Halloysite nanotubes (often abbreviated as HNTs) are technologically important owing to their unique structural and morphological features. Some of these features pre-exist in the naturally hydrated halloysite-(10 Å) parent clay mineral; others may develop during its dehydration towards halloysite-(7 Å). This is the first infrared spectroscopic study of the transition to halloysite-(7 Å), which, in combination with X-ray diffraction (XRD), aimed at advancing the structural description of the process. Three cylindrical and two polygonal halloysite-(10 Å) samples, in both their H- and D-forms, were measured by attenuated total reflectance (ATR), non-invasively and in situ, following step-wise equilibration from 70% relative humidity (RH) to <10% RH and back to 70% RH at ambient temperature. This approach allowed for recording the spectrum of the dehydrating (but not rehydrating) interlayer in the νO–D range, without interference from the inner νOH groups, or from the inner-surface νOH of anhydrous interlayers already present in the parent material. Besides the well-known ‘hole’ H2O species, a new type of H2O-decorated defect was detected at frequencies normally dominated by the inner νOH. This defect is linked to the microenvironment created by the detachment between layer packets and forming ‘crevices’ or ‘slits’ upon dehydration. In addition, the study of the νSi–O spectrum demonstrated that the dehydration of halloysite-(10 Å) leads to the parallel formation of localized, ordered, kaolinite-like domains co-existing with regions of accumulated disorder. The as-produced halloysite-(7 Å) had a non-ideal, open structure that resisted rehydration because the kaolinite-like domains do not rehydrate and act as permanent cross-links.

Transmission electron microscopy-energy dispersive X-ray analysis (TEM-EDX) represents an effective tool for determining the stoichiometric composition of clay minerals, but the methodology is often hampered by analytical difficulties. Studies of beam-sensitive minerals, such as smectites, are associated with low count intensities and dynamic loss of cations (e.g. K+, Na+, and Al3+), which can lead to erroneous quantifications of composition. After exploring how to minimize cation migration by reducing the beam current density to <5 pA cm–2, the most reliable and consistent compositions were determined using 1 μm2 area measurements of particles acquired in normal TEM mode where the electron beam was parallel, the degree of specimen damage was at its minimum and good acquisition intensities (>10,000 cps) were acquired. Based on 528 TEM-EDX area analyses, the composition of Wyoming montmorillonites (SWy-1, SWy-2, and SWy-3) was studied in their natural and Ca-saturated states from thin (<50 nm thick) particle aggregates lying on lacey carbon films. Overall, the TEM-EDX results confirmed the heterogeneous charge distributions of montmorillonite at the particle and sample levels. The average composition per formula unit of SWy-1 to -3 was determined as: (Na0.12Ca0.04Mg0.03K0.02)(Si3.91Al0.09)(Al1.57Mg0.27Fe0.19)2.03 O10(OH)2 · nH2O, where the tetrahedral and octahedral layer charges are –0.09 and –0.19 per O10(OH)2, respectively, and the total layer charge ranges from –0.25 to –0.30 per O10(OH)2 (mean of –0.28). This study demonstrates how TEM-EDX can provide new insight into the natural heterogeneities of smectite chemistry as long as adequate calibration and specimen damage control procedures are implemented.

Individuals may experience health issues attributable to environmental pollution, sedentary lifestyles, and unhealthy dietary habits. In response, numerous non-pharmaceutical treatments and techniques have emerged, with therapy mud being one such approach. The primary aim of this research was to analyze the chemical and mineralogical compositions of peloids obtained from six salt lakes: Taigan (LI), Duruu (LII), Khadaasan (LIII), Ikhes (LIV), Tonkhil (LV), and Khulmaa (LVI) in the Gobi-Altai province of Mongolia. Sample analyses involved X-ray diffraction for mineralogical assessment and inductively coupled plasma-mass spectrometry (Agilent Technologies 7800 series in Canada) for determining the chemical composition of the solid phase. Among essential macro- and microelements, Mg, Cа, Na, K, Sr, Ga, Mo, and Se had been leached from peloid to artificial sweat. Sn (0.01 μg g–1) at LIV and LVI lakes and Cu (0.01 μg g–1) at LV lake transferred from peloids to sweat, but no mobility of these elements in other peloids was detected. Li (0.02–0.04 μg g–1) was adsorbed from the sweat to potential peloids in LV, LIV, LIII, and LI lakes, while As (0.04–0.09 μg g–1) leached from peloids to sweat in all lakes except for LII. Zn (0.01 μg g–1) and Cr (0.04 μg g–1) transferred from the sweat to peloids in all lakes. Macroelements (Na, K, Ca, and Mg) and microelements (Mo, Se), which are essential for the human body, leached from the peloid to sweat. However, the mobility of toxic elements was minimal. Among micro-elements, the transition of Sr occurred the most, which can be explained by the Sr content in the peloid.

The increasing contamination of water by organic dyes causes water pollution in the enviroment. Factories discharge untreated effluents into nearby water courses adding to the existing water pollution; this poses a significant environmental challenge. Hence there is a pressing demand to develop efficient technology for wastewater treatment, and photocatalysis has emerged as an advanced oxidation process with a green chemical approach for such treatment. This study aims to synthesize montmorillonite/TiO2 (Mnt/TiO2) photocatalysts and clarify the effect of montmorillonite content on the photodegradation of the organic dye rhodamine B (RhB). Mnt/TiO2 was prepared by a chemical method with various mass ratios of mMnt:mTiO2 based on the cation exchange capacity (CEC) of Mnt. The physicochemical properties of the samples prepared were determined by the following methods: energy-dispersive X-ray spectroscopy (EDX), scanning electron microscopy (SEM), Brunauer–Emmett–Teller (BET), X-ray diffraction (XRD), and Fourier transform infrared spectroscopy (FTIR). The photocatalytic degradation efficiency of the RhB solution of Mnt/TiO2 was investigated by UV-Vis spectroscopy under UVC irradiation. Liquid chromatography-mass spectrometry (LCMS) was used to identify the photocatalytic by-products. The results showed that the structure of the nanocomposites has a ‘house-of-cards’ form with TiO2 nanoparticles randomly distributed on the surface and sheets of clay minerals. The best mass ratio of mMnt:mTiO2 is 10:1, corresponding to a 10 ppm RhB solution decolorization efficiency of 91.5% in 210 min. In this study, Mnt/TiO2 successfully cleaved the dye chromophore structure and broke the RhB rings into small and broken-ring compounds.

This study investigates the hydrogenetic ferromanganese crust (HFMC) from the Magellan Seamounts in the northwest Pacific Ocean, focusing on its mineralogy, crystal chemistry, and paleoclimatic records. Given that ferromanganese is composed of poorly crystalline MnOx phases, such as vernadite, structural determination using conventional X-ray diffraction (XRD) methods is challenging and has very limited effectiveness. Therefore, synchrotron-based pair-distribution function (PDF) analysis of total X-ray scattering and high-resolution electron microscopy techniques were employed to characterize the structures and compositions of HFMC. The results from the synchrotron XRD and transmission electron microscopy (TEM) reveal that the studied HFMC consists primarily of poorly crystalline Fe-bearing vernadite. The chemical analysis of the HFMC layers indicates that the rare-earth elements (REE) and P were preferentially adsorbed on the Fe-rich vernadite, whereas platinum-group elements (PGE), Co, and Ni were enriched in the Mn-rich vernadite. The top layers of the HFMC display fine-scale compositional variations (cycle of ~1600 y) that signify millennial-scale paleoclimate oscillations during the Middle-Late Pleistocene and Holocene periods linked to the glacial termination event that occurred ~126,000 y ago. This millennial-scale oscillation correlates with sea-level variations influenced by the expansion and contraction of ice sheets, offering a crucial signal for understanding the paleoclimatic interpretation throughout the glacial periods. To fully decipher the fine-scale paleoclimate signals and assist in forecasting future climatic conditions, a more extensive examination of ferromanganese crusts from diverse depths, sources, and locations is necessitated.

Models of cation exchange mechanisms and driving forces have proven effective predictors of clay behavior and chemistry, but are largely theoretical, particularly in complex systems involving high ionic strength brines or systems where hydration is controlled by relative humidity. In arid and cold environments, such as Mars, cyclical relative humidity variations may play a role in chemical alteration, particularly if clay minerals such as smectite are in the presence of salts. This study examines the effects of relative humidity on smectite-salt mixtures using environmental scanning electron microscopy (ESEM) to observe the physiochemical effects of salt deliquescence and desiccation on smectite textures and elemental distributions. Results demonstrate that even reaction periods as short as a few minutes allow ample time for relative humidity to affect the smectite-salt mixtures. In addition to smectite swelling and salt deliquescence, we also observed rapid changes in element distributions within the smectite and new crystal growth in the presence of high relative humidity. Even in the absence of bulk liquid water, exchangeable cations migrated out of the smectite and formed new crystals at the smectite-salt interface. The observed microscopic changes in elemental distributions indicate that the migration of cations driven by cation exchange led to secondary mineral precipitation, likely a CaSO4 mineral, within a sub-micrometer-thick layer of water on the smectite grains. The results of this study demonstrate that during periods of elevated relative humidity, active smectite mineral alteration and secondary mineral precipitation may be possible on present-day Mars where salts and smectites are in direct physical contact.

The mobility of rare-earth elements (REE) in low-grade diagenetic regimes, potentially leading to their clay-mediated fractionation, remains poorly understood. This study draws evidence from the argillitized Miocene tuff of the Southwestern Pannonian Basin (SPB) and adjacent Dinarides intramontane basins (DIB) to investigate the role of illite-smectite (I-S) in controlling early diagenetic REE behavior. The present research relies on detailed mineralogical, geochemical, and gas adsorption characterization of altered tuff, focusing on comparative analyses of the REE chemistry obtained by in situ laser ablation inductively coupled plasma mass spectrometry of glass shards and that of spatially related authigenic clay minerals. The depositional environment, in which the volcanic glass alteration took place, gave rise to the composition of secondary paragenesis, revealing a dominance of I-S. The normalized REE geochemistry of clay separates show similarities to unaltered glass, but notable differences indicate fluctuations in fluid/rock ratio environments. The redox conditions during glass alteration are reflected in Ce and Eu anomalies and indicate the ranges from oxic to anoxic across the analyzed tuffs. The results showed that I-S, formed through volcanic glass diagenesis, inherits magmatic REE signatures but also fractionates REE based on more reducing physiochemical conditions. The strong correlation between smectite content of I-S and a total budget of fractionated REE posits the smectite interlayers as prime factors controlling the REE fractionation during volcanic ash diagenesis. Furthermore, greater specific surface area values and development of slit-shaped porosity along the non-basal edges of I-S particles contributed to REE adsorption. These findings contribute to our understanding of REE behavior in low-temperature diagenetic environments, emphasizing the significance of clay minerals in retaining and fractionating these elements which may lead ultimately to the formation of economically viable ion-adsorption clay deposits.

One potential solution to the rising threat of antibacterial drug resistance is the application of therapeutic clays to treat wound infections. Clays with antibacterial activity have been identified from a range of sources with their antibacterial properties often attributed to the release of toxic metal ions such as Fe(II) and Al(III). Here, clays from Afghanistan, Azerbaijan and Bangladesh that are utilized for washing and healing purposes were examined. Their antibacterial activities were assessed in suspension and as aqueous leachates against representative Gram-negative, Escherichia coli, and Gram-positive, Bacillus subtilis, bacteria. The majority of the clays conferred no deleterious effect and, in fact, tended to promote bacterial growth, likely as a result of released organic and inorganic nutrients. However, one of the clays, obtained from the Dhaka region of Bangladesh, displayed significant bactericidal activity against E. coli and B. subtilis as a clay suspension but not as an aqueous leachate. Further experiments confirmed that contact between clay and the bacteria was necessary for most of the antibacterial effects. Detailed analysis of bulk and <2 μm clay fraction mineralogy and geochemistry revealed no single defining parameter or mineral component that could be used to easily distinguish natural clays with antibacterial properties from those without. Overall, the results suggest a mechanism of antibacterial action of the Dhaka clay that arises from acidic conditions, likely enabled by the absence of calcite in the bulk clay, metal release, the presence of interstratified chlorite-smectite, and direct clay–bacteria interactions.

The alteration of bentonite under alkaline conditions and the subsequent changes in properties such as permeability and self-sealing ability should be evaluated for the performance assessment of radioactive waste repositories. As the period of evaluation for alterations is extremely long, natural analog (NA) studies that can observe long-term phenomena similar to the system of radioactive waste repositories have significant advantages. However, locations that can be set up as NA study sites with significant similarity are limited and should be pursued by localizing analog systems. This literature review summarized studies reporting secondary phases formed at low temperatures (<100°C) under a broader range of natural sites which are chemically similar to the alkaline conditions expected at bentonite in radioactive waste repositories, including near pyrometamorphic rocks, near ophiolites, and in alkaline saline lakes. This review provides insights into the species, formation conditions, and stability of secondary phases that could be formed during cement–bentonite interactions and the timescale for mineralogical transitions from a metastable to a stable phase. The findings could be useful for selecting secondary phases to be considered in reactive transport modeling for predicting cement–bentonite interactions in radioactive waste repositories.

The Dolná Ves K-bentonite deposit is one of a few known economic accumulations of illite-smectite in the world. Several studies have been done on the illite-smectitic component isolated from the Dolná Ves K-bentonite, but there is a shortage of analytical data on the K-bentonite itself. The main goal of the present study was to perform mineralogical and physico-chemical characterizations of various technological types of K-bentonites from the Dolná Ves deposit to better understand the relationships between the various qualitative types and their properties. The type I (high-grade) K-bentonite contains 88–91 wt.% of illite-smectite. The type II (low-grade) K-bentonite contained substantially less illite-smectite, ranging from 37 to 63 wt.%. The illite-smectites isolated from the type I K-bentonites displayed greater expandability, contained more octahedral Mg and less octahedral Fe, had greater cation exchange capacity (CEC), smaller thickness of fundamental particles, and thinner illite-smectite crystals in comparison with illite-smectites from the type II K-bentonites. The LOI (loss-on-ignition) and Al2O3 content increased with increasing amount of illite-smectite. The increase in the expandability by 10% corresponded to an increase in CEC by ~10 meq/100 g. The type I K-bentonites had much greater mass loss at <250°C due to greater expandability. The best tilemaking performance was expected for the type I K-bentonite. This raw material could also be potentially valuable for the pharmaceutical, cosmetic and food industries. Overall, the results showed that the studied technological types of K-bentonites from the Dolná Ves deposit differ not only in terms of illite-smectite contents but also in terms of the nature of the illite-smectites.

Phyllosilicates are hypothesized to be primarily of pedogenic origin in shallowly buried paleosols (≤3 km depth), regardless of the age of the paleosol. To test this hypothesis, this work evaluates the possible presence of detrital and diagenetic phyllosilicates in middle and upper Pennsylvanian paleosols, collected from three drill cores along a north–south transect in the Illinois Basin. The abundances of 2M1 muscovite, quartz, and K-feldspar are greater in a morphologically immature Protosol from the southernmost core; 1Md illite and interstratified illite-smectite with R1 and R0 stacking orders are more abundant in the more mature Vertisols of the central and northern cores. K-Ar age values of multiple clay-size fractions from each paleosol averaged ~260 Ma in the northern core, 270 Ma in the central core, and 295 Ma in the southern core. While considering the complex tectonic and thermal history of the Illinois Basin, detrital minerals are more abundant in immature paleosols that experienced relatively greater maximum burial depths and thus greater sediment supply whereas illitization in more mature paleosols was probably initiated primarily during protracted burial diagenesis. As the present study found evidence for diagenetic and detrital minerals in clay-size fractions of shallowly buried, deep-time paleosols, caution is advised when using paleosol minerals for ancient climate and environment reconstructions.

The identification of raw materials and an effective maturation process for the development of peloids is essential to ensure consistent comparisons between commonly used peloids in ‘thermal centers’ (places that offer a variety of health and wellness treatments, also known as spas) and their therapeutic and well-being effects. The present study supports the need for scientific research which examines the variations in physicochemical, technological, and biological properties of peloids resulting from varying maturation conditions. These studies are necessary for establishing quality and safety standards and expanding our understanding of the therapeutic significance of peloids. The objective of the present study was to characterize an experimental maturation procedure using a specific Portuguese clay (bentonite) sourced from Benavila—Avis, which has particular physico-chemical characteristics, in conjunction with two distinct Portuguese mineral-medicinal waters (Hotel Cró and Thermal Spa, and Caldas da Rainha Thermal Hospital) as raw materials. The main aim of the study was to assess and characterize the resulting peloids by evaluating their physicochemical, technological, and biological properties. The experiment was conducted over a period of 90 days under carefully controlled lighting and agitation conditions. The rheological, mineralogical, and chemical properties relevant to a peloid intended for topical application and its potential transdermal delivery of elements were characterized. Additionally, the study investigated the biological activity within the maturation habitat, including chlorophyll, microalgae, and microorganisms. Eight samples, representing the four maturation conditions (stirring with light; stirring without light; no stirring with light, and no stirring and no light), were examined for 30, 60, and 90 days. The study showcased the influence of different mineral-medicinal waters on maturation conditions and on the final bentonite characteristics. Furthermore, it reinforced the importance of establishing quality-control procedures throughout the maturation cycle for bentonitic peloids, as well as the importance of monitoring their usage, reutilization, and disposal.

Geologic repositories for spent nuclear fuel use bentonite as a buffer to protect the metallic containers confining the radioactive material. Sulfate-reducing bacteria, which may be present in groundwater, at the bentonite–host rock interface or eventually within the bentonite may produce sulfide, representing a potential threat for the metallic canisters, particularly copper. Bentonites can act as potential sulfide scavengers. Little is yet known, however, regarding the underlying mechanisms, the maximum extent of sulfide consumption, and the potential impacts on bentonite structure under repository conditions. In the current study, concentrated (4–150 mM) sulfide solutions were reacted in batch experiments with six natural Fe-bearing bentonites, with various purified Fe-bearing components of bentonite (a series of purified montmorillonites and three iron (oxyhydr)oxides), and with one synthetic mixture, for up to 1.5 months at pH values ranging from 7 to 13. The solutions were analyzed by colorimetry to determine sulfide and polysulfide concentrations and the solids were analyzed by 57Fe Mössbauer spectrometry to determine iron speciation. Important sulfide consumption coupled with a reduction of structural Fe in the clay samples was observed. Not all clay structural Fe was reactive toward sulfide; the proportion of active structural Fe depended on the clay structure and pH. In the presence of excess sulfide in solution regarding Fe in the solid sample, the clay structural Fe was found to be the main reactant while the reaction with iron (oxyhydr)oxides was largely inhibited. Three bentonite groups were distinguished, based on the sulfide oxidation capacity of their main clayey component.

Diagenetic illite growth in porous sandstones leads to significant modifications of the initial pore system which result in tight reservoirs. Understanding and quantifying these changes provides insight into the porosity-permeability history of the reservoir and improves predictions on petrophysical behavior. To characterize the various stages of diagenetic alteration, a focused ion beam – scanning electron microscopy (FIB-SEM) study was undertaken on aeolian sandstones from the Bebertal outcrop of the Parchim Formation (Early Permian Upper Rotliegend group). Based on 3D microscopic reconstructions, three different textural types of illite crystals occur, common to many tight Rotliegend sandstones, namely (1) feldspar grain alterations and associated illite meshworks, (2) tangential grain coats, and (3) pore-filling laths and fibers. Reaction textures, pore structure quantifications, and numerical simulations of fluid transport have revealed that different generations of nano-porosity are connected to the diagenetic alteration of feldspars and the authigenic growth of pore-filling illites. The latter leads to the formation of microstructures that range from authigenic compact tangential grain coatings to highly porous, pore-filling structures. K-feldspar replacement and initial grain coatings of illite are composed primarily of disordered 1Md illite whereas the epitaxially grown illite lath- and fiber-shaped crystals occurring as pore-filling structures are of the trans-vacant 1Mtv polytype. Although all analyzed 3D structures offer connected pathways, the largest reduction in sandstone permeability occurred during the initial formation of the tangential illite coatings that sealed altered feldspars and the subsequent growth of pore-filling laths and fibrous illites. Analyses of both illite pore-size and crystallite-size distributions indicate that crystal growth occurred by a continuous nucleation and growth mechanism probably controlled by the multiple influx of potassium-rich fluids during late Triassic and Jurassic times. The detailed insight into the textural varieties of illite crystal growth and its calculated permeabilities provides important constraints for understanding the complexities of fluid-flow in tight reservoir sandstones.

The present study introduces an overview of gentamicin-clay mineral systems for applications in biomedicine and then focuses on the development of a series of gentamicin/clay hybrid materials to be used as the bioactive phase of hydroxypropylmethylcellulose (HPMC) to produce bionanocomposite membranes possessing antimicrobial activity of interest in wound-dressing applications. Gentamicin (Gt) was adsorbed from aqueous solutions into a montmorillonite (Cloisite®-Na+) to produce intercalation compounds with tunable content of the antibiotic. The hybrids were characterized by CHN chemical analysis, energy-dispersive X-ray analysis, X-ray diffraction, Fourier-transform infrared spectroscopy, and thermogravimetric analysis, confirming the intercalation of Gt by an ion-exchange mechanism. The release of Gt from the hybrids was tested in water and in buffer solution to check their stability. Hybrids with various amounts of Gt were incorporated into a HPMC matrix at various loadings and processed as films by the casting method. The resulting Gt-clay/HPMC bionanocomposites were characterized by means of field-emission scanning electron microscopy, and were also evaluated for their water-adsorption and mechanical properties to confirm their suitability for wound-dressing applications. The antimicrobial activity of the bionanocomposite films was tested in vitro toward various microorganisms (Escherichia coli, Pseudomonas aeruginosa, Staphylococcus aureus, methicillin-resistant Staphylococcus aureus (MRSA), vancomycin-resistant Enterococcus faecium, Acinetobacter baumannii, and Klebsiella pneumonia), showing a complete bacterial reduction even in films with small Gt contents.

Varved clay deposits from ice-dammed lakes are a particularly important and broadly applied raw material used for the production of high-quality ceramics (red bricks, roof tiles, etc.), but the mineralogy and geochemistry of these sediments are not fully understood. The aim of the present study was to determine the chemical and mineralogical composition of ice-dammed lake sediments of the Lębork deposit. Major-element analysis of the compositions of selected samples from the ice-dammed lake clays was performed by X-ray fluorescence (XRF) and trace elements were determined by inductively coupled plasma-mass spectrometry. The mineralogical composition of clay samples was determined by X-ray diffraction (XRD). Analyses of the chemical composition of the ice-dammed lake clays of the Lębork deposit showed that the dominant component was SiO2 with a mean content of 56.13 wt.%; the second most abundant component was Al2O3, with a mean content for the entire deposit of 11.61 wt.%. Analysis by ICP-MS indicated the presence of rare earth elements (REE), e.g. cerium, neodymium, lanthanum, and praseodymium; their mean contents are: 56.9, 27.0, 26.3, and 7.3 ppm, respectively. Mineralogical analysis of the varved clays identified quartz, muscovite, calcite, and clay minerals – illite, kaolinite, and montmorillonite. The material filling the Lębork basin is characterized by small lateral and vertical variability in chemical composition. The results of the present study may be of considerable importance in determining the parent igneous, metamorphic, and sedimentary rocks, the weathering products of which supplied material to the ice-dammed lake, as well as in determining the mechanisms and character of the sedimentation process itself.

A common design of a high-level radioactive waste (HLW) disposal system consists of the waste canisters emplaced in tunnels or shafts, with the space between the heat-emitting canisters and the surrounding rock filled with a bentonite-based material. Understanding the behavior of this barrier, in particular the effect of prolonged heating on its properties, is important to assess the barrier’s long-term performance. The objective of the present study was to add to this understanding and to supply experimental data about the state of bentonite hydrated and heated for a long period of time. To that end, a 50 cm long column of Wyoming-type bentonite pellets was heated at its base at 140 °C (simulating the waste canister) while a synthetic sodium-chloride-rich groundwater including sulfate, calcium, and magnesium was supplied through its upper surface for almost 10 y. At the end of the experiment the upper half of the column was saturated, but in the lower half the water content decreased sharply toward the heater, where it was close to 0%. No relevant mineralogical changes occurred, and the main component of the bentonite continued to be a predominantly sodium montmorillonite with no structural changes with respect to the initial one. In the area where the temperatures were >60°C and the material very dry, however, the smectite was not able to completely develop the 1-layer hydrate after 48 h of stabilization at RH 55%, although its expandability was fully recovered when the smectite was hydrated with liquid water. The ions solubilized as a result of the water-content increase were transported toward the heater and concentrated in two distinct areas: sodium and calcium chlorides closer to the heater than calcium and sodium sulfates. At the heater contact, the bentonite microstructure was of dense packets with carbon and Na-S-coated cavities. Precipitation of calcite and calcium sulfates and possibly dissolution of silica minerals also took place close to the heater.

Conventional superplasticizers based on polycarboxylate ether (PCE) show an intolerance to clay minerals due to intercalation of their polyethylene glycol (PEG) side chains into the interlayers of the clay mineral. An intolerance to very basic media is also known. This makes PCE an unsuitable choice as a superplasticizer for geopolymers. Bio-based superplasticizers derived from starch showed comparable effects to PCE in a cementitious system. The aim of the present study was to determine if starch superplasticizers (SSPs) could be a suitable additive for geopolymers by carrying out basic investigations with respect to slump, hardening, compressive and flexural strength, shrinkage, and porosity. Four SSPs were synthesized, differing in charge polarity and specific charge density. Two conventional PCE superplasticizers, differing in terms of molecular structure, were also included in this study. The results revealed that SSPs improved the slump of a metakaolin-based geopolymer (MK-geopolymer) mortar while the PCE investigated showed no improvement. The impact of superplasticizers on early hardening (up to 72 h) was negligible. Less linear shrinkage over the course of 56 days was seen for all samples in comparison with the reference. Compressive strengths of SSP specimens tested after 7 and 28 days of curing were comparable to the reference, while PCE led to a decline. The SSPs had a small impact on porosity with a shift to the formation of more gel pores while PCE caused an increase in porosity. Throughout this research, SSPs were identified as promising superplasticizers for MK-geopolymer mortar and concrete.

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.