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1.
The O 1s spectrum is examined for 19 uranyl minerals of different composition and structure. Spectra from single crystals were measured with a Kratos Axis Ultra X-ray Photoelectron Spectrometer with a magnetic-confinement charge-compensation system. Well-resolved spectra with distinct maxima, shoulders and inflections points, in combination with reported and measured binding energies for specific O2− species and structural data of the uranyl minerals are used to resolve the fine structure of the O 1s envelope. The resolution of the O 1s spectra includes, for the first time, different O2− bands, which are assigned to O atoms linking uranyl with uranyl polyhedra (UOU) and O atoms of uranyl groups (OUO). The resolved bands in the O 1s spectrum occur at distinct ranges in binding energy: bands for (UOU) occur at 529.6-530.4 eV, bands for (OUO) occur at 530.6-531.4 eV, bands for O2− in the equatorial plane of the uranyl polyhedra linking uranyl polyhedra with (TOn) groups (T = Si, S, C, P, Se) (TO) occur at 530.9-532.2 eV; bands for (OH) groups in the equatorial plane of the uranyl polyhedra (OH) occur at 532.0-532.5 eV, bands of (H2O) groups in the interstitial complex of the uranyl minerals (H2Ointerst) occur at 533.0-533.8 eV and bands of physisorbed (H2O) groups on the surface of uranyl minerals (H2Oadsorb) occur at 534.8-535.2 eV. Treatment of uranyl minerals with acidic solutions results in a decrease in UOU and an increase in OH. Differences in the ratio of OH : OUO between the surface and bulk structure is larger for uranyl minerals with a high number of UOU and TO species in the bulk structure which is explained by protonation of underbonded UO, UOU and TO terminations on the surface. The difference in the ratio of H2Ointerst : OUO between the bulk and surface structures is larger for uranyl minerals with higher percentages of H2Ointerst as well as, with a higher number of interstitial H2O groups that are not bonded to interstitial cations, resulting in easier dehydration of interstitial H2O groups in uranyl minerals during exposure to a vacuum.  相似文献   

2.
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3.
Edge sites of clay minerals play a key role for pH dependent sorption of ions from solutions of electrolytes. Pyrophyllite, Al2[Si4O10](OH)2, is an important structural prototype for a variety of 2:1 dioctahedral phyllosilicates but in contrast to the other clays has no permanent structural charge. The structure of thin water films confined between most common edges of 1Tc pyrophyllite: (0 1 0), (1 1 0) and (1 0 0), was analyzed by means of ab initio molecular dynamic simulations. The system setup allowed for a full flexibility of the interfaces and a proton exchange between the edges of pyrophyllite and water molecules in solution. The structure of hydrated surfaces is compared with the recent predictions of static geometry optimizations for edge-vacuum interfaces. All surfaces studied reveal a strong hydrophilic character of edge similar to the hydrated silica surface and the facets of simple layered hydroxides. Spontaneous proton transfer between different surface sites were observed in molecular dynamics simulations of the (0 1 0) interface. The proton bound to the SiOH site was found to exchange with the AlOH group by the mechanism . The direction of the proton transfer agrees with the scale of relative proton affinities for surface sites obtained from the static calculations. Alternatively, the proton attached to the AlOH2 site exchanges with the AlOH group. In both reactions, the protons are transferred through the chains of hydrogen bonds formed between water molecules in the solution and the surface sites. The observed mechanisms might be one of the basic schemes for the surface proton diffusion in compacted clays. Kinetics of the proton transfer at edge sites is limited by the rate of rearrangements of the water molecules near interface.  相似文献   

4.
Goethite(α-FeOOH), an abundant and highly reactive iron oxyhydroxide mineral, has been the subject of numerous studies of environmental interface reactivity. However, such studies have been hampered by the lack of experimental constraints on aqueous interface structure, and especially of the surface water molecular arrangements. Structural information of this type is crucial because reactivity is dictated by the nature of the surface functional groups and the structure or distribution of water and electrolyte at the solid-solution interface. In this study we have investigated the goethite (1 0 0) surface using surface diffraction techniques, and have determined the relaxed surface structure, the surface functional groups, and the three dimensional nature of two distinct sorbed water layers. The crystal truncation rod (CTR) results show that the interface structure consists of a double hydroxyl, double water terminated interface with significant atom relaxations. Further, the double hydroxyl terminated surface dominates with an 89% contribution having a chiral subdomain structure on the (1 0 0) cleavage faces. The proposed interface stoichiometry is ((H2O)(H2O)OH2OHFeOOFeR) with two types of terminal hydroxyls; a bidentate (B-type) hydroxo group and a monodentate (A-type) aquo group. Using the bond-valence approach the protonation states of the terminal hydroxyls are predicted to be OH type (bidentate hydroxyl with oxygen coupled to two Fe3+ ions) and OH2 type (monodentate hydroxyl with oxygen tied to only one Fe3+). A double layer three dimensional ordered water structure at the interface was determined from refinement of fits to the experimental data. Application of bond-valence constraints to the terminal hydroxyls with appropriate rotation of the water dipole moments allowed a plausible dipole orientation model as predicted. The structural results are discussed in terms of protonation and H-bonding at the interface, and the results provide an ideal basis for testing theoretical predictions of characteristic surface properties such as pKa , sorption equilibria, and surface water permittivity.  相似文献   

5.
The present study focuses on four A-type fluorite-bearing granitic plutons in the Eastern Desert of Egypt which are classified into post-orogenic subsolvus (Homrit Waggat, 535 Ma; Homer Akarem, 541 Ma and Ineigi, 571 Ma) and anorogenic hypersolvus (Gabal Gharib, 476 Ma) granites. All the granites are Si- and alkali-rich and MgCaTi poor. Whereas both granite types appear relatively homogeneous in terms of most of their major and trace elements, they differ in that the subsolvus granites are depleted in TiO2, FeO*, Ba, Sr and Zr and enriched in Rb and Y with respect to the hypersolvus granites. The two granite types, however, can be distinguished more easily by their rare-earth element (REE) patterns. Chondrite-normalized REE patterns of the hypersolvus granite display a gull-wing shape, characterized by a large negative Eu anomaly and moderate-to-high LREE contents. Relative to the hypersolvus granite, subsolvus granite is depleted in LREE and more enriched in HREE contents. The increase of HREE in the subsolvus granite is presumably caused by F complexing during the late stage of its evolution. This is supported by the abundance of fluorite veins cross-cutting the subsolvus granite. The negative Eu anomalies in the subsolvus granite point to the role of feldspars as residual phase in the source, and as a crystallizing phase during magmatic differentiation.Field relations, textural, mineralogical and geochemical data of the post-orogenic subsolvus granite are consistent with its derivation from a parental basic magma through crystal-liquid fractionation of alkali feldspar, plagioclase, amphibole, FeTi oxides, titanite, zircon, monazite and allanite. Crystallization occurred in a water-enriched and rather oxidizing environment, as a result of which the entire suite has a transitional character between that of a post-orogenic and an anorogenic setting. On the other hand, the most credible mechanism for the origin of the anorogenic hypersolvus granite is partial melting of I-type granodiorite-monzogranite source rocks in the study area.  相似文献   

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7.
Nanoglobules are a form of organic matter found in interplanetary dust particles and primitive meteorites and are commonly associated with 15N and D isotopic anomalies that are suggestive of interstellar processes. We report the discovery of two isotopically-anomalous organic globules from the Stardust collection of particles from Comet 81P/Wild 2 and compare them with nanoglobules from the Murchison CM2 meteorite. One globule from Stardust Cometary Track 80 contains highly aromatic organic matter and a large 15N anomaly (δ15N = 1120‰). Associated, non-globular, organic matter from this track is less enriched in 15N and contains a mixture of aromatic and oxidized carbon similar to bulk insoluble organic material (IOM) from primitive meteorites. The second globule, from Cometary Track 2, contains non-aromatic organic matter with abundant nitrile (CN) and carboxyl (COOH) functional groups. It is significantly enriched in D (δD = 1000‰) but has a terrestrial 15N/14N ratio. Experiments indicate that similar D enrichments, unaccompanied by 15N fractionation, can be reproduced in the laboratory by electron irradiation of epoxy or cyanoacrylate. Thus, a terrestrial origin for this globule cannot be ruled out, and, conversely, exposure to high-energy electron irradiation in space may be an important factor in producing D anomalies in organic materials. For comparison, we report two Murchison globules: one with a large 15N enrichment and highly aromatic chemistry analogous to the Track 80 globule and the other only moderately enriched in 15N with IOM-like chemistry. The observation of organic globules in Comet 81P/Wild 2 indicates that comets likely sampled the same reservoirs of organic matter as did the chondrite parent bodies. The observed isotopic anomalies in the globules are most likely preserved signatures of low temperature (<10 K) chemistry in the interstellar medium or perhaps the outer regions of the solar nebula. In other extraterrestrial samples, D isotopic anomalies, but not those of 15N, may be explained in part by exposure to ionizing electron radiation.  相似文献   

8.
The adsorption of gentisic acid (GA) by hematite nano-particles was examined under static and dynamic conditions by conducting batch and column tests. To simulate natural sediments, the iron oxide was deposited on 10 μm quartz particles. The GA adsorption was described by a surface complexation model fitted to pH-adsorption curves with GA concentrations of 0.1-1 mM in a pH range of 3-10. The surface was described with one type of site (FeOH°), while gentisic acid at the surface was described by two surface complexes (FeLH2°, log Kint = 8.9 and FeLH−, log Kint = −8.2). Modeling was conducted with PHREEQC-2 using the MINTEQ database. From a kinetic point of view, the intrinsic chemical reactions were likely to be the rate-limiting step of sorption (∼10−3 s−1) while external and internal mass transfer rates (∼102 s−1) were much faster. Under flow through conditions (column), adsorption of GA to hematite-coated sand was about 7-times lower than under turbulent mixing (batch). This difference could not be explained by chemical adsorption kinetics as shown by test calculations run with HYDRUS-1D software. Surface complexation model simulations however successfully described the data when the surface area was adjusted, suggesting that under flow conditions the accessibility to the reactive surface sites was reduced. The exact mechanism responsible for the increased mobility of GA could not be determined but some parameters suggested that decreased external mass transfer between solution and surface may play a significant role under flow through conditions.  相似文献   

9.
In this study the physico-chemical, titration and sorption characteristics of Na-illite du Puy (Na-illite) have been measured and modelled. Samples of illite, collected in the region of le Puy-en-Velay, France, were purified and conditioned to the Na-form and physico-chemically characterised. Potentiometric titrations on suspensions of the Na-illite were carried out using a batch backtitration technique in 0.01, 0.1 and 0.5 M NaClO4 background electrolytes from pH∼3 to ∼11.5 in an inert atmosphere glove box. The supernatant solutions from each titration experiment in each series were analysed for K, Mg, Ca, Sr, Si, Al, Fe and Mn. The titration data were modelled in terms of the protolysis of two amphoteric edge sites (SW1OH and SW2OH) without an electrostatic term. Sorption edges (solid/liquid distribution ratios versus pH at trace sorbate concentrations and constant ionic strength) were determined for the transitions metals Ni(II) and Co(II), the lanthanide Eu(III), and the heavy metal Sn(IV) on Na-illite with NaClO4 as the background electrolyte under anoxic conditions (CO2 ? 2 ppm, O2 ? 2 ppm). The study thus encompasses a broad range of metals with different thermodynamic characteristics and with valence states ranging from II to IV. The results from the modelling of the titration data, in combination with a non electrostatic surface complexation and cation exchange sorption model were applied to quantitatively describe the uptake characteristics of the metals listed above on Na-illite. Since sorption edges were measured at trace concentrations, metal uptake was modelled as occurring on strong type sites (SSOH) only. This sorption model, the two site protolysis non electrostatic surface complexation and cation exchange model (2SPNE SC/CE model) had been previously developed and used to describe metal uptake on montmorillonite.  相似文献   

10.
Molecular dynamics simulations of water in contact with the (0 0 1) and (0 1 0) surfaces of orthoclase (KAlSi3O8) were carried out to investigate the structure and dynamics of the feldspar-water interface, contrast the intrinsic structural properties of the two surfaces, and provide a basis for future work on the diffusion of ions and molecules in microscopic mineral fractures. Electron density profiles were computed from the molecular dynamics trajectories and compared with those derived experimentally from high-resolution X-ray reflectivity measurements by Fenter and co-workers [Fenter P., Cheng L., Park C., Zhang H. and Sturchio N. C. (2003a) Structure of the orthoclase (0 0 1)- and (0 1 0)-water interfaces by high-resolution X-ray reflectivity. Geochim. Cosmochim. Acta67, 4267-4275]. For each surface, three scenarios were considered whereby the interfacial species is potassium, water, or a hydronium ion. Excellent agreement was obtained for the (0 0 1) surface when potassium is the predominant interfacial species; however, some discrepancies in the position of the interfacial peaks were obtained for the (0 1 0) surface. The two surfaces showed similarities in the extent of water ordering at the interface, the activation energies for water and potassium desorption, and the adsorption localization of interfacial species. However, there are also important differences between the two surfaces in the coordination of a given adsorbed species, adsorption site densities, and the propensity for water molecules in surface cavities and those in the first hydration layer to coordinate to surface bridging oxygen atoms. These differences may have implications for the extent of dissolution in the low-pH regime since hydrolysis of Si(Al)OSi(Al) bonds is a major dissolution mechanism.  相似文献   

11.
Structures, stabilities and vibrational spectra have been calculated using molecular quantum mechanical methods for As(OH)3, AsO(OH)3, As(SH)3, AsS(SH)3 and their conjugate bases and for several species with partial substitution of S for O. Properties for the neutral gas-phase molecules are calculated with state-of-the-art methods which yield AsL distances within 0. 01 Å and AsL stretching frequencies within 10 cm−1 of experiment. Similar accuracy is obtained for neutral molecules in solution using a polarizable continuum model (PCM). For monoanions such as and frequencies can be calculated to within 20 cm−1 of experiment using the polarizable continuum model. Multiply charged anions remain a challenge for accurate frequency calculations, but we have obtained results within the PCM model which at least semiquantitatively reproduce the available data. This allows us to assign the controversial features D, E and F in the Raman data of (Wood S. A., Tait C. D. and Janecky D. R. (2002) A Raman spectroscopic study of arsenite and thioarsenite species in aqueous solution at 25 °C. Geochem. Trans. 3, 31-39).To help in the assignment of the arsenic sulfide spectra we have also calculated energetics for the oxidation of As(III) to As(V) compounds by polysulfides, disproportionation of As(III) compounds and for the dissociation of the oxo- and thio-acids. We have determined that As(III) oxyacids can be transformed to thioacids which can in turn be oxidized to As(V) sulfides by polysulfides and that the pKa1s of the acids involved can be ordered as follows: AsS(SH)3 < As(SH)3 < AsO(OH)3 < As(OH)3 in order of increasing pKa1. We have also established from the calculated energies that the most stable form of the As(III) oxyacid in acidic aqueous solution is indeed As(OH)3, consistent with previous assignments.  相似文献   

12.
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13.
Characterization of humic substances is challenging due to their structural complexity and heterogeneity. Solid state nuclear magnetic resonance (NMR) is regarded as one of the best tools for elucidating structures of humic substances. The primary solid state NMR technique that has been used so far is the routine 13C cross polarization-magic angle spinning (CP-MAS) technique. Although this technique has markedly advanced our understanding of humic substances, the full potential of NMR for characterizing humic substances has yet to be realized. Recent technical developments and applications of advanced solid state NMR have revealed the promise to provide deeper insights into structures of humic substances. In this paper, we summarized and demonstrated the systematic solid state NMR protocol for characterization of humic substances using a humic acid as an example. This protocol included (1) identification of specific functional groups using spectral editing techniques, occasionally assisted by 1H13C two-dimensional heteronuclear correlation (2D HETCOR) NMR, (2) quantification of specific functional groups based on direct polarization-magic angle spinning (DP-MAS) and DP-MAS with recoupled dipolar dephasing, combined with spectral editing techniques, (3) determination of connectivities and proximities of specific functional groups by 1H13C 2D HETCOR or 2D HETCOR combined with spectral editing techniques, and (4) examination of domains and heterogeneities by 1H13C 2D HETCOR with 1H spin diffusion. We used a soil humic acid as an example to demonstrate how this protocol was applied to the characterization of humic substances step by step. Afterwards, based on typical 13C NMR spectra of humic substances we described how we could combine different NMR techniques to identify specific functional groups band by band from downfield to upfield. Finally, we briefly mentioned the potential new NMR techniques that could be developed to enrich the current systematic protocol. This systematic protocol is not only applicable to humic substances but also to other natural organic matter samples.  相似文献   

14.
The 2 site protolysis non electrostatic surface complexation and cation exchange (2SPNE SC/CE) sorption model has been used over the past decade or so to quantitatively describe the uptake of metals with oxidation states from II to VI on 2:1 clay minerals; montmorillonite and illite. One of the main features in this model is that there are two broad categories of amphoteric edge sorption sites; the so called strong (SSOH) and weak (SW1OH) sites. Because of their different sorption characteristics, it was expected that the coordination environments of the surface complexes on the two site types would be different. Zn isotherm data on two montmorillonites, Milos and STx-1, were measured and modelled using the 2SPNE SC/CE sorption model. The results were used to define the most favourable experimental conditions under which Zn sorption was either dominated by the strong (SSOH, ∼2 mmol kg−1) or by the weak sites (SW1OH, ∼40 mmol kg−1). Highly oriented self-supporting films were prepared for polarised extended X-ray absorption fine structure (P-EXAFS) investigations.Montmorillonites often contain Zn incorporated in the clay matrix. The Zn bound in this form was quantified and the results from the analysis of the P-EXAFS spectra were taken into account in the interpretation of the spectra measured at low Zn loadings (∼2 mmol kg−1) and medium Zn loadings (∼30 mmol kg−1). The Zn spectra on the “strong sites” exhibited a pronounced angular dependency and formed surface complexes in the continuity of the Al-octahedral sheets at the montmorillonite edges. In contrast, the Zn “weak site” spectra showed only a weak angular dependency. The spectroscopic evidence indicates the existence of two distinct groups of edge surface binding sites which is consistent with a multi-site sorption model and in particular with the strong/weak site concept intrinsic to the 2SPNE S/CE sorption model.  相似文献   

15.
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16.
The thermal dehydroxylation of a goethite-carbonate solid solution was studied with combined Fourier-transform infrared (FTIR)-Temperature programmed desorption (TPD) experiments. The TPD data revealed dehydroxylation peaks involving the intrinsic dehydroxylation of goethite at 560 K and a low temperature peak at 485 K which was shown to be associated to the release of non-stoichiometric water from the goethite bulk and surface. The FTIR and the TPD data of goethite in the absence of adsorbed carbonate species revealed the presence of adventitious carbonate mostly sequestered in the goethite bulk. The release of carbonate was however not only related to the dehydration of goethite but also from the crystallization of hematite at temperatures exceeding 600 K. The relative abundance of surface hydroxyls was shown to change systematically upon goethite dehydroxylation with a preferential stripping of singly-coordinated OH sites followed by a dramatic change in the dominance of the different surface hydroxyls upon the formation of hematite.  相似文献   

17.
Proton binding constants for the edge and basal surface sites of kaolinite were determined by batch titration experiments at 25 °C in the presence of 0.1 M, 0.01 M and 0.001 M solutions of NaNO3 and in the pH range 3-9. By optimizing the results of the titration experiments, the ratio of the edge sites to the basal surface sites was found to be 6:1. The adsorption of Cd(II), Cu(II), Ni(II), Zn(II) and Pb(II) onto kaolinite suspensions was investigated using batch adsorption experiments and results suggested that in the lower pH range the metallic cations were bound through non-specific ion exchange reactions on the permanently charged basal surface sites (X−). Adsorption on these sites was greatly affected by ionic strength. With increasing pH, the variable charged edge sites (SOH) became the major adsorption sites and inner-sphere specifically adsorbed monodentate complexes were believed to be formed. The effect of ionic strength on the extent of adsorption of the metals on the variable charged edge sites was much less than those on the permanently charged sites. Two binding constants, log K(X2Me) and log K(SOMe), were calculated by optimizing these constants in the computer program FITEQL. A model combining non-specific ion exchange reactions and inner-sphere specific surface complexations was developed to predict the adsorption of heavy metals onto kaolinite in the studied pH range. Linear free energy relationships were found between the edge site binding constants and the first hydrolysis constants of the metals.  相似文献   

18.
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19.
The stability and structure of aqueous complexes formed by trivalent antimony (SbIII) with carboxylic acids (acetic, adipic, malonic, lactic, oxalic, tartaric, and citric acid), phenols (catechol), and amino acids (glycine) having O- and N-functional groups (carboxyl, alcoholic hydroxyl, phenolic hydroxyl and amine) typical of natural organic matter, were determined at 20 and 60 °C from solubility and X-ray absorption fine structure (XAFS) spectroscopy measurements. In organic-free aqueous solutions and in the presence of acetic, adipic, malonic acids and glycine, both spectroscopic and solubility data are consistent with the dominant formation of SbIII hydroxide species, , at strongly acid, acid-to-neutral and basic pH, respectively, demonstrating negligible complexing with mono-functional organic ligands (acetic) or those having non adjacent carboxylic groups (adipic, malonic). In contrast, in the presence of poly-functional carboxylic and hydroxy-carboxylic acids and catechol, SbIII forms stable 1:1 and 1:2 complexes with the studied organic ligands over a wide pH range typical of natural waters (3 < pH < 9). XAFS spectroscopy measurements show that in these species the central SbIII atom has a distorted pseudo-trigonal pyramidal geometry composed of the lone pair of 5s2 electrons of Sb and four oxygen atoms from two adjacent functional groups of the ligand (OC-OH and/or COH), forming a five-membered bidendate chelate cycle. Stability constants for these species, generated from Sb2O3 (rhomb.) solubility experiments, were used to model Sb complexing with natural humic acids possessing the same functional groups as those investigated in this study. Our predictions show that in an aqueous solution of pH between 2 and 10, containing 1 μg/L of Sb and 5 mg/L of dissolved organic carbon (DOC), up to 35% of total dissolved Sb binds to aqueous organic matter via carboxylic and hydroxy-carboxylic groups. This amount of complexed Sb for typical natural DOC concentrations is in agreement with that estimated from dialysis experiments performed with commercial humic acid in our work and those available in the literature for a range of standardized IHSS humic acids. Our results imply that a significant part of Sb is likely to be bound with humic acids via hydroxy-carboxylic moieties, in the form of bidendate complexes. However, following the strong chemical affinity of SbIII for reduced sulfur, some undefined fraction of SbIII might also be bound to the minor thiol-bearing moieties of humic acids; further studies are required to check this hypothesis.  相似文献   

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