Many environmental applications in the inorganic remediation field are based on the swelling and ion-exchange capacities of smectites, even though these can be affected by hydrothermal treatment in water and acidic media. Here a systematic study of the properties of layered silicates that could affect their hydrothermal stability at different pH is described: type of layers, octahedral occupancy, layer charge, and origin of the layer charge. The silicates studied were selected on the basis of their different characteristics associated with these properties. Kanemite (1:0 phyllosilicate), kaolinite (1:1 phyllosilicate), and pyrophyllite and talc (2:1 phyllosilicates with no-layer charge) were examined in order to determine the effect of layer structure, whereas the hydrothermal reactivity of silicates with different layer charge was analyzed by comparing the talc-hectorite-Laponite® and talc-saponite-trioctahedral vermiculite series. Samples were treated hydrothermally at 300ºC for 48 h in pure water and in a 0.01 M HNO3 solution and the final products were analyzed by X-ray diffraction, scanning electronic microscopy, and solid-state nuclear magnetic resonance spectroscopy. All layered silicates, except for kanemite, were found to remain intact after hydrothermal treatment in water and acidic media, with only minimal short-range structural changes observed. The extent of the structural changes depended on the octahedral sheet occupancy (greater extent) and the number of isomorphic substitutions (lesser extent), both of which weaken the structure.

Simple extended constant capacitance surface complexation models have been developed to represent the adsorption of polyaromatic dyes (9-aminoacridine, 3,6-diaminoacridine, azure A and safranin O) to kaolinite, and the competitive adsorption of the dyes with Cd. The formulation of the models was based on data from recent publications, including quantitative adsorption measurements over a range of conditions (varying pH and concentration), acid-base titrations and attenuated total reflectance-Fourier transform infrared spectroscopic data. In the models the dye molecules adsorb as aggregates of three or four, forming outer-sphere complexes with sites on the silica face of kaolinite. Both electrostatic and hydrophobic interactions are implicated in the adsorption processes. Despite their simplicity, the models fit a wide range of experimental data, thereby supporting the underlying hypothesis that the flat, hydrophobic, but slightly charged silica faces of kaolinite facilitate the aggregation and adsorption of the flat, aromatic, cationic dye molecules.

Crystal chemical analysis of various dioctahedral 2:1 phyllosilicates consisting of trans-vacant (tv) and cis-vacant (cv) layers and interstratified cv and tv layers shows that there is compositional control over the distribution of octahedral cations over trans and cis sites. Fe3+ and Mg-rich dioctahedral micas (celadonite, glauconite, leucophyllite and most phengite) occur only as tv varieties. Similarly, the occurrence of tv illites and tv illite fundamental particles in illite-smectite (I-S) does not depend significantly on the cation composition of the 2:1 layers. In contrast, compositional restrictions exist to control the occurrence of pure cv1M illite, which can form only as Fe- and Mg-poor varieties. Similarly, proportions of cv and tv layers in illite fundamental particles depend on the amount of Al in octahedral and tetrahedral sheets of the 2:1 layers.

Simulations of atomic coordinates and interatomic distances for periodic tv1M and cv1M illite structures allow us to reveal the main structural factors that favor the formation of cv layers in illite and I-S. It is shown that in contrast to the tv1M structure, interlayer K in cv1M illite has an environment which is similar to that in 2M1 muscovite. This similarity along with a high octahedral and tetrahedral Al content probably provides stability for cv1M illite in low-temperature natural environments. Because of structural control, the occurrence of monomineral cv1M illite, its association with tv 1M illite, and interstratified cv-tv illite fundamental particles is confined by certain physical and chemical conditions. These varieties are most often formed by hydrothermal activity of different origin. The initial material for their formation should be Al-rich and the hydrothermal fluids should be Mg- and Fe-poor. They occur mostly around ore deposits, in bentonites and in sandstone sedimentary rocks.

The factors governing the formation of tv and cv layers in dioctahedral smectite are probably related to the layer composition and local order-disorder in the distribution of isomorphous octahedral cations, because there is no influence from fixed interlayer cations. In particular, the occurrence of Mg-OH-Mg cation arrangements is more favorable for the formation of cv montmorillonite layers.

The degree of preferred orientation of mineral grains in powder X-ray diffraction (XRD) samples prepared by standard techniques has been evaluated by means of a correction model implemented in the Rietveld program, BGMN. It is demonstrated that neither front- nor side-loading of mineral powders obtained by wet grinding in a McCrone micronizing mill yield powder mounts with randomly oriented particles. Despite fine grinding, the primary sizes and shapes of mineral grains contained in multi-phase samples influence the degree of preferred orientation in XRD powder mounts. Two minerals, both of platy habit, were found to show different degrees of preferred orientation in front- and side-loaded samples. In contrast to these methods of sample preparation, the spray-drying technique yielded perfect randomness of the particles. The experiments on artificial mineral mixtures demonstrate that the model applied can effectively correct for preferred orientation allowing reliable Rietveld quantitative phase analysis of moderately textured samples prepared by standard techniques.

Aflatoxin contamination of diets results in disease and death in humans and animals. The objective of the present paper was to review the development of innovative enterosorption strategies for the detoxification of aflatoxins. NovaSil clay (NS) has been shown to decrease exposures to aflatoxins and prevent aflatoxicosis in a variety of animals when included in their diets. Results have shown that NS clay binds aflatoxins with high affinity and high capacity in the gastrointestinal tract, resulting in a notable reduction in the bioavailability of these toxins without interfering with the utilization of vitamins and other micronutrients. This strategy is already being utilized as a potential remedy for acute aflatoxicosis in animals and as a sustainable intervention via diet. Animal and human studies have confirmed the apparent safety of NS and refined NS clay (with uniform particle size). Studies in Ghanaians at high risk of aflatoxicosis have indicated that NS (at a dose level of 0.25% w/w) is effective at decreasing biomarkers of aflatoxin exposure and does not interfere with levels of serum vitamins A and E, iron, or zinc. A new spinoff of this strategy is the development and use of broad-acting sorbents for the mitigation of environmental chemicals and microbes during natural disasters and emergencies. In summary, enterosorption strategies/therapies based on NS clay are promising for the management of aflatoxins and as sustainable public health interventions. The NS clay remedy is novel, inexpensive, and easily disseminated.

Clay-rich deposits of Upper Cretaceous levels in the Taveiro (Reveles and S. Pedro) and Aveiro (Bustos) regions of west-central Portugal are economically and environmentally important, but detailed chemical and mineralogical characterization is lacking. The purpose of this study was to partially fill that gap by correlating the trace-element geochemistry (particularly the rare earth elements, REE) with the mineralogy of both the whole rock and of the <2 μm fraction along selected stratigraphic levels of the formations. The results will help the ceramics industry in the region and will be important in paleoreconstruction environmental studies.

Mineralogical and chemical characterizations were carried out using X-ray diffraction (XRD), X-ray fluorescence (XRF), and instrumental neutron activation analysis (INAA). The following clay-mineral associations were identified: (1) at Reveles — smectite, illite, and kaolin minerals; (2) at S. Pedro — kaolin minerals and illite; and (3) at Bustos — illite, kaolin minerals, and mixed-layer illite-smectite. The distribution of trace elements in the <2 μm fraction depended on the clay mineralogy, suggesting that the trace elements were incorporated in, adsorbed to, or even replaced major elements in the clays, as follows: (1) first-row transition elements, particularly Zn and Ga, were enriched when smectite predominated; (2) As, Rb, and Cs were enriched in this fraction of the S. Pedro deposit, the only one with Fe (oxyhydr)oxides and a high proportion of illite; and (3) REE were more concentrated when kaolin minerals predominated. Eu was enriched in the <2 μm fraction, which was due to preferential incorporation in the Fe (oxyhydr)oxides and/or carbonates.

Organic, ionic soil stabilizers (OISS) are designed to regulate directly the hydration properties of clay minerals to improve their engineering behavior. The steps involved in this regulation by OISS are unclear and this might limit their application in the current construction environment in China. The purpose of the present study was to reveal the origin of changes in hydration properties of four typical clay samples (with clay mineral contents of >90 wt.%: Na-bentonite, Ca-bentonite, illite, and kaolinite) as affected by OISS. The water-retention capacity of each clay was measured first through liquid limit and water-vapor adsorption tests. Then, the changes in hydration sites, such as exchangeable cations and the surfaces of minerals, were investigated by a series of microscopic measuring and testing techniques. Finally, infrared spectroscopy (IR) and thermal analysis were performed to verify the regulation of hydration properties by OISS. The results suggested that the exchangeable cation and surface changes controlled the regulation of hydration properties. OISS could cause some of the exchangeable cations to become free ions and disrupt the interaction between some cations and water molecules by its long organic chains; thus, the amount of hydrated cations decreased. In addition, the long organic chains covered the mineral surface and weakened its adsorption capacity. Furthermore, the long chains had cementitious qualities, connecting them to the crystalline layer and resulting in more aggregated clay particles and a smaller specific surface area (SSA). With the decrease in the number of cations and in the SSA by OISS, the hydration of the four clay samples decreased, especially in the case of bentonite.

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

This paper examines, from a Thomistic perspective, the possible consequences of the twentieth-century reform of the ‘Kyrie eleison’ from ninefold set of invocations to a sixfold call-and-response structure. First, we present Aquinas’s distinctly Trinitarian exegesis of the ‘Kyrie’ in light of the history of troped liturgical texts. Next, we will account for the historical diversity of the troped ‘Kyrie’ genre while emphasizing importance of the Trinitarian elements. The third section recounts recent work on Aquinas’s theory of the passions and their effects of language formation; this leads to the fourth section, which casts a philosophical eye on the role of melisma in the liturgy. To conclude this study, we suggest the restoration of some troped ‘Kyrie’ texts in the Roman Rite.

The study of hard rock conversion into fine earths and clayey materials in the pedosphere is important in understanding the relative proportions of recent soil features to features that were inherited from ancient epochs. Cold environments are widely thought to be areas of physical weathering, but the coexistence of physical and chemical processes have also been shown. To further examine mafic rock (dolerite) weathering in soil environments and the conversion into clayey materials, Entic Podzols formed in the cold continental climate were studied. The key study was located in the central part of the flood basalt complex, or traps (traprocks), of the Central Siberian Plateau (Russia). The qualitative mineralogy was studied using X-ray diffraction and the quantitative mineral composition was determined using X-ray diffraction and subsequent Rietveld analysis. The micromorphological characteristics of the soils were studied in thin sections. Dolerite fragments and fine earths were sampled from soil profiles underlain by dolerite. XRD analyses indicated that pyroxene and especially plagioclase contents in the dolerite fragments and fine earths decreased from the bottom to the top soil horizons mostly in the mature soil profiles that were affected by chemical weathering of dolerite. The dioctahedral and trioctahedral smectites in the soils were inherited from a dolerite previously subjected to chemical weathering. The smectite was conserved in the inherited aggregates and protected against dissolution even in acidic soil horizons. Recent pedogenesis processes fractured individual fragments, converted it into soil micromass, and slightly decreased the total smectite content of the <1 µm soil fraction. However, in soil samples collected from the bottom to the top horizons of a mature soil profile, trioctahedral smectite contents decreased as dioctahedral smectite contents increased. This suggests that dioctahedral smectites formed by pedogenic alteration of inherited trioctahedral smectites.

A magnetic composite was prepared by wet-impregnating a powder of a natural zeolite with a magnetic Fe oxide-containing synthetic material. Both starting materials were first characterized with X-ray diffraction, scanning electron microscopy, Mössbauer spectroscopy, and by isoelectric-point using vibrating-sample magnetometry. The synthetic Fe oxide-containing material was characterized as a mixture of magnetite (Fe3O4) and goethite (α-FeOOH). From the Fe Mössbauer analysis, the relative subspectral area for magnetite corresponds to 93(2)%; the remaining spectrum is assignable to goethite. After the impregnation process, magnetite was still identified in the composite material as a magnetic layer surrounding the zeolite particles; no magnetically ordered goethite could be detected. The Mössbauer pattern for this sample indicates a much more complex structure than for the precursor material, based on Fe oxides, with some more altered magnetite and an intense central doublet of (super)paramagnetic Fe3+, probably due to small Fe (hydr)oxides and/or to a residual contribution of Fe-bearing species from the starting zeolite material. The composite preparation procedure also promoted the change of the characteristic A-type zeolite to mordenite. The resulting magnetic composite presented a magnetic coercivity of as much as 0.140 A m−1, at 77 K. The final composite is now being evaluated as an adsorbent: results to date confirm that this novel magnetic material may have applications in the remediation of contaminated water bodies.

Alumina-pillared montmorillonite clays (Al-PILC), prepared under ultrasonic (US) agitation and normal stirring (S) methods, have been used as a host material to encapsulate Co phthalocyanine (CoPc) complex. The amount of Co varies from 0.27 to 1.48 wt.% in the samples, depending on the input concentration of Co. Powder X-ray diffraction and other characterization techniques reveal that the structure of Al-PILC remains intact after the incorporation of the complex into the pores through a pyridine solution of the complex by ultrasonic agitation. A substantial decrease in the BET surface area and total pore volume of Al-PILC points to the occupation of the CoPc moieties within the porous structure of the pillared clay. This is further supported by the observation of a band at 1489 cm−1 in the Fourier transform infrared (FTIR) spectra of the encapsulated samples. The FTIR and diffuse reflectance ultraviolet-visible (DRUV-Vis) spectral results indicate that the encapsulated CoPc complex in the clay matrix undergoes distortion in order to accommodate itself within the pores of the Al-PILC. The encapsulated samples prepared by ultrasonification show better dispersion of the complex than the samples prepared under normal stirring conditions. Compared to the ‘neat’ complex, the encapsulated samples (CoPc in Al-PILC) exhibit greater turnover in the test reaction of the oxidation of benzyl alcohol to benzaldehyde with tertbutyl hydroperoxide as the oxidant at 373 K. The method of preparation and consequent site isolation of CoPc in Al-PILC influence the catalytic activity.

Soil formation usually results in an increase in magnetic susceptibility. The magnetic properties of the products of transformation of ferrihydrite, a typical precursor of other soil Fe oxides, were examined in the present work. Synthetic 2-line ferrihydrite was aged at two temperatures (25 and 50°C) and two different relative humidities (80 and 100%) in the presence of silicate, phosphate, citrate, and tartrate as adsorbed ligands (molar anion/Fe ratio = 1–3%). The ligands delayed or prevented the transformation of ferrihydrite to hematite. The magnetic susceptibility of the ferrihydrite transformation products increased with aging, the rate of increase depending on the type of ligand added and its concentration. The largest increase in magnetic susceptibility, sixfold, was obtained with ferrihydrite in a citrate/Fe ratio of 1%, after 1500 days. The resulting magnetic products exihibited superparamagnetic behavior at room temperature and high coercivity at 5 K. The formation of an intermediate ferrimagnetic phase in the ferrihydrite-to-hematite transformation might explain the magnetic enhancement observed in many aerobic soils lacking other sources of magnetic minerals.

The structure and composition of short-range ordered aluminosilicates (SROAS) may control their affinity for organic acids with potential effects on soil organic matter stabilization. Adsorption mechanisms of model organic acids were studied to resolve the effect of Si incorporation. Adsorption of oxalic, salicylic, and octanoic acid on Al-rich (Al:Si = 3.7) and Si-rich (Al:Si = 1.4) SROAS was quantified by analyses of dissolved organic carbon using catalytic high-temperature combustion. The initial pH of 5 and 6.5 increased to 6.3–8.2 during adsorption of oxalic and salicylic acid, demonstrating hydroxyl release by ligand exchange. Minor changes in pH indicated weak interactions of octanoic acid with both SROAS. Adsorbates were characterized by Fourier-transform infrared spectroscopy. Asymmetric stretching of carboxylate groups at 1720 and 1700 cm–1, and symmetric stretching at 1430 cm–1 evinced the formation of chelate complexes for oxalic acid. An absorption band centered at 1545 cm–1 indicated partial inner-sphere binding of salicylic acid on both SROAS. Silicon-rich SROAS adsorbed 80–90% less than Al-rich SROAS, suggesting that adsorption of oxalic and salicylic acid was controlled by surface aluminol groups. Fast kinetics of oxalate adsorption on Al sites was studied by a conductivity-based stopped-flow technique. Ligand exchange proceeded at a rate constant of 3.5 s–1 (25°C), similar to solute Al complexation, with an activation energy of up to 34.1 kJ mol–1. A slow process with a rate constant of 0.13 s–1 (25°C) was attributed to diffusion of oxalate at the surface or into SROAS particles. As supported by structural characterization of Si-rich SROAS, the much lower susceptibility of Si-rich SROAS to ligand exchange relates to Al speciation. The formation of tetrahedral Al precludes its complexation by carboxyl groups.

Increasing use of irrigation in India has exacerbated the problems of soil salinity and sodicity. The present study was undertaken on shrink-swell soils from Maharastra State to determine if changes in soil chemistry due to irrigation have affected the clay mineralogy. Twenty six samples (15 locations) of irrigation-induced, saline-sodic, shrink-swell soils and 27 samples (22 locations) of normal un-irrigated (rain-fed) shrink-swell soils were studied using X-ray powder diffraction (XRPD), infrared spectroscopy (FTIR), and scanning and transmission electron microscopy (SEM, TEM). The XRPD analysis of the <0.2 µm fraction of rain-fed, shrink-swell soils indicates a predominance of dioctahedral smectite with minor to trace amounts of kaolinite and chlorite. Traces of palygorskite (1–4%) were detected in three samples. In contrast, palygorskite is a common component (1–20%) of the fine-clay fraction of saline-sodic soils. Quantitative analysis of palygorskite by XRPD in whole-soil (<2 mm) samples showed that saline-sodic soils contain up to 20 wt.% of palygorskite, whereas palygorskite was only detectable (1.5 wt.%) in one sample of the rain-fed set. The SEM, TEM, and FTIR confirm the presence of Fe-rich palygorskite in saline-sodic soils and demonstrate that the fibrous palygorskite crystals are exceedingly small (∼0.5 µm long). Delicate palygorskite fibers radiate from the margins of smectite plates suggestive of a pedogenic origin and a close genetic relationship between smectite and palygorskite. The compositions of saturation-paste extracts display a shift from the stability field of smectite in rain-fed soils to that of palygorskite in saline-sodic soils. Thus the occurrence and formation of palygorskite appears to be related to the change in land management from rain-fed to irrigated agriculture. This change has occurred over a period of no more than 40–50 y, implying that palygorskite formation in the irrigated, saline-sodic soils has been an extremely rapid process.

The aim of the present study was to examine effects of black liquor-montmorillonite (BL-Mnt) complexes on the mechanical and thermal properties of epichlorohydrin rubber. Considering the stability effect of lignin and the barrier property of clay minerals, a significant enhancement of thermo-oxidative aging properties of ECO/BL-Mnt composites was expected. Poly (epichlorohydrin-co-ethylene oxide) (ECO) composites filled with BL-Mnt complex were prepared by mechanical mixing on a two-roll mill. The ECO/BL-Mnt composites were characterized using X-ray diffraction (XRD), transmission electron microscopy (TEM), thermogravimetric analysis (TGA), and differential scanning calorimetry (DSC). Both XRD and TEM data showed that the filler particles were well dispersed throughout the ECO/BL-Mnt composites. The tensile strength, elongation at break, and 100% modulus of the rubber composite were 14.0 MPa, 457%, and 3.9 MPa, respectively, at a 50% loading of BL-Mnt. The retention of tensile strength was 99% after thermal oxidative aging in an air-circulating oven for 72 h at 100°C. Evidence indicated that ECO/BL-Mnt composites with good mechanical properties and thermo-oxidative aging properties were obtained.

Siderophores are low molecular weight organic ligands synthesized by aerobic microorganisms to acquire Fe. In addition to Fe(III), siderophores may complex other metals such as Pb and Cd. This study compared the effects of the trihydroxamate siderophores desferrioxamine-B (DFO-B), desferrioxamine-D1 (DFO-D1), desferrioxamine-E (DFO-E), and the monohydroxamate siderophore-like ligand acetohydroxamic acid (aHA) on Pb and Cd (except for DFO-E) adsorption to kaolinite (KGa-1b) at pH 4.5 to 9, in 0.1 M NaClO4, at 22°C, in the dark. At pH >6, all of the studied ligands decreased Pb adsorption to kaolinite: aHA by 5–40% and DFO-B, DFO-D1 and DFO-E by 30–75%; the greater effects were at higher pH. The studied ligands decreased Cd adsorption to kaolinite at pH >8: aHA by 5–20% and the trihydroxamates by as much as 80%. We also observed enhancement of Pb adsorption in the presence of DFO-B at pH ≈5–6.0, probably due to adsorption of the doubly positively charged H3Pb (DFO-B)2+ complex, although spectroscopic evidence is needed.

The formation of mixed-metal-Al layered double hydroxide (LDH) phases similar to hydrotalcite has been identified as a significant mechanism for immobilization of trace metals in some environmental systems. These precipitate phases become increasingly stable as they age, and their formation may therefore be an important pathway for sequestration of toxic metals in contaminated soils. However, the lack of thermodynamic data for LDH phases makes it difficult to model their behavior in natural systems. In this work, enthalpies of formation for Ni LDH phases with nitrate and sulfate interlayers were determined and compared to recently published data on carbonate interlayer LDHs. Differences in the identity of the anion interlayer resulted in substantial changes in the enthalpies of formation of the LDH phases, in the order of increasing enthalpy carbonate<sulfate<nitrate. Substitution of silica for carbonate resulted in an even more exothermic enthalpy of formation, confirming that silica substitution increases the stability of LDH precipitates. Both mechanical mixture and solid-solution models could be used to predict the thermodynamic properties of the LDH phases. Modeling results based on these thermodynamic data indicated that the formation of LDH phases on soil mineral substrates decreased Ni solubility compared to Ni(OH)2 over pH 5–9 when soluble Al is present in the soil substrate. Over time, both of these precipitate phases will transform to more stable Ni phyllosilicates.