The most potent and significant polyphenolic molecule from tea catechins is epigallocatechin gallate (EGCG); it has potential anti-cancer and anti-inflammatory properties. Methods are needed to mitigate its presence in the environment and protect humans from exposure. The objective of the present study was to investigate a functionalized, low-cost clay mineral as an adsorbent for the tea polyphenol EGCG. Hydrophilic bentonite (Bn) was functionalized using Aliquat 336 (A336) and isobutyl(trimethoxy)silane (IBTS). The degree of clay functionalization depended on the extent of introduction of alkyl linkages between the superimposed clay layers. Results revealed that Aliquat 336 functionalized clay (A336-Bn) exhibited maximum thermal stability at 500°C and it is a promising adsorbent for ECGC with a maximum adsorption capacity of 196.26 mg/g at equilibrium. Experimental data were analyzed using pseudo-first order and pseudo-second order models. Adsorption isotherms were interpreted from the Freundlich adsorption isotherm.

Natural zeolites may represent one of the greatest under-utilized resources of the mineral world. Even with their unique character and properties, issues of consistency, homogeneity and purity preclude them from many premium applications. We report a simple method to upgrade mineral sedimentary Na-chabazite from the well known Bowie, Arizona, deposit to near synthetic purity and consistency. During this alkaline-silicate digestion process, initially soft chabazite ore granules gain substantial mechanical strength. This may allow direct employment in adsorption and purification processes without the need for binding and forming. These granules manifest significantly improved adsorption properties, including enhanced water and CO2 adsorptivity.

The role of Mn oxide in the abiotic formation of humic substances has been well demonstrated. However, information on the effect of crystal structure and surface-chemical characteristics of Mn oxide on this process is limited. In the present study, hexagonal and triclinic birnessites, synthesized in acidic and alkali media, were used to study the influence of the crystal-structure properties of birnessites on the oxidative polymerization of hydroquinone and to elucidate the catalytic mechanism of birnessites in the abiotic formation of humic-like polymers in hydroquinone-birnessite systems. The intermediate and final products formed in solution and solid-residue phases were identified by UV/Visible spectroscopy, atomic absorption spectrometry, Fourier-transform infrared spectroscopy, X-ray diffraction, solid-phase microextraction-gaschromatography-mas ss pectrometry, ion chromatography, and ultrafiltration. The degree of oxidative polymerization of hydroquinone wasenhanced with increase in the interlayer hydrated H+, the average oxidation state (AOS), and the specific surface area of birnessites. The nature of the functional groups of the humic-like polymers formed was, however, almost identical when hydroquinone was catalyzed by hexagonal and triclinic birnessites with similar AOS of Mn. The results indicated that crystal structure and surface-chemistry characteristics have significant influence on the oxidative activity of birnessites and the degree of polymerization of hydroquinone, but have little effect on the abiotic formation mechanism of humic-like polymers. The proposed oxidative polymerization pathway for hydroquinone isthat, asit approachesthe birnessite, it formsp recursor surface complexes. Asa strong oxidant, birnessite accepts an electron from hydroquinone, which is oxidized to 1,4-benzoquinone. The coupling, cleavage, polymerization, and decarboxylation reactionsaccompany the generation of 1,4-benzoquinone, lead to the release of CO2 and carboxylic acid fragments, the generation of rhodochrosite, and the ultimate formation of humic-like polymers. These findings are of fundamental significance in understanding the catalytic role of birnessite and the mechanism for the abiotic formation of humic substances in nature.

The present work is part of a study focused on the use of organo-zeolite conditioner to remediate soil polluted by toxic elements. The Neapolitan yellow tuff (NYT) was utilized as a component of an organo-mineral sorbent/exchanger soil conditioner with pellet manure (NYT/PM) to reduce the mobility of Cd and Pb and recover plant performance in heavily polluted soils from illegal dumps near Santa Maria La Fossa (Lower Volturno river basin, Campania Region, southern Italy). Pot experiments were performed by adding the NYT/PM mixture (1:1, w/w) to polluted soil at the rates of 0%, 25%, 50% or 75% (w/w). Wheat (Triticum aestivum) was used as the test plant. The addition of organo-zeolite NYT/PM mixture significantly reduced the DTPA (diethylene-triamine-pentaaceti c acid)-extractable Cd and Pb from 1.01 and 97.5 mg kg−1 in the polluted soil, to 0.14 and 11.6 mg kg−1, respectively, in the soil amended with 75% NYT/PM. The best plant response was observed in amended soil systems treated with 25% NYT/PM, whereas larger additions induced plant toxicities due to increased soil salinity.

Seven species of Cliostomum Fr. recorded from Australia are treated. These include the widespread C. griffithii (Sm.) Coppins, the austral C. praepallidum (Müll. Arg.) Kantvilas & Fryday and the Tasmanian endemic C. vezdae Kantvilas, a reinstated name previously subsumed under C. flavidulum Hafellner & Kalb. Three species are described as new: C. latisporum Kantvilas, a corticolous species containing atranorin and gangaleoidin from coastal Tasmania and New South Wales, characterized by pale pink, soon immarginate apothecia, 0.3–0.9 mm wide, non-capitate, unpigmented paraphyses, and relatively wide, 1(–3)-septate ascospores, 9–15 × 4–6 μm; C. litorale Kantvilas, a saxicolous species containing atranorin and confluentic acid, recorded only from Tasmania, with relatively large, usually pale pinkish apothecia, 0.6–1.5 mm wide, non-capitate paraphyses, and 1(–2)-septate ascospores, 9–13 × 4−6 μm; and C. saxatile Kantvilas, a saxicolous species containing atranorin and lecanoric acid, also known only from Tasmania, with dark brown to black apothecia, 0.3–0.5 mm wide, pigmented with Laurocerasi-brown, capitate paraphyses, and 1-septate ascospores, 7–14 × 3–5 μm. The widespread, coastal Australasian species Tylothallia verrucosa (Müll. Arg.) Kantvilas is transferred to Cliostomum, with the additional synonym Catillaria brisbanensis Räsänen. Megalaria variegata (Müll. Arg.) D. J. Galloway, based on a New Zealand type, is a further synonym of Cliostomum griffithii. All species are illustrated and described on the basis of Australian and Tasmanian specimens.

Emanation thermal analysis (ETA), based on radon release measurements from previously labeled samples, was used for the first time in the characterization of the thermal behavior of natural Mg2+-vermiculite (Santa Olalla, Huelva, Spain) and of Na+- and ${\text{NH}}_4^{+}$-exchanged vermiculite samples. In addition, vermiculite samples subjected to a chemical treatment with an aqueous solution of (NH4)2SiF6 and partially or totally re-saturated with Na+ ions were also investigated by ETA. The ETA results of natural Mg2+-vermiculite, Na+-vermiculite and ${\text{NH}}_4^{+}$-vermiculite gave supplementary information about microstructure changes of the samples observed under dynamic heating conditions. The method has proved to be very useful for characterization of microstructure changes due to modification in the interlayer space of samples during the heat treatment. The crystallization of vermiculite into new phases, such as enstatite (for ${\text{NH}}_4^{+}$-vermiculite and Mg2+-vermiculite) and forsterite (for Na+-vermiculite) was also observed by ETA.

In order to better understand the possible interactions between steel canisters and a claystone host rock, in this case the Callovo-Oxfordian rock (COx), the present study investigated in detail, under conditions relevant to high-level radioactive waste repositories (anoxic conditions, temperature of 90°C), the reactions between metallic iron and: (1) COx; (2) the clay fraction extracted from COx (CF); and (3) mixtures of CF with quartz, calcite, or pyrite. Batch experiments were then carried out in the presence of NaCl-CaCl2 background electrolyte, for durations of 1, 3, and 9 months. Solid and liquid end-products were characterized by a combination of techniques including liquid analyses, transmission and scanning electron microscopies, X-ray diffraction, N2 adsorption at 77 K, and Mössbauer spectroscopy. The interaction between CF and metallic iron appeared to proceed by means of pathways similar to those illustrated in previous studies on interactions between metallic iron and purified clays. In spite of the many similarities with previous studies, significant differences were observed between the behavior of COx and CF, particularly in terms of pH and Eh evolution, iron consumption, chemical composition of the neoformed particles, and textural evolution. Such differences demonstrate the important role played by non-clay minerals in reaction pathways. The addition of carbonates or pyrite to CF did not lead to significant change in reactivity. In contrast, under the conditions used in the present study, i.e. for relatively low iron:clay ratios, the presence of quartz strongly influenced reaction pathways. In the presence of quartz, magnetite was observed only in trace abundances whereas the amounts of magnetite were significant in experiments without quartz. Furthermore, filamentous serpentine particles with a small Al:Si ratio appeared which could develop from an FeSiAl gel that only forms in the presence of quartz. Considering that most clay rocks currently being considered for radioactive waste disposal contain significant amounts of quartz, the results obtained in the present study may be of significant interest for predicting the long-term behavior of clay barriers in such sites.

This article revisits ‘the problem of Classical Ionia’, the long-persisting idea put forward by John Manuel Cook in 1961 that Ionia experienced regional economic impoverishment in the fifth century BCE. By looking comprehensively at the dataset of coinage available from fifth-century Ionia, this article argues that there is actually significant evidence for regional networking in Classical Ionia, and that various communities, even if not continually emitting new coinages at all points in the fifth century, adopted various strategies for maintaining their economic reach and extending their network of trading partners. Formal network analysis is applied to the coinage dataset, taking the shared weight standards to which communities minted their coins as indicative of participation in common economic networks. The network patterns are tested against two other patterns, specifically the distribution of fifth-century Chian and Samian amphoras, and the pattern of Ionian-coin-containing hoards from within and beyond Ionia. Together, these patterns strengthen the case for a high-level Ionian economic resilience, offering a radically different position to Cook and reaffirming that continuing economic networking was crucial to the activities of fifth-century Ionian states.

Occurrences of halloysite-rich material in altered volcanic rocks, principally trachyandesites, dacites, and tuffs, extend over an area of ∼1 km2 in the southwestern part of Limnos, Island, northeast Aegean Sea, Greece. The present study was designed to investigate the alteration processes which acted on the biotite in these volcanic rocks, to describe in detail the mechanism of formation of the halloysite, and to specify the mechanisms of formation of anatase during the alteration processes. Samples were examined using polarized-light microscopy, X-ray powder diffraction, scanning electron microscopy, scanning electron microscopy-energy dispersive spectroscopy, and Fourier-transform-Raman techniques. The extensive alteration of the parent rocks, triggered by the circulation of hydrothermal fluids through faults and fractures, resulted in the alteration of biotite to halloysite. Six stages of alteration were recognized. Nanoparticles of halloysite were initially formed on the mica layers, which progressively grew through short-tubular to well formed tubular halloysite, with increasing alteration. In the most altered samples, laths and interconnected laths with the composition (Al3.96Fe0.04)Si4O10(OH)8, were the dominant halloysite morphologies. Anatase was encountered as an alteration product of both ilmenite and biotite. Ilmenite was altered to anatase and Fe oxides. The altered ilmenite crystals constrained most of the newly formed anatase within the space occupied previously by ilmenite, leading to the formation of skeletal anatase. The layered structure of the micas was the main factor governing the morphology of newly formed anatase developed outside ilmenite margins in the form of layers parallel to those of mica. An unusual ring-like structure of anatase was thought to be the result of the uncommon alteration of inner parts of mica folia to tubular halloysite oriented perpendicular to the mica layers. The detachment of the halloysite tubes by circulating hydrothermal fluids was considered to be the reason for the creation of holes which were subsequently surrounded by the anatase ring forms.

Most previous studies of the kaolin deposits in the southeastern United States have focused on their mineralogy and petrology to understand better the depositional and diagenetic environments of the kaolins. Many studies suggest, however, that much of the information held within the minerals was changed during extensive post-depositional groundwater and microbial alteration. Organic δ13C and biomarker analyses were used, therefore, to provide further information on the nature of the original sediments, the depositional environment(s), and the amount of diagenetic alteration that has occurred in Georgia kaolin deposits.

Two different types of kaolin can be discerned, based on their total organic carbon contents: organic-lean kaolin and lignitic kaolin. The bulk organic δ13C in the Georgia kaolins ranges from ~−26 to −19% (VPDB, Vienna Pee Dee Belemnite standard), with a noticeable enrichment in 13C with decrease in organic carbon concentration. The lean kaolins are by far the more dominant types, with an organic-matter composition primarily of C16–C22n-alkanes, C16 and C18 fatty acids, and unresolved complex mixtures. Lignitic kaolin has a distinctly different organic matter (OM) composition. The lignitic material is primarily C15–C33n-alkanes with a greater abundance of C23–C31n-alkanes and lesser amounts of resinous and microbial constituents along with the oxidized forms of the saturated lipid fractions.

Biomarker data suggest that the lignitic material is primarily terrestrially derived from conifers with minor input from microbial lipids. The OM in both types of kaolin shows strong signs of microbial decomposition that yield the organically lean kaolins. The oxidation of the detrital organic matter would subsequently yield organic acids that would have exerted significant influence on the mineralogy and metal mobility.

Outer main-belt asteroids are predominantly of the C-type (carbonaceous), suggesting that they are likely parent bodies of carbonaceous chondrites. Abundant phyllosilicates in some classes of carbonaceous chondrites have chemical compositions, mineral associations, and textures that preserve direct evidence of the processes by which carbonaceous chondrites and their parent asteroids originated and evolved to their present state. Serpentine is the dominant hydroxyl-bearing mineral in the most abundant (CM) group of carbonaceous chondrites. Serpentine may have formed as a direct nebular condensate during cooling of the solar nebula, or by aqueous alteration of anhydrous Mg,Fe-silicate precursors. Such alteration of anhydrous precursors may have occurred in the solar nebula prior to assembly of the meteorites’ parent bodies or on the parent bodies. The relative proportions of Fe and Mg in fine-grained CM2 serpentines have been used to compare the degree of aqueous alteration of different CM2 chondrites with one another. The Mg content of serpentine increases with increasing overall degree of aqueous alteration, so CM2 chondrites with Mg-rich serpentines experienced a more advanced degree of aqueous alteration than CM2 chondrites with Fe-rich serpentines. Attempts to quantify aqueous alteration of CM chondrites by interpreting electron microprobe analyses in terms of charge-balance and site-occupancy constraints from serpentine stoichiometry have met with mixed success. Despite its imperfections, one widely used alteration index based on serpentine stoichiometry is strongly correlated with the elapsed time since the fall and recovery of witnessed CM chondrite falls. Additionally, volatile organic contaminants introduced during sample processing in the laboratory are associated with serpentine and other matrix phyllosilicates. Together, these post-recovery changes in scientifically important sample attributes imply that oxidation-reduction and other types of weathering and contamination affect these meteorites even during curatorial storage and laboratory processing. The same phyllosilicates that make their carbonaceous-chondritic host rocks scientifically important research targets also render those same rocks extraordinarily vulnerable to terrestrial contamination of some of their most scientifically important attributes. This has possible implications for reconstructing pre-terrestrial (parent body) aqueous alteration phenomena from carbonaceous chondritic meteorites and eventually from samples returned by future missions to asteroids with spectral reflectance properties similar to carbonaceous chondrites.

The increasing levels of industrial wastewater released to the environment present a serious threat to human health, living resources, and ecological systems. Fe-modified zeolites were developed and tested for removal of Cu2+ and Zn2+ from contaminated water. The surfaces of the naturally occurring zeolite, clinoptilolite, were modified with Fe(III) oxyhydroxides using three different methods, denoted I, II, and III (FeCli1, FeCli2, and FeNaCli1, respectively). The oxyhydroxides were prepared in Method I using 0.1 M FeCl3·6H2O in an acetate buffer (pH = 3.6); in Method II, using 10ai] FeCl3·6H2O solution in 0.1 M KOH (pH = 10); and Method III was the same as Method I except the clinoptilolite was pretreated with NaCl. Newly synthesized materials from these three methods were then tested for their ability to enhance the sorption capacity for Cu and Zn compared to the natural sample (Cli). Powder X-ray diffraction measurements and the chemical composition of these modified samples confirmed that clinoptilolite maintained its structure while amorphous Fe3+ species were synthesized. The specific surface area (BET method) of both the natural and modified clinoptilolite increased by 2 and 7.5 times for Methods I and II, respectively. Scanning electron microscopy and energy dispersive X-ray spectroscopy revealed that CaO was formed during Method I (FeClii). Throughout the adsorption process, the hydrolysis of CaO and the release of OH− caused the precipitation of Cu and Zn hydroxide, which made the determination of the sorption capacity of FeClii impossible. This phenomenon was avoided in Method III (FeNaClii) because of the absence of exchangeable Ca2+. The adsorption experiments with Method II resulted in double-enchanced adsoprtion capacity. Laboratory batch experiments revealed that the sorption capacities increased in the following order: Cli < FeCli2 < FeNaCli1, for Cu: 0.121 mmol/g < 0.251 mmol/g < 0.403 mmol/g and for Zn: 0.128 mmol/g < 0.234 mmol/g < 0.381 mmol/g.

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.

A hybrid of montmorillonite (Mnt) and rifampicin (RIF) was synthesized and the structure and stability of the drug carrier system clarified. Density functional theory calculations involving dispersion corrections (DFT-D3) were performed to characterize interactions acting in the interlayer space of montmorillonite intercalated with rifampicin. The structure and stability of the RIF-Mnt intercalated complex were determined. Calculations revealed the deformation of the molecular structure of rifampicin after intercalation into the Mnt interlayer space due to the clay environment. The ansa chain of RIF was bent in the interlayer space compared with the structure of the RIF molecule in the monocrystal. RIF was keyed into the Mnt surface by means of numerous hydrogen bonds of weak to moderate strength. The calculated vibrational spectrum from ab initio molecular dynamics (AIMD) was in good agreement with the FTIR measured spectra and helped to analyze the overlapped vibrational bands. Based on analysis of structural stability, theoretical calculations revealed that Mnt is a suitable drug carrier for delayed release of the RIF drug. Batch adsorption experiments showed the large adsorption capacity of montmorillonite for RIF.

Attempts at optical resolution and asymmetric syntheses using smectite clay minerals are described. Use of the method was prompted by the discovery that the saturated adsorption of a tris(chelated) metal complex, [Ru(1,10-phenanthroline)3]2+, by Na-montmorillonite depended heavily on the stereochemical properties. The pure enantiomer was adsorbed by cation exchange at negative surface sites of the clay mineral, while the racemic mixture was adsorbed to two times excess of the cation exchange capacity. The chelate takes a uniform orientation on a clay mineral surface due to the matching between the molecular symmetry and the two-dimensional network of a phyllosilicate layer. On a clay mineral surface covered with the enantiomeric chelates, a vacant space capable of chiral discrimination was generated. Based on this, an ion-exchange adduct of smectite and the chiral chelate was used as an adsorbent for separating racemic mixtures or selectively producing either one of the optical isomers.

Micromorphological studies were performed in order to understand the factors and processes involved in the formation of calcium carbonate (CaCO3) in twenty three soil series of Vertisols representing sub-humid, semi-arid and arid climatic regions of Peninsular India. The study indicates that Vertisols contain both pedogenic calcium carbonate (PC) and non-pedogenic calcium carbonate (NPC) irrespective of the ecosystems to which they belong. The NPCs are part of the parent material of Vertisols. Dissolution of NPCs and recrystallization of dissolved Ca2+ ions are responsible for the formation of PCs. Vertisols of arid and semi-arid climates contain more PC in their soil control section (SCS) than those of sub-humid climates. Formation of PC is the prime chemical reaction responsible for the increase in pH, the decrease in the Ca/Mg ratio of exchange site with depth and in the development of subsoil sodicity. Petrographic and scanning electron microscopic (SEM) examination of quartz, feldspars and micas indicate little or no alteration, discounting the possibile formation of smectite during Vertisol formation. X-ray diffraction (XRD) analysis of clays indicates that smectites of Vertisols are fairly well crystallized and do not show any sign of transformation except for hydroxy interlayering. The preservation of the crystallinity of smectite and the lack of transformation of primary minerals thus validate the hypothesis of positive entropy change during the formation of Vertisols.

The precise cause-effect relationship between CaCO3 of pedogenic and non-pedogenic origin, and exchangeable Mg, Na and Ca percentages (EMP, ESP and ECP) has been established in the study. This indicates that impoverishment of Ca2+ ions on the exchange sites of Vertisols needs to be controlled by rehabilitation methods that can replenish Ca2+ ions, and thus the study provides relevant information for future land resource management programmes not only on Vertisols of India but also on similar soils occurring elsewhere.

Among the many techniques used to remove toxic dyes from the environment, layered double hydroxides (LDH) are considered to be especially environmentally friendly, but, this quality may be altered by variations in the octahedral Mg/Al molar ratios in the LDH structure. The aim of the present study was to synthesize environmentally sound LDH for use as an economically viable sorbent for the adsorption of reactive brilliant orange X-GN. Layered double hydroxides with Mg/Al molar ratios of 2:1 and 4:1 were prepared by co-precipitation. The materials obtained were characterized by powder X-ray diffraction (XRD), Fourier-transform infrared (FTIR) spectroscopy, X-ray fluorescence spectroscopy (XRF), and surface-area analysis. Batch experiments were carried out to investigate the effects of contact time, pH, adsorbent dosage, and initial dye concentration on the adsorption behavior of the reactive brilliant orange X-GN by Mg-Al LDH. The results showed that the optimum pH value for dye adsorption was 3.0, at which the adsorption capacities of the reactive brilliant orange X-GN by the 2:1 LDH and the 4:1 LDH at 298 K were 79.370 mg/g and 83.343 mg/g, respectively. Further analysis of the dye-adsorption kinetics show that they fit the pseudo second-order model well. The adsorption equilibrium data showed that the Langmuir model provided better correlation of the equilibrium data than the Freundlich model. This result indicates that LDH provide specific homogeneous sites where monolayer dye adsorption occurs. The results of XRD and FTIR analyses of LDH before and after the dye adsorption demonstrated that the adsorption mechanisms were ion exchange and coulombic attraction.