Mária Čaplovičová

Smectite-to-illite alteration in salt-bearing bentonites (the East Slovak Basin)

The effect of a saline environment on illitization in volcanoclastic rocks is examined in deep boreholes in the East Slovak Basin. Based on X-ray diffraction analysis, it is concluded that illite-smectite (I–S) expandability is always less in the salt-bearing bentonites (SBB) than in the salt-free bentonites (SFB) for a given depth interval. These two lithologies can be distinguished easily by water-leachate chemistry. Within the depth interval 2100–2500 m, the expandability in SBB varies within the range 25–10% expandable with R1 and R3 ordering in SBB and 68–35% expandable with R0 ordering in SFB. In two shallow SBB samples the expandability is close to that of SFB, suggesting that salinity alone does not enhance the illitization; but salinity may enhance it when combined with higher burial temperature. Vitrinite reflectance and Tmax of RockEval pyrolysis measured in adjacent shales confirm that the increased illitization in SBB is not due to heating and/or erosion. The model of burial and thermal history calibrated by organic maturity suggests that the same thermal history produces two different expandabilities in the two lithologies (SBB and SFB). Particle thickness measurements and K-Ar data were used to deduce the crystal growth mechanism of illitization in SBB. Whereas surface-controlled growth is typical for SFB, simultaneous nucleation and growth played a more important role in the case of SBB. The effect of a salty environment on the illitization is not yet fully understood and may have severe consequences for the utilization of bentonites as engineering barriers in radioactive waste disposal sites if salt formations used as host rocks are taken into account.

Structural Incorporation of As5+ into Hematite

Hematite (α-Fe2O3) is one of the most common iron oxides and a sink for the toxic metalloid arsenic. Arsenic can be immobilized by adsorption to the hematite surface; however, the incorporation of As in hematite was never seriously considered. In our study we present evidence that, besides adsorption, the incorporation of As into the hematite crystals can be of great relevance for As immobilization. With the coupling of nanoresolution techniques and X-ray absorption spectroscopy the presence of As (up to 1.9 wt %) within the hematite crystals could be demonstrated. The incorporated As(5+) displays a short-range order similar to angelellite-like clusters, epitaxially intergrown with hematite. Angelellite (Fe4As2O11), a triclinic iron arsenate with structural relations to hematite, can epitaxially intergrow along the (210) plane with the (0001) plane of hematite. This structural composite of hematite and angelellite-like clusters represents a new immobilization mechanism and potentially long-lasting storage facility for As(5+) by iron oxides.

Evolution of pyrophyllite particle sizes during dry grinding

Abstract The Bertaut-Warren-Averbach (BWA) technique and high-resolution transmission electron microscopy (HRTEM) were used to characterize the products of dry-ground pyrophyllite. Mean crystallite thickness and crystallite thickness distributions were measured for each sample using the BWA technique. Mean crystallite thickness decreases during the treatment with respect to grinding time and energy applied per unit mass. The BWA data were checked by HRTEM measurements and good fits were obtained for samples having small mean particle thicknesses. Samples with thicker particles could not be measured properly by HRTEM because the number of particles counted from images is statistically insufficient. The shape of the crystallite and the particle-size distribution were used to determine the mechanism of pyrophyllite particle degradation. Particles initially having a lognormal size distribution are first delaminated randomly, then some are delaminated preferentially, thereby producing polymodal thickness distributions. Finally all particles undergo delamination yielding a lognormal thickness distribution.

High-resolution transmission electron microscopy of mixed-layer clays dispersed in PVP-10: a new technique to distinguish detrital and authigenic illitic material

Abstract The results of a new technique for the measurement of the thickness distribution of fundamental particles are reported. The technique is based on high-resolution transmission electron microscopy (HRTEM) of Na-saturated mixed-layer illite-smectite dispersed in polyvinylpyrrolidone (PVP-10). Intercalation of PVP-10 increases the spacing of expandable interlayers and changes the arrangement of particles so that the number of layers per fundamental particle can be counted easily on HRTEM images. The data obtained by HRTEM on PVP-10-intercalated illite-smectite of hydrothermal origin are compared with data from the Pt-shadowing technique. A good agreement between the two methods for the measured thickness distributions, mean thickness and expandability confirms the reliability of the new technique. The same technique is applied to a set of four sedimentary samples with different expandabilities (83-18%). The thickness of illite particles from shales and claystones has a lognormal distribution. Detrital and discrete illite particles can be distinguished from the thickness distribution of authigenic illite.

CdS/ZnS nanocomposites: from mechanochemical synthesis to cytotoxicity issues.

CdS/ZnS nanocomposites have been prepared by a two-step solid-state mechanochemical synthesis. CdS has been prepared from cadmium acetate and sodium sulfide precursors in the first step. The obtained cubic CdS (hawleyite, JCPDS 00-010-0454) was then mixed in the second step with the cubic ZnS (sphalerite, JCPDS 00-005-0566) synthesized mechanochemically from the analogous precursors. The crystallite sizes of the new type CdS/ZnS nanocomposite, calculated based on the XRD data, were 3-4 nm for both phases. The synthesized nanoparticles have been further characterized by high-resolution transmission electron microscopy (HRTEM) and micro-photoluminescence (μPL) spectroscopy. The PL emission peaks in the PL spectra are attributed to the recombination of holes/electrons in the nanocomposites occurring in depth associated with Cd, Zn vacancies and S interstitials. Their photocatalytic activity was also measured. In the photocatalytic activity tests to decolorize Methyl Orange dye aqueous solution, the process is faster and its effectivity is higher when using CdS/ZnS nanocomposite, compared to single phase CdS. Very low cytotoxic activity (high viability) of the cancer cell lines (selected as models of living cells) has been evidenced for CdS/ZnS in comparison with CdS alone. This fact is in a close relationship with Cd(II) ions dissolution tested in a physiological solution. The concentration of cadmium dissolved from CdS/ZnS nanocomposites with variable Cd:Zn ratio was 2.5-5.0 μg.mL(-1), whereas the concentration for pure CdS was much higher - 53 μg.ml(-1). The presence of ZnS in the nanocrystalline composite strongly reduced the release of cadmium into the physiological solution, which simulated the environment in the human body. The obtained CdS/ZnS quantum dots can serve as labeling media and co-agents in future anti-cancer drugs, because of their potential in theranostic applications.

PARTIAL DISSOLUTION OF GLAUCONITIC SAMPLES: IMPLICATIONS FOR THE METHODOLOGY OF K-Ar AND Rb-Sr DATING

The K-Ar dating of glauconite has been used as an important stratigraphic tool for many decades. The application of this technique is limited to pure glauconites, free of detrital contamination by K-bearing phases, often not easy to detect. This study extends the application of isotope dating to the contaminated glauconites and offers a precise technique for detecting the detrital contamination of glauconites.The most common K-bearing detrital contaminants have smaller (K-feldspars, Al-rich dioctahedral micas) or greater (trioctahedral micas) dissolution rates than glauconite in extremely low pH solutions. The differences in the dissolution rates can be applied to evaluate the purity of the glauconite and its crystallization age.The interlaboratory GLO glauconite standard and grain-size fractions separated from glauconitic sandstones of the Paleogene (sample GL) and Jurassic (sample GW8) ages were treated with acid (3M HCl, at 99±2°C) for different reaction times (0.5–7 h) and measured for their apparent isotopic ages.Microporous amorphous silica with large specific surface area is the solid product of the reaction and its content increases with reaction time. The K-Ar dates (apparent ages) of the solid residues increase significantly with reaction time: from 44.6 to 107 Ma for the GL sample and from 125.7 to 394.7 Ma for GW8. The increase is negligible in the case of the GLO standard. The Rb-Sr data of the GL sample were modeled using initial 87Sr/Sr ratios of 0.707–0.709, which resulted in a 29.9–35.8 Ma date for the untreated portions of GL, and ∼42.6 Ma after 7 h of treatment.The increase of isotopic K-Ar date with increasing time of dissolution is interpreted to be a result of increasing concentration of detrital, acid-resistant, K-bearing minerals, observed also with the electron microscope and X-ray diffraction. Probabilistic modeling based on single (K-Ar) or double (K-Ar and Rb-Sr) isotopic systems evaluated the isotopic ages of the detrital and authigenic minerals, and their K2O and Rb concentrations. The crystallization ages computed using these two methods are: 24.0, 26.5, and 32.3 Ma for the GL material, and 117.3–121.8 Ma for the GW8 series.The proposed method based on partial dissolution is a potential tool for evaluating the reliability of glauconite dating.

Structural Evolution of Sputtered Indium Oxide Thin Films

Structural Evolution of Sputtered Indium Oxide Thin Films The indium oxide thin films were deposited at room temperature by reactive magnetron sputtering in the mixture of oxygen and argon on silicon and oxidized silicon substrates. The influence of the oxygen flow in the reactive mixture and post-deposition annealing on the structural properties were investigated. The as deposited In2O3 films showed a dominating randomly oriented nanocrystalline structure of cubic In2O3. The grain size decreased with increasing oxygen concentration in the plasma. Annealing in reducing atmospheres (vacuum, nitrogen and argon), besides improving the crystallinity, led to a partial cubic to rhombohedral phase transition in the indium oxide films.

The Effect of Salivary Gland Extract of Lucilia sericata Maggots on Human Dermal Fibroblast Proliferation within Collagen/Hyaluronan Membrane In Vitro: Transmission Electron Microscopy Study

BACKGROUND: Lucilia sericata maggots are applied to chronic wounds to aid healing when conventional treatments have failed. After their application into a necrotic wound, they potentially influence wound healing with a combination of specific proteinases that are involved in the remodeling of extracellular matrix. These proteases cause changes in fibroblast adhesion and spread upon extracellular matrix protein surfaces, affecting integrity of the protein surfaces—especially fibronectin—while maintaining cell viability. OBJECTIVE: This study focused on in vitro monitoring of the effect of homogenate substances prepared from maggot salivary gland of L sericata on the ultrastructure of human neonatal fibroblasts. METHODS: Collagen/hyaluronan membrane was used as the synthetic substitute of extracellular matrix. The cultured human neonatal fibroblasts B–HNF-1 were seeded on the surface of the collagen/hyaluronan membrane and cultured with maggot salivary gland extract (SGE) at a concentration of 2.4 glands/1 mL. RESULTS: The authors observed increased cell metabolism and protein production (euchromatic nucleus, voluminous nuclear membrane, large reticular nuclei, distended and filled cisterns of rough endoplasmic reticulum, Golgi apparatus with saccules, and vesicles packed with fine fibrillar material) after incubating the cells in culture medium with SGE. CONCLUSION: The authors believe that increased cell metabolism and protein production corresponded with formation of microfibrillar net used for migration of fibroblasts in culture, but mainly for proper production of extracellular matrix. The authors suggest that their results may help explain the effect of SGE on wound healing and support implementation of maggot therapy into human medicine.

Preparation, properties and anticancer effects of mixed As4S4/ZnS nanoparticles capped by Poloxamer 407

Arsenic sulfide compounds have a long history of application in a traditional medicine. In recent years, realgar has been studied as a promising drug in cancer treatment. In this study, the arsenic sulfide (As4S4) nanoparticles combined with zinc sulfide (ZnS) ones in different molar ratio have been prepared by a simple mechanochemical route in a planetary mill. The successful synthesis and structural properties were confirmed and followed via X-ray diffraction and high-resolution transmission electron microscopy measurements. The morphology of the particles was studied via scanning electron microscopy and transmission electron microscopy methods and the presence of nanocrystallites was verified. For biological tests, the prepared As4S4/ZnS nanoparticles were further milled in a circulation mill in a water solution of Poloxamer 407 (0.5wt%), in order to cover the particles with this biocompatible copolymer and to obtain stable nanosuspensions with unimodal distribution. The average size of the particles in the nanosuspensions (~120nm) was determined by photon cross-correlation spectroscopy method. Stability of the nanosuspensions was determined via particle size distribution and zeta potential measurements, confirming no physico-chemical changes for several months. Interestingly, with the increasing amount of ZnS in the sample, the stability was improved. The anti-cancer effects were tested on two melanoma cell lines, A375 and Bowes, with promising results, confirming increased efficiency of the samples containing both As4S4 and ZnS nanocrystals.

Formation of silica aggregates in sorghum root endodermis is predetermined by cell wall architecture and development

Background and Aims Deposition of silica in plant cell walls improves their mechanical properties and helps plants to withstand various stress conditions. Its mechanism is still not understood and silica-cell wall interactions are elusive. The objective of this study was to investigate the effect of silica deposition on the development and structure of sorghum root endodermis and to identify the cell wall components involved in silicification. Methods Sorghum bicolor seedlings were grown hydroponically with (Si+) or without (Si-) silicon supplementation. Primary roots were used to investigate the transcription of silicon transporters by quantitative RT-PCR. Silica aggregation was induced also under in vitro conditions in detached root segments. The development and architecture of endodermal cell walls were analysed by histochemistry, microscopy and Raman spectroscopy. Water retention capability was compared between silicified and non-silicified roots. Raman spectroscopy analyses of isolated silica aggregates were also carried out. Key Results Active uptake of silicic acid is provided at the root apex, where silicon transporters Lsi1 and Lsi2 are expressed. The locations of silica aggregation are established during the development of tertiary endodermal cell walls, even in the absence of silicon. Silica aggregation takes place in non-lignified spots in the endodermal cell walls, which progressively accumulate silicic acid, and its condensation initiates at arabinoxylan-ferulic acid complexes. Silicification does not support root water retention capability; however, it decreases root growth inhibition imposed by desiccation. Conclusion A model is proposed in which the formation of silica aggregates in sorghum roots is predetermined by a modified cell wall architecture and takes place as governed by endodermal development. The interaction with silica is provided by arabinoxylan-ferulic acid complexes and interferes with further deposition of lignin. Due to contrasting hydrophobicity, silicification and lignification do not represent functionally equivalent modifications of plant cell walls.