ATR-FTIR spectroscopic studies of boric acid adsorption on hydrous ferric oxide

Boron is an important micronutrient for plants, but high B levels in soils are often responsible for toxicity effects in plants. It is therefore important to understand reactions that may affect B availability in soils. In this study, Attenuated Total Reflectance Fourier transform Infrared (ATR-FTIR) spectroscopy was employed to investigate mechanisms of boric acid (B(OH)₃) and borate (B(OH)₄⁻) adsorption on hydrous ferric oxide (HFO). On the HFO surface, boric acid adsorbs via both physical adsorption (outer-sphere) and ligand exchange (inner-sphere) reactions. Both trigonal (boric acid) and tetrahedral (borate) boron are complexed on the HFO surface, and a mechanism where trigonal boric acid in solution reacts to form either trigonal or tetrahedral surface complexes is proposed based upon the spectroscopic results. The presence of outer-sphere boric acid complexes can be explained based on the Lewis acidity of the B metal center, and this complex has important implications for boron transport and availability. Outer-sphere boric acid is more likely to leach downward in soils in response to water flow. Outer-sphere boron would also be expected to be more available for plant uptake than more strongly bound boron complexes, and may more readily return to the soil solution when solution concentrations decrease.     

Bridging arsenate surface complexes on the hematite (0 1 2) surface

The fate of the oxoanion arsenate in diverse systems is strongly affected by its adsorption on the surfaces of iron (oxyhydr)oxide minerals. Predicting this behavior in the environment requires an understanding of the mechanisms of arsenate adsorption. In this study, the binding site and adsorption geometry of arsenate on the hematite (0 1 2) surface is investigated. The structure and termination of the hematite (0 1 2)-water interface were determined by high resolution X-ray reflectivity, revealing that two distinct terminations exist in a roughly 3:1 proportion. The occurrence of multiple terminations appears to be a result of sample preparation, and is not intrinsic to the hematite (0 1 2) surface. X-ray standing wave (XSW) measurements were used to determine the registry of adsorbed arsenate to the hematite structure, and thus the binding site and geometry of the resulting surface complex. Arsenate forms a bridging bidentate complex on two adjacent singly coordinated oxygen groups on each of the two distinct terminations present at the hematite surface. Although this geometry is consistent with that seen in past studies, the derived As-Fe distances are longer, the result of the topology of the FeO₆ octahedra on the (0 1 2) surface. As EXAFS-derived As-Fe distances are often used to determine the adsorption mechanism in environmental samples (e.g., mine tailings, contaminated sediments), this demonstrates the importance of considering the possible sorbent surface structures and arrangements of adsorbates when interpreting such data.As multiple functional groups are present and multiple binding geometries are possible on the hematite (0 1 2) surface, the XSW data suggest that formation of bridging bidentate surface complexes on singly coordinated oxygen sites is the preferred adsorption mechanism on this and most other hematite surfaces (provided those surfaces contain adjacent singly coordinated oxygen groups). These measurements also constrain the likely reaction stoichiometry, with only the protonation state of the surface complex undetermined. Although bridging bidentate inner-sphere surface complexes comprised the majority of the adsorbed arsenate present on the hematite (0 1 2) surface, there is an additional population of sorbed arsenate species that could not be characterized by the XSW measurements. These species are likely more disordered, and thus more weakly bound, than the bridging bidentate complexes, and may play a role in determining the fate, transport, and bioavailability of arsenate in the environment. Finally, the possibility of obtaining species-specific XSW measurements by tuning the incident beam energy to specific features in a XANES spectrum is described.     

Fractal characterization of hematite aggregates by X-ray microscopy

X-ray microscopy supplies the actual morphology of hematite aggregates in an aqueous dispersion medium. The fractal dimension of hematite aggregates has been determined below and above the critical coagulation concentration. The box-counting method has been used as a morphometric tool. The values obtained are not in accordance with the values produced by numerical approaches.     

Microstructure characterization of mechanically activated hematite using XRD line broadening

The effect of dry milling in a vibratory mill on the structural changes and microstructural characteristics of hematite using different methods was investigated. We have described the line profile analysis (LPA) to extract the size of coherently diffracting domains and the lattice strain of activated hematite in a vibratory mill. The Warren–Averbach and Williamson–Hall methods were used as the main tools for characterization. The changes in the particle size, surface area and new phase formation of hematite concentrate were also investigated. It was concluded that the breakage and agglomeration of particles take place mainly at lower and higher levels of specific energy input, respectively. The pores in agglomerates remain accessible for the nitrogen gas. Milling of hematite increased specific surface area up to 18.4 m²/g. The hematite milled under various levels of specific energy input did not undergo a significant reaction or phase transformation during milling. The Williamson–Hall method confirms its merit for a rapid overview of the line broadening effects and possible understanding of the main causes. The anisotropic character of line broadening for deformed hematite as a function of specific energy input was revealed. Higher level of specific energy input favors the generation of small crystallite size, higher microstrain, BET surface area, amorphization and line breadth. The Warren–Averbach method suggested that the nanocrystalline hematite with grain sizes of 73.5–12.2 nm was formed by mechanical treatment using different milling intensities in the vibratory mill. The root mean square strain (RMSS) at L = 10 nm varies between 1.7 × 10^− 3 and 4.0 × 10^− 3 depending on the level of energy input. Limits in the applicability of Williamson–Hall method and reliability of the results are discussed in detail.     

Adatom Fe(III) on the hematite surface: Observation of a key reactive surface species

The reactivity of a mineral surface is determined by the variety and population of different types of surface sites (e.g., step, kink, adatom, and defect sites). The concept of "adsorbed nutrient" has been built into crystal growth theories, and many other studies of mineral surface reactivity appeal to ill-defined "active sites." Despite their theoretical importance, there has been little direct experimental or analytical investigation of the structure and properties of such species. Here, we use ex-situ and in-situ scanning tunneling microcopy (STM) combined with calculated images based on a resonant tunneling model to show that observed nonperiodic protrusions and depressions on the hematite (001) surface can be explained as Fe in an adsorbed or adatom state occupying sites different from those that result from simple termination of the bulk mineral. The number of such sites varies with sample preparation history, consistent with their removal from the surface in low pH solutions.     

The distribution of strontium between coexisting silicate and carbonate liquids at elevated pressures and temperatures

Strontium is characteristically enriched in carbonatites and associated igneous rocks. Experiments between 600 and 800°C at 5 and 10 kb show that Sr fractionates strongly toward both liquid phases of a carbonate liquid-silicate liquid-solid assemblage, with the crystalline phases depleted in Sr. Considering that the alkalic igneous rocks associated with carbonatites are not significantly depleted in Sr compared with the carbonatites, it is concluded that these complexes are formed by a pair of immiscible magmas, rather than the carbonatites being late-stage fractionation products of the alkalic silicate magmas.     

IR spectroscopic characterization of NH4-analcime

 The IR spectrum of ammonium-exchanged natural analcime (basalt, Nidym River, Siberian platform) exhibits several features that suggest a lowered symmetry for the NH₄ ⁺ ion and that this is influenced by hydrogen bonding within the framework. These features are: the pronounced splitting into three components and high-frequency shift of the ν₄-bending mode; appearance of the ν₁-stretching mode which is predicted to become IR-active when the ideal T _d symmetry of NH₄ ⁺ ion is violated, and the low-frequency shift of the ν₁- and ν₃-stretching modes. The absence of absorption lines in the 1800–2400-cm⁻¹ region indicates that hydrogen bonding between the framework and the NH⁺ ₄ ion is very weak. The three-component splitting of the ν₄-bending mode indicates that the symmetry of NH⁺ ₄ ion is lower than C_3v. This implies that at least two N–H bonds of the NH⁺ ₄ ion are disturbed by hydrogen bonding. Computer analysis of the normal vibrations of the NH⁺ ₄ molecule for different symmetry types (using harmonic approximation) indicates that the best fit to the observed ν₄ triplet frequencies for C₁ symmetry implies a deviation of the valent angle ∠H–N–H from ideal T _d symmetry of around ±2.5°. The factors governing the behaviour of the NH⁺ ₄ ion in the analcime structure are discussed. The geometry of the nearest environment of the NH⁺ ₄ ion in the analcime structure is analyzed with respect to the present IR data. Received: 2 January 2002 / Accepted: 26 June 2002 Acknowledgements We thank Dr. D. Harlov and an anonymous reviewer for their helpful comments, as well as Dr. I.A. Belitsky and Dr. S.V. Goryainov for discussion of the material. This work is supported by RFBR grants 01-05-65414, 00-05-65305 and 02-05-65313.     

Sedimentology of coexisting travertine and tufa deposits in a mounded geothermal spring carbonate system,Obruktepe, Turkey

The recent discoveries of deeply buried Cretaceous reservoir bodies in the Atlantic Ocean revealed that relationships between the distribution of spring carbonate deposits and faults are poorly understood. The well‐exposed Quaternary deposits at Obruktepe (Denizli Basin, Turkey) provide an opportunity to reconstruct the three‐dimensional sedimentary architecture of such a system. Integration of sedimentological, lithofacies and geochemical analyses reveals complexity in the lateral relationships between sedimentary environments, faults and geothermal spring carbonates. Five environmental systems are distinguished based on the lithofacies analysis: (i) vent; (ii) smooth slope; (iii) travertine‐terrace; (iv) tufa‐barrage; and (v) flood systems. Encrusting, baffling and settling sedimentary processes are reflected in data acquired at several scales, from lithofacies observations to the morphology and arrangement of geobodies, together with microfabrics and stable carbon and oxygen isotope data. Mean values of +4·9‰ δ¹³C and −8·74‰ δ¹⁸O Vienna PeeDee Belemnite reflect geothermal circulation of springwaters. The environmental distribution and lithofacies indicate a lateral continuum between travertine and tufa deposits within this hot spring system. This finding supports two depositional models in which water flow variation is the main control on both CaCO₃ precipitation and the resulting formation of travertine and tufa. The proposed models address the factors responsible for the development of these complex mound‐shaped carbonate spring deposits, and how they are related to fluid circulation at depth and in association with faults.     

Site-specific incorporation of uranyl carbonate species at the calcite surface

Spatially resolved luminescence spectra from U(VI) co-precipitated at the (101?4) growth surface of synthetic calcite single crystals confirm heterogeneous incorporation corresponding to the distribution of structurally non-equivalent steps composing the vicinal surfaces of spiral growth hillocks. Spectral structure from U(VI) luminescence at the “-” vicinal regions and featureless, weak luminescence at the “+” vicinal regions are consistent with previously reported observations of enrichment at the former sites during calcite growth. Luminescence spectra differ between the non-equivalent regions of the crystal, with the spectral features from the “-” vicinal region corresponding to those observed in bulk calcite samples. Subtle spectral shifts are observed from U(VI) co-precipitated with microcrystalline calcite synthesized by a different method, and all of the U(VI)-calcite sample spectra differ significantly from that of U(VI) co-precipitated with aragonite.The step-selective incorporation of U(VI) can be explained by a proposed model in which the allowed orientation for adsorption of the dominant calcium uranyl triscarbonate species is controlled by the atomic arrangement at step edges. Differences in the tilt angles of carbonate groups between non-equivalent growth steps favor adsorption of the calcium uranyl triscarbonate species at “-” steps, as observed in experiments.     

Polarized XANES and EXAFS spectroscopic investigation into copper(II) complexes on vermiculite

Interaction of heavy metals with clay minerals can dominate solid-solution reactions in soil, controlling the fate of the metals in the environment. In this study we used powdered and polarized extended X-ray absorption fine structure (EXAFS) spectroscopy and X-ray absorption near edge spectroscopy (XANES) to investigate Cu sorbed on Llano vermiculite and compare the results to reported Cu sorption mechanism on Wyoming (WY) smectite and reduced South African (SA) vermiculite. Analysis of the Cu K-edge spectra revealed that Cu sorbed on Llano vermiculite at high ionic strength (I) has the greatest degree of covalent bond character, followed by Cu sorbed on montmorillonite at high I, and Cu sorbed on reduced SA vermiculite at high I. Cu sorbed on clay minerals at low I has the least covalent character. EXAFS data from Cu sorbed Ca- and K-equilibrated Llano vermiculites showed the presence of a second-shell Al, Si, or Mg backscatterer at 3.02 Å. This distance is consistent with Cu sorbing via a corner-sharing monodentate or bidentate bond. Polarized XANES and EXAFS results revealed that the angle between the Cu atom and the mineral sorption sites is 68° with respect to the [001] direction. From the bond angle and the persistence of the second-shell backscatterer when the interlayer is collapsed (K-equilibration), we conclude that Cu adsorption on the Llano vermiculite is not occurring in the interlayer but rather Cu is adsorbing onto the edges of the vermiculite. Results from this research provide evidence that Cu forms inner-sphere and outer-sphere complexes on clay minerals, and does not form the vast multinuclear surface precipitates that have been observed for Co, Zn, and Ni.     

Evidence for surface reaction-controlled growth of carbonate concretions in shales

Estimates for the rate of concretionary growth in shales are based on models which assume that growth is diffusion-controlled. However, laboratory and field studies of CaCO₃ precipitation in organic carbon-rich sediments indicate that surface reactions control growth, due to inhibition by various dissolved species. The spatial distribution of carbonate concretions in the Jet Rock (Lower Jurassic, England) is also inconsistent with diffusion-controlled precipitation of CaCO³ into concretions, and growth must have been at least partly surface reaction-controlled.     

巴西桑托斯盆地湖相微生物碳酸盐岩储层内幕刻画及定量表征方法

微生物碳酸盐岩研究是近年来国内外关注的热点,虽然已经取得了一定的成果和认识,但是在储层精细描述方面研究相对薄弱。以巴西桑托斯盆地盐下白垩系湖相微生物碳酸盐岩油田为例,利用露头、岩心、测井、地震等资料综合分析了研究区储层沉积特征、岩性、物性特征及其主控因素,并在此基础上对储集体内幕结构进行分类和描述,初步建立其定量表征方法。结果表明: ①研究区由3个独立的碳酸盐岩台地沉积组成,可细分为微生物灰岩丘、高能颗粒滩、丘间洼地和台间洼地4个亚相; ②微生物灰岩、生物碎屑颗粒灰岩、介壳颗粒灰岩、层纹岩等是主要的储层岩石类型; ③储层物性较好,孔隙度4%~27%,集中在5%~15%,平均12.5%; 渗透率为(0.01~3 000)×10-3 µm2,平均120×10-3 µm2; ④储层发育受沉积和成岩双重作用,古构造控制优势储层的发育,准同生期溶蚀作用对储层改造作用加强,周期性暴露溶蚀使生物碎屑颗粒填充至丘间洼地形成高孔高渗条带; ⑤研究区储层的内幕结构以微生物灰岩丘群为基础,细分为丘基、丘核、丘翼、丘间和丘间甜点。建立以沉积相和成岩相控制因素为基础的丘群组合模式定量表征方法,在应用中获得了较好的效果。     

Theoretical study of the local charge compensation and spectroscopic properties of B-type carbonate defects in apatite

The structure and spectroscopic properties of selected models of B-type carbonate defects in apatite locally compensated by fluoride or hydroxyl ions are investigated using first-principles quantum mechanical calculations. Theoretical infrared absorption spectra and ¹³C, and ¹⁹F nuclear magnetic resonance chemical shifts are determined. Among the investigated models, only the clumped (CO₃ ^2?, F^?) defect, with the carbonate group close to the sloping face of the tetrahedral site and the F^? ion at the remaining apex, corresponds to previous experimental observations performed on carbonate-fluorapatite samples. Although the substitution of hydroxyl by fluoride ions is commonly observed in minerals, the clumped (CO₃ ^2?, OH^?) defects are unlikely to occur in apatite, considering both their theoretical spectroscopic properties and relative stability. Anionic F^? for OH^? exchange between channel and B sites displays a preference of ~20 kJ/mol for the local charge compensation by fluoride ions at the B-site, pointing to a significantly different behavior of F^? and OH^? ions in the charge compensation mechanism. This difference is ascribed to the poor H-bond acceptor character of available oxygen atoms surrounding the apex of the tetrahedral site. The explicit calculation of the infrared absorption spectra of the defect models is also used to interpret the significant difference observed in the linewidth of the ν₂ and ν₃ CO₃ infrared powder absorption bands of carbonated apatite samples. It is shown that for a concentration of 4.4 wt% of CO₂, long-range electrostatic effects already significantly contribute to the broadening of the ν₃ CO₃ bands in apatite.     

Effect of hematite on thiosulphate leaching of gold

Hematite, as a typical iron oxide slime in sulphide ore slurries, was artificially added into the leaching systems of pure gold and a sulphide ore respectively, in an attempt to investigate the effect of iron oxide slimes on the ammoniacal thiosulphate leaching of gold. The presence of hematite significantly reduced the dissolution of gold and this detrimental effect became more pronounced with increasing hematite concentration. Hematite formed coatings on gold surfaces, which could prevent leach solution from diffusing to the gold surfaces and hence, inhibit gold dissolution. Hematite catalysed the oxidative decomposition of thiosulphate to polythionates with oxygen present. XPS studies indicated a thin layer of iron oxide coating as well as the deposition of some copper and sulphur species on gold surfaces. SEM images revealed a lesser extent of corrosion for gold after leaching in the presence of hematite. The gold extraction from the sulphide ore was reduced with the addition of hematite and this effect became more noticeable with an addition of hematite at a higher concentration. A natural guar type surfactant (Gempolym M47) reduced the detrimental effect of hematite on gold extraction likely due to the prevention of hematite coating on gold and mineral particles and the dispersion of the mineral slurry. Gempolym M47 stabilised thiosulphate by weakening the interaction between cupric ions and thiosulphate and by minimising the catalytic effect of hematite on thiosulphate decomposition.     

Infrared spectroscopic and X-ray diffraction characterization of the nature of adsorbed arsenate on ferrihydrite

Fourier transformed infrared (FTIR) spectroscopy was used to characterize arsenate-ferrihydrite sorption solids synthesized at pH 3-8. The speciation of sorbed arsenate was determined based on the As-O stretching vibration bands located at 650-950 cm⁻¹ and O-H stretching vibration bands at 3000-3500 cm⁻¹. The positions of the As-O and O-H stretching vibration bands changed with pH indicating that the nature of surface arsenate species on ferrihydrite was strongly pH dependent. Sorption density and synthesis media (sulfate vs. nitrate) had no appreciable effect. At acidic pH (3, 4), ferric arsenate surface precipitate formed on ferrihydrite and constituted the predominant surface arsenate species. X-ray diffraction (XRD) analyses of he sorption solids synthesized at elevated temperature (75 °C), pH 3 clearly showed the development of crystalline ferric arsenate (i.e. scorodite). In neutral and alkaline media (pH 7, 8), arsenate sorbed as a bidentate surface complex (in both protonated FeO₂As(O)(OH)⁻ and unprotonated forms). For the sorption systems in slightly acidic media (pH 5, 6), both ferric arsenate and surface complex were probably present on ferrihydrite. It was further determined that the incorporated sulfate in ferrihydrite during synthesis was substituted by arsenate and was more easily exchangeable with increasing pH.     

塔河油田碳酸盐岩缝洞型油藏远井储集体定量化表征及动用技术

塔河油田奥陶系碳酸盐岩储层主要储集空间为溶洞和裂缝,直接钻遇溶洞比例达50%。针对目前远井储集体特征认识模糊、动用难度大等问题,基于物质平衡原理及注水指示曲线、液面恢复曲线等资料,对远井储集体的规模、裂缝导流系数、地层能量进行定量化研究,形成了一套远井储集体参数定量化表征技术。基于远井储集体特征,运用酸化、高压注水、复合措施等方法提高对远井储集体的动用,并在塔河油田推广应用,高效井占75%以上,有较好的应用前景。     

Geotechnical characterization of carbonate marls for the construction of impermeable dam cores

Fine-grained, more or less cohesive carbonate materials are extremely widespread in terms of surface area and are, therefore, commonly used as materials to construct impermeable cores for dams. However, it has not been adequately documented whether the carbonate content in fine-grained soils significantly affects their engineering behaviour. The present study shows that the carbonate content substantially influences the engineering behaviour of clayey material. For this, we subjected 32 samples to different laboratory tests, such as the normal Proctor, the Atterberg limits, granulometric analysis, oedometric and undrained triaxial tests. The resulting parameters were correlated with the carbonate content of the samples.

The materials studied in this work had been used in the construction of the impermeable core of the San Clemente Dam, belonging to the hydrographic basin of the Guadalquivir River (southern Spain). These marls present, as their prime characteristic, a carbonate content of the fine fraction consistently exceeding 50%, giving them special importance in the study of this phenomenon.

In this study, a direct relationship was found between the geotechnical properties of the soils studied and their degree of compaction, with the carbonate content and the type of minerals in the clay being the main factors determining the behaviour of these soils. Finally, we conclude that the percentage of carbonates should be used as a classification criterion for the soils used to construct the cores of earth-filled dams.     

Dehydration experiments on natural omphacites: qualitative and quantitative characterization by various spectroscopic methods

A series of natural omphacites from a wide range of P, T occurrences were investigated by electron microprobe (EMP), infrared (IR)-, Mössbauer (MS)- and optical spectroscopy in the UV/VIS spectral range (UV/VIS), secondary ion mass spectrometry (SIMS) and single crystal structure refinement by X-ray diffraction (XRD) to study the influence of hydrogen loss on valence state and site occupancies of iron. In accordance with literature data we found Fe²⁺ at M1 as well as at M2, and in a first approach assigned Fe³⁺ to M1, as indicated by MS and XRD results. Hydrogen content of three of our omphacite samples were measured by SIMS. In combination with IR spectroscopy we determined an absorption coefficient: ε _i,tot = 65,000 ± 3,000 lmol_H2O ^?1 cm^?2. Using this new ε _i,tot value, we obtained water concentrations ranging from 60 to 700 ppm H₂O (by weight). Hydrogen loss was simulated by stepwise heating the most water rich samples in air up to 800°C. After heat treatment the samples were analyzed again by IR, MS, UV/VIS, and XRD. Depending on the type of the OH defect, the grade of dehydration with increasing temperature is significantly different. In samples relatively poor in Fe³⁺ (<0.1 Fe³⁺ pfu), hydrogen associated with vacancies at M2 (OH bands around 3,450 cm^?1) starts to leave the structure at about 550°C and is completely gone at 780°C. Hydrogen associated with Al³⁺ at the tetrahedral site (OH bands around 3,525 cm^?1, Koch-Müller et al., Am Mineral, 89:921–931, 2004) remains completely unaffected by heat treatment up to 700°C. But all hydrogen vanished at about 775°C. However, this is different for a more Fe³⁺-rich sample (0.2 Fe³⁺ pfu). Its IR spectrum is characterized by a very intense OH band at 3,515 cm^?1 plus shoulder at 3,450 cm^?1. We assign this intense high-energy band to vibrations of an OH dipole associated with Fe³⁺ at M1 and a vacancy either at M1 or M2. OH release during heating is positively correlated with decrease in Fe²⁺ and combined with increase in Fe³⁺. That dehydration is correlated with oxidation of Fe²⁺ is indirectly confirmed by annealing of one sample in a gas mixing furnace at 700°C under reducing conditions keeping almost constant OH^? content and giving no indication of Fe²⁺-oxidation. Obtained data indicate that in samples with a relatively high concentration of Fe²⁺ at M2 and low-water concentrations, i.e., at a ratio of Fe^{2+ M2}/H > 10 dehydration occurs by iron oxidation of Fe²⁺ exclusively at the M2 site following the reaction: \( {\left[ {{\text{Fe}}^{{{\text{2 + [ M2]}}}}{\text{OH}}^{ - } } \right]} = {\left[ {{\text{Fe}}^{{{\text{3 + [ M2]}}}} {\text{O}}^{{{\text{2}} - }} } \right]} + {\text{1/2}}\;{\text{H}}_{{\text{2}}} \uparrow . \) In samples having relatively low concentration of Fe²⁺ at M2 but high-water concentrations, i.e., ratio of Fe^{2+ M2}/H < 5.0 dehydration occurs through oxidation of Fe²⁺ at M1.