Showing papers in "Clays and Clay Minerals in 2018"

Modifications of 2:1 Clay Minerals in a Kaolinite-Dominated Ultisol under Changing Land-Use Regimes

Abstract: Chemical denudation and chemical weathering rates vary under climatic, bedrock, biotic, and topographic conditions. Constraints for landscape evolution models must consider changes in these factors on human and geologic time scales. Changes in nutrient dynamics, related to the storage and exchange of K+ in clay minerals as a response to land use change, can affect the rates of chemical weathering and denudation. Incorporation of these changes in landscape evolution models can add insight into how land use changes affect soil thickness and erodibility. In order to assess changes in soil clay mineralogy that result from land-use differences, the present study contrasts the clay mineral assemblages in three proximal sites that were managed differently over nearly the past two centuries where contemporary vegetation was dominated by old hardwood forest, old-field pine, and cultivated biomes. X-ray diffraction (XRD) of the oriented clay fraction using K-, Mg-, and Na-saturation treatments for the air-dried, ethylene glycol (Mg-EG and K-EG) solvated, and heated (100, 350, and 550°C) states were used to characterize the clay mineral assemblages. XRD patterns of degraded biotite (oxidized Fe and expelled charge-compensating interlayer K) exhibited coherent scattering characteristics similar to illite. XRD patterns of the Mg-EG samples were, therefore, accurately modeled using NEWMOD2® software by the use of mineral structure files for discrete illite, vermiculite, kaolinite, mixed-layer kaolinite-smectite, illite-vermiculite, kaolinite-illite, and hydroxy-interlayered vermiculite. The soil and upper saprolite profiles that formed on a Neoproterozoic gneiss in the Calhoun Experimental Forest in South Carolina, USA, revealed a depth-dependence for the deeply weathered kaolinitic to the shallowly weathered illitic/vermiculitic mineral assemblages that varied in the cultivated, pine, and hardwood sites, respectively. An analysis of archived samples that were collected over a five-decade growth period from the pine site suggests that the content of illite-like layers increased at the surface within 8 y. Historical management of the sites has resulted in different states of dynamic equilibrium, whereby deep rooting at the hardwood and pine sites promotes nutrient uplift of K from the weathering of orthoclase and micas. Differences in the denudation rates at the cultivated, pine, and hardwood sites through time were reflected by changes in the soil clay mineralogy. Specifically, an increased abundance of illite-like layers in the surface soils can serve as a reservoir of K+.

Customized Spectral Libraries for Effective Mineral Exploration: Mining National Mineral Collections

Abstract: Infrared (Visible-Near Infrared-Shortwave Infrared (VNIR-SWIR)) spectroscopy is a cost-effective technique for mineral identification in the field. Modern hand-held spectrometers are equipped with on-board spectral libraries that enable rapid, qualitative analysis of most minerals and facilitate recognition of key alteration minerals for exploration. Spectral libraries can be general or customized for specific mineral deposit environments. To this end, careful collection of spectra in a controlled environment on pure specimens of key minerals was completed using the National Mineral Reference Collection (NMC) of the Geological Survey of Canada. The spectra collected from specimens in the ‘Kodama Clay Collection’ were processed using spectral plotting software and each new example was validated before being added to a group of spectra considered for incorporation into the on-board library of the handheld ASD-TerraSpec Halo near-infrared (NIR) mineral identification instrument. Spectra from an additional suite of mineral samples of the NMC containing REE, U, Th, and/or Nb are being prepared for a new, publicly available spectral library. These minerals commonly occur in carbonatite or alkali intrusive deposits, and as such will assist in the exploration for critical metals.

Relating the cation exchange properties of the boom clay (belgium) to mineralogy and pore-water chemistry

Abstract: The Boom Clay in northern Belgium has been studied intensively over recent decades as a potential host rock in the context of disposal of radioactive waste. One of the parameters of interest is the cation exchange capacity (CEC) as it is related to the sorption potential of radionuclides to the clay host rock. In the past, the CEC was determined using various methods on a limited number of samples, leading to significant variations. To constrain the CEC of the Boom Clay better, a sample set covering the entire stratigraphy was measured using the quick copper(II) triethylenetetramine method. Part of the sample set was also measured using the cobalt(III) hexamine method, as a quality control for the results of the former method. In addition, the exchangeable cation population of the Boom Clay was quantified systematically for the first time and these results were compared to the {tiin situ} pore-water chemistry, indicating a strong coupling between the pore-water composition and the exchangeable sites of clay minerals.

Quantitative Mineralogy of Clay-Rich Siliciclastic Landslide Terrain of the Sorrento Peninsula, Italy, Using a Combined XRPD And XRF Approach

Abstract: Quantitative mineralogical analysis of clay-bearing rocks is often a non-trivial problem because clay minerals are characterized by complex structures and are often affected by structural disorder, layer-stacking disorder, and interstratification. In the present study, internal-standard Rietveld X-ray powder diffraction (XRPD) analyses were combined with X-ray fluorescence (XRF) chemical analyses for the mineralogical characterization and quantitative analysis of heterogeneous clay-rich sedimentary rocks that are involved in a slow-moving landslide in the Termini-Nerano area, Sorrento Peninsula (Italy), in order to investigate the relationship between the mineralogy of these rocks and landslides. Slow-moving landslides are usually considered to be associated with the more weathered and surficial parts of structurally complex slopes, and mineralogical analysis can help to clarify the degree of weathering of siliciclastic rocks. XRPD quantitative analyses were conducted by combining the Rietveld and internal standard methods in order to calculate the amounts of poorly ordered phyllosilicate clays (considered amorphous phases in Rietveld refinements) by difference from 100%. The vbAffina program was used to refine the amounts of mineral phases determined with XRPD using the element compositions determined by XRF analysis. XRPD analyses indicated that the samples mainly contain several different clay minerals, quartz, mica, and feldspars. Analysis of the clay fraction identified kaolinite, chlorite, and interstratified illite-smectite (I-S) and chlorite-smectite (C-S). The mineralogy of the materials involved in the landslide in comparison with the mineralogy of the “undisturbed” rocks showed that the landslide is located in the weathered realm that overlies an arkosic bedrock. The interstratified I-S and C-S occurred at landslide activity locations and confirmed that areas more susceptible to sliding contained the most weathered parts of the rocks and perhaps represent areas of past and currently active fluid flow.

Sorption of Diclofenac from Aqueous Solution on an Organobentonite and Adsorption of Cadmium on Organobentonite Saturated with Diclofenac

Abstract: Toxic pollutants such as diclofenac (DCF) and cadmium(II) have been detected together in various water sources; these compounds have adverse effects on human health. The objective of the present study was to investigate the sorption of DCF and Cd(II) from aqueous solutions on an organobentonite. The organobentonite was synthesized by adsorbing the surfactant hexadecyltrimethylammonium (HDTMA) on bentonite; this was designated OBHDTMA. The sorption of DCF and Cd(II) on OBHDTMA and of Cd(II) on OBHDTMA saturated with DCF (OBHDTMA-DCF) were then studied. The bentonite, OBHDTMA, and OBHDTMA-DCF were characterized by X-ray diffraction, thermogravimetric analysis, and Fourier-transform infrared spectroscopy. The capacity of OBHDTMA for adsorbing DCF depended on the solution pH, ionic strength, and temperature. The effect of pH on the adsorption capacity of OBHDTMA was anomalous because, depending on the concentration of DCF at equilibrium, the adsorption capacity increased or decreased by raising the pH. The capacity of OBHDTMA was enhanced by increasing the temperature from 15 to 35°C and by reducing the ionic strength from 1 to 0.01 N. The dependence of the adsorption capacity on the operating conditions was explained by considering the interactions between the DCF in solution and the surface of OBHDTMA. The maximum sorption capacity of the OBHDTMA for DCF was 388 mg/g at T = 25°C and at pH = 7 and was comparable to those of carbon materials. The adsorption of DCF on OBHDTMA was scarcely reversible, but the desorption percentage increased with pH. The adsorption of DCF on OBHDTMA was due to partition and electrostatic attraction. More Cd(II) was adsorbed on OBHDTMA-DCF than on OBHDTMA and this was influenced by the loading of DCF on the OBHDTMA-DCF. The OBHDTMA-DCF may be used to remove Cd(II) from water solution.

Quantitative x-ray powder diffraction and the illite polytype analysis method for direct fault rock dating: a comparison of analytical techniques

Abstract: Illite polytypes are used to elucidate the geological record of formations, such as the timing and provenance of deformations in geological structures and fluids, so the ability to characterize and identify them quantitatively is key. The purpose of the present study was to compare three X-ray powder diffraction (Q-XRPD) methods for illite polytype quantification for practical application to directly date clay-rich fault rocks and constrain the provenance of deformation-related fluids in clay-rich brittle rocks of the upper crust. The methods compared were WILDFIRE© (WF) modeling, End-member Standards Matching (STD), and Rietveld whole-pattern matching (BGMN®). Each technique was applied to a suite of synthetic mixtures of known composition as well as to a sample of natural clay gouge (i.e. the soft material between a vein wall and the solid vein). The analytical uncertainties achieved for these synthetic samples using WF modeling, STD, and Rietveld methods were ±4–5%, ±1%, and ±6%, respectively, with the caveat that the end-member clay mineral used for matching was the same mineral sample used in the test mixture. Various particle size fractions of the gouge were additionally investigated using transmission electron microscopy (TEM) to determine polytypes and laser particle size analysis to determine grain size distributions. The three analytical techniques produced similar 40Ar/39Ar authigenesis ages after unmixing, which indicated that any of the methods can be used to directly date the formation of fault-related authigenic illite. Descriptions were included for pre-calculated WF illite polytype diffractogram libraries, model endmembers were fitted to experimental data using a least-squares algorithm, and mixing spreadsheet programs were used to match end-member natural reference samples.

Thiourea-Induced Change Of Structure And Color Of Brick-Red Palygorskite

Abstract: 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 Mossbauer 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.

Mineralogy and Geochemistry of Limonite as a Weathering Product of Ilvaite in the Yeshan Iron Deposit, Tongling, China

Abstract: Limonite is mainly derived from weathering of Fe sulfide, iron-bearing carbonate, or silicate minerals. The weathering of Fe sulfide or carbonate minerals to yield limonite from the Tongling mineralization cluster has been studied extensively. Knowledge of the mineralogical and geochemical characteristics of the limonite from weathering of Fe-bearing silicate minerals is still incomplete, however. To address this, black limonite containing ilvaite (a silicate mineral) found in Yeshan iron deposit, Tongling, China, was studied using mineralogical and chemical analysis. The mineralogical characteristics indicated that Mn goethite was present as nano-granular (<15 nm) or acicular (50–100 nm long, ~10 nm wide, i.e. high length/width ratio) crystals with low crystallinity. Groutite, ramsdellite, and pyrolusite were identified in the limonite as ~5 nm nanoparticles, and coated on the goethite surface. Amorphous Fe-Mn phases and silica were highly developed in the limonite studied. Ilvaite crystals showed idiomorphic granular morphology and were replaced by Fe-Mn oxides/hydroxides; pyrite was also present as inclusions within the ilvaite and the ilvaite structural formula calculated was Ca1.04(Fe1.57Mn0.31Mg0.04)(Fe1.09Al0.01)[Si1.95O]O(OH). According to the relatively high CuO and ZnO values and the low Al2O3 value in the black limonite, the negative correlations between (Fe2O3+MnO) and (CuO+ZnO+BaO), (Fe2O3+MnO) and Al2O3, high Mn and Si contents, and the characteristics of the textural relationships and compositions between the black limonite and ilvaite, a semi-enclosed environment with acidic to weakly alkaline conditions was deduced; ilvaite was found to be responsible for the formation and enrichment of limonite.

Reflectance Spectroscopy of Organic Matter in Sedimentary Rocks at Mid-Infrared Wavelengths

Abstract: Reflectance spectroscopy is a rapid, non-destructive technique capable of characterizing mineral and organic components within geologic materials at spatial scales that range from μm to km. The degree to which reflectance spectra can be used to provide quantitative information about organic compounds remains poorly understood, particularly for rocks with low organic content that are common in the Earth’s ancient rock record and that may be present on other planetary bodies, such as Mars. In the present study, reflectance spectra (0.35–25 μm) were acquired for a suite of Proterozoic shales and the kerogen was isolated to assess how spectral properties of aliphatic and aromatic C-H absorption bands can be used to predict organic matter abundance (total organic content, TOC, and H/C ratio). A number of spectral parameters were evaluated for organic absorption bands observed in the 3–4 μm wavelength region for comparison with independently measured TOC and H/C values. Ratios of the strengths of aliphatic to aromatic absorption bands were directly correlated to H/C values, but the reflectance spectra for pure kerogens with H/C 1 wt.% or as high as 10 wt.%. Organic detection limits for reflectance spectra are, thus, controlled by both TOC and H/C values, but these parameters can be predicted for clay-rich, kerogen-dominated samples for a range of values that are relevant to drill cores, outcrops, meteorites, and planetary surfaces.

Nanoscale elastic properties of dry and wet smectite

Abstract: 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.

Study of Defluoridation of Water Using Natural Clay Minerals

Abstract: Fluoride is an essential component in the mineralization of bones and in the formation of dental enamel. Excessive intake may result, however, in teeth mottling and dental and skeletal fluorosis. With an average fluoride concentration of ~2.4 mg L−1 in Tunisian drinking water, the present study focused on promoting low-cost materials for removal of excess fluoride. Two Tunisian raw clays were used as adsorbents in a batch process to eliminate excess fluoride ions from drinking water and, thus, avoid fluorosis phenomena. Physicochemical characterization and chemical analysis of the raw clays were carried out using X-ray fluorescence, X-ray diffraction, and the BET method. For fluoride removal, the effects of contact time, adsorbent dose, and pH were evaluated. The optimum defluoridation capacity was at 30 min of contact time, 20 g/L of clay dose, and at pH = 3. The kaolinite tested removed more fluoride than smectite. The selected clay was used successfully to remove fluoride from contaminated water with high concentrations of foreign ions that exceeded the potability limits. Adsorption isotherms revealed that the data fitted well to both the Langmuir and Freundlich adsorption isotherms, thus confirming both monolayer and multilayer adsorption.

A new look at the occurrences of the rare-earth elements in the georgia kaolins

Abstract: The high-density siliciclastic minerals (e.g. zircon) in the coarse fractions (>44 mm, informally known as grit) of the mined Georgia kaolins are potential and significant sources of the rare-earth elements (REE). The abundances and provenance of the REE signature have not been studied extensively for the Georgia kaolins. The objective of the present study was, therefore, to define the contribution of these heavy minerals (e.g. zircon) to the REE inventory of the coarse fractions of Georgia kaolins. Heavy-mineral subfractions separated from the coarse fractions contained 1647 mg/kg REE from the Jeffersonville Member of the Lower Tertiary Huber Formation and 5012 mg/kg REE from the Buffalo Creek Kaolin Member of the Upper Cretaceous Galliard Formation, respectively. These heavy-mineral subfractions were enriched 10–100 times in the heavy rare-earth elements (HREE, Gd—Lu,), Hf, and Zr relative to the concentrations of these elements in Upper Continental Crust. The heavy-mineral subfractions comprised 5% of the coarse fractions (grit) of these two kaolin-producing formations. The heavy-mineral subfractions consisted of zircon, anatase, rutile, kaolinite, and minor amounts of muscovite, trace ilmenite, and staurolite. The large concentrations of REE were obtained by separating the dense heavy minerals from the coarse fraction (grit) obtained during the typical production of kaolin-group minerals (kaolinite) from kaolin ore. The amount of zircon (estimated from the 6–11 wt.% Zr) and the absence of monazite did not explain the high concentrations of REE in the heavy-mineral subfractions. The large amounts of REE could have resulted from the sorption of REE released during weathering reactions, or from the presence of small amounts (0.025 wt.%) each of monazite and xenotime in addition to the presence of zircon. This heavymineral subfraction represented a novel domestic resource of extractable REE, especially the HREE, of a grade as high as 0.50 wt.% total REE.

Experimental and Atomic Modeling of the Adsorption of Acid Azo Dye 57 to Sepiolite

Abstract: Sepiolite is a hydrated magnesium silicate with a microporous and mesoporous structure. The fibrous morphology and the alternating blocks and tunnels along the fiber direction of sepiolite make it an ideal material to sequester a variety of organic and inorganic contaminants. The adsorption of various surfactants by organo sepiolites have been experimentally investigated. How this hydrophobic material adsorbs dye molecules at the atomic level, however, is a great mystery. For this reason, the present study focused on the adsorption of acid azo 57 dye molecules to modified sepiolite. For this purpose, the amenability of sepiolite to remove the anionic textile dye (acid azo red dye 57) was first studied in detail. Additionally, a typical cationic surfactant, hexadecyltrimethylammonium Br (HTAB), was used to modify sepiolite to increase the adsorption capacity. Zeta potential measurements on the sepiolite and the HTAB modified sepiolite were also carried out. Moreover, Density Functional Theory (DFT) studies were performed to understand the mechanism of the adsorption of dye molecules to natural and modified sepiolite surfaces. On the basis of the experimental studies, three general systems were theoretically examined: (i) HTAB molecules on sepiolite basal surfaces to represent four Si tetrahedra, (ii) neutral or charged acid azo red dye 57 molecules on sepiolite basal surfaces to represent four Si tetrahedra, and (iii) HTAB on the surface of neutral or charged acid azo red dye 57 molecules as a substrate. The results clearly indicated good agreement between the experimental studies and the theoretical computational DFT studies. For example, the double layer structure found in experimental studies was also demonstrated in DFT studies and confirmed increased adsorption in the presence of acid azo dye 57.

Effects of Dye Surface Concentration on the Molecular Aggregation of Xanthene Dye in Colloidal Dispersions of Montmorillonite

Abstract: The molecular aggregation of organic dyes onto clay mineral particles is a very complex phenomenon including dye adsorption, the migration of dye molecules, rearrangement of initially formed aggregates, etc. Some details of this complex process are not yet fully understood. The objective of the present study was to understand the influence of dye surface concentration on the dynamic processes in dye molecular aggregation. A stopped-flow rapid mixing device was used for accurate measurements of the molecular aggregation of the cationic dye rhodamine 123 (R123) in montmorillonite (MntK) colloidal dispersions. The influence of dye surface concentration, which was changed by altering the ratio of the amount of R123 to the mass of MntK (nR123/mMntK), was examined in detail. Chemometric analysis was used to reconstruct the spectral matrix to obtain linearly uncorrelated spectral profiles of the major components and their concentrations at the respective reaction times. The conversion of isolated R123 cations into oblique J-aggregates (head-to-tail molecular assemblies) was observed over time and the existence of a J-dimers intermediate was hypothesized. The reaction kinetics followed a biphasic exponential function. An unexpected effect of dye surface concentration on R123 aggregation was observed: the initial formation of the molecular aggregates increased significantly with dye surface concentration, but an inverse trend was observed after longer reaction times. While dye aggregates were formed slowly at low dye loadings, systems with high R123/MntK ratios (nR123/mMntK) reached spectral stability after the first few seconds of the reaction. After longer reaction times, the greatest degree of dye aggregation was achieved in the dispersion of the lowest dye loading. Such a phenomenon is described for the first time. The results presented here are important for understanding the complex processes occurring in systems based on organic cations and clay minerals, and should be considered in the development of functional hybrid materials of dyes and nanoparticles with a layered structure.

Evaluation Of Zinc-Bearing Palygorskite Effects on Growth Performance, Nutrient Retention, Meat Quality, and Zinc Accumulation in Blunt Snout Bream Megalobrama Amblycephala

Abstract: 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 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. KeyWords-Blunt Snout Bream, Growth Performance, Meat Quality, Zinc-bearing Palygorskite.

Optical trapping and orientation manipulation of 2d inorganic materials using a linearly polarized laser beam

Abstract: Because inorganic nanosheets, such as clay minerals, are anisotropic, the manipulation of nanosheet orientation is an important challenge in order to realize future functional materials. In the present study, a novel methodology for nanosheet manipulation using laser radiation pressure is proposed. When a linearly polarized laser beam was used to irradiate a niobate (Nb6O 17 4- ) nanosheet colloid, the nanosheet was trapped at the focal point so that the in-plane direction of the nanosheet was oriented parallel to the propagation direction of the incident laser beam so as to minimize the scattering force. In addition, the trapped nanosheet was aligned along the polarization direction of the linearly polarized laser beam.

Tuning the photophysical properties of cyanine dyes with clay minerals

Abstract: Dye molecular aggregation and other interactions on clay mineral surfaces cause phenomena such as methachromasy (change in color), fluorescence enhancement, or quenching, which represent significant changes in the spectral properties of the dye. These phenomena can be used to control the photophysical properties of hybrid systems based on cationic organic dyes. In the present study, the aggregation of two structurally similar cyanine dyes, 3,3’-diethyl-oxocyanine iodide (OxCy) and 3,3’-diethyl-2,2’-thiacyanine iodide (ThCy), in colloidal dispersions of three smectites (saponite, hectorite, and montmorillonite) was studied by absorption and fluorescence spectroscopy for a broad range of dye/smectite loadings. Spectral data were analysed by chemometric methods (principal component analysis, PCA, and multivariate curve resolution, MCR). Detailed analysis of the OxCy absorption spectra by the chemometric methods revealed the formation of two types of oblique aggregates exhibiting light absorption in both H- and J-bands. The existence of such similar aggregates, with similar splitting of excitation energies, appears to be related to the existence of two stable conformational isomers of this dye. On increasing the smectite CEC and dye/smectite loading, fluorescence quenching occurred. The ThCy dye exhibited a stronger tendency for molecular aggregation than OxCy. On increasing the smectite CEC, the formation of oblique aggregates with dominant H-bands also increased. On aging of the hybrid dispersions, equilibria of ThCy aggregates were shifted to the species with dominant J-bands. This behavior had a significant impact on the shape and intensity of the fluorescence emission of the hybrid dispersions. Using different smectites enables control of the dye aggregation and significant change to the photophysical properties of the hybrid systems. These systems can be used for the detailed study of the photophysical properties of cyanine dyes in various states. The colloidal systems with cyanine dyes can be used as precursors for the preparation of novel hybrid materials. In addition, the sensitive response of the photophysical properties of cyanine dyes to the clay mineral surface can be applied to the characterization of clay minerals.

Hydrothermal experiments reveal the influence of organic matter on smectite illitization

Abstract: Smectite illitization is an important diagenetic phenomenon of mudstones, but only rarely has the influence of organic matter (OM) on this process been examined. In the present study, hydrothermal experiments were conducted with smectite (M1, total organic carbon (TOC) 1%). X-ray diffraction (XRD), infrared, X-ray fluorescence (XRF), and organic carbon analyses were employed to characterize the mineralogy and OM of the samples and the effect of OM on smectite illitization. The XRD patterns showed changes in clay mineral parameters with increased temperature. These changes varied in both M1 and M2 and indicated a difference in the degree of smectite illitization. Moreover, the OM in M2 was mainly adsorbed in smectite interlayers, the OM was largely desorbed/decomposed at temperatures above 350°C, and the OM was the main reason for differences in the degree of smectite illitization between M1 and M2. Bulk mineral composition, elemental content, and infrared absorption band intensities were changed with increased temperature (especially above 350°C). This indicated the formation of new minerals (e.g., ankerite). Overall, OM entered the interlayer space of smectite in M2 and delayed the exchange of K+ by interlayer cations, and thus, suppressed the transformation of smectite to illite and resulted in differences in smectite illitization of M1 and M2. In particular, the formation of CO2 after the decomposition of OM at temperatures above 300°C led to the formation of ankerite in M2. This demonstrated the effect of organic-inorganic interactions on smectite illitization and mineral formation. The disparities in smectite illitization between M1 andM2, therefore, were linked to differences in the mineral formation mechanisms of a water-rock system (M1) and a water-rock-OM system (M2) in natural environments. The insights obtained in the present study should be of high importance in understanding organic-mineral interactions, hydrocarbon generation, and the carbon cycle.

Pore geometry as a limiting factor for anion diffusion in argillaceous rocks

Abstract: Several barrier types are envisaged to minimize the release of radionuclides from waste matrices into groundwater. In a number of countries argillaceous rocks make up the natural barrier that will isolate radioactive substances from the aquifer. The present study addresses the influence of pore geometry as a limiting factor for anion diffusion in argillaceous rocks. Irrespective of the pore core size, anion diffusion can be limited by the pore-size opening, i.e. if the pore opening is so narrow that the electric double layers overlap and form a barrier to anions irrespective of the pore size. This so-called ‘bottleneck effect’ limits the anion diffusion. The present study extends previous investigations that focused on other factors which limit anion diffusion, e.g. mineralogy or interlayer equivalent pores. The existence of bottleneck pores was confirmed by effective tortuosity calculations and retention-potential measurements using mercury intrusion porosimetry. On the basis of two different core samples from argillaceous rocks from Switzerland, Opalinus Clay and Helvetic Marl, this work shows evidence of the existence of bottleneck pores. The larger permanent anion exclusion in the Helvetic Marl sample compared to the Opalinus Clay sample can be explained by the larger retention potential and larger effective tortuosity of the Helvetic Marl rock, which indicates more pores with bottleneck effects than is the case for the Opalinus Clay rock.

Isothermal crystallization properties and improved rheological performance of waxy crude oil using polyoctadecylacrylate-modified montmorillonite composite as a pour point depressant

Abstract: Recently, studies on the use of polymer nanomaterial composites as pour-point depressants (PPD) have drawn much attention, but the crystallization properties and improved rheological performance of waxy crude oils using nanoclay-based composite PPDs have rarely been reported. In this paper, montmorillonite (Mnt) was first organically modified using octadecyltrimethylammonium chloride (C21H46NCl, or stearyltrimethylammonium chloride) in aqueous solution. Then, the organically modified Mnt (OMnt) material was dispersed into a polyoctadecylacrylate (POA) matrix to prepare a POA/OMnt composite PPD by melt blending. The composition, structure, and morphology of Mnt, OMnt, and the POA/OMnt composite PPDs were investigated. The results showed that the OMnt and POA were compatible and that the OMnt was exfoliated into several sheets in the POA matrix. Subsequently, the isothermal crystallization kinetics of the POA/OMnt composite PPDs showed that small amounts of OMnt had a dramatic impact on POA chain motion during crystallization and facilitated POA crystallization. After it was added to a waxy crude oil, the POA/OMnt composite PPDs produced better rheological properties and performance than identical concentrations of the neat POA. The POA/OMnt composite PPDs can act as wax nucleation sites for wax molecule precipitation and result in larger and more compact wax crystal flocs, which adversely affect the formation of a wax crystal network and, thus, favor the improvement of waxy crude oil rheology.

Role of micelle-clay complexes and quaternary amine cations in removal of bacteria from water: adsorption, biostatic, and biocidal effects

Abstract: The present report is a review of uses of quaternary ammonium cations (QACs) as free monomers or immobilized in micelle-clay complexes in bacteria removal from water. The removal of bacteria from water by filtration through a bed of a granulated QAC-clay micelle was improved by minute concentrations of QAC that were released from the complex during filtration, which exerted biostatic or biocidal effects on the bacteria that emerged from the filter. The relationships between antibacterial activity (minimum inhibition concentration, MIC; minimum lethal concentration, MLC) and structural parameters of the QACs (head group size and alkyl chain length) are discussed. The antibacterial activity of QACs in aqueous phases is mainly due to the free monomeric species. Bacterial inactivation is enhanced by QACs with longer alkyl chains. In most recorded cases, however, minimum MIC and MLC values occurred at n = 14–16 and mostly at n = 16, where n is the number of C atoms in the alkyl chain. This outcome is explained by the combination of two antagonistic effects: (i) An increase in alkyl chain length (i.e., QAC hydrophobicity) enhances QAC binding, penetration, and destabilization of bacterial membranes; and (ii) an increase in alkyl chain length lowers the critical micelle concentration (CMC) of QACs and, thus, reduces QAC monomer concentrations, which more efficiently inactivate bacteria than the micelles. The octadecyltrimethylammonium (ODTMA, n = 18) MLC value (0.25 μm) for the cyanobacterium genus Aphanizomenon is significantly lower than the CMC (300 mm) value. Hence, a test to determine the minimum MLC value at n = 16 is of interest. Removal of bacteria from water by filtration is expected to be made more efficient by small increases in the ODTMA/clay ratio in the complex, which will act to increase the concentrations of ODTMA cations released during filtration.

Securing the future: clay-based solutions for a comprehensive and sustainable potable-water supply system

Abstract: Today’s water-treatment plants combine practices designed to cope individually with various types of purification challenges. In some cases, the solution to one has detrimental effects on others, e.g. disinfection by chlorination forming hazardous organic contaminants. Water-treatment plants have large ecological footprints and operational costs, making the availability of high-quality water in developing areas almost impossible, due to lack of resources and infrastructure. Indeed, >2 billion people are exposed to diseases caused by contaminated water. Clearly, bringing safe, clean drinking water to people’s homes is essential to a good quality of life. Clay minerals may offer technologies and innovative practices which would help to develop a reliable, low-maintenance device with a small environmental footprint that processes stream, lake, or pond water into high-quality potable water. The basis for such technologies has already been established and improved approaches are being introduced on an ongoing basis by clay scientists: nanocomposite pre-treatment and disinfection, photodegradation of organic pollutants using clay-based catalysts, polishing of inorganic contaminants, and removal of biological pathogens by adsorption or deactivation onto specifically designed clay-based filters, etc. This short review presents a vision for combining those technologies in a tandem system for the delivery of high-quality water that is low-maintenance, affordable, and environmentally sustainable for the benefit of mankind.

Formation of arrested states in natural di- and trioctahedral smectite dispersions compared to those in synthetic hectorite - a macro- and microrheological study

Abstract: The effect of natural clay-mineral properties on the rheological behavior of dispersion is very important in new geotechnical and industrial applications. The colloidal behavior of natural clay minerals with various octahedral structures was investigated using macro- and microrheological measurements and compared with the behavior of synthetic hectorite. In the present study montmorillonite (dioctahedral smectite of Volclay), natural hectorite (trioctahedral smectite of SHCa-1 Source Clay), and the synthetic trioctahedral smectite Laponite®, with lateral layer dimensions of 277, 100, and 30 nm, respectively, were used. The structure formation, kinetics of aging, and broad bandwidth viscoelastic response (10-2 — 106 rad/s) of their dispersions were obtained using mechanical shear and squeeze flow rheometry combined with diffusing wave spectroscopy (DWS) and multiple particle tracking (MPT) microrheology. State diagrams were determined at inherent pH considering the clay-mineral and NaCl concentrations as well as the kinetics of structure formation and sample aging. Due to the larger mean layer diameter and greater layer-charge density of natural clay-minerals, their sol—gel transitions occurred at higher solid and NaCl concentrations than those of Laponite®. Structure formation was faster at pH pHPZC,edge (point of zero charge at the edge). The long-term aging of natural clay-mineral samples was less pronounced in the glass state than in the gel state, in contrast to the findings for Laponite®. The storage modulus, G’, of clay-mineral dispersions in arrested states remained essentially constant in a wide frequency range (up to 100 rad/s), as expected. The corresponding plateau value of G’ depends on the number of particle contacts per volume and, hence, increased with decreasing particle size at a given concentration. The dissipation mechanisms determining the high-frequency loss modulus, G", however, are independent of particle size and, accordingly, the high-frequency crossover of G’ and G" shifted to higher values when the particle size decreased. The MPT data revealed structural refinement on the submicrometer length scale during the aging of weak hectorite gels, which was similar to the results for Laponite®. No refinement, however, occurred for montmorillonite in the glass or strong gel state.

Removal of phosphate by ivory coast shale in a homogeneous reactor and under hydrodynamic conditions: influence of soluble species

Abstract: Developing low cost and effective phosphate adsorbents is crucial to prevent eutrophication of natural waters. Here, phosphate removal by a natural and abundant shale from the Ivory Coast was investigated in both batch and column experiments with special attention devoted to understand the adsorption process. Batch experiments were carried out to assess the influence of initial phosphate concentration, sorbent dosage, contact time, and pH on phosphate removal. The phosphate removal efficiency increased with increased shale dosage while phosphate uptake decreased. Aqueous Ca, Mg, Al, and Fe species concentrations decreased in the presence of phosphate. Additionally, phosphate uptake strongly decreased with pH increases in the range 2–11, but then increased at pH 12. The kinetics were well described using a pseudo-second order model, and Langmuir adsorption isotherms were used for the equilibrium surface reactions. Adsorption to nanoparticles of goethite was hypothesized to be the major phosphate removal mechanism in the pH range 4–10. Column experiments with a flow rate of 1 mL min–1 and an initial phosphate concentration of 25 mg L–1 showed a breakthrough point at a V/Vp value of ~17, where V is the volume of phosphate solution added to the column and Vp is the pore volume. A V/Vp value of ~17 corresponded to a phosphate uptake of 0.17 mg/g, which was in agreement with the batch experiments. Column experiments revealed a strong correlation between the aqueous concentrations of Ca, Mg, Al, and Fe species and phosphate removal and, thus, suggest that phosphate removal by the shale occurred by aqueous dissolution/precipitation.

An evaluation of the supplementation of dietary-modified palygorskite on growth performance, zearalenone residue, serum metabolites, and antioxidant capacities in broilers fed a zearalenone-contaminated diet

Abstract: –Zearalenone (ZEA), a common contaminant in food and feedstuffs, threatens human and animal health. The present study aimed to investigate the protective effects of modified palygorskite (MPal), a ZEA-targeted adsorbent, on broilers (young chickens) fed a ZEA-contaminated diet. Broilers were subjected to one of three treatments for a period of 42 days: a basal diet (control group), a ZEA- contaminated diet, and a ZEA-contaminated diet supplemented with 1 g/kg of MPal. Blood was collected for serum metabolite assay, and liver and kidney were sampled to determine ZEA residue and antioxidant- related parameters, using commercial spectrophotometric kits. Compared with the basal diet, the ZEA- contaminated diet resulted in compromised growth performance (reduced daily gain and feed intake during finisher period), disordered relative liver weight (decreased at 21 days but increased at 42 days), increased ZEA residue in liver and kidney, abnormal serum metabolites (decreased total protein content but increased alanine aminotransferase activity at 21 and 42 days, reduced albumin content at 21 days, and elevated aspartate aminotransferase activity at 42 days), and disrupted antioxidant capacities of broilers (increased total superoxide dismutase (T-SOD) activity in liver at 21 and 42 days, decreased T-SOD activity in kidney at 21 and 42 days, and in serum at 42 days, greater malondialdehyde accumulation in liver and kidney at 42 days, and lower glutathione content in kidney at 21 days). The adverse consequences resulting from the ZEA-contaminated diet were relieved by the supplementation of MPal (except albumin concentration in serum and T-SOD activity in liver at 21 days), with the values of growth-performance parameters, liver weight, renal ZEA accumulation, total protein content, transaminase activity at 42 days, and antioxidant indexes being similar to those in the control group. These results suggested that MPal supplementation could promote growth performance, attenuate liver damage, and improve the antioxidant abilities of broilers fed ZEA-contaminated diet by reducing ZEA accumulation.

Iron-Pillared Montmorillonite As An Inexpensive Catalyst For 2-Nitrophenol Reduction

Abstract: Many types of oxidative pollutants are dangerous chemicals and may pose a health risk, but an inexpensive and effective method for mitigating those risks would offer significant advantages. The objective of this study was, therefore, to investigate the potential for Fe-pillared montmorillonite to fill that gap. Surface mediated reduction reactions by ferrous species often play an important role in governing the transport, transformation, and fate of hazardous oxidative contaminants. Compared to the untreated montmorillonite (Mnt), the synthetic polyhydroxyl-Fe pillared montmorillonite (Fe-Mnt) was found to be somewhat similar to goethite in promoting the ability of specifically adsorbed Fe(II) to reductively transform 2-nitrophenol (2-NP). The 2-NP was efficiently removed within 30 min from solutions at the optimum neutral pH in a mixed reduction system of Fe(II)/Fe-Mnt under an anoxic atmosphere. This demonstrated that the specifically adsorbed Fe(II) of Fe-Mnt can enhance 2-NP reduction. The highly enhanced 2-NP reduction by Fe(II) through Fe-Mnt surface catalysis can, therefore, be ascribed to clearly increased amounts of an adsorbed Fe(II) species surface complex, which gave rise to enhanced Fe(II) reductive activity that enabled the rapid reduction of 2-NP. The reduction processes produced a faster transformation of 2-NP in a Fe-Mnt suspension than in a Mnt suspension. The transformation kinetics were described using pseudo-first-order rate equations. Moreover, in addition to the effects of mineral surface properties, the interactions were affected by the aqueous chemistry, and the removal rates of 2-NP were increased at pHs of 6.0–7.3. In the present study, the structure and surface reactivity of Fe-Mnt was characterized in depth. The polyhydroxyl-Fe added to Mnt and the pH were determined to be the two key controlling factors to mediate the reductive transformation of 2-NP in the presence of Fe-Mnt in comparison to goethite and Mnt. Finally, the catalysis mechanism responsible for the enhanced 2-NP reduction by Fe(II) was elucidated using cyclic voltammetry.

Removal of Water-Soluble Polymers from an Aqueous Solution by Adsorption onto an Acidic Clay

Abstract: Due to the wide range of uses of water-soluble polymers in commercial products, water contamination by polymers has become a serious environmental concern. Adsorption onto an acidic clay, obtained from Tsunagi mine, Niigata, Japan, of water-soluble polymers from aqueous solutions was investigated as a means of purifying water. Poly(vinylpyrrolidone) (PVP) was used as a sample polymer in an attempt to find optimal conditions for extracting the greatest proportion of polymer from the aqueous solution. The adsorption isotherms at lower equilibrium concentrations were of type L, indicating a strong affinity between the acidic clay and PVP. A larger amount of PVP was adsorbed when a higher-molecularweight PVP (comparison between MWs of 160,000 and 10,000) was used. From the Langmuir equation, the adsorption capacity was calculated as 0.029 g/g clay for the adsorption of poly(vinylpyrrolidone) from an aqueous solution. The adsorption of PVP from a NaCl solution (simulated sea water) was also possible though the amount of adsorption was slightly less than from an aqueous solution. A polymer removal efficiency of >90% was achieved when 200 mg of the acidic clay was added to 50 mL of 0.001 wt.% PVP aqueous solution. The acidic clay was also used for adsorption of poly(ethylene glycol), poly(vinyl alcohol), and polyacrylamide from aqueous solutions.

Mineralogical evolution of the paleogene formations in the kyzyltokoy basin, kyrgyzstan: implications for the formation of glauconite

Abstract: Although several hypotheses for the formation of glauconite have been proposed, the sedimentary environment and mechanism of glauconitization are still poorly understood. In this contribution, the mineralogy and chemical compositions of sediments from Paleogene formations (Fms) in the Kyzyltokoy basin (Kyrgyzstan) were examined to better understand glauconitization processes. The samples were analyzed using microscopic petrography, X-ray diffraction (XRD), electron probe microanalysis (EPMA), and X-ray fluorescence (XRF). Interlayered diatomite-argillaceous rocks were newly identified within the diatomites of the Isfara Fm. Glauconite from the Kyzyltokoy basin displayed two stages of maturity: 1) early stage (nascent) glauconite grains composed of c3.5% K2O and ~8% FeOT; 2) late-stage (highly evolved) glauconite grains composed of 7–9% K2O and ~27% FeOT. The early stage glauconite grains in the Hanabad Fm green clay (green clay is clay with a greenish color) indicate interruptions in glauconitization processes, whereas the (highly) evolved glauconite grains show a completed glauconitization process along the contact between the Hanabad and Sumsar Fms. Hematite was detected in the red clay (clay with reddish color) of the Sumsar Fm and probably formed by glauconite disintegration. Accordingly, the Paleogene Fms depositional conditions were of three types: 1) beginning of glauconitization with interruptions, 2) completion of glauconitization, and 3) glauconite disintegration. Glauconitization in the Kyzyltokoy basin, thus, likely occurred via a combination of dissolution, precipitation, and recrystallization processes.

MICROSTRUCTURE-RELATED Pb2+ ADSORPTION CAPABILITY OF Ti-PILLARED MONTMORILLONITE IN AQUEOUS SOLUTION

Abstract: The elimination of Pb2+ and recovery of lead metal during the treatment of industrial sewage is an important research topic. Montmorillonite (Mnt) is a promising material in this regard. The purpose of the present study was to improve the Pb2+ adsorption ability of Na-containing Mnt (Na-Mnt) by pillaring titania (anatase) into its interlayer spaces using a sol-gel method. The samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). The ratio of Ti to Mnt affected the crystal phase of titania-pillared Na-Mnt (Ti-Mnt), and changed the interlayer spacing of the (001) plane of Ti-Mnt and the growth of anatase. The Pb2+-adsorption capabilities of Ti-Mnt were tested using an aqueous solution of lead nitrate as a wastewater model. The Ti-Mnt prepared adsorbed >99.99% of the Pb2+; leached and activated Ti-Mnt adsorbed >95.7% of the Pb2+, indicating that Ti-Mnt could be recycled effectively. Furthermore, the Pb2+-adsorption capability of Ti- Mnt was related to the interlayer spacing of Mnt, the distribution of anatase particles pillared in Mnt, and the specific surface area, especially with respect to the relationship between the anatase particles and the interlayer spacing of the (001) plane.

Occurrence of Fibrous Chrysotile and Tremolite in the Çankiri and Ankara Regions, Central Anatolia, Turkey

Abstract: Numerous occurrences of asbestos minerals, notably chrysotile and tremolite, are to be found on fracture surfaces in thrust fault deformation zones of Cretaceous dunite-harzburgite and pyroxenite in the Cankiri and Ankara regions, central Anatolia, Turkey. Consequently, potential exists for the development of regional malignant mesothelioma. The means of serpentinization, such as reaction of seawater during accretion of the upper ophiolitic mantle crust in a subduction zone and/or following uplift of ophiolitic units and the influence of hydrothermal/meteoric fluids along fractures, were investigated. Cretaceous dunite-harzburgite and localized pyroxenite rocks are mainly composed of serpentinized olivine and pyroxene associated with opaque minerals and Fe-(oxyhydr)oxide phases. Smectite, chlorite, illite, kaolinite, hydromagnesite, goethite, quartz, and opal-CT are also present. Chrysotile and localized tremolite occur either as a mesh, a suboriented to oriented long-fiber bundle, or as fiber-filling millimetric micro-vein textures on relicts of olivine and pyroxene (enstatite, augite). The chrysotile and tremolite have non-pseudomorphic textures developed under high pressure and temperature. The textures suggest authigenic formation of chrysotile and tremolite via a dissolution and precipitation mechanism. Additionally, spherical structures of opal-CT and locally platy hydromagnesite crystals either enclose or are developed within chrysotile/tremolite fiber bundles. The leaching of MgO, Fe2O3, Al2O3, Ni, Cr, and Nb, an increase in the LREE/HREE ratio, and negative Eu anomalies in the dunite-harzburgite and pyroxenite, and asbestos samples suggest that the chrysotile and tremolite were derived from the serpentinization of olivine and pyroxene. The chrysotile and tremolite were developed along fractures by hydrothermal fluid alteration during accretion and/or following the uplift of ophiolitic units of the region under high pressure and temperature conditions. This interpretation is also supported by isotope data and the calculated formation temperature of 170–555°C for chrysotile and tremolite. The average structural formulae for chrysotile and tremolite are (NanK0.03)(Mg5.54Fe0.09Al0.05Ca0.01Mn0.001) (Si3.96Al0.03)O10(OH)8 and (Na0.17K0.07)(Ca1.59Mg0.19Mn0.002)(Mg4.72Fe0.28)(Si7.86Al0.1Fe0.06)O22(OH)2, respectively.