Volume 67 - 15 April 2019
Original Paper
Adaptation of an Analytical Procedure for Concurrent Determination of Np and Pu in clay samples
- Tobias Renz, Markus Plaschke, Francesca Quinto, Andreas Bauer, Markus Lagos, Heinrich Taubald, Horst Geckeis
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- Published online by Cambridge University Press:
- 01 January 2024, pp. 183-189
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Np and Pu are two important actinides of concern for the safe long-term disposal of nuclear waste. Both actinides are, in addition, constituents of global nuclear fallout. Investigation of their environmental behavior requires ultra-sensitive analytical methods, but current methods for a concurrent determination in clay minerals are lacking. In the present study, a Pu isotope was investigated for use as a non-isotopic yield tracer for Np in extraction, purification, and mass spectrometric determination of Np and Pu isotopes in clay materials. Inductively coupled plasma mass spectrometry was used in this developmental study, but the method is intended for future ultra-trace analysis of global-fallout Np and Pu in clay-rich soil materials by the more sensitive accelerator mass spectrometry. Another field of application may be the investigation of diffusion patterns of actinides in compacted clay liners and potential host rocks for radioactive waste disposal. The analytical procedure includes the following steps: (1) extraction of Np and Pu from clay samples; (2) adjustment of Np and Pu to Np(IV) and Pu(III); (3) pre-concentration of Np and Pu by co-precipitation with iron hydroxide; (4) adjustment of Pu to Pu(IV); (5) extraction chromatographic separation of Pu and Np from iron and matrix elements; and (6) determination of Np and Pu by mass spectrometry. The analytical procedure was applied successfully to spiked montmorillonite and illite test portions of up to 1 g. High chemical yields near 90% were obtained for both Np and Pu. The suitability of Pu as a non-isotopic tracer for Np was indicated by Np/Pu chemical yield ratios close to unity. Accurate pH adjustment during the reductive co-precipitation and short processing times are vital to obtain high chemical yields and Np/Pu yield ratios close to unity.
Article
Photocatalytic Activity of La-Containing Mixed- Metal Oxides Derived from Layered Double Hydroxides to Degrade Methylene Blue in the Presence of H2O2
- Minhong Xu, Mengxia Qian, Guoxiang Pan, Yuhua Guo, Tao Wu
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- 01 January 2024, pp. 253-264
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Photocatalytic degradation of polluted water by means of minerals, such as clays and oxides, which have surfaces that exhibit catalytic properties, has been suggested to be a useful new strategy to promote both organic and inorganic pollutant degradation. Nevertheless, much still remains to be studied about the capability of mixed metal oxides derived from lanthanum-containing layered double hydroxides to promote pollutant removal by means of photocatalytic degradation with the mineral surfaces. The objective of the present study was to investigate the synthesis of ternary MgAlLa mixed-metal oxides (MgAlLa-M) with various Mg/Al/La molar ratios through a hydrotalcite-like precursor route by co-precipitation of appropriate amounts of metal salts from homogeneous solution, followed by calcination at 600°C. The crystal structure, surface morphology, and optical properties of the samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier-transform infrared spectroscopy (FTIR), and UV-Vis diffuse reflectance spectroscopy (DRS). Analysis by XRD showed that MgO, La2O3, MgAl2O4, and La10Al4O21 phases coexisted in calcined samples as MgAlLa-M. The samples showed a small band gap of 3.11–3.35 eV according to DRS. The photocatalytic activities of the samples were evaluated by degradation of methylene blue (MB) under visible light irradiation. MgAlLa-M had better photocatalytic properties than hydrotalcite precursors, and the MgAlLa-0.5-M possessed the best photocatalytic activity. The photocatalytic degradation efficiency of MB dye with MgAlLa-0.5-M under visible light irradiation for 1 h was 99.89% in the presence of H2O2, which exceeded the binary MgAl-M (84.06%) under the same conditions. The high photocatalytic activity of the sample was attributed to the addition of La(III). In addition, the possible mechanism of photocatalytic degradation of MB by MgAlLa-M was discussed. The results showed that •O2– plays a major role in the MgAlLa-0.5-M/H2O2 system.
Eighteen years of steel–bentonite interaction in the FEBEX in situ test at the Grimsel Test Site in Switzerland
- Jebril Hadi, Paul Wersin, Vincent Serneels, Jean-Marc Greneche
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- 01 January 2024, pp. 111-131
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Corrosion of steel canisters containing buried high-level radioactive waste is a relevant issue for the long-term integrity of repositories. The purpose of the present study was to evaluate this issue by examining two differently corroded blocks originating from a full-scale in situ test of the FEBEX bentonite site in Switzerland. The FEBEX experiment was designed initially as a feasibility test of an engineered clay barrier system and was recently dismantled after 18 years of activity. Samples were studied by ‘spatially resolved’ and ‘bulk’ experimental methods, including Scanning Electron Microscopy, Elemental Energy Dispersive Spectroscopy (SEM-EDX), μ-Raman spectroscopy, X-ray Fluorescence (XRF), X-ray Diffraction (XRD), and 57Fe Mössbauer spectrometry, with a focus on Fe-bearing phases. In one of the blocks, corrosion of the steel liner led to diffusion of Fe into the bentonite, resulting in the formation of large (width > 140 mm) red, orange, and blue colored halos. Goethite was identified as the main corrosion product in the red and orange zones while no excess Fe2+ (compared to the unaffected bentonite) was observed there. Excess Fe2+ was found to have diffused further into the clay (in the blue zones) but its speciation could not be unambiguously clarified. The results indicate the occurrence of newly formed octahedral Fe2+ either as Fe2+ sorbed on the clay or as structural Fe2+ inside the clay (following electron transfer from sorbed Fe2+). No other indications of clay transformation or newly formed clay phases were found. The overall pattern indicates that diffusion of Fe was initiated when oxidizing conditions were still prevailing inside the bentonite block, resulting in the accumulation of Fe3+ close to the interface (up to three times the original Fe content), and continued when reducing conditions were reached, allowing deeper diffusion of Fe2+ into the clay (inducing an increase of 10–12% of the Fe content).
Geology, Mineralogy, Geochemistry, and Genesis of Bentonite Deposits in Miocene Volcano–Sedimentary Units of the Balikesir Region, Western Anatolia, Turkey
- Selahattİn Kadİr, Tacİt Külah, Hülya Erkoyun, George E. Christidis, Raffİ Arslanyan
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- 01 January 2024, pp. 371-398
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The widespread Balıkesir bentonite deposits within the Miocene volcano-sedimentary units in western Anatolia have economic potential; they are important raw materials for the paper and bleaching industries in Turkey. No detailed geological, mineralogical, geochemical, or genesis characterizations of these bentonite deposits have been carried out to date. The present study was undertaken to close this gap. The mineralogical characteristics of the bentonites and their parent rocks were examined using polarized-light microscopy, X-ray powder diffractometry (XRD), scanning- and transmission-electron microscopies (SEM–EDX and TEM), and chemical (ICP–AES and –MS) methods. In the bentonite deposits, smectite is associated with smaller amounts of illite, chlorite, quartz, feldspar, dolomite, calcite, opal-CT, and amphibole. The smectite was identified by sharp basal reflections at 14.42–14.93 Å. Plagioclase and sanidine crystals in volcanic units are altered and sericitized. Biotite and hornblende are partly to completely Fe-(oxyhydr)oxidized and chloritized. Smectite flakes occur on altered feldspar and mica grains and devitrified volcanic glass fragments in association with or without calcite ± dolomite crystals. Increasing Al+Fe+Mg/Si ratios with increasing degree of alteration reveal that hydration of volcanogenic grains (feldspar, mica, hornblende, glass shard) favored precipitation of smectite with montmorillonite composition, with an average structural formula: (Ca0.31Na0.05K0.08)(Al2.72Fe0.17Mg1.27Ti0.011Mn0.01)(Si7.94Al0.06)O20(OH)4. The concentration of Al2O3 and MgO and increase of LREE/HREE ratio, and a distinct, negative Eu anomaly show that smectite was probably formed as a result of the decomposition of volcanic feldspar, mica, amphibole, and volcanic glass. Association of carbonate rocks within the smectite-rich material and the absence of chlorite and detrital materials such as rock fragments in the bentonites suggest that the bentonite deposits formed authigenetically as ‘primary bentonites’ from volcanoclastic materials deposited in a calm lacustrine–palustrine environment during an early diagenetic process.
Synthesis, Structure, and Ferroelectricity of a Kaolinite-p--Aminobenzamide Intercalation Compound
- Shun-Ping Zhao, Yu Guo, Miao-Miao Zhu, Jie Wang, Xiao-Liang Feng, Qiao Qiao, Heng Xu
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- 01 January 2024, pp. 461-470
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The construction of organic-inorganic hybrid ferroelectric materials with larger, high-polarity guest molecules intercalated in kaolinite (K) faces difficulties in terms of synthesis and uncertainty of structure-property relationships. The purpose of the present study was to optimize the synthesis method and to determine the mechanism of ferroelectric behavior of kaolinite intercalated with p-aminobenzamide (PABA), with an eye to improving the design of intercalation methods and better utilization of clay-based ferroelectric materials. The K-PABA intercalation compound (chemical formula Al2Si2O5(OH)4∙(PABA)0.7) was synthesized in an autoclave and then characterized using X-ray diffraction (XRD), infrared spectroscopy (IR), thermogravimetric analysis (TGA), and scanning electron microscopy (SEM). The experimental results showed that PABA expanded the kaolinite interlayer from 7.2 Å to 14.5 Å, and the orientation of the PABA molecule was ~70° from the plane of the kaolinite layers. The amino group of the PABA molecule was close to the Si sheet. The presence of intermolecular hydrogen bonds between kaolinite and PABA and among PABA molecules caused macro polarization of K-PABA and dipole inversion under the external electric field, resulting in K-PABA ferroelectricity. Simulation calculations using the Cambridge Sequential Total Energy Package (CASTEP) and the ferroelectricity test revealed the optimized intercalation model and possible ferroelectric mechanism.
Research Article
The Influence of Clays on Human Health: A Medical Geology Perspective
- Robert B. Finkelman
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- 01 January 2024, pp. 1-6
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Clay is unique especially from the perspective of medical geology, that is, the impacts of geologic materials and geologic processes on animal and human health. Clay is the only natural material that can impact human health through all routes of exposure: ingestion, inhalation, and dermal contact. Moreover, these impacts can be harmful as well as beneficial. Ingestion of clay, a form of geophagy, has been practiced for millennia and is still widely practiced today. Humanoids have been ingesting clay for at least two million years to ease indigestion and counteract poisons. Some additional benefits may accrue from eating clays such as providing some nutrients but these benefits are far outweighed by the likely negative consequences such as tissue abrasion, intestinal blockage, anemia, exposure to pathogens and toxic trace elements, and potassium overdose. Inhalation of airborne minerals including clays has impacted the heath of millions. In the 1930s thousands of people living in the Dust Bowl in the U.S. southwest inhaled copious amounts of clay contributing to deadly ‘dust pneumonia.’ Using clay as a poultice to stem bleeding and cure certain skin ailments is an age-old practice that still has many adherents. A classic recent example of the antibacterial properties of clay is the use of certain clays to cure Buruli ulcer, a flesh eating disease. However, walking barefoot on clays in certain volcanic soils can result in non-filarial podoconiosis or elephantiasis. The absence of clays in soils can have serious health consequences. In South Africa, clay-poor soils yield crops lacking in essential nutrients and may be the principal cause of Msileni joint disease. Clearly, a detailed knowledge of the clays in the environment can have significant benefits to human health and wellbeing.
Article
Improved Matrix Methodology for Calculating Diffraction Intensity Profiles from Interstratified Phyllosilicates
- Hongji Yuan, David L. Bish
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- 01 January 2024, pp. 399-409
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Diffraction effects from interstratified phyllosilicates have been studied extensively, and several computer programs such as NEWMOD© are available to facilitate interpretation of X-ray diffraction (XRD) profiles. However, accurate quantification of samples containing multiple interstratified phyllosilicate minerals is difficult due to the generally subjective nature of interpretations. More recent automated fitting interpretations require extensive computational effort, involving numerous calculations of profiles with different fitting-parameter values. Computational cost in time per calculation is the key factor influencing the overall efficiency of automated profile fitting. In general, the matrix methodology developed by Kakinoki and Komura is more efficient than the NEWMOD© architecture. A new matrix methodology was developed that reduces the number of matrix operations such as multiplication and addition, and these modifications improve calculation efficiency by up to a factor of three, with even greater improvement for small crystallite sizes (< 20 layers). A new computer program, ClayStrat, based on the modified matrix methodology, was developed to calculate one-dimensional XRD profiles from interstratified phyllosilicates along the Z direction.
Original Paper
The Interaction between Surfactants and Montmorillonite and its Influence on the Properties of Organo-Montmorillonite in Oil-Based Drilling FluIDS
- Guanzheng Zhuang, Zepeng Zhang, Shanmao Peng, Jiahua Gao, Francisco A. R. Pereira, Maguy Jaber
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- 01 January 2024, pp. 190-208
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The increasing demands for oil and gas and associated difficult drilling operations require oil-based drilling fluids that possess excellent rheological properties and thermal stability. The objective of the present work was to investigate the rheological properties and thermal stability of organo-montmorillonite (OMnt) modified with various surfactants and under various loading levels in oil-based drilling fluids, as revealed by the interaction between organic surfactants and montmorillonite. The influence of the structural arrangement of surfactants on the thermal stability of organo-montmorillonite (OMnt) in oil-based drilling fluids was also addressed. OMnt samples were prepared in aqueous solution using surfactants possessing either a single long alkyl chain two long alkyl chains. OMnt samples were characterized by X-ray diffraction, high-resolution transmission electron microscopy, thermal analysis, and X-ray photoelectron spectroscopy. Organic surfactants interacted with montmorillonite by electrostatic attraction. The arrangements of organic surfactants depended on the number of long alkyl chains and the geometrical shape of organic cations. In addition to the thermal stability of surfactants, intermolecular interaction also improved the thermal stability of OMnt/oil fluids. A tight paraffin-type bilayer arrangement contributed to the excellent rheological properties and thermal stability of OMnt/oil fluids. The deterioration of rheological properties of OMnt/oil fluids at temperatures up to 200°C was due mainly to the release of interlayer surfactants into the oil.
Research Article
Natural Antibacterial Clays: Historical Uses and Modern Advances
- Lynda B. Williams
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- 01 January 2024, pp. 7-24
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Antibacterial clays in nature include a variety of clay mineral assemblages that are capable of killing certain human pathogens. Although clays have been used for medicinal applications historically, only in the last decade have analytical methods and instrumentation been developed that allow researchers to evaluate the antibacterial mechanisms of various clays applied medicinally. Comparisons of the mineralogical and chemical compositions of natural clays that kill bacteria have promoted a better understanding of the mineral properties that are toxic to a broad-spectrum of human pathogens, including bacteria that have developed resistance to antibiotics. Popular literature is filled with reports of ‘healing’ clays, that, when tested against pathogens in vitro and compared to controls, do not appear to have bactericidal properties. It is important, however, to differentiate what properties make a clay ‘healing,’ versus what makes a clay ‘antibacterial.’ Most antibacterial clays identified to date buffer pH conditions of a hydrated clay outside the range of conditions in which human pathogens thrive (circum-neutral pH) and require oxidation reactions to occur. It is the change in oxidation state and pH imposed by the hydrated clay, applied topically, that leads to a chemical attack of the bacteria. Healing clays, on the other hand, may not kill bacteria but have soothing effects that are palliative. This article reviews some of the historical uses of clays in medicine but focuses primarily on the common characteristics of natural antibacterial clays and early studies of their antibacterial mechanisms. In this era of bacterial resistance to antibiotics, mimicking the antibacterial mechanisms exhibited by natural clays could be advantageous in the development of new antimicrobial agents.
Article
Preparation of a Hierarchical Pore Zeolite with High-Temperature Calcination and Acid-Base Leaching
- Chengdong Wang, Jinhong Li, Xiang Wang, Zhiwei Yang, Kaiyue Huang
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- 01 January 2024, pp. 265-274
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Microporous structure in zeolite leads to diffusion limitation, which causes coke formation and is harmful to catalytic reactions. Hierarchical zeolite containing primary microporosity and secondary porosity at the meso- and macroscales has received much attention due to its enhanced mass transport. Hierarchical Y zeolites were obtained by treating NH4-Y zeolite with high-temperature calcining and acid-base leaching. The results demonstrated that the calcined zeolite showed great crystallinity after acid-base leaching. The mechanism of introduction of mesopores was demonstrated in detail. The calcination transformed framework Al to extra-framework Al and enlarged the defect by acid and alkali. The mesopores increased with the calcining temperature and holding time. The relationship between the heating rate and the removal of Al species was non-linear; a heating rate of 100°C/h exhibited good protection for the zeolite structure.
Bentonite/Magnetite Composite for Removal of Nitrofurazone
- Olga V. Alekseeva, Anna N. Rodionova, Andrew V. Noskov, Alexander V. Agafonov
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- 01 January 2024, pp. 471-480
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The presence of pharmaceutical pollutants in the environment is one of the most pressing environmental problems. Adsorption from solution is an effective way to remove pharmaceuticals from liquid media, but the problem then is to separate the adsorbent from the liquids. The objective of the present study was to remove nitrofurazone from aqueous solutions using a bentonite/magnetite composite, prepared by co-precipitation of magnetite with bentonite, which could then be collected by magnetic separation. The bentonite/magnetite composite was characterized using diverse techniques, such as X-ray diffraction, scanning electron microscopy, low-temperature N2 adsorption/desorption, laser diffraction, and magnetization measurements. The particle size of the composite material did not exceed 50 μm and the particle size distribution was mono-modal with a maximum at 3.2 μm. The strong hysteresis in the magnetization curve revealed that the bentonite/magnetite particles were ferromagnetic. Adsorption of nitrofurazone by the bentonite/magnetite composite from aqueous solutions was measured and the amount of nitrofurazone adsorbed was 3.2×10–2 mmol/g. The adsorption kinetics of nitrofurazone to the bentonite/magnetite composite followed a pseudo-second-order kinetics equation. Upon adsorption, hydrogen bonds were formed between the amide groups of nitrofurazone and oxygen groups in bentonite.
Surfactant-Modified Clay Sorbents for the Removal of p-nitrophenol
- Ruta Ozola, Andrejs Krauklis, Juris Burlakovs, Maris Klavins, Zane Vincevica-Gaile, William Hogland
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- 01 January 2024, pp. 132-142
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Organic pollutants are widespread and a known problem for the environment. p-nitrophenol (PNP) is one such pollutant found in effluents from various industries involved with pesticides, pharmaceuticals, petrochemicals, plastic, paper, and other materials. The objective of this research was to prepare and test organically modified clays using four different surfactants and to evaluate the removal efficiency of PNP from aqueous solutions. Organically modified clays have attracted great interest due to their wide applications in industry and environmental protection as sorbents for organic pollutants. Two natural smectite-dominated clay types from outcrops in Latvia and Lithuania as well as industrially manufactured montmorillonite (Mt) clay were modified using different nonionic (4-methylmorpholine N-oxide (NMO) and dimethyldodecylamine N-oxide (DDAO)) and cationic (benzyltrimethyl ammonium chloride (BTMAC) and dodecyltrimethyl ammonium chloride (DTAC)) surfactants. Modified clay materials were characterized by Fourier-transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD), scanning electron microscopy (SEM), and the Brunauer-Emmett-Teller method (BET) for surface area analysis. Sorption of PNP was investigated under various conditions, e.g. surfactant loading, initial PNP concentration, contact time, and pH. The novelty of the present study was to prepare innovative organo-sorbents based on manufactured as well as natural clay samples using cationic surfactants and nonconventional nonionic surfactants as modifiers. The sorption data combined with FTIR and XRD supplementary results suggests that nonionic organo-clay (Mt-DDAO_2) is the most effective sorbent and may serve as a low-toxicity immobilizer of pollutants such as phenols.
Research Article
Vectorized Clay Nanoparticles in Therapy and Diagnosis
- Goeun Choi, Huiyan Piao, Sairan Eom, Jin-Ho Choy
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- 01 January 2024, pp. 25-43
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Over the past several decades, clay minerals have been applied in various bio-fields such as drug and drug additives, animal medicine and feed additives, cosmetics, biosensors, etc. Among various research areas, however, the medical application of clay minerals is an emerging field not only in academia but also in industry. In particular, cationic and anionic clays have long been considered as drug delivery vehicles for developing advanced drug delivery systems (DDSs), which is the most important of the various research fields including new drugs and medicines, in vitro and in vivo diagnostics, implants, biocompatible materials, etc., in nanomedicine. These applications are obviously related to global issues such as improvements in welfare and quality of life with life expectancy increasing. Many scientists, therefore, in various disciplines, such as clay mineralogy, material chemistry, molecular biology, pharmacology, and medical science, have been endeavoring to find solutions to such global issues. One of the strategic approaches is probably to explore new drugs possessing intrinsic therapeutic effects or to develop advanced materials with theranostic functions. With this is mind, discussions of examples of cationic and anionic clays with bio- and medical applications based on nanomedicine are relevant. In this tutorial review, nanomedicine based on clay minerals are described in terms of synthetic strategies of clay nanohybrids, in vitro and in vivo toxicity, biocompatibility, oral and injectable medications, diagnostics, theranosis, etc.
Original Paper
Effect of Mechanical Activation on the Pozzolanic Activity of Muscovite
- Geng Yao, Haoyu Zang, Junxiang Wang, Peng Wu, Jun Qiu, Xianjun Lyu
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- 01 January 2024, pp. 209-216
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In order to provide a theoretical foundation for the utilization of tailings as supplementary cementitious materials, the pozzolanic activity of muscovite—a typical mineral phase in tailings—before and after mechanical activation was investigated. In this study, significant pozzolanic activity of muscovite was obtained as a result of the structural and morphological changes that were induced by mechanical activation. The activated muscovite that was obtained after mechanical activation for 160 min satisfies the requirements for use as an active supplementary cementitious material, and the main characteristics of the pozzolana were as follows: median particle size (D50) of 11.7 μm, BET specific surface area of 28.82 m2 g−1, relative crystallinity of 14.99%, and pozzolanic activity index of 94.36%. Continuous grinding led to a gradual reduction in the relative crystallinity and an increase in the pozzolanic activity index due to the dehydroxylation reaction induced by mechanical activation, which occurred despite the fact that the specific surface area showed a decreasing trend when the grinding time was prolonged. Mechanically activated muscovite exhibited the capacity to react with calcium hydroxide to form calcium silicate hydrate, which is a typical characteristic of pozzolana. This experimental study provided a theoretical basis for evaluating the pozzolanic activity of muscovite using mechanical activation.
Article
Synthesis of Magnetic Fe3O4 Nanorings for BSA Protein Adsorption
- Xiaonan Liu, Youkui Zhang, Liang Bian, Jinshan Li
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- 01 January 2024, pp. 275-282
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The adsorption of bovine serum albumin (BSA) protein is important for protein research but remains a great challenge. Here, the hydrothermal method and calcination in a hydrogen-argon mixed atmosphere were used to obtain ordered mono-crystalline magnetic Fe3O4 nanorings with controllable size and uniform structure, which were applied to the adsorption of BSA protein. The results showed that the magnetic Fe3O4 nanorings prepared have the advantages of good crystallinity, controllable morphology, and excellent magnetic response. The Fe3O4 nanorings had an outer diameter of ~160–180 nm, inner diameter of ~80–110 nm, and height of 70 to ~110 nm. The amount of BSA adsorbed by magnetic Fe3O4 nanorings increased with increasing protein concentration; when the concentration of BSA was ~2.75 mg·mL-1 the adsorption amount approached saturation. When the pH value of the solution was ~5, the Fe3O4 nanorings absorption of BSA was greatest. With increasing adsorption time, the amount adsorbed increased gradually. Adsorption equilibrium was reached after 3 h. According to the formula, the saturated adsorption capacity of BSA per gram of magnetic Fe3O4 nanorings was 325.2 mg.
Graphical Abstract
Removal Efficiency of Basic Blue 41 by Three Zeolites Prepared from Natural Jordanian Kaolin
- Mousa Gougazeh, Fethi Kooli, J.-Ch. Buhl
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- 01 January 2024, pp. 143-153
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The conventional method of zeolite synthesis involves an expensive hydrothermal step whereby a mixture of a metakaolinite, sodium hydroxide, and water is preactivated by thermal treatment between 400°C and 1000°C. The objective of the current study was to determine whether Jordanian kaolinite could be converted to zeolite materials without thermal pre-activation. The alkaline hydrothermal transformation of kaolinite into hydroxysodalite (HS) was achieved, then followed by a reaction with citric acid and solid sodium hydroxide to obtain Zeolite A, or by adding solid Na2SiO3 to prepare zeolite X. These materials were tested for their ability to serve as removal agents for Basic Blue 41 (BB-41) dye from artificially contaminated water, at concentrations ranging from 25 to 1000 mg/L. The maximum removal capacities were estimated using the Langmuir model, with a value of 39 mg/g for hydroxysodalite. Zeolite-X achieved the lowest value (19 mg/g). The feasibility of BB-41 removal was deduced from the Freundlich model for the zeolites studied. The reported low-cost method is proposed as an alternative way to reduce the cost of synthesizing zeolite, and the materials were shown to be potential candidates for the removal of BB-41 dye.
Giant Multistep Crystalline vs. Osmotic Swelling of Synthetic Hectorite in Aqueous Acetonitrile
- Raphael Kunz, Sonja Amschler, Andreas Edenharter, Lina Mayr, Sebastian Herlitz, Sabine Rosenfeldt, Josef Breu
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- 01 January 2024, pp. 481-487
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Intercalation of large organocations into 2:1 clay minerals may be hampered by two problems: on one hand, the solubility of organocations in water is limited and the resulting high selectivity for adsorption in the polar solvent may lead to non-equilibrium structures. On the other hand, the large expansion of the interlayer space will slow down kinetics of ion exchange considerably. The best workaround for these obstacles is to suspend the clay minerals in mixtures of water with more hydrophobic organic solvents that nevertheless trigger a considerable expansion of the interlayer space by swelling. This in turn fosters ion exchange. The current study, therefore, revisited pioneering work by Bradley (1945) and investigated the swelling behavior of synthetic sodium hectorite (Na-hec) as a function of the composition of the swelling solvent, a mixture of acetonitrile and water. Up to a maximum acetonitrile content of 65 vol.%, delamination by osmotic swelling occurred. At even higher acetonitrile concentrations, swelling was limited to the crystalline swelling regime where a step-like adjustment of the d value was observed. Several mixtures were identified yielding a well defined and uniform interlayer height as evidenced by rational 00l-series with the d spacing decreasing with increasing acetonitrile content. Surprisingly, for a specific acetonitrile:water ratio even an ordered interstratification of two strictly alternating interlayer heights with distinctly different solvent compositions was observed.
Original Paper
The Effects of Oxyanion Adsorption on Reactive Oxygen Species Generation by Titanium Dioxide
- Mary R. Arenberg, Yuji Arai
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- 01 January 2024, pp. 410-418
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The growing use of nano titanium dioxide (TiO2) in consumer and agricultural products has accelerated its introduction into terrestrial environments, where its impact has not been documented extensively. TiO2 toxicity arises primarily from its ability to photochemically generate reactive oxygen species (ROS), including hydrogen peroxide (H2O2). While common ligands in soil porewaters can either hinder or enhance the degradation of organic contaminants by TiO2, their effects on ROS production by TiO2 have not been understood clearly. The objective of this study was to assess the effect of phosphate (P) and nitrate on UV-irradiated anatase, nano-TiO2. Accordingly, H2O2-generation kinetics experiments were conducted in UV-irradiated TiO2 under environmentally relevant concentrations of the ligands (0, 50, 100, and 250 μM) and pH values (4.00 ± 0.02 and 8.00 ± 0.02) from 0–100 min. Under all conditions, H2O2 grew logarithmically and reached between 5.38 and 22.98 μM after 100 min. At pH 4.00 ± 0.02, H2O2 production was suppressed by P but not by nitrate. Conversely, at pH 8.00 ± 0.02, nitrate did not affect H2O2 concentration while P increased it. Non-specific, minimal adsorption of nitrate prevented interference with the photoreactivity of TiO2. Due to the pH-dependent behavior of suspended TiO2 and H2O2 degradation rates, specific adsorption of P on TiO2 impeded its ability to produce H2O2 photochemically at pH 4.00 ± 0.02 but amplified it at pH 8.00 ± 0.02.
Iron Mineralogy and Magnetic Susceptibility of Soils Developed on Various Rocks in Western Iran
- Shamsollah Ayoubi, Vali Adman
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- 01 January 2024, pp. 217-227
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The characterization of magnetic minerals and the relationship of these minerals to the magnetic susceptibility of soils that have developed on various parent materials can provide valuable information to various disciplines, such as soil evolution and environmental science. The aim of the study reported here was to investigate variations in the magnetic susceptibility (χ) of soils in western Iran due to differences in lithology and to examine the relationship of χ to ferrimagnetic minerals. Eighty samples were collected from eight parent materials taken from both intact rocks and associated soils. The soil parent materials included a range of igneous and sedimentary rocks, such as ultrabasic rocks (Eocene), basalt (Eocene), andesite (Eocene), limestone (Permian), shale (Cretaceous), marl (Cretaceous), and the Qom formation (partially consolidated fine evaporative materials, early Miocene). The 80 samples were analyzed for χ using a dual-frequency magnetic sensor and for mineralogy using X-ray diffraction (XRD). The highest χ values were found in the ultrabasic rocks and associated soils, while the lowest χ values were observed in the limestone rocks and associated soils. The pedogenic processes significantly enhanced the χ values of soils developed on the sedimentary rocks due to the formation of ferrimagnetic minerals. In contrast, χ values decreased as a result of pedogenic processes in soils developed on igneous rocks due to the dilution effects of diamagnetic materials, such as halite, calcite, phyllosilicates, and organic matter. The significant positive correlation between the XRD peak intensity of the maghemite/magnetite particles and χ values confirmed that χ values in soils are largely controlled by the distribution and content of ferrimagnetic minerals. These results show that χ measurements can be used to quantify low concentrations of ferrimagnetic minerals in the soils of semiarid regions.
Article
Surface-Modified Sepiolite Nanofibers as a Novel Lubricant Additive
- Fei Wang, Peizhang Gao, Jinsheng Liang, Baizeng Fang, Tingting Zhang, Huimin Liu
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- Published online by Cambridge University Press:
- 01 January 2024, pp. 283-290
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Lubricants are an essential component in high-performance mechanical equipment, but traditional lubricants are becoming inadequate for meeting the increasing demands for anti-friction and anti-wear properties and they discharge harmful chemicals to the environment. The purpose of the present study was to explore the use of sepiolite as a novel oil additive to extend the performance of lubricants. Sepiolite nanofibers were first treated by acid followed by a dry air flow, aimed at increasing the pore volume and decreasing the particle size. Then the nanofibers were further modified by an organosilane coupling agent to reduce the surface free energy and to improve the dispersion stability in lubricant. A significant improvement in the performance of the lubricant was achieved by using the modified sepiolite nanofibers as an additive. When the amount of modified sepiolite nanofibers added was 1.5 wt.%, the best performance was demonstrated by the lubricant, showing a viscosity increase at 40°C and 100°C, and an increase in resistance to oxidation. Moreover, the acid value and pour point decreased, and the copper sheet corrosion level dropped to its lowest value.