The formation of manganese (Mn) oxides is influenced by environmental conditions and, in some red soils, Mn oxides occur as coatings on the surface of kaolinite particles in the form of colloidal films or fine particles. The present study aimed to explore the types of formation mechanisms of Mn oxide minerals on the surface of kaolinite. Mn oxide minerals synthesized by reducing the Mn in KMnO4 with a divalent Mn salt (MnSO4) were examined using X-ray diffraction (XRD) and scanning electron microscopy (SEM). The effects of various initial molar ratios of Mn2+/Mn7+ (R = 1:0.67, 1:1, 1:2, and 1:4), cationic species (Na+ or Mg2+), synthesis temperatures (30, 60, and 110°C), and amount of added kaolinite (0.25, 0.5, 1.0, 2.0, and 5.0 g) on the formation of Mn oxides were studied. The results showed that Mn oxide mineral types were affected by the initial R value and the background cation. With decreases in the initial R value, the synthesized minerals transformed from cryptomelane to birnessite. The relative mass ratios of kaolinite to Mn oxide were calculated as 1:0.92, 1:0.63, 1:1.15, and 1:1.63. The sodium cation (Na+) had a greater role than Mg2+ in promoting the dissolution–recrystallization of birnessite to cryptomelane. The synthesis temperature had no effect on mineral types, but Mn content increased as temperature increased. When the amount of added kaolinite was increased from 0.25 to 5.0 g, Mn oxide minerals formed gradually and transformed from birnessite to cryptomelane. This work revealed a possible formation process and reaction mechanism on the surface of kaolinite particles in some red soils.

The increased detection of pharmaceuticals in finished drinking water has become a growing cause of concern in recent years. The removal of atenolol, ranitidine, and carbamazepine by sepiolite, following functionalization of its surface by organosilane grafting, constituted the subject of this investigation. Silylated surfaces include octyl, γ-aminopropyl, 3-chloropropyl, and triphenyl moieties. The sorption of atenolol and ranitidine was higher on sepiolite functionalized with 3-chloropropyl, while carbamazepine showed a higher sorption on sepiolite with triphenyl groups. Filtration experiments of both ranitidine and carbamazepine on octyl- and triphenyl-sepiolite, respectively, showed a higher retention of ranitidine in comparison to carbamazepine, in spite of the fact that the number of sorption sites was lower due to its higher binding rate.

X-ray diffraction patterns of oriented mounts of clay minerals are often used in clay mineralogy for qualitative and quantitative purposes. Fequently occurring stacking defects, in particular, can be characterized by this technique. Modeling of these diffraction profiles has become an important tool in obtaining structural information about the nature of stacking order. Manual matching of calculated and observed patterns is time consuming and user dependent. Automatic refinement procedures are, therefore, desirable. An improved approach for the treatment of disordered layer structures within a Rietveld refinement is presented here. The recursive calculation of structure factors, similar to that of the simulation program DIFFaX, was introduced in the Rietveld code BGMN. Complete implementation is formulated within the interpreter language of the Rietveld code and is transparent as well as flexible. Such a method has opened the application of Rietveld refinement to patterns of oriented mounts where only basal reflections of stacking disordered structures were recorded. The DIFFaX code was used to simulate basal reflections of illite-smectite mixed layers (I-S) with different ratios of illitic and smectitic layers and with different degrees of long-range ordering (Reichweite). Rietveld refinements with these simulated patterns were used to evaluate the application of this new approach. Several I-S with different degrees of ordering were also chosen as tests for the refinement of basal reflections. The samples were prepared as standard airdried and ethylene glycol-solvated, oriented specimens. Realistic structural parameters were obtained for the composition and ordering of the I-S.

The overuse of antibiotics in medicine has led to concerns over management of wound infections where antibiotic-resistant bacteria are involved. Wound infections exhibit both acquired and biofilm-associated antibiotic resistance; innovative non-antibiotic therapeutic and preventive treatments are needed to limit emergence of conventional antimicrobial resistance and to address biofilm-associated resistance. Toward this goal, natural antibacterial clays have been identified that are effective at killing drug-resistant human pathogens in planktonic and biofilm states, in vitro. To move toward clinical testing of antibacterial clays, the present study was conducted to evaluate the topical application of a natural antibacterial clay to wounds in mice experimentally infected with methicillin-resistant Staphylococcus aureus (MRSA). Five preliminary animal trials were conducted to test various methods of applying hydrated antibacterial clay to infected wounds. None of the experiments yielded significantly reduced MRSA infection in vivo, compared to controls. Several hypotheses were tested to explore the diminished clay antibacterial activity in vivo including: (1) pH and Eh of mineral-bacterial suspensions may differ in wound fluids compared to growth media; (2) antibacterial reactants may complex with components of the wound; (3) hydrated clays may dry out in the wound; and (4) limited dissolved oxygen may reduce Fenton reactions. Ancillary in vitro tests were performed to explore these hypotheses. Results indicate that the clay application to wounds may require enhanced oxidation and possibly a longer treatment regimen. The experimental results foster understanding of the natural clay–bacterial interactions in wounds and may improve designs for medicinal applications.

Traditionally, land subsidence resulting from groundwater over-pumping has often been described by the theory of consolidation. The mechanism of land subsidence due to the dehydration of clay minerals has not been well addressed. Therefore, this study develops a smectite dehydration model to describe the effect of the release of water from the smectite interlayer upon land subsidence. Using a thermodynamic solid-solution model and laboratory studies of clay-water systems, a complete description of the dehydration relationships among the swelling pressure, basal spacing and mw/mc in a Na-smectite water system at 25°C under variable pressure conditions was derived. Accordingly, the evaluation model of the ‘hydration state of smectite’, and the ‘solid-solution model of smectite dehydration’ were formulated rigorously. These two models were applied to quantify the effects of smectite dehydration on the accumulated land subsidence in the Yun Lin offshore industrial infrastructure complex and in the Tai-Shi area. The result reveals that smectite dehydration is of importance in assessing and predicting land subsidence in a shallow sedimentary basin.

Synthesis of the Li-Al-Fe layered double hydroxides was performed by the coprecipitation method at constant pH (11.0±0.2) and temperature (40±2°C). Structural features of the as-synthesized samples were investigated by X-ray diffraction (XRD), infrared (IR) spectroscopy, scanning electron microscopy and Mössbauer spectroscopy. The samples consisted of well crystallized [LiFexAl2-x(OH)6]2CO3·nH2O phases with strict ordering of M+ and M3+ cations in the sheets. However, only a proportion of Al3+ could be substituted by Fe3+ ions. The excess Fe3+ cations formed a separate ferrihydrite phase. Incorporation of Fe into the hydrotalcite-like structure resulted in an increase in the a lattice parameter determined by XRD. In addition, a shift of IR absorption bands, ascribed to the stretching vibrations of interlayer CO32− anions as well as the transitional motions of oxygen in the layers, to lower frequencies was observed. The presence of Fe3+ in the octahedral sheets caused a splitting of the band assigned to the stretching vibrations of the layer OH groups. Mössbauer experiments revealed that Fe exists in the synthesized samples in two different chemical environments. A proportion of the Fe3+ cations is incorporated as isolated ions in the [LiFexAl2-x(OH)6]2CO3.nH2O crystal structure. However, Fe3+ ions forming the ferrihydrite phase are dominant in the Fe-rich materials.

Brick-red deposits with palygorskite (Pal) as the main ingredient are widely distributed in nature, but these have not been deployed at a large scale in industry because of their inherent deep colors. In the present study, the brick-red Pal deposit was treated hydrothermally in various reaction media including water, a urea solution, and a thiourea solution. The effects of these processes on the structure, physicochemical features, and color of Pal were studied intensively to understand the structure and composition of the brick-red Pal deposit and to lay a theoretical foundation for the extension of its industrial application. The changes in structural features after hydrothermal treatment were studied by Fourier-transform infrared spectroscopy, X-ray diffraction, scanning electron microscopy, magic-angle spinning nuclear magnetic resonance, and Mössbauer spectroscopy techniques. The results indicated that the color of brick-red Pal did not change after hydrothermal treatment in water or in a urea solution, and the color changed to gray-white after treatment in the thiourea solution. The rod-like crystal morphology of Pal was retained throughout the experiments and no significant change in the main associated minerals, including feldspar, muscovite, and quartz, was observed after hydrothermal treatment. The dissolution of associated hematite (α-Fe2O3 and the reduction of Fe(III) species are the main reason for the change of Pal from brick-red to gray-white.

The current study demonstrates how co-existing zeolite and clay minerals formed by the alteration of tephra in a closed-basin lacustrine and lake-margin environment can retain the overall composition of the original bulk tephra for many elements, even when diagenetic conditions and resulting authigenic mineral assemblages change. Zeolite and clay minerals co-exist in the closed-basin, saline-alkaline lacustrine altered tephra of Pleistocene Olduvai Gorge, Tanzania, and their diagenetic histories can be reconstructed using variations in their textures and compositions. The authigenic minerals in the altered tephra of the Olduvai paleolake form a classic ‘bull’s-eye’ pattern, with clay-dominated tephra in the distal lake margin, chabazite and phillipsite in the proximal margin, and phillipsite ± K-feldspar in the intermittently dry lake and lake center. Fifteen representative samples of altered volcanic ash lapilli (designated Tuff IF) were analyzed by X-ray diffraction (XRD), X-ray fluorescence (XRF), electron probe microanalysis (EPMA), and scanning electron microscopy (SEM) to determine their authigenic mineral assemblages and bulk compositions, and to texturally and compositionally compare their clay mineral and zeolite components.

Textural observations indicate that clay minerals formed first, followed by zeolites and finally feldspars. Clay minerals, however, persist even in the most altered samples. The overall composition of Tuff IF shows only limited change in Fe, Si, Al, and Na between fresh, clay-altered, and zeolite-dominated diagenetic environments, despite significant differences in authigenic assemblage. Where zeolites dominate the assemblage, the remaining clay minerals are rich in Mg, Fe, and Ti, elements that are not readily incorporated in zeolite structures. Where clay minerals dominate, they are more Al-rich. A ‘mixing model’ combining clay-mineral and zeolite compositions yields a close approximation of the original volcanic glass for most elements (exceptions including Mg, Ca, and K). This initial composition was preserved in part by the redistribution of elements between co-existing clay minerals and zeolites.

The nanoscale elastic properties of moist clay minerals are not sufficiently understood. The aim of the present study was to understand the fundamental mechanism for the effects of water and pore size on clay mineral (K+-smectite) elastic properties using the General Utility Lattice Program (GULP) with the minimum energy configurations obtained from molecular dynamics (MD) simulations. The simulation results were compared to an ideal configuration with transversely isotropic symmetry and were found to be reasonably close. The pressures computed from the MD simulations indicated that the changes due to water in comparison to the dry state varied with the water content and pore size. For pore sizes of around 0.8–1.0 nm, the system goes through a process where the normal pressure is decreased and reaches a minimum as the water content is increased. The minimum normal pressure occurs at water contents of 8 wt.% and 15 wt.% for pore sizes of around 0.8 nm and 1 nm, respectively. Further analyses of the interaction energies between water and K+-smectite and between water and water revealed that the minimum normal pressure corresponded to the maximum rate of slope change of the interaction energies (the second derivative of the interaction energies with respect to the water content). The results indicated that in the presence of water the in-plane stiffness parameters were more correlated to the pressure change that resulted from the interplay between the interactions of water with K+-smectite and the interactions of water with water rather than the water content. The in-plane stiffness parameters were much higher than the out-of-plane parameters. Elastic wave velocities for the P and S waves (VP and VS) in the dry K+-smectite with a pore size of ~1 nm were calculated to be 7.5 and 4.1 km/s, respectively. The P and S wave velocity ratio is key in the interpretation of seismic behavior and revealed that VP/VS = 1.64–1.83, which were values in favorable agreement with the experimental data. The results might offer insight into seismic research to predict the mechanical properties of minerals that are difficult to obtain experimentally and can provide complimentary information to interpret seismic surveys that can assist gas and oil exploration.

Organic dyes such as methylene blue (MB) are often used in the characterization of clays and related minerals, but details of the adsorption mechanisms of such dyes are only partially understood from spectroscopic data, which indicate the presence of monomers, dimers, and higher aggregates for varying mineral surfaces. A combination of quantum (density functional theory) and classical molecular simulation methods was used to provide molecular detail of such adsorption processes, specifically the adsorption of MB onto kaolinite basal surfaces. Slab models with vacuum-terminated surfaces were used to obtain detailed structural properties and binding energies at both levels of theory, while classical molecular dynamics simulations of aqueous pores were used to characterize MB adsorption at infinite dilution and at higher concentration in which MB dimers and one-dimensional chains formed. Results for the neutral MB molecules are compared with those for the corresponding cation. Simulations of the aqueous pore indicate preferred adsorption on the hydrophobic siloxane surface, while charge-balancing chloride ions adsorb at the aluminol surface. At infinite dilution and in the gas-phase models, MB adsorbs with its primary molecular plane parallel to the siloxane surface to enhance hydrophobic interactions. Sandwiched dimers and chains are oriented perpendicular to the surface to facilitate the strong hydrophobic intermolecular interactions. Compared with quantum results, the hybrid force field predicts a weaker MB adsorption energy but a stronger dimerization energy. The structure and energetics of adsorbed MB at infinite dilution are consistent with the gas-phase binding results, which indicate that monomer adsorption is driven by strong interfacial forces rather than by the hydration properties of the dye. These results inform spectroscopic studies of MB adsorption on mineral surfaces while also revealing critical areas for development of improved hybrid force fields.

The purpose of this study was to investigate the structural and chemical modifications of phyllosilicates that occur under natural conditions, using the progressive deformation of chlorite (sudoite) present in quartz-rich veins from the Internal Zone of the Rif range (Morocco) as the model system. Signs of chlorite deformation include kinks, chevron-like folds, and fractures. The samples also contain later, undeformed grains, which sealed the fractures or grew with (001) perpendicular to the compressive stress. Deformation-induced structural changes consist mainly of basal cleavages associated with ordered replacement of brucite sheets by hydrated layers, thus leading to irregular microdomains of mixed-layer chlorite-vermiculite and sudoite. Such structural modifications represent a mechanism for accommodating the compressive stress. Structural changes were accompanied by minor chemical ones, which lead from di,tri-chlorite (sudoite) to phases with a more trioctahedral character (mixed-layer chlorite-vermiculite). The hydration reaction occurred throughout a topotactic replacement of the pre-existing sudoite grains. Later, undeformed grains consist of mixed-layer chlorite-vermiculite intergrown with retrogressive kaolinite and minor Fe oxide, and are interpreted as having formed through a dissolution-precipitation process, during deformation. Retrogression of sudoite probably occurred during the latest stage of exhumation, in low-temperature conditions.

Zinc (Zn) is widely known as an essential trace element for fish and new ways to supply it to them are needed. Palygorskite (Pal) is a natural silicate clay mineral and the palygorskite structure contains nano-channels, which are filled with water and exchangeable ions. Zn-bearing palygorskites (Zn-Pal) prepared using ion exchange have attracted attention due to the durable antibacterial properties that limit pathogens and as a potential new Zn source for livestock. The present study was conducted to evaluate the effects of Zn-Pal supplementation on the growth performance, nutrient retention, meat quality, Zn accumulation, and intestinal Zn transporter protein gene expression in blunt snout bream Megalobrama amblycephala. The fish were fed a basal diet without an exogenous Zn source and the basal diet was supplemented with 125 mg/kg Zn as Zn sulfate (ZnSO4) or 35, 80, or 125 mg/kg Zn as Zn-Pal. Each diet was tested using three replicates for 7 weeks. The results showed that dietary Zn-Pal supplementation quadratically (P<0.05) increased growth performance, nutrient retention, total and Cu/Zn superoxide dismutase activity, Zn content in scales, and intestinal Zn transporter protein gene expression. The muscular cooking loss in blunt snout bream decreased with the optimum Zn-Pal Zn level of 35 mg/kg. Compared to the fish treated with ZnSO4, the fish supplemented with 35 mg/kg as Zn-Pal exhibited similar growth performance and nutrient retention (P>0.05), increased mRNA expression of the metal-response element-binding transcription factor-1 in the intestine (P<0.05), and decreased cooking loss of muscle (P<0.05).The results suggested that 35 mg/kg Zn supplementation as Zn-Pal could improve the growth performance and body composition, increase nutrient retention and tissue Zn concentrations, enhance the muscle water-holding capacity, and enhance antioxidant status in blunt snout bream. The Zn-Pal was more efficient and could be used as an alternative Zn source to ZnSO4 in the diet of blunt snout bream.

The present work shows the results of X-ray diffraction (XRD), Fourier transform infrared (FTIR), and thermal analysis of untreated (RMnt) and acid-treated red mud (RMa), a bauxite ore-processing waste, exchanged with Pb2+, Cd2+, and Zn2+ cations. These studies were performed in order to investigate the changes in the sorbent structure caused by the exchange with metals of different ionic radii.

The XRD pattern of RMnt, analyzed according to the Rietveld method, showed a mixture of eight different phases. However, just three phases made up 78 wt.% of the RMnt: cancrinite (33 wt.%), hematite (29 wt.%), and sodalite (16 wt.%). X-ray diffraction patterns of RMnt exchanged with Pb2+ and Cd2+ cations revealed two additional phases, namely hydrocerussite [Pb3(CO3)2(OH)2 (10 wt.%))] and octavite [CdCO3 (8 wt.%)].

These two phases probably originated from the carbonate precipitation processes which were due to the decarbonation of cancrinite. Hydrocerussite and octavite were not found in the case of acid-treated red mud samples.

In the FTIR spectra, the introduction of cations caused a distinct shift to higher wavenumbers in the peak at ∼1100 cm−1, which is attributed to the asymmetric stretch of Si-O-Al. This effect may be associated with the Pb2+, Cd2+, and Zn2+ adsorbed by the red muds which caused a deformation of the initial structure.

Thermal analysis data of the red mud samples were obtained by thermogravimetric/differential thermogravimetric analysis, and these methods were employed to evaluate the desorption behavior of water and to clarify the thermal stability of the chemical phases of the different red mud samples. The loss of metal-bound water in the red mud samples was found to depend on the size of non-framework cations and water loss consistently followed the order: Zn2+>Cd2+>Pb2+.

An analysis of Betty Smith’s bestselling coming-of-age novel A Tree Grows in Brooklyn reveals how popular literature can serve as an important introduction to signature issues of the Gilded Age and Progressive Era. Industrialization, urbanization, and immigration are highlighted in the novel—as well as attendant problems including poverty, machine politics, child labor, and prejudice and discrimination. Profound ignorance about sexuality and conception abound in a religious culture that made premarital sex and birth control sinful and shameful, with unhappy marriages and unwanted children the result. As poverty and deviant sexuality abound, eugenics is touted as a sensible solution. The novel helps to explain why there was no organized rebellion or revolution when the struggling poor found that the promise of upward mobility was elusive. Characters have differing definitions of the American Dream. Some seek respite in religion, leisure activities, or alcohol. Others find hope in a variety of reform measures, including public health and education, settlement houses, and unions. The novel ends as the technology that made the nation’s industrialization and urbanization possible continues to produce new marvels that will transform the lives of the urban poor, bringing the Gilded Age and Progressive Era to a close.

The formation of illite through the smectite-to-illite (S-I) reaction is considered to be one of the most important mineral reactions occurring during diagenesis. In biologically catalyzed systems, however, this transformation has been suggested to be rapid and to bypass the high temperature and long time requirements. To understand the factors that promote the S-I reaction, the present study focused on the effects of pH, temperature, solution chemistry, and aging on the S-I reaction in microbially mediated systems. Fe(III)-reduction experiments were performed in both growth and non-growth media with two types of bacteria: mesophilic (Shewanella putrefaciens CN32) and thermophilic (Thermus scotoductus SA-01). Reductive dissolution of NAu-2 was observed and the formation of illite in treatment with thermophilic SA-01 was indicated by X-ray diffraction (XRD) and high-resolution transmission electron microscopy (HRTEM). A basic pH (8.4) and high temperature (65°C) were the most favorable conditions forthe formation of illite. A long incubation time was also found to enhance the formation of illite. K-nontronite (non-permanent fixation of K) was also detected and differentiated from the discrete illite in the XRD profiles. These results collectively suggested that the formation of illite associated with the biologically catalyzed smectite-to-illite reaction pathway may bypass the prolonged time and high temperature required for the S-I reaction in the absence of microbial activity.

For a series of mixed-layer illite-smectite (I-S) minerals from a drillhole near the Kakkonda geothermal field, one-dimensional structure analysis by X-ray diffraction (XRD) was performed using Casaturated specimens in both air-dried and ethylene glycol-solvated states. The expandability characteristics of component layers were also examined by means of alkylammonium exchange and Li saturation. The K content in the illite layers was 1.5–1.7/O20(OH)4 in the I-S series from 3 to 85% of I-layer content (% I). The layer charge of the smectite layer varied slightly within the range of 0.3–0.5/O10(OH)2 by alkylammonium exchange experiments and the expandability was independent of the beidellite content within a range of 0–0.5 by the Li-saturation test. The degree of long-range ordering represented by Reichweite (R) parameters varied from R0 to R3 via R1 and R2 with increase in % I. The I-S samples contained <10% vermiculite as the third component and the vermiculite content tended to decrease with progressive illitization.

In contrast to the smectitic R0 samples (<10% I), more illitic R0 (e.g. 35% I) and >R1 I-S samples showed complicated expandability with alkylammonium exchange. The XRD patterns of dodecylammonium-exchanged I-S samples can be interpreted by random interstratification of several types of sub-units such as layer-doublets, layer-triplets and layer-quartets present in the crystallites. This interpretation is consistent with the variation in the occurrence probabilities of layer-multiplets calculated from the junction probabilities and the proportions of layers. Because the interpretation indicates that I-S is a stack of various types of the sub-units, the smectite illitization can be described by a systematic change in the type and proportion of the sub-units constituting crystallites.

The adsorption behavior of quaternary ammonium cationic surfactants with different hydrocarbon chain lengths, i.e. HDTMA (hexadecyltrimethylammonium), TDTMA (tetradecyltrimethylammonium) and DDTMA (dodecyltrimethylammonium), onto clinoptilolite has been investigated. The adsorption isotherms of these surfactants are correlated with the ζ potential curves of clinoptilolite. Accordingly, the applicability of the hemimicelle hypothesis to the adsorption of cationic surfactants at the clinoptilolite/water interface considering in the electrical double layer (EDL) of clinoptilolite is discussed. Even though the adsorption occurs in the EDL of clinoptilolite, the adsorption of HDTMA, TDTMA and DDTMA onto clinoptilolite is not conveniently described by the hemimicelle hypothesis. The absence of all expected marked increase in the ζ potential curves at the hemimicelle concentration is ascribed to the large external cation exchange capacity of clinoptilolite. The hydrocarbon chain length of surfactant molecules is found to have a significant effect on the ion exchange as well as hydrophobic interaction mechanisms. The effectiveness of both ion exchange and hydrophobic interactions increases with increasing chain length, and so the greatest surfactant adsorption onto clinoptilolite was obtained by HDTMA.

Recognizing weathering effects is significant for any work carried out on glauconites at the surface. The mineralogy and chemistry of glauconite grains exposed to weathering in a hot arid climate for a maximum of 42 y were studied here. The objective of the study was to find the mineralogical and chemical differences between weathered glauconite from the surface and fresh glauconite from the subsurface.

One specific glauconite-bearing layer at the surface (Layer 16) of the Abu Tartur phosphate mine, located in the Western Desert of Egypt, was studied in detail and compared to a fresh, subsurface glauconitic sandstone from the underground mine.

Even within this single surface layer, the brownish-green glauconite grains vary in color and chemical composition. From top to bottom, the grains show an increase in Fe and K and a decrease in Al and S. In addition, the grains show an internal color zonation caused by variation of Fe and K contents between the center and rim of the grains. The differences in color and chemical composition are even more pronounced between the weathered-glauconite grains from the surface and the fresh glauconite grains from the subsurface which are dark green and enriched in Fe and K.

The clay fractions consisted of mixed-layer glauconite (illite)-smectite, with the surface samples containing more expandable smectite (50%) than the subsurface samples (20%). In the charge-distribution diagram for muscovite-pyrophyllite-celadonite, the weathered glauconites at the surface showed a clear trend from smectitic glauconite at the top to illitic glauconite at the bottom of the layer, whereas the fresh subsurface sample plotted exactly in the glauconite field.

The color, mineralogy, and chemistry indicate that the surface samples were strongly altered by weathering processes and that glauconite transformed progressively into Fe-rich mixed-layer illite-smectite and then into smectites.Weathering can thus completely reverse the glauconitization process. For any chemical and mineralogical characterization of glauconites at the surface, these weathering effects must be taken into consideration.