Volume 70 - April 2022
Original Paper
Palygorskite Supporting Homogeneously Dispersed Ag Nanoparticles: Molten Salt Method and Enhanced Antibacterial Performance
- Qiuzhi He, Qingze Chen, Runliang Zhu, Jing Du, Shiya He, Guocheng Lv, Cheng Gu, Aiqin Wang
-
- Published online by Cambridge University Press:
- 01 January 2024, pp. 809-823
-
- Article
- Export citation
-
Supported silver nanoparticles (Ag NPs) have been used extensively as antibacterial agents in biomedicine, biotechnology, and environmental remediation. However, a facile and scalable method for preparing Ag NPs dispersed homogeneously on supports remains a challenge. In this study, a novel molten salt method was developed successfully to synthesize the supported, homogeneously dispersed Ag NPs on palygorskite. Abundant pores and ample surface hydroxyl groups of palygorskite served as anchoring sites, preventing the rapid growth, aggregation, and sintering of Ag NPs. Typically, palygorskite was mixed with AgNO3 (as a precursor) and NaNO3 (as a dispersant), and then the mixture was heated slowly. During the heating process, the AgNO3 decomposed gradually into Ag NPs and the molten NaNO3 with a high concentration of ions dispersed the newly formed Ag NPs. The Ag NPs were dispersed homogeneously on the palygorskite and had very small particle sizes (~5.8 nm) even for a significant loading amount (~9 wt.%). As antibacterial agents, the Ag/palygorskite nanocomposites showed enhanced antibacterial activity, compared with those synthesized without the introduction of molten NaNO3. In addition, the key effect of the surface hydroxyl groups of palygorskite on the characteristics of the loaded Ag and the corresponding antibacterial activity were also elucidated. As such, the present work provided a novel and facile strategy for the synthesis, without a chemical reductant or surfactant, of supported, highly dispersed Ag NPs on clay minerals and this could have potential in the scalable production and practical application of Ag-based antibacterial materials.
Influence of Thermal Treatment of Moroccan Red Clay on its Physicochemical and Mechanical Behavior
- M. A. Harech, T. Labbilta, Y. Abouliatim, Y. Elhafiane, A. Benhammou, A. Abourriche, A. Smith, L. Nibou, M. Mesnaoui
-
- Published online by Cambridge University Press:
- 01 January 2024, pp. 601-615
-
- Article
- Export citation
-
Red clay is considered to be of significant value to the economy in Morocco, particularly in the Safi region, because of its abundance. This raw material has long been known for its quality in the manufacture of clay materials, but its use was limited to traditional ceramics. The red clay raw material was the subject of the current study with the objective of opening new industrial applications that will give added value to the Safi red clay. The physicochemical, mineralogical, and thermal properties of the Moroccan red clay were determined by X-ray fluorescence (XRF), inductively coupled plasma-atomic emission spectroscopy (ICP-AES) analysis, X-ray diffraction (XRD), oriented aggregate, and particle-size analyses, powder density by helium pycnometry, carbonate content using the Bernard method, differential thermal analysis (TG–DTA), and the BET surface area. The compacted dry powder particles were calcined at three sintering temperatures: 900, 1000, and 1100°C for 2 h. The effect of sintering temperature on ceramic properties, such as apparent porosity, water adsorption, bulk density, and mechanical strength, was examined. Dense ceramics with lower porosity and greater mechanical resistance (~300%) were produced by increasing the sintering temperature from 900 to 1100°C. The conclusion was that the evolution of physicochemical and thermal properties is related to mineralogical changes, which show that anorthite is the major phase at higher temperatures.
Synthesis and Characterization of Non-leaching Inorgano- and Organo-montmorillonites and their Bactericidal Properties Against Streptococcus Mutans
- Aslı Şahiner, Günseli Özdemir, T. Hakan Bulut, Saadet Yapar
-
- Published online by Cambridge University Press:
- 01 January 2024, pp. 481-491
-
- Article
- Export citation
-
The direct application of heavy metal- and quaternary ammonium-based antibacterial agents can cause inconvenience such as irritation, short-term applicability, discoloration of the tissue, and environmental concerns. The immobilization of these agents on montmorillonite (Mnt) was expected to diminish these effects by hindering direct contact of the ions with the target tissues. The objective of the present study was, therefore, to prepare inorgano(I)- and organo(O)-montmorillonites (I/O-Mnt) and to determine their potential uses in such biomedical applications. Na-montmorillonite (Mnt-Na) was modified by hydrothermal and microwave irradiation methods using Cu2+/Zn2+, and quaternary ammonium and/or anionic surfactants. The effect of the structures formed by immobilization on Mnt surfaces on antibacterial activity was investigated. Quaternary ammonium surfactants were cetyltrimethyl ammonium bromide (CTAB) with a linear alkyl chain, cetylpyridinium chloride (CPC) with a single aromatic ring, and benzethonium chloride (BZT) with double aromatic rings. N-lauroyl sarcosinate (SR) was the anionic surfactant. The samples were subjected to thermogravimetric (TGA) and scanning electron microscopy (SEM) analyses. Desorption tests showed that the antibacterial efficacy against Streptococcus mutans stemmed from I/O-Mnt and not from the ions released from the material surfaces to the aqueous phase. The results of the antibacterial studies showed that the existence of a linear alkyl chain and a double aromatic ring were the structural factors causing the greatest antibacterial effect. The time-kill tests revealed that Mnt-CTA, Mnt-BZT, and Mnt-CP-SR were effective against Streptococcus mutans within 5 min of contact. With the new findings, they were identified as possible selective and potent bactericidal agents and promising candidates for biomedical applications.
Extraction of 40Ar-39Ar Ages from a Multicomponent Mixture: A Case Study From the Tatra Mountains, Poland
- Artur Kuligiewicz, Michał Skiba, Marek Szczerba, Chris M. Hall, Dorota Bakowska
-
- Published online by Cambridge University Press:
- 01 January 2024, pp. 1-19
-
- Article
- Export citation
-
Extraction of meaningful information on the timing of fault activity from clay gouges using radiometric dating methods, such as those based on the K-Ar system, can be challenging. One of the factors complicating interpretation of the radiometric dating results is the presence of multiple K-bearing components in the gouge material. In the current study, an attempt was made to develop a new interpretative method for K-Ar and 40Ar-39Ar dating, capable of handling a three-component mixture. In addition, the mineral composition of clay gouges from the Tatra Mountains (Poland), which has not been investigated before, is reported. The mineral compositions of the bulk clay gouge material and separated size fractions were determined by X-ray diffractometry and Fourier-transform infrared spectroscopy. The gouge samples were composed of quartz, dioctahedral mica (as a discrete phase and as a component of mixed-layered illite-smectite), and chlorite, commonly with plagioclase and more rarely with K-feldspar, dioctahedral smectite, calcite, anatase, or trace kaolinite. One feldspar-free sample containing three mica polytypes (1Md, 1M, and 2M1) was chosen for dating with the 40Ar-39Ar method. The results of 40Ar-39Ar dating were interpreted using three concepts: Illite Age Analysis (IAA), a method based on the MODELAGE software, and a newly developed three-component concept. The age values obtained with IAA were −14 Ma ± 31 Ma and 180 ± 91 Ma for authigenic (1Md) and inherited (1M + 2M1) components, respectively. The MODELAGE-based approach returned –4 ± 40 Ma and 165 ± 62 Ma. The three-component approach returned age values of polytypes as follows: 1Md, 15 ± 37 Ma; 1M, 135 ± 57 Ma; 2M1, 121 ± 56 Ma based on the medians and the interquartile ranges of non-normal distributions of Monte Carlo-simulated age values. The results obtained indicated that the 1Md polytype was probably formed during the most recent stage of fault activity, while 1M and 2M1 polytypes are of equal age, roughly.
Creep Mechanical Properties and Constitutive Model of Hard Brittle Mud Shale
- Xinxin Fang, Hong Feng, Fengling Li, Hao Wang
-
- Published online by Cambridge University Press:
- 01 January 2024, pp. 307-327
-
- Article
- Export citation
-
Mud shale is characterized by low strength and strong swelling, with rheological effects and deformation caused by drilling fluid and formation water. Establishing a rheological model to characterize the deformation characteristics is key to solving the problem of wellbore stability. The influence of moisture content on rock strength and creep mechanical properties were studied by means of water absorption, uniaxial compression, and creep tests. The tests showed that with the increase in moisture content, the elastic modulus and strength of hard brittle mud shale decreased. Further, under the same load, the instantaneous strain increased with increasing moisture content. Meanwhile, under various loading stresses, rock creep exhibited non-linear characteristics, which can be divided into three different creep stages: attenuated creep, stable creep, and accelerated creep. Starting with a non-linear viscous dashpot, and then introducing aging degradation and water-bearing weakening effects, based on the water-bearing creep characteristics of hard brittle shale as well as the modeling ideas of the classic component combination model, a new improved creep model based on the Nishihara model was established to describe the characteristics of the accelerated creep stage of hard brittle mud shale with various moisture contents. Subsequently, the Levenberg–Marquardt non-linear, least-squares method was adopted to invert the creep parameters. The results showed that the simulated creep curves achieved by employing the new creep model were consistent with the experimental results, thereby confirming the ability of the new non-linear creep model to provide a theoretical reference for the study of wellbore stability of hard brittle mud shale.
Article
Effects of Metal-Polycation Pillaring and Exchangeable Cations on Aflatoxin Adsorption by Smectite
- Ahmad Khan, Mohammad Saleem Akhtar, Saba Akbar, Khalid Saifullah Khan, Mazhar Iqbal, Ana Barrientos-Velazquez, Youjun Deng
-
- Published online by Cambridge University Press:
- 01 January 2024, pp. 155-164
-
- Article
- Export citation
-
Natural smectites bind aflatoxins from water effectively, but the complex chemical environment in the guts of mammals and other animals can limit binding of aflatoxins. Many efforts have been made to enhance the adsorption capacity and affinity of smectites for aflatoxins in the presence of biological compounds. The main objective of the present study was to modify smectite structures by pillaring and cation exchange to enhance aflatoxin B1 adsorption capacity and selectivity. Smectite was pillared with Al and Al-Fe polycations or saturated with Ca, Mg, Zn, or Li. Structural changes in smectites with or without heat treatment were determined using X-ray diffraction and Fourier-transform infrared spectroscopy. Equilibrium aflatoxin B1 adsorption to the smectites was measured in aqueous solution and in simulated gastric fluid. Pillaring with the polycations expanded smectites in the z-direction to 18.6 Å and the expansion was stable after heating at 500°C. Changes in the Al–OH–Al infrared bands in the stretching region supported the formation of pillared clays. Migration of Mg, Zn, and Li into the octahedral sites of the smectite was observed as Mg and Zn saturation yielded a d spacing of 15 Å at 200°C which collapsed to 9.6 Å at 400°C. The 14.6 Å peak of the Li-saturated smectite collapsed to 9.6 Å at 200°C while the 15 Å Ca-saturated smectite peak was stable up to 400°C. The unheated Al- and AlFe-pillared smectites adsorbed significantly more aflatoxin B1 from an aqueous suspension than did unpillared clay. In both water and simulated gastric fluid, heat treatment decreased aflatoxin B1 adsorption to pillared smectites, but heat treatment increased aflatoxin B1 adsorption to unpillared smectites. Without heat treatment, smectites saturated with divalent cations (Ca, Mg, Zn) adsorbed more aflatoxin B1 from an aqueous suspension than the smectite saturated with a monovalent cation (Li). Ca-saturated smectite showed the greatest aflatoxin B1 adsorption, 114 g kg–1, from aqueous suspension after 400°C heat treatment. The Zn-, Mg-, and Li-saturated smectites showed maximum aflatoxin adsorption of 107, 93, and 90 g kg–1, respectively, after 200°C heat treatment. From simulated gastric fluid with pepsin, the 200°C heated, Zn-saturated smectite had maximum aflatoxin B1 adsorption of 68 g kg–1. Pillared smectites effectively adsorbed aflatoxin B1 from aqueous suspension, but Ca- and Zn-saturated smectites after heat treatment might improve the selectivity of smectites for aflatoxin B1 over pepsin and enhance the efficacy of smectite as a feed additive.
Original Paper
Clay Minerals in Interbedded Sandstones and Shales of the Miocene Surma Group, Sylhet Trough, Bengal Basin (northeastern Indian Plate): Implications for Future Hydrocarbon Exploration
- Farida Khanam, M. Julleh Jalalur Rahman, Rashed Abdullah
-
- Published online by Cambridge University Press:
- 01 January 2024, pp. 328-353
-
- Article
- Export citation
-
Clay minerals are common constituents of the Miocene Surma Group reservoir rocks in the Sylhet Trough, Bengal Basin, and may exert significant controls on reservoir quality. The relationship between diagenetic clay minerals and reservoir quality in the petroliferous Sylhet Trough is poorly understood, however. The current study was aimed at the origin and diagenetic pattern of clay minerals in interbedded sandstones and shales using thin-section petrography, scanning electron microscopy (SEM), and X-ray diffraction (XRD), and understanding their diagenetic effects on reservoir quality. The results showed that the clay mineral cements in sandstones comprise mainly chlorite, illite/illite-smectite, and minor smectite and kaolinite. In the early diagenetic stage, clay rims and growth of vermiform kaolinite occur and partly occlude the pore throats. Deep burial effects include pore-filling, pore-lining, and grain-coating authigenic clays (mainly chlorite and illite). Diagenetic clay minerals and mechanical clay infiltration showed a systematic distribution in sandstones lying in the vicinity of sequence and parasequence boundaries. In a lowstand systems tract (LST), clay minerals within the sandstones commonly include mechanically infiltrated smectitic clays that eventually evolved to grain-coating chlorite and/or illite during the meso-diagenesis stage. The presence of clays/clay minerals has no significant impact upon reservoir quality of sandstones. The Surma Group shales are enriched in illite with significant proportions of chlorite and kaolinite and are likely to be mainly detrital, with diagenetic changes of smectite to illite.
Evaluation of the Hydraulic Conductivity of Geosynthetic Clay Liners
- Juan Hou, Yuyang Teng, Shifen Bao, Hao Li, Lei Liu
-
- Published online by Cambridge University Press:
- 01 January 2024, pp. 20-33
-
- Article
- Export citation
-
The hydraulic conductivity of geosynthetic clay liners (GCLs) is not fully understood and certain gaps in knowledge are still present, such as the effect of coupled mechanical and chemical processes. The current study aimed to develop a simplified mathematical model to predict the hydraulic conductivity of GCLs, particularly regarding the coupled effects of mechanical and chemical processes. Based on Darcy's Law and Poiseuille’s Law, the method combines diffuse double layer (DDL) theory and fractal theory. External factors such as confining pressure and the concentration of the permeating solution, and inherent properties such as exchangeable cations, ionic radius, montmorillonite surface fractal dimension, the distance between two montmorillonite layers (m) after swelling at the exchangeable cation i (i denotes the primary exchangeable cations, such as Na+, Ca2+, K+, and Mg2+ in bentonite), density, and coefficient of viscosity of interlayer water between two montmorillonite layers, were considered. The proposed theoretical model gave relatively accurate predictions. A practical estimate of GCL hydraulic conductivity was also derived. The predictions were compared with experimental results and good qualitative agreement was found. From the experimental results, the proposed prediction model has a maximum deviation of ~1:10–10:1, and the empirical model has a mean deviation of ~1:15–15:1.
Characteristics and Formation Pathways of Iron- and Magnesium-Silicate-Hydrates and Smectites Under Natural Alkaline Conditions
- Misato Shimbashi, Shingo Yokoyama, Ryosuke Kikuchi, Tsubasa Otake, Tsutomu Sato
-
- Published online by Cambridge University Press:
- 01 January 2024, pp. 492-513
-
- Article
- Export citation
-
Understanding the behavior of secondary minerals under alkaline conditions is important for predicting the potential alteration of the constituent minerals in radioactive-waste disposal facilities. A previous study reported the formation of uncommon Fe- and Mg-bearing clays under natural alkaline conditions in the Philippines; these were referred to as iron-magnesium-silicate-hydrates (F-M-S-H) and nontronite-like minerals. The current study aimed to investigate the structural and chemical characteristics and to understand the formation pathways of these clays by performing a detailed characterization. F-M-S-H comprised tetrahedral–octahedral–tetrahedral (TOT) layers, imperfect interlayer hydroxide sheets, and interlayer Ca ions. The systematic changes in the characteristics of F-M-S-H at different sampling depths, such as the gradual decrease of the interlayer hydroxide sheets to form smectitic domains, were caused by the differing interaction periods between each sediment at different sampling depths and alkaline seepage. Furthermore, F-M-S-H was ferrous in form prior to oxidation. In contrast, a nontronite-like mineral comprised nontronite and part of an interlayer hydroxide sheet. This mineral was inferred to be formed under chemically different conditions from F-M-S-H, and probably formed in the presence of aqueous Fe3+ and Mg ions.
Evolution of Alkali Release by an Illitic Rock for Use as Supplementary Cementitious Material
- Roxana Lemma, Silvina Marfil, Viviana Rahhal
-
- Published online by Cambridge University Press:
- 01 January 2024, pp. 616-627
-
- Article
- Export citation
-
The levels of CO2 emissions generated by the cement industry and the growth in demand for its products have led to a search for ways to reduce these emissions. The use of supplementary cementitious materials has become one of the solutions proposed for this problem. Illite, which is found all over the world, is a possible supplementary cementitious material. Before illite can be used, it must be milled and treated thermally in order to activate it, so that the alkalis (Na+ and K+) are free and available to react. Alkalis in cement participate in deleterious reactions (alkali-silica reaction) or have a beneficial effect (alkaline activation). The alkalis present in the rocks can play an active role in these phenomena, however. In addition, the material could be influenced by the alkaline environment produced by the cement. The current study was aimed at analyzing whether an alkali release occurs and if so, how it is affected when a milled and thermally treated illitic rock is in contact with water or an alkaline solution. The material was characterized by X-ray fluorescence, polarizing microscopy, and X-ray diffraction (XRD). The sample was treated thermally at 300, 600, and 900°C, and the thermal activation was evaluated through XRD, density, and Atterberg limits. The evolution of alkali release was studied by determining the sodium and potassium concentration of contact water obtained by mixing the samples with different pH solutions for various lengths of time. In addition, the calcium concentration was determined. The concentrations of sodium and potassium in the contact water were determined by flame photometry, and of calcium by EDTA (ethylenediaminetetraacetic acid) titration. The results showed that with increasing age, increasing solution pH, and higher treatment temperatures, alkali release occurred and increased, whereas Ca2+ concentration decreased.
Molecular Modeling to Predict the Optimal Mineralogy of Smectites as Binders of Aflatoxin
- Marek Szczerba, Youjun Deng, Mariola Kowalik-Hyla
-
- Published online by Cambridge University Press:
- 01 January 2024, pp. 824-836
-
- Article
- Export citation
-
Numerous experiments have verified that smectites can adsorb aflatoxin B1 (AfB1) effectively and the efficiency of this process depends heavily on the chemical, physical, and mineralogical characteristics of the smectite. Several relationships between these characteristics and AfB1 sorption have been determined experimentally, but the molecular mechanisms underlying these were not investigated. In the current study the effects of charge density, type of exchange cation, and charge origin (octahedral vs. tetrahedral) on AfB1 sorption on smectites were analyzed by a series of molecular simulations. The calculations confirmed the formation of water bridges between carbonyl groups of AfB1 molecules and interlayer cations. Flat orientation of AfB1 molecules on smectite surfaces was also confirmed. For larger amounts of AfB1 molecules in the intercalates, self-association of two AfB1 molecules bound by π–π interaction was shown. The thermodynamics of AfB1 sorption depends heavily on the water content in the structure, being optimal for basal distances corresponding to two layers of water. A clear preference for sorption of AfB1 on smectites with bivalent cations (Ba2+, Ca2+) and an octahedral origin of its layer charge was confirmed and this was explained as steric hindrance between hydrated ions and AfB1 molecules, which tend to lie flat on smectite surfaces devoid of ions. Ba-montmorillonite with a charge of 0.4 per half unit cell was shown to have the smallest and thus the best potential energy of adsorption compared to the other layer charges.
Aflatoxin B1 Sorption and Safety of Dietary Sodium Bentonite in Sprague-Dawley Rats
- Alicia G. Marroquín-Cardona, Youjun Deng, Jose F. Garcia-Mazcorro, Natalie M. Johnson, Nicolle J. Mitchell, Lili Tang, Jia-Sheng Wang, Roger B. Harvey, Timothy D. Phillips
-
- Published online by Cambridge University Press:
- 01 January 2024, pp. 165-181
-
- Article
- Export citation
-
Bentonites are readily available clays used in the livestock industry as feed additives to reduce aflatoxin (AF) exposure; their potential interaction with nutrients is the main concern limiting their use, however. The objective of the present study was to determine the safety of a dietary sodium-bentonite (Na-bentonite) supplement as a potential AF adsorbent, using juvenile Sprague Dawley (SD) rats as a research model. Animals were fed either a control diet or a diet containing Na-bentonite at 0.25% and 2% (w/w) inclusion rate. Growth, serum, and blood biochemical parameters, including selected serum vitamins (A and E) and elements such as calcium (Ca), potassium (K), iron (Fe), and zinc (Zn) were measured. The mineral characteristics and the aflatoxin B1 sorption capacity of Na-bentonite were also determined. By the end of the study, males gained more weight than females in control and Na-bentonite groups (p ≤ 0.0001); the interaction between treatment and sex was not significant (p = 0.6780), however. Some significant differences between the control group and bentonite treatments were observed in serum biochemistry and vitamin and minerals measurements; however, parameters fell within reference clinical values reported for SD rats and no evidence of dose-dependency was found. Serum Na and Na/K ratios were increased, while K levels were decreased in males and females from Na-bentonite groups. Serum Zn levels were decreased only in males from Na-bentonite treatments. Overall, results showed that inclusion of Na-bentonite at 0.25% and 2% did not cause any observable toxicity in a 3-month rodent study.
Synthesis of Magnetic Sulfonated Carbon/Fe3O4/Palygorskite Composites and Application as a Solid Acid Catalyst
- Mei Wu, Xingjun Yao, Jinlong Jiang, Yingnian Ji, Yaxi Gu, Qiulin Deng, Jing Ouyang
-
- Published online by Cambridge University Press:
- 01 January 2024, pp. 514-526
-
- Article
- Export citation
-
Sulfonated carbon is a green, solid acid catalyst but its surface area, separation, and recovery after utilization need to be improved. The objective of the present study was to provide an environmentally friendly and economical method to prepare magnetic sulfonated carbon composite catalyst with a large surface area using palygorskite (Plg) as the support. A magnetic sulfonated carbon/Fe3O4/Plg composite catalyst was prepared via simultaneous calcination and sulfonation of the mixture of source, p-toluenesulfonic acid (TsOH), and Fe3O4/Plg. Fe3O4 nanoparticles and Plg nanorods were encased by a carbon layer derived from sucrose and TsOH. The composite catalyst exhibited good magnetic properties and high catalytic performance for the esterification of oleic acid with methanol. Oleic acid conversion reached 88.69% after the first catalytic cycle. Plg nanorods replaced sucrose and increased the catalyst’s surface area. The introduction of Fe3O4 nanoparticles improved further the acid content and oleic-acid conversion and achieved 70.31% after five cycles. The catalyst was recycled easily using an external magnetic field and its magnetic property remained unchanged due to the protection of the carbon layer.
Genesis of Smectites associated with a Coal Seams Succession in the Neogene Orhaneli and Keles Coal Deposits (Bursa), NW Turkey
- Hülya Erkoyun, Selahattin Kadir, Tacit Külah
-
- Published online by Cambridge University Press:
- 01 January 2024, pp. 628-659
-
- Article
- Export citation
-
The Bursa-Orhaneli and Keles-Harmanalan coal deposits were developed in swampy and fluvial-lacustrine environments in western Anatolia under the E–W-trending graben zone during the Neogene. The present study aimed to determine the mineralogical and geochemical properties of clays interlayering the coal seams to define the origin of clay minerals, in particular, smectite. These deposits, comprising argillaceous sediment, marl, coal seam, mudstone, organic-rich shale, and sandstone, were deposited in a lacustrine environment accompanied by volcanogenic materials. The characteristics of sediments and their parent rocks were examined using X-ray diffraction, scanning electron microscopy, energy dispersive spectroscopy, palynology, and chemical analyses. The association of abundant smectite with quartz, amphibole, accessory chlorite, and a decrease in feldspar in fluvial-lacustrine sediments compared to those in the smectite accompanied by feldspar and volcanic glass and the absence of quartz and amphibole in the pyroclastic units suggest that smectite had detrital and authigenic origins. Flaky smectite shows either detrital, irregularly outlined coating and filling pores of terrigenous sediments or in situ precipitation edging resorbed feldspar and devitrified volcanic glass. Chemical analyses of the smectite-rich fraction show montmorillonite compositions with an average structural formula of: (Ca0.42Na0.25K0.08)(Al2.76Fe0.47Mg0.59Ti0.07Mn0.002)(Si7.65Al0.35)O20(OH)4.
The positive correlation of Al2O3 vs. TiO2 and K2O vs. Rb may be related to the abundant detrital input. Feldspar and biotite were replaced by illite during diagenesis.
An increase in the Ni/Co and V/(V + Ni) ratios in the altered units also suggest oxic, suboxic to anoxic conditions, under the control of a dry, warm to subtropical climate in fresh water and lakes during the Late Eocene to Middle Miocene. The slight enrichment of light rare earth elements (LREE) compared to heavy rare earth elements (HREE) with positive Eu and positive/negative Ce anomalies reflect fractional crystallization of feldspar. The δ18O and δD values of smectite and illite fractions and the wide range of δ34S isotope values (–1.5 to 15‰) for pyrite and chalcopyrite associated with coal indicate a signature of both diagenetic and partial hydrothermal origin.
Aqueous Solubility of Zn Incorporated into Mg-Al-Layered Double Hydroxides
- Anna Dabizha, Michael Kersten
-
- Published online by Cambridge University Press:
- 01 January 2024, pp. 34-47
-
- Article
-
- You have access Access
- Open access
- HTML
- Export citation
-
Hydrotalcite minerals are layered double hydroxides (LDH) which play an important role in immobilizing hazardous compounds to decontaminate industrial wastewaters. The stability of an LDH is mostly evaluated in terms of its low solubility in water. However, the solubility of divalent trace metals immobilized by Mg-Al-type LDHs is not well known. Hydrotalcites containing Zn in solid solution, (Mg+Zn)3-Al-LDH, were synthesized by alkaline co-precipitation. A series of eleven LDH phases with Zn mole fractions XZn = Zn/(Mg+Zn) of 0–1 were characterized by powder X-ray diffractometry (XRD), Fourier-transform infrared (FTIR) spectroscopy, thermogravimetry (TGA), scanning and transmission electron microscopy (SEM/TEM), Brunauer-Emmett-Teller (BET) surface area analysis, and inductively coupled plasma mass (ICP-MS) spectrometry. The XRD analysis provided sharp characteristic spacings for d003 and d006 which occurred for all samples, confirming a layered LDH structure. Cell parameters (a, c) obeyed Vegard’s law and confirmed the formation of a regular solid-solution series without a mixing gap. An aqueous equilibrium time was determined by kinetic dissolution experiments. Steady-state solubility occurred after 120 days, but the experiments continued up to 240 days. The XRD and SEM/TEM analyses indicated no phase changes during the long-term dissolution experiments; neither were phase impurities detected after 240 days. The solubility products of the Mg- and Zn-bearing endmember compositions were calculated from experimentally determined total cation and anion concentrations using the Visual Minteq code for considering element speciation and ion pairing. The solubility product decreased as the Zn mole fraction increased, suggesting that the Zn-bearing LDH phases were more stable than the pure Mg3-Al-LDHs. Solid-solution aqueous-solution thermodynamic equilibrium modeling using the Lippmann “total solubility product” approach and applying Lippmann diagrams with logarithmic x-axes revealed a log-linear decrease in aqueous Zn solubility. The results are promising for remediation of metal-bearing liquid wastes because the metals that co-precipitated with the LDH were more strongly retained and, therefore, less soluble than the hydroxides or carbonates of the trace metal.
Preparation and Properties of Antibacterial Polyhexamethylene Biguanide/Palygorskite Composites as Zearalenone Adsorbents
- Yu R. Kang, B. Mu, G. Zhu, Yong F. Zhu, Ai Q. Wang
-
- Published online by Cambridge University Press:
- 01 January 2024, pp. 182-195
-
- Article
- Export citation
-
Due to the environmental problems derived from the use of common surfactants as modifiers for clay mineral adsorbents to mitigate mycotoxin contamination of animal feeds, finding non-toxic modifiers to prepare safe and efficient adsorbents is necessary. The objective of the present study was, therefore, to modify acidified palygorskite with polyhexamethylene biguanide (PHMB) to obtain antibacterial polyhexamethylene biguanide/palygorskite (PHMB/Plg) composites for the removal of zearalenone, a common mycotoxin. The PHMB/Plg composites were characterized and analyzed by X-ray diffraction, Fourier-transform infrared spectroscopy, field-emission scanning electron microscopy, and isothermal nitrogen adsorption analysis. The adsorption properties of the composites with respect to zearalenone and their antibacterial activity with respect to Escherichia coli and Staphylococcus aureus were studied. The results indicated that the hydrophobicity of palygorskite was enhanced after modification with PHMB, which could effectively improve the adsorption property of palygorskite toward the nonpolar zearalenone molecules. The adsorption capacity of PHMB/Plg increased with increasing amounts of polyhexamethylene biguanide and increasing pH. The adsorption data were described well by pseudo-second order kinetics and by the Langmuir adsorption model. The maximum adsorption capacity was 2777 μg/g. When the amount of PHMB added increased to 15 wt.%, the composites obtained exhibited good antibacterial performance, and the minimum inhibitory concentrations for Escherichia coli and Staphylococcus aureus were both at 2.5 mg/mL.
Comparison of Pretreatment Methods for Organic-matter Removal and their Effects on the Hydrogen Isotope (δ2H) Composition of Kaolinite
- Arpita Samanta, M. K. Bera, Sruthi P. Sreenivasan, Anindya Sarkar
-
- Published online by Cambridge University Press:
- 01 January 2024, pp. 837-849
-
- Article
- Export citation
-
The hydrogen isotopic composition (δ2H) of authigenic clay minerals has been used extensively in paleoclimate studies. The separation of clay minerals from sediments/soils, using various chemicals, is a prerequisite for isotope ratio measurements, where carbonate, Fe-(oxyhydr)oxides, and organic matter are removed successively from the sediments for a greater clay yield. The commonly adopted organic matter-removal method using hydrogen peroxide (H2O2) is thought to either alter directly the pristine δ2H values of the smectite clay minerals or to introduce organic hydrogen-bearing impurities through the ineffective removal of organic matter. The objective of the present study was to test whether H2O2 treatment can alter the δ2H values of kaolinite (Kln) by comparing two organic matter-removal methods, namely, H2O2 and disodium peroxodisulfate (Na2S2O8) combined with a neutral buffer. In doing so, kaolinite-rich, old (~56 Ma) sediment samples and pure kaolinite internal laboratory reference materials were used to understand the effectiveness and suitability of the above-mentioned methods in clay-sample preparation for δ2H measurements. The δ2H values of the H2O2-treated aliquots show smaller δ2H values than those for the Na2S2O8-treated aliquots. Estimated ambient water δ18O values (−4‰) from the Na2S2O8-treated aliquots agreed well with the bio-phosphate (fish vertebrae) based environmental water δ18O estimation (−3.3‰). The present study indicated, therefore, that δ2H values obtained after Na2S2O8 treatment are likely to be more realistic for paleoclimate reconstruction.
Efficacy of Two Texas Bentonites in Binding Aflatoxin B1 and in Reducing Aflatoxicosis in Broilers
- Ana Luisa Barrientos-Velazquez, Radhika Kakani, Justin Fowler, Akram-ul Haq, Christopher A. Bailey, Youjun Deng
-
- Published online by Cambridge University Press:
- 01 January 2024, pp. 354-369
-
- Article
- Export citation
-
The incorporation of bentonites in aflatoxin-contaminated animal feeds to remedy aflatoxicosis has been tested widely in animal trials. Yet, a large variation in efficacy among samples has been observed which has been attributed to variations in the properties of the clay mineral adsorbents. The objectives of the current study were: (1) to evaluate the mineral and chemical composition of two selected bentonites to find minerals or elements which are potentially of concern; (2) to characterize the aflatoxin B1 (AfB1) adsorption (selectivity, capacity, reversibility, and interlayer accessibility) by the bentonites; and (3) to evaluate the safety and efficacy of selected clays as amendments of aflatoxin-contaminated feed for broiler chickens. The mineral, chemical, and exchange cation composition of the clays were analyzed, and they appeared to be safe for use in feed. The bentonites and their fractions showed that adsorption capacities range from 0.48 to 0.97 mol/kg. The interlayer spaces of both montmorillonites were accessible by AfB1, and the adsorption was irreversible. Three-day old broiler chickens were given clean and high-aflatoxin-concentration (1400 mg/kg) diets with and without the presence of the two bentonites. After three weeks the chickens were sacrificed and biomarkers were evaluated. The presence of aflatoxins reduced the body weight by 58% and resulted in a 25% mortality rate. Adding bentonites 1TX and 4TX increased the body weight of the chickens by 14 and 23%, respectively, but did not improve the mortality rates. The results suggested that selected bentonites could effectively sequester aflatoxins in vivo but did not eliminate the total toxicity present in highly contaminated poultry feed.
Development and Characterization of Sintered Zeolite and Zeolite-Kaolin Wick Structure for Thermosiphon Heat-Pipe Application
- Muhammad Aon Ali, Tzong-Shyng Leu, Chih-Yuan Weng, Hafiz Muhammad Ali
-
- Published online by Cambridge University Press:
- 01 January 2024, pp. 850-864
-
- Article
- Export citation
-
A wick structure is the core part of a heat pipe that produces capillaries to move liquid from a condenser to an evaporator. The purpose of the current study was to develop a wick structure from zeolite and kaolin using various sintering methods. Due to significant porosity and water-adsorption properties, zeolite and kaolin can produce a large capillary force inside the heat pipe. A porous wick specimen is developed from pure zeolite together with a mixture of zeolite and kaolin by using pressureless (loosely packed) and conventional pressurized sintering for thermosiphon heat-pipe applications. Major properties such as porosity, water adsorption, and permeability were noted to be better under pressureless sintering compared to pressurized sintering. Significant and uneven shrinkage in both radial and linear directions is a major problem in loosely packed sintering of pure zeolite. However, the addition of kaolin helps to overcome the problem of porosity and shrinkage in pure zeolite; but the permeability and strength of the wick structure are reduced with the addition of kaolin. A general trend is that increasing porosity causes increasing permeability. Due to grain size and compaction, however, permeability is reduced with the addition of kaolin. Based on the experimental results for porosity and permeability, the wick structure formed from zeolite with 5–10% of kaolin has better thermal properties for heat-pipe applications.
Review
Design Approaches, Functionalization, and Environmental and Analytical Applications of Magnetic Halloysite Nanotubes: A Review
- Meriem Fizir, Wei Liu, Xue Tang, Fangqi Wang, Yassmine Benmokadem
-
- Published online by Cambridge University Press:
- 01 January 2024, pp. 660-694
-
- Article
- Export citation
-
Researchers have long been committed to developing alternative, low-cost nanomaterials that have comparable capacity to carbon nanotubes. Halloysite nanotubes (HNTs) are naturally hollow, multi-walled, tubular structures that have high porosity, enlarged volumes and surface areas, and hydroxyl groups ready for modification. In addition, HNTs are non-toxic, biocompatible, inexpensive, abundant in nature, and easy to obtain. Magnetic nanocomposites have aroused widespread attention for their diverse potential applications in analytical fields and so magnetic halloysite nanotubes (MHNTs) have emerged as outstanding magnetic nano-adsorbent materials. Owing to their superparamagnetism, selective adsorption ability, and easy separation and surface modification, these captivating nanomaterials excel at extracting and enriching various analytes from environmental, biological, and food samples. The current review article gives an insight into recent advances in the design, functionalization, characterization, and application of MHNTs as magnetic, solid-phase extraction sorbents for separation of antibiotics, pesticides, proteins, carcinogens such as polycyclic aromatic hydrocarbons (PAHs), dyes, radioactive ions, and heavy-metal ions in complex matrices.