minimum are due mostly to liquids with (XCaOLiq + XMgOLiq)/XAl2O3Liq < 1. The correlations with optical basicity imply that the electron donor power is an important factor in determining the thermodynamic properties of aluminosilicate liquids.For a constant NBO/T, ln(γCaOLiq/γAl2O3Liq) and ln(γMgOLiqγAl2O3Liq) form curves in terms of XSiO2Liq/XAl2O3Liq. The same liquids that generate minima in the Λ plots are also associated with minima in ln(γCaOLiqγAl2O3Liq) and ln(γMgOLiqγAl2O3Liq) as a function of XSiO2Liq/XAl2O3Liq. In addition, there are maxima or sharp changes in slope for NBO/T > 0.3, which occur for XSiO2Liq/XAl2O3Liq ranging from ∼0 to ∼6 and increase with increasing NBO/T. The systematic variations in activity coefficients as a function of composition and optical basicity reflect underlying shifts in speciation as the composition of the liquid is changed. On the basis of correlations among the activity coefficients, it is likely that the use of CaO, an exchange component such as SiMg−1 and two of MgO, CaAl2O4, or MgAl2O4 would yield significant savings in the number of parameters required to model the excess free energy surface of liquids over large portions of CMAS relative to the use of oxide end members.Systematic behavior of thermodynamic properties extends to small amounts of other elements dissolved in otherwise CMAS liquids. For example, ln(XFe2+Liq/XFe3+Liq) at constant oxygen fugacity is linearly correlated with ln(γCaOLiq). Similarly, ln(CS), where CS is the sulfide capacity is linearly correlated at constant temperature with each of the optical basicity, ln(aCaOLiq) and ln(γCaOLiq), although the correlation for the latter breaks down for low values of Λ. The well-known systematic behavior of sulfide capacity as a function of optical basicity for systems inside as well as outside CMAS suggests that ln(γCaSLiq) is also a simple function of optical basicity and that the relationships observed among the activity coefficients in CMAS may hold for more complex systems.     

Sorption of uranyl and arsenate on SiO2, Al2O3, TiO2 and FeOOH

Migration of uranium and arsenic in aquatic environments is often controlled by sorption on minerals present along the water flow path. To investigate the sorption behaviour, batch experiments were conducted for uranium and arsenic as single components and also solutions containing both uranium and arsenic in the presence of SiO₂, Al₂O₃, TiO₂ and FeOOH at a pH ranging from 3 to 9. In solutions containing only U(VI) or As(V) with the minerals, the sorption of U(VI) was low at acidic pH range and increases with increasing pH, whereas As(V) showed opposite sorption behaviour to Al₂O₃, TiO₂ and FeOOH from acidic pH range to alkaline condition. For the As(V)–SiO₂ system, the sorption was low for almost all pH. Sorption of U(VI) and As(V) on SiO₂ and FeOOH is almost similar in solutions containing either U(VI) or As(V) separately, or both together. In the U(VI)–As(V)–Al₂O₃ system, a significant retardation in uranyl sorption and an enhancement in arsenate sorption on Al₂O₃ were observed for a wide range of pH. The sorption behaviour of U(VI) and As(V) was changed when Al₂O₃ was replaced by TiO₂, where an increase in sorption was observed for both elements. The sorption behaviour of uranyl and arsenate in the U(VI)–As(V)–TiO₂ system gives evidence for the formation of uranyl–arsenate complexes. The change in sorption retardation/enhancement of U(VI) and As(V) could be explained by the formation of uranyl–arsenate complexes or due to the competitive sorption between uranyl and arsenate species.     

Thermochemistry of high pressure garnets and clinopyroxenes in the system CaO-MgO-Al2O3-SiO2

The enthalpies of solution of several synthetic garnets on the join Mg₃Al₂Si₃O₁₂-Ca₃Al₂Si₃O₁₂ (pyrope-grossular) and of several synthetic clinopyroxenes on the join CaMgSi₂O₆-CaAl₂SiO₆ (diopside-Ca-Tschermak's molecule) were measured in a melt of composition 2PbO · B₂O₃ at 970 K. The determinations were made with sufficient precision so that thermochemical characterizations of the solid solutions could be achieved.The pyrope-grossular solutions show positive enthalpies of mixing. The non-ideality in the range 0–30 mole % grossular is relatively the largest and is in good agreement with the predictions of Ganguly and Kennedy (1974) based largely on cation partitioning of natural high grade metamorphic garnets with biotite, and with the deductions of Hensenet al. (1975) based on measurement of the compositions of synthetic pyrope-rich garnets equilibrated with anorthite, Al₂SiO₅ and quartz. However, the garnets show smaller excess enthalpies at higher grossular contents. This would lead to an asymmetric solvus with a critical temperature lower than predicted by the symmetrical regular solution model of Ganguly and Kennedy (1974). The composition-dependent non-ideality can be understood by simple ionic size considerations in solid substitution and is analogous to the situations for the calcite-dolomite and enstatite-diopside solvi.The heats of solution of pyropes crystallized in the range 1000–1500°C were all the same, within the precision of measurement, and thus we have found no evidence for temperature-dependent cation disordering as a possible explanation of the high entropy of pyrope, as suggested by Charluet al. (1975). Positional disorder of dodecahedral Mg is a more probable reason.The diopside-CaTs join is also non-ideal, with the larger positive enthalpy deviations near the diopside end. The calorimetric data in the magnesian range are consistemt with the model for completely disordered tetrahedral Si and Al which results from the free energy derivations of wood (1975) based on syntheses of diopside-rich aluminous pyroxenes in the presence of anorthite and quartz. At higher Al concentrations the calorimetric data seem more consistent with the ‘local charge-balance’ model of Wood (1975).No evidence for temperature-dependent disorder was found for either the diopside or CaTs end-members.     

Al_2O_3/Ti:风化与蚀变过程中的原岩示踪

Al_2O_3和Ti在风化和热液蚀变等地球化学过程中通常被认为是不活动元素,两者的比值Al_2O_3/Ti常被用来指示地球化学作用过程。通过对中国157件火成岩样品元素含量平均值的统计发现,火成岩样品中Al_2O_3/Ti与SiO_2含量值之间存在着较好的幂函数关系:ln(Al_2O_3/Ti)=0.073×SiO_2-0.89,式中Al_2O_3和SiO_2和Ti含量单位均为%。本文基于得到的经验方程和TAS图解构建了一个新的判别岩石类型的图解——Al_2O_3-Ti图解。该图解可以区分酸性岩、中酸性岩、中性岩、中基性岩-基性岩四类岩性。通过对三个火成岩风化剖面的研究发现,花岗岩风化剖面从新鲜基岩到风化形成的土壤在Al_2O_3-Ti图解中均落在酸性岩区,花岗闪长岩风化剖面从新鲜基岩到风化形成的土壤样品均落在中酸性岩区,玄武质安山岩风化剖面从新鲜基岩到风化形成的土壤样品均落在中基性岩-基性岩区。不同风化程度的风化产物与其母岩在Al_2O_3-Ti图解中所在的区域一致,即Al_2O_3-Ti图解可以用来追溯火成岩风化产物的母岩岩性。通过对胶东焦家金矿和豫西牛头沟金矿两个矿区岩石的研究发现,黑云母花岗岩从新鲜岩石到其蚀变岩及其形成矿石的样品在Al_2O_3-Ti图解中均落在酸性岩区。玄武质安山岩从新鲜岩石到其蚀变岩及其形成矿石的样品在Al_2O_3-Ti图解中均落在中基性岩-基性岩区。即不同蚀变程度的蚀变产物与其原岩在Al_2O_3-Ti图解中所在的区域一致,这表明新构建的Al_2O_3-Ti图解可以用来示踪蚀变岩的原岩性质。     

Thermochemistry of glasses along joins of pyroxene stoichiometry in the system Ca2Si2O6-Mg2Si2O6-Al4O6

Enthalpies of solution in 2PbO · B₂O₃ at 974 K have been measured for glasses along the joins Ca₂Si₂O₆ (Wo)-Mg₂Si₂O₆ (En) and Mg₂Si₂O₆-MgAl₂SiO₆ (MgTs). Heats of mixing are symmetric and negative for Wo-En with W_H = ?31.0 ± 3.6 kJ mol^?. Negative heats of mixing were also found for the En-MgTs glasses (W_H = ?33.4 ± 3.7 kJ mol^?).Enthalpies of vitrification of pyroxenes and pyroxenoids generally increase with decreasing alumina content and with decreasing basicity of the divalent cation.Heats of mixing along several glassy joins show systematic trends. When only non-tetrahedral cations mix (outside the aluminosilicate framework), small exothermic heats of mixing are seen. When both nontetrahedral and framework cations mix (on separate sublattices, presumably), the enthalpies of mixing are substantially more negative. Maximum enthalpy stabilization near compositions with Al/Si ≈ 1 is suggested.     

http://www.sciencedirect.com/science/article/pii/S1674987112001296

We present field, petrographic, major and trace element data for komatiites and komatiite basalts from Sargur Group Nagamangala greenstone belt, western Dharwar craton. Field evidences such as crude pillow structure indicate their eruption in a marine environment whilst spinifex texture reveals their komatiite nature. Petrographic data suggest that the primary mineralogy has been completely altered during post-magmatic processes associated with metamorphism corresponding to greenschist to lower amphibolite facies conditions. The studied komatiites contain serpentine, talc, tremolite, actinolite and chlorite whilst tremolite, actinolite with minor plagioclase in komatiitic basalts. Based on the published Sm-Nd whole rock isochron ages of adjoining Banasandra komatiites (northern extension of Nagamangala belt) and further northwest in Nuggihalli belt and Kalyadi belt we speculate ca. 3.2–3.15 Ga for komatiite eruption in Nagamangala belt. Trace element characteristics particularly HFSE and REE patterns suggest that most of the primary geochemical characteristics are preserved with minor influence of post-magmatic alteration and/or contamination. About 1/3 of studied komatiites show Al-depletion whilst remaining komatiites and komatiite basalts are Al-undepleted. Several samples despite high MgO, (Gd/Yb)_N ratios show low CaO/Al₂O₃ ratios. Such anomalous values could be related to removal of CaO from komatiites during fluid-driven hydrothermal alteration, thus lowering CaO/Al₂O₃ ratios. The elemental characteristics of Al-depleted komatiites such as higher (Gd/Yb)_N (>1.0), CaO/Al₂O₃ (>1.0), Al₂O₃/TiO₂ (<18) together with lower HREE, Y, Zr and Hf indicate their derivation from deeper upper mantle with minor garnet (majorite?) involvement in residue whereas lower (Gd/Yb)_N (<1.0), CaO/Al₂O₃ (<0.9), higher Al₂O₃/TiO₂ (>18) together with higher HREE, Y, Zr suggest their derivation from shallower upper mantle without garnet involvement in residue. The observed chemical characteristics (CaO/Al₂O₃, Al₂O₃/TiO₂, MgO, Ni, Cr, Nb, Zr, Y, Hf, and REE) indicate derivation of the komatiite and komatiite basalt magmas from heterogeneous mantle (depleted to primitive mantle) at different depths in hot spot environments possibly with a rising plume. The low content of incompatible elements in studied komatiites suggest existence of depleted mantle during ca. 3.2 Ga which in turn imply an earlier episode of mantle differentiation, greenstone volcanism and continental growth probably during ca. 3.6–3.3 Ga which is substantiated by Nd and Pb isotope data of gneisses and komatiites in western Dharwar craton (WDC).     

The relation between Li, V, P2O5, and Al2O3 contents in marls and mudstones as indicators of environment of deposition

The contents of Li, V, P₂O₅, and Al₂O₃ in marls and mudstones collected from three different formations, cropping out in northern Iraq, showed that the ratios of Li/Al₂O₃, V/Al₂O₃, and P₂O₅/Al₂O₃ in these rocks can be used to discriminate environments of deposition of these formations. Relatively high values of the above ratios characterize the deep marine Shiranish environment while lowest values characterize freshwater environment of deposition of the Injana rocks. Despite that marls of the Fatha formation were deposited in marine lagoonal environment, the ratios P₂O₅/Al₂O₃ and V/Al₂O₃ could not be discriminated from the freshwater Injana mudstones. The well-known phenomenon that marine surface water and down to a depth of 50 m almost lacks soluble P explain this behavior. In such water, almost all the soluble P is consumed by surface organism rendering it unavailable for adsorption by the sediments. The high salinity of the lagoonal environment prevented adsorption of soluble V on clay minerals because of its inability to compete with other species of much higher concentrations.     

The effects of uranium speciation on the rate of U(VI) reduction by Shewanella oneidensis MR-1

We measured the kinetics of U(VI) reduction by Shewanella oneidensis MR-1 under anaerobic conditions in the presence of variable concentrations of either EDTA or dissolved Ca. We measured both total dissolved U and U(VI) concentrations in solution as a function of time. In separate experiments, we also measured the extent of U(VI) adsorption onto S. oneidensis in order to quantify the thermodynamic stabilities of the important U(VI)-bacterial surface complexes. In the EDTA experiments, the rate of U(IV) production increased with increasing EDTA concentration. However, the total dissolved U concentrations remained constant and identical to the initial U concentrations during the course of the experiments for all EDTA-bearing systems. Additionally, the U(VI) reduction rate in the EDTA experiments exhibited a strong correlation to the concentration of the aqueous U⁴⁺-EDTA complex. We conclude that the U(VI) reduction rate increases with increasing EDTA concentration, likely due to U⁴⁺-EDTA aqueous complexation which removes U(IV) from the cell surface and prevents UO₂ precipitation.In the Ca experiments, the U(VI) reduction rate decreased as Ca concentration increased. Our thermodynamic modeling results based on the U(VI) adsorption data demonstrate that U(VI) was adsorbed onto the bacterial surface in the form of a Ca-uranyl-carbonate complex in addition to a number of other Ca-free uranyl complexes. The observed U(VI) reduction rates in the presence of Ca exhibit a strong negative correlation to the concentration of the Ca-uranyl-carbonate bacterial surface complex, but a strong positive correlation to the total concentration of all the other Ca-free uranyl surface complexes. Thus, the concentration of these Ca-free uranyl surface complexes appears to control the rate of U(VI) reduction by S. oneidensis in the presence of dissolved Ca. Our results demonstrate that U speciation, both of U(VI) before reduction and of U(IV) after reduction, affects the reduction kinetics, and that thermodynamic modeling of the U speciation may be useful in the prediction of reduction kinetics in realistic geologic settings.     

稀土氧化物及黏土负载La2O3除磷性能的实验研究

地表水体富营养化现象与磷的积累有密切关系,去除水体中溶解态磷是降低富营养化风险的技术关键。近十余年来,稀土元素被用于污水除磷剂的开发,并获得了良好的应用成效。本文实验比较了8种结晶态稀土氧化物(Y_2O_3、La_2O_3、CeO_2、Pr6O11、Nd_2O_3、Sm_2O_3、Eu_2O_3和Dy_2O_3)的除磷性能,结果表明La_2O_3的除磷性能最好,Pr6O11、Y_2O_3、Eu_2O_3、Nd_2O_3次之,Sm_2O_3和Dy_2O_3效果微弱,CeO_2完全没有除磷能力;研究表明稀土氧化物表面磷吸附的动力学行为更符合准一级反应模型,吸附等温线符合Langmuir模型。实验表征了除磷后的稀土氧化物和除磷过程中溶液p H值的变化,认为稀土氧化物除磷是一个表面吸附占主导,氧化物溶解出来的离子辅助沉淀的吸附过程。为了避免稀土氧化物颗粒在水体中发生团聚并降低表面吸附能力,将稀土氧化物La_2O_3微纳米颗粒负载在不同黏土矿物上,发现负载于黏土矿物表面的稀土氧化物除磷能力有较好提升,磷吸附量均提高25%左右。负载等量La_2O_3的3种黏土矿物的除磷性能差异不显著,黏土矿物提高稀土氧化物颗粒分散度可能是后者除磷能力提升的主要原因。     

The bearing of the system CaMgSi2O6CaAl2SiO6CaFeAlSiO6 on fassaitic pyroxene

The system CaMgSi₂O₆CaAl₂SiO₆CaFeAlSiO₆ has been studied in air at 1 atm. The phase assemblage at subsolidus temperatures in the CaMgSi₂O₆-rich portion is Cpx + An + Mel and that in the CaMgSi₂O₆-poor portion Cpx + An + Mel + Sp. At subsolidus temperatures the sigle-phase field of clinopyroxene increases with an increase in the CaFeAlSiO₆ component of the system. The Al₂O₃ content of clinopyroxene, however, continues to increase beyond the single-phase field and attains at least 16.04 wt.% Al₂O₃ with 3.9 wt.% Fe₂O₃. The stability field of fassaite in the system over a range of pressures and oxygen fugacities has been estimated from data in the literature as well as the present data. The CaFeAlSiO₆ content of fassaite is dependent on oxygen fugacity, but is not influenced by pressure. The stability field is strongly influenced by oxygen fugacity at low and high pressure, and decreases with decreasing oxygen fugacity. Clinopyroxenes in both volcanic and metamorphic rocks from various localities, when plotted on the CaMgSi₂O₆CaAl₂SiO₆CaFeAlSiO₆ triangle, show that there is no compositional gap between diopside and fassaitic pyroxene in metamorphic rocks, and that the fassaitic pyroxene in alkalic rocks becomes richer in both CaAl₂SiO₆ and CaFeAlSiO₅ components as crystallization proceeds. These results agree with those obtained in the experimental study.     

FeO*-Al2O3-TiO2-Rich Rocks of the Tertiary Bana Igneous Complex, West Cameroon

FeO*‐Al₂O₃‐TiO₂‐rich rocks are found associated with transitional tholeiitic lava flows in the Tertiary Bana plutono‐volcanic complex in the continental sector of the Cameroon Line. These peculiar rocks consist principally of iron‐titanium oxides, aluminosilicates and phosphates, and occur as layers 1–3 m thick occupying the upper part of lava flows on the southwest (site 1) and northwest (site 2) sites of the complex. Mineral constituents of the rocks include magnetite, ilmenite, hematite, rutile, corundum, andalusite, sillimanite, cordierite, quartz, plagioclase, alkali feldspar, apatite, Fe‐Mn phosphate, Al phosphate, micas and fine mixtures of sericite and silica. Texturally and compositionally, the rocks can be subdivided into globular type, banded type, and Al‐rich fine‐gained massive type. The first two types consist of dark globule or band enriched in Fe‐Ti oxides and apatite and lighter colored groundmass or bands enriched in aluminosilicates and quartz, respectively. The occurrence of andalusite and sillimanite and the compositional relations of magnetite and ilmenite in the FeO*‐Al₂O₃‐TiO₂‐rich rocks suggest temperatures of crystallization in a range of 690–830°C at low pressures. The Bana FeO*‐Al₂O₃‐TiO₂‐rich rocks are characterized by low concentrations of SiO₂ (25–54.2 wt%), Na₂O + K₂O (0–1%), CaO (0–2%) and MgO (0–0.5%), and high concentrations of FeO* (total iron as FeO, 20–42%), Al₂O₃ (20–42%), TiO₂ (3–9.2%), and P₂O₅ (0.26–1.30%). TiO₂ is positively correlated with Al₂O₃ and inversely correlated with FeO*. The bulk rock compositions cannot be derived from the associated basaltic magma by crystal fractionation or by partial melting of the mantle or lower crustal materials. In ternary diagrams of (Al₂O₃)?(CaO + Na₂O + K₂O)?(FeO*+ MnO + MgO) and (SiO₂)?(FeO*)?(Al₂O₃), the compositional field of the rocks is close to that of laterite and is distinct from the common volcanic rocks, suggesting that the rocks are derived from lateritic materials by recrystallization when the materials are heated by the basaltic magmas. A hydrothermal origin is discounted because the rocks contain high‐temperature mineral assemblages and lack sulfide minerals. It is proposed that the FeO*‐Al₂O₃‐TiO₂‐rich rocks of the Bana complex were formed by pyrometamorphism of laterite by the heat of basaltic magmas.     

Uranyl adsorption onto montmorillonite: Evaluation of binding sites and carbonate complexation

The fate and transport of uranium in contaminated soils and sediments may be affected by adsorption onto the surface of minerals such as montmorillonite. Extended X-ray absorption fine structure (EXAFS) spectroscopy has been used to investigate the adsorption of uranyl (UO₂²⁺) onto Wyoming montmorillonite. At low pH (∼4) and low ionic strength (10⁻³ M), uranyl has an EXAFS spectrum indistinguishable from the aqueous uranyl cation, indicating binding via cation exchange. At near-neutral pH (∼7) and high ionic strength (1 M), the equatorial oxygen shell of uranyl is split, indicating inner-sphere binding to edge sites. Linear-combination fitting of the spectra of samples reacted under conditions where both types of binding are possible reveals that cation exchange at low ionic strengths on SWy-2 may be more important than predicted by past surface complexation models of U(VI) adsorption on related montmorillonites. Analysis of the binding site on the edges of montmorillonite suggests that U(VI) sorbs preferentially to [Fe(O,OH)₆] octahedral sites over [Al(O,OH)₆] sites. When bound to edge sites, U(VI) occurs as uranyl-carbonato ternary surface complexes in systems equilibrated with atmospheric CO₂. Polymeric surface complexes were not observed under any of the conditions studied. Current surface complexation models of uranyl sorption on clay minerals may need to be reevaluated to account for the possible increased importance of cation exchange reactions at low ionic strengths, the presence of reactive octahedral iron surface sites, and the formation of uranyl-carbonato ternary surface complexes. Considering the adsorption mechanisms observed in this study, future studies of U(VI) transport in the environment should consider how uranium retardation will be affected by changes in key solution parameters, such as pH, ionic strength, exchangeable cation composition, and the presence or absence of CO₂.     

Adsorption of organic matter at mineral/water interfaces: I. ATR-FTIR spectroscopic and quantum chemical study of oxalate adsorbed at boehmite/water and corundum/water interfaces

The types and structures of adsorption complexes formed by oxalate at boehmite (γ-AlOOH)/water and corundum (α-Al₂O₃)/water interfaces were determined using in situ attenuated total reflectance fourier transform infrared (ATR-FTIR) spectroscopy and quantum chemical simulation methods. At pH 5.1, at least four different oxalate species were found at or near the boehmite/water interface for oxalate surface coverages (Γ_ox) ranging from 0.25 to 16.44 μmol/m². At relatively low coverages (Γ_ox < 2.47), strongly adsorbed inner-sphere oxalate species (IR peaks at 1286, 1418, 1700, and 1720 cm⁻¹) replace weakly adsorbed carbonate species, and a small proportion of oxalate anions are adsorbed in an outer-sphere mode (IR peaks at 1314 and 1591 cm⁻¹). IR peaks indicative of inner-sphere adsorbed oxalate are also observed for oxalate at the corundum/water interface at Γ_ox = 1.4 μmol/m². With increasing oxalate concentration (Γ_ox > 2.47 μmol/m²), the boehmite surface binding sites for inner-sphere adsorbed oxalate become saturated, and excess oxalate ions are present dominantly as aqueous species (IR peaks at 1309 and 1571 cm⁻¹). In addition to these adsorption processes, oxalate-promoted dissolution of boehmite following inner-sphere oxalate adsorption becomes increasingly pronounced with increasing Γ_ox and results in an aqueous Al(III)-oxalate species, as indicated by shifted IR peaks (1286 → 1297 cm⁻¹ and 1418 → 1408 cm⁻¹). At pH 2.5, no outer-sphere adsorbed oxalate or aqueous oxalate species were observed. The similarity of adsorbed oxalate spectral features at pH 2.5 and 5.1 implies that the adsorption mechanism of aqueous HOx⁻ species involves loss of protons from this species during the ligand-exchange reaction. As a consequence, adsorbed inner-sphere oxalate and aqueous Al(III)-oxalate complexes formed at pH 2.5 have coordination geometries very similar to those formed at pH 5.1.The coordination geometry of inner-sphere adsorbed oxalate species was also predicted using quantum chemical geometry optimization and IR vibrational frequency calculations. Geometry-optimized Al₈O₁₂ and Al₁₄O₂₂ clusters with the reactive surface Al site coordinated by three oxygens were used as model substrates for corundum and boehmite surfaces. Among the models considered, calculated IR frequencies based on a bidentate side-on structure with a 5-membered ring agree best with the observed frequencies for boehmite/oxalate/water samples at Γ_ox = 0.25 to 16.44 μmol/m² and pH 2.5 and 5.1, and for a corundum/oxalate/water sample at Γ_ox = 1.4 μmol/m² and pH 5.1. Based on these results, we suggest that oxalate bonding on boehmite and corundum surfaces results in 5-coordinated rather than 4- or 6-coordinated Al surface sites.