Auswahl der wissenschaftlichen Literatur zum Thema „Ca-bentonite“

Removal of fluoride from aqueous solution by using Ca-bentonite and H-bentonite (acid-treated bentonite) was studied by batch equilibrium method. The fluoride sorption capacity of Ca-bentonite increases with the fluoride concentration increase or the pH-value decrease. H-bentonite has better affinity to fluoride than Ca-bentonite. H-bentonite can be used effectively for fluoride removal as a low cost adsorbent. The adsorption type of H-bentonite is ion exchange and the adsorption type of Ca-bentonite can be explained by ion exchange and physical adsorption.

This study aims to investigate workability and microstructural characteristics of sodium hexametaphosphate (SHMP)-treated calcium bentonite (Ca-bentonite) as a potential material for soil–bentonite slurry trench cutoff walls. First, a series of Marsh viscosity, filtrate loss, density, and pH experiments are performed on bentonite – tap water slurries containing Ca-bentonite amended with 0%–8% SHMP dosages. Subsequently, scanning electron microscopy (SEM), X-ray diffraction (XRD), Fourier transform infrared spectroscopy, and zeta potential tests are conducted to explore microstructural characteristics that control the mechanisms of SHMP treatment. The results indicate that the workability of the slurry is significantly improved with SHMP addition. The SEM, XRD, and zeta potential analyses show that SHMP-amended Ca-bentonite possesses a more dispersed structure and higher negative zeta potential relative to the unamended Ca-bentonite. The mechanisms of SHMP amendment are identified to be exchange of bivalent calcium cations in Ca-bentonite by monovalent sodium cations in the SHMP, sorption of the SHMP anions that give the clay system a steric stabilization and increased negative surface charge density, and sequestration of the bivalent calcium cations on the Ca-bentonite. Overall, the SHMP treatment is effective in making the Ca-bentonite slurry amenable for use in the soil–bentonite slurry trench wall construction.

Four kinds of bentonite samples were studied in this paper. Mainly discussing the particle size distribution, mineral composition and physicochemical properties of bentonite, the aim was to provide a useful reference for the efficient development and utilization of bentonite resources. The results indicated that NM-bent., HB-bent. and EZ-bent. were Ca (Mg)-bentonite while XZJ-bent. was Na-bentonite. The physicochemical properties of bentonite mainly depended on interlayer cations. Many properties indexes of Na-bentonite were better than that of Ca (Mg)-bentonite. Some properties indexes showed a poor reproducibility when tested by standard methods. The natural Na-bentonite has excellent properties and extensive application prospects while Ca (Mg)-bentonite needed for further processing to meet the demand of the application field.

Phenolic compounds areorganic pollutants that are toxic and carcinogenic.The presence of phenol in the environmentcan be adverse to humanand the environmentalsystem. One methodthat iseffective toreduce thephenolisadsorption. In this study, the adsorption of phenol in aqueous solution using Ca-bentonite/chitosan composite was investigated. Chitosan is the deacetylation product of chitin from shrimp waste. Characterization of Ca-bentonite/chitosan composite was done by using Fourier Transform Infrared (FTIR) and Scanning Electron Microscopy-Energy Dispersive X Ray Spectroscopy (SEM-EDX). Batch adsorption studies were performed to evaluate the effects of some parameters such as initial concentration of phenol, composite weight, pH and contact time. The results showed that FTIR spectra of Ca-bentonite/chitosan composite presented the characteristic of peak of Ca-bentonite and chitosan that confirmed the successful synthesis of composite. The SEM-EDX characterizationresultsshowedCa-bentonite surfacecoverage by chitosanand the presence ofcarbonandnitrogenelementsinCa-bentonite/chitosancompositeindicated that chitosan had bonded with bentonite. The optimum condition of adsorption of Ca-bentonite/chitosan to phenol was obtained at 125 mg.L-1 of concentration in which the weight of composite was 1.0 g, the pH of solution was 7, the contact time was 30 minutes, and the capacity of adsorption was 12.496 mg.g-1.

Hunyuan Ca-based bentonite is one of large-type bentonite deposits in China, the reserve of which is more than 0.15 billion tons. However, they are not completely utilized in the pellet production. Process mineralogy investigation shows that the bentonite is a kind of typical Ca-bentonite (Ca-Bent). The sodium modification of the sample is studied by suspension method in this study. Results present the alkali coefficient K of modified Na-bentonite that is increased from 0.34 to 1.33, and the 2HWA, dilation, and colloid index are, respectively, increased to 601%, 32.4 mL/g and 87.6 mL/(3 g) under optimal conditions of Na2CO3 dosage 3.0%, pulp density 20%, sodium temperature 55°C, and sodium time 0.5 h. The XRD patterns show that d(001) of the sample bentonite is reduced from 1.5539 nm down to 1.2467 nm, and 2θ(001) of the sample bentonite is increased from 5.6875° to 7.0907°, indicating that the sample Ca-Bent is effectively modified into Na-Bent.

Modified calcium bentonite (Ca-bentonite) is extensively used in engineered barrier systems (EBSs) for municipal and industrial disposal sites due to its high swelling potential and low hydraulic conductivity. However, few studies have focused on the micromechanism of hydration and swelling under the effect of inorganic chemical solution. In this study, free swell index (FSI) and the type and content of modified Ca-bentonite bound water under the inorganic chemical solution were quantitatively studied by using the free swell test and nuclear magnetic resonance (NMR). According to the results, modification of sodium and polymer significantly increases the FSI of Ca-bentonite, bringing it close to that of natural sodium bentonite. In addition, the chemical stability of polymer-modified bentonite is significantly higher than that of sodium-modified bentonite but less than that of natural Na-bentonite. The FSI of modified Ca-bentonite decreases with the increase of cation valence and ionic strength. T2 distribution curves of the two types of modified bentonite are three-peak curves. With the increase of ionic strength, the content of total water and permeated hydrated water (accounting for 69%–95%) in bentonite decreases gradually, whereas the surface hydration water (accounting for 2%–31%) and free water content (accounting for 0–15%) increase. A uniform linear relationship exists between the FSI and corresponding total peak area of NMR (independent of ion valence, concentration, and bentonite type). Furthermore, a linear relationship exists between the FSI of the same type of bentonite and the T2 relaxation time. Research results can provide data and theoretical basis for quantitative analysis and mechanism of the hydration swelling of bentonite.

The thermal and acid stability of the bentonite clays (Na- and Ca-bentonite) have been tested. The thermal stability testing has been carried out by heating 5 gram of the clays for five hours at 200, 300 and 500 °C respectively, meanwhile acid stability testing was performed by immersing 5 gram clays into 100 mL sulphuric acid 1M, 2M and 3M for 24 hours. The tested clays, then were characterized by means of X-Ray difractometry and IR-spectroscopy methods. The characterization results showed that upon heating, both Ca- and Na-bentonites indicated same thermal stability. However, upon acid treatment, Na-bentonite was found relatively stabiler and more resistance then Ca-bentonite. Keywords: bentonite, clay, thermal stability, acid stability.

To fully evaluate the usability of a raw Ca-bentonite source and to deeply understand the property of bentonite mineral are critical for applications of these special layered materials. Due to sodium bentonites have several advantages over calcium bentonites, especially in expansibility, cation exchange capacity, cohesive force, dispersibility, and thermostability, sodium-modification of Ca-bentonite is regarded as a top priority of effective utilization of abundant Ca-bentonite source in China. In present work, the purified Na-montmorillonite was synthesized by purification and sodium-modification of a raw Ca-bentonite source (Liaoning, China) by tri-roller grinder. Important influencing factor rolling times in purification and sodium modification process was investigated. Mineral compositions, microscopic morphology, and thermal stability were characterized by using different techniques. The crystalline phases and compositions were identified by X-ray powder diffraction (XRD). The morphology and structure were evaluated by scanning electron microscopy (SEM). The thermal properties were investigated using differential thermal gravity analysis (DTG) and differential thermal analysis (DTA) analysis.

With the aim to determine the influence of dominant interlayer cation on the sorption and diffusion properties of bentonite, diffusion experiments with Sr on the compacted homoionous Ca- and Na-forms of Czech natural Mg/Ca bentonite using the planar source method were performed. The bentonite was compacted to 1400 kg·m−3, and diffusion experiments lasted 1, 3 or 5 days. Two methods of apparent diffusion coefficient Da determination based on the analytical solution of diffusion equation for ideal boundary conditions in a linear form were compared and applied. The determined Da value for Ca-bentonite was 1.36 times higher than that for Na-bentonite sample. Values of Kd were determined in independent batch sorption experiments and were extrapolated for the conditions of compacted bentonite. In spite of this treatment, the use of Kd values determined by batch sorption experiments on a loose material for the determination of effective diffusion coefficient De values from planar source diffusion experiments proved to be inconsistent with the standard Fickian description of diffusion taking into account only the pore diffusion in compacted bentonite. Discrepancies between Kd and De values were measured in independent experiments, and those that resulted from the evaluation of planar source diffusion experiments could be well explained by the phenomenon of surface diffusion. The obtained values of surface diffusion coefficients Ds were similar for both studied systems, and the predicted value of total effective diffusion coefficient De(tot) describing Sr transport in the Na-bentonite was four times higher than in the Ca-bentonite.

Clays are considered as potential host rocks and backfill material for deep geological repositories for radioactive waste. Therefore, profound understanding of radionuclide retention processes at clay mineral surfaces is essential for a long-term safety assessment. This understanding has already been generated in the past for simple chemical systems, in which experiments are easy to conduct and interpretation is straightforward. However, there is still a lack of molecular process understanding when considering complex natural systems (low radionuclide concentrations, high ionic strength, high pH values, multi-mineral solid phases, complex solution composition). This thesis aims to close some of these knowledge gaps, focusing on U(VI) and Np(VI) sorption on clays at (hyper)alkaline conditions. pH values between 10 and 13 can prevail in the near-field of a radioactive waste repository as a result of the degradation of concrete, which is part of the geo-engineered barrier. Existing studies on radionuclide sorption on clays do not exceed pH 10. Therefore, within this work, a comprehensive investigation in the pH range 8-13 was conducted. This included the quantification of radionuclide retention in batch sorption experiments as well as spectroscopic investigations to generate understanding about the underlying retention mechanisms on a molecular level. Beside the pH, additional focus was on the influence of dissolved carbonate and calcium on radionuclide sorption at (hyper)alkaline conditions. Next to two small chapters dealing with the stability and surface charge of Ca-bentonite at (hyper)alkaline conditions (chapter 4.1) and the influence of ISA on U(VI) sorption at high pH values (chapter 4.3), the thesis can be subdivided in two major parts. The first part (chapter 4.2) is a detailed investigation of U(VI) sorption on Ca-bentonite at (hyper)alkaline conditions in mixed electrolyte solutions. Batch sorption experiments were conducted, varying a number of experimental parameters (sorption time, S/L ratio, U(VI) concentration, pH value, carbonate concentration) and assessing their effect on U(VI) sorption. In order to be able to explain the observed sorption behavior, next to U(VI) solubility tests, spectroscopic techniques were applied. The aqueous speciation of U(VI) was investigated with TRLFS, while its surface speciation was probed with ATR FT-IR, site-selective TRLFS, EXAFS and CTR/RAXR. Since the results of this chapter indicated a great importance of the presence of calcium (see below), the second major part of the thesis (chapter 4.4) was dedicated to a careful evaluation of the influence of calcium on An(VI) sorption on clay minerals at (hyper)alkaline conditions. This encompasses the sorption of Ca(II) on Ca-bentonite and its effect on the bentonite surface charge. Furthermore, U(VI) batch sorption experiments with Na-montmorillonite, synthetic kaolinite and muscovite were conducted in 0.1 M NaCl as well as in 0.1 M NaCl + 0.02 M CaCl2 at pH 8-13, in order to quantify the influence of calcium on U(VI) sorption on supposedly Ca-free mineral phases. Site-selective TRLFS was applied with the aim to observe U(VI) sorption species involving calcium. Finally, complementary sorption experiments Np(VI) on muscovite were performed in order to check whether its sorption behavior is analogous to U(VI) under the given conditions. Batch sorption experiments demonstrate that U(VI) retention on Ca-bentonite can be very effective at pH > 10, even in the presence of carbonate and despite the prevalence of anionic aqueous species. Above a certain pH, depending on the concentration of carbonate in solution, carbonate does not play a role in the aqueous U(VI) speciation anymore due to the predominance of hydrolysis. TRLFS measurements revealed a clear correlation between sorption behavior and aqueous U(VI) speciation, showing that retention reaches a maximum at pH 10-12, where UO2(OH)3− is the predominant aqueous species. This raised the question whether the strong retention can be achieved by adsorption of an anionic species to the negatively charged mineral surface or rather by precipitation of uranates. By in situ ATR FT-IR and CTR/RAXR experiments the formation of U(VI) precipitates on the mineral surface was observed at U(VI) concentrations of 2×10-5 M and 5×10-5 M, respectively. However, solubility tests at sub-micromolar U(VI) concentrations, which were also applied in the batch sorption experiments, showed that the observed complete U(VI) removal at pH 10-12 cannot be attributed to precipitation of (earth) alkali-uranates from the solution. In order to unambiguously distinguish between surface precipitation and surface complexation, direct spectroscopic investigations of the U(VI) complexes on the Ca-bentonite surface were performed with site-selective TRLFS and EXAFS. The occurrence of luminescence line-narrowing and the frequency of the total symmetric stretch vibration obtained from the site-selective TRLFS emission spectra, indicate the presence of two U(VI) surface complexes. Also EXAFS spectroscopy confirmed the presence of two independent U(VI) sorption species on Ca-bentonite at pH 8-13. With increasing pH, the nature of the retained U(VI) complexes shifts from bidentate inner-sphere surface complexes with an overall equatorial coordination of five adsorbed on aluminol or silanol edge sites to surface complexes with a 4-fold equatorial coordination, resembling the aqueous species UO2(OH)42−. For the first time, a 4-fold coordination in the equatorial plane of U(VI) was univocally proven with the help of a multiple-scattering feature originating from the strong symmetry of the complexes, and without the need for error-prone shell fitting. The lack of scattering paths from the substrate and the comparatively high value for the total symmetric stretch vibration indicate that the high-pH-component is an outer-sphere complex. Concerning the character of the second sorption species at very high pH it was hypothesized that the anionic uranyl hydroxide complexes are mediated to the surface by calcium cations. It was found that calcium sorbs strongly on Ca-bentonite between pH 8 and 13. Also zeta potential measurements showed a partial compensation of the strongly negative surface charge of Ca-bentonite due to adsorption of calcium. U(VI) sorption on kaolinite and muscovite was strongly reduced in the absence of calcium at pH > 10. An increased retention upon addition of calcium proved the sorption enhancing effect of calcium at pH 10-12. Site-selective TRLFS allowed the spectroscopic observation and identification of calcium-induced U(VI) sorption complexes on muscovite. The obtained spectra correspond to the outer-sphere species found on Ca-bentonite. Combining the findings from batch sorption, zeta potential, TRLFS and EXAFS suggests that calcium adsorbs to the mineral surface in the first place, displaying locally positively charged sites which enable an electrostatically driven attachment of anionic uranyl hydroxides. The same effect could also be demonstrated for Np(VI) sorption on muscovite, which was also strongly enhanced in the presence of calcium at pH 9-12. ISA leads to a mobilization of U(VI) at (hyper)alkaline conditions only when present in very high excess of U(VI). A reduction of sorption on Ca-bentonite and the formation of aqueous U(VI)-ISA complexes, detected with TRLFS, occurred at an U:ISA ratio of 1:100,000. Such conditions are not likely to be found in deep geological repository environments. Based on these findings it can be concluded that under certain alkaline repository conditions, where precipitation does not occur (due to very low concentrations or kinetic restraints), U(VI) and Np(VI) are still effectively retained in argillaceous minerals and rocks by adsorption despite the anionic character of prevailing aqueous species. Repulsive forces between the actinide species and the mineral surfaces are overcome by mediating Ca2+. This finding is of great relevance, as also the migration of very small amounts of uranium or neptunium out of waste repositories could lead to a hazardous accumulation in the long term. The achieved knowledge gain concerning radionuclide retention at environmental conditions helps to take the next step towards realistic long-term safety assessment of nuclear waste repositories.

The report summarizes the results obtained by the Institute of Resource Ecology of the Helmholtz-Zentrum Dresden-Rossendorf within the BMWi-financed Joint Research Project “Geochemical retention of radionuclides on cement alteration phases (GRaZ)”. The project focused on the retention behavior of Ca-bentonite and cementitious material, both constituents of the geo-engineered barrier of deep geological repositories for high-level radioactive waste, towards radionuclides. Specifically, the influence of increased salinities and of hyperalkaline conditions on interaction processes in the system radionuclides – organics – clay/cementitious materials – aquifer was studied. For this purpose, complexation, sorption and desorption studies were performed at alkaline to hyperalkaline pH conditions (pH 8-13) and under variation of the ionic strength (0.1 to 4 M) applying complex solution compositions. For the U(VI) citrate system molecular structures dominating in the pH range 2-9 were studied spectroscopically (NMR, UV-Vis, FT-IR). As dominating species 2:2, 3:3, 3:2 and, above critical concentrations also 6:6 and 9:6 U(VI) citrate complexes were identified or confirmed and complex formation constants were determined. U(VI) sorption on Ca-bentonite at (hyper)alkaline conditions in mixed electrolyte solutions was studied by means of batch sorption experiments. The U(VI) retention on Ca-bentonite was shown to be very effective at pH>10, even in the presence of carbonate and despite the prevalence of anionic aqueous uranyl species. The presence of two independent U(VI) surface complexes on Ca-bentonite at pH 8-13 was shown by site-selective TRLFS and EXAFS spectroscopy. The sorption of anionic uranyl hydroxide complexes to the mineral surface was shown to be mediated by calcium cations. In further experiments, the effect of isosaccharinic acid (ISA) and polycarboxylate ether (PCE) on U(VI) and Eu(III) sorption, respectively, on Ca-bentonite was studied. An effect of ISA on U(VI) sorption on Ca-bentonite only occurs when ISA is present in very high excess to U(VI). The effect of PCE, as a commercial cement superplasticizer, on Eu(III) sorption onto Ca-bentonite was negligible already at moderate ionic strengths. The retention of U(VI) and Cm(III) by various C-(A-)S-H phases, representing different alteration stages of concrete, was studied by batch sorption experiments. Sorbed or incorporated actinide species were identified by TRLFS. The stability of U(VI) and Cm(III) doped C-(A-)S-H phases at high ionic strengths conditions was studied in solutions simulating the contact with North German claystone formation water. Potential changes of actinide speciation as well as formation of secondary phases due to leaching effects were followed spectroscopically. The results of this project show that both bentonite and cementitious material constitute an important retention barrier for actinides under hyperalkaline conditions and increased ionic strength.

Bentonite clays are exposed in Paleogene strata stretching over 650 km parallel to the Texas coastline. This study focuses on a white and blue and a yellow and brown commercial Ca-montmorillonite bentonite near the city of Gonzales, Gonzales county, Texas. The deposits have stratigraphic ages of Late Eocene (~36.7 - 32.7 Ma). The bentonites in these deposits have varying colors, purities and brightness affording them diverse industrial uses. The distribution and geologic character of the high purity white and blue bentonite suggests that the deposit represents an accumulation of volcanic ash in a secondary tidal channel during the ash-fall event. A low rate of terrigenous clastic sedimentation and rapid accumulation of fresh ash were critical to the formation of high purity clay. The lower purity yellow and brown bentonites appear to have a fluvial origin marked by higher rates of detrital sedimentation and episodic accumulation of clay and ash. The bentonite and associated strata were studied using optical microscopy, SEM, XRD and REE analyses to constrain their textural, mineralogic, and chemical character. vii Eocene pyroclastic volcanism is well documented from sources in southwestern North America, specifically in the Sierra Madre Occidental (Mexico), Trans-Pecos (Texas) and Mogollan-Datil (New Mexico) volcanic fields. Projected Eocene wind patterns support this region as a potential source for the Gonzales bentonites. A comparison of the trace and REE fingerprints of the white and blue bentonites and the yellow and brown bentonites with data available for Late Eocene volcanics in the North American Volcanic Database provides a couple of potential matches. The strongest potential match for the Late Eocene bentonite protolith is described as a sample of silicic tuff with an age range of 32.2 – 30.6 Ma, located in the southern Mexican state of Oaxaca. While the trace and REE match is strong, the tuff is somewhat young compared to the Jackson Group sediments. In addition, the sample location is due almost directly south of the Gonzales deposits, rather than the western location expected for a Gonzales bentonite source. The other potential matches are located in New Mexico, and the Mexican state of Chihuahua. These potential matches only have 6 REE available for comparison, and require further investigation. Many Paleogene volcanic units in southern North America are undocumented with regard to REE data or precise absolute ages. As additional geochemical analyses become available for a more extensive suite of Paleogene volcanic units, stronger matches with Gulf of Mexico Basin bentonites are expected to emerge.
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For the disposal system of high-level radioactive waste in Japan, Na-type bentonite is used as one of backfilling and buffer materials for preventing the migration of groundwater and radionuclide. However, the alteration to Ca-type bentonite will cause the degradation of the barrier performance. On the other hand, silicate minerals around the repository dissolve under the high alkaline condition of groundwater (about pH 13) altered by alkaline components leaching from cementitious materials used for the construction of the repository. Such high-concentration silicic acid becomes supersaturated with the decrease in pH by mixing with natural downstream groundwater (pH 8) because of the change in the solubility of silicic acid. So far, the authors have examined the deposition rates of supersaturated silicic acid on Ca-type bentonite under the condition of room temperature, showing the clogging effect of flow-paths with the deposition. However, the dynamic behaviors of silicic acid are much sensitive to temperature change. Therefore, the present study focuses on the effect of temperature on the deposition rate of silicic acid on Ca-type bentonite. As a result, in the range up to 323 K, the deposition of supersaturated silicic acid on Ca-type bentonite was promoted with the increase in temperature. This suggests that the deposition of silicic acid will clog the flow-paths in Ca-type bentonite in this temperature range.

The authors describe progress in the development of low temperature vitrification with BiPbO2I (BPI) as a promising immobilization technique by which Iodine-129 is recovered by BiPbO2NO3 to form BPI, and then solidified into a lead-boron-zinc glass matrix (PbO-B2O3-ZnO) using a low temperature vitrification process. The microscopic structure of BPI glass was analyzed by various analytical techniques, such as XRD (X-ray diffraction), NMR (nuclear magnetic resonance analysis), and XPS (X-ray photoelectron spectroscopy), using several types of glass samples. The results obtained provide structural information on key elements in BPI glass and can be applied for modeling the structure of the BPI glass, simulated by molecular dynamics. The previous work suggested that the leaching behavior of iodine from BPI glass depended upon the chemical conditions of the solution. Further leaching tests using solutions under varying conditions were carried out in order to predict mechanisms of iodine leaching. Normalized elemental mass loss values of iodine in simulated seawater and bentonite pore water are almost the same as those of boron, showing that iodine dissolves congruently with BPI glass, whereas iodine dissolves incongruently in Ca(OH)2 solutions of pH 9 and 11. To demonstrate the feasibility of the BPI vitrification process, recovery tests of iodine from spent iodine filters were conducted and a prototype melting furnace was developed for scale-up tests of glass sample. It was found that more than 95% of iodine can be recovered from the spent iodine filter and that the prototype furnace can produce approximately 0.5 liters of homogeneous glass.