Thallium fractionation in polluted environmental samples using a modified BCR three-step sequential extraction procedure and its determination by electrothermal atomic absorption spectrometry

Determination of thallium in polluted environmental samples and their extracts obtained by a modified BCR three-step sequential extraction procedure was used to study thallium distribution and mobility in the monitored polluted area affected by acidification (Šobov, Central Slovakia). The results of fractionation applied to 5 soil certified reference materials and 14 environmental samples show that the vast majority of thallium occurred in the residual fraction. This means that highly toxic thallium is strongly entrapped in the parent rock materials remains immobile and its environmental toxicity is therefore reduced. The limit of detection for thallium in the studied fractions was lower than 0.050 mg kg⁻¹, the precision (RSD) of the ultratrace determination of thallium in the studied fractions was better than 17 % and the accuracy of the used method was verified by analyzing certified reference materials. Presented at the XVIIIth Slovak Spectroscopic Conference, Spišská Nová Ves, 15–18 October 2006.     

TERMANAL 2005 — XVII. Conference on Thermal Analysis and Calorimetry

October 2–5, 2005 Congress Center ACADEMIA Stará Lesná, Slovak Republic Guest Editor: Peter Šimon     

Kinetic and thermodynamic treatment of gasification process for some s-triazines

Solid-gas phase transition processes of some triazines were studied from kinetic and thermodynamic viewpoint. DSC measurements and Clausius-Clapeyron equation were used to determine enthalpy values related to these processes. Model-fitting methods (based on Arrhenius, Šatava equations and Šesták-Berggren equations) and model-free methods (based on Ozawa-Flynn-Wall and Kissinger equations) allow to hypothesis R2 mechanism. An attempt to determine the activation parameters (ΔH ^#, ΔG ^#, ΔS ^#) related to these processes was carried out. Accordance between the activation enthalpy values with those of activation energy obtained by means of kinetic methods and with the experimental (DSC) and calculated (Clausius-Clapeyron) enthalpy values was found. This revised version was published online in August 2006 with corrections to the Cover Date.     

Adsorption of cesium on domestic bentonites

Bentonite is a natural clay and one of the most promising candidates for use as a buffer material in the geological disposal systems for spent nuclear fuel and high-level nuclear waste. It is intended to isolate metal canisters with highly radioactive waste products from the surrounding rocks because of its ability to retard the movement of radionuclides by adsorption. Slovak Republic avails of many significant deposits of bentonites. Adsorption of Cs on five Slovak bentonites of deposits (Jelšovy potok, Kopernica, Lieskovec, Lastovce and Dolná Ves) has been studied with the use of batch technique. In the case of Dolná Ves deposit, the mixed-layer illite–smectite has been identified as the main clay component. Natural and irradiated samples, in two different kinds of grain size: 45 and 250 μm have been used in the experiments. The adsorptions of Cs on bentonite under various experimental conditions, such as contact time, adsorbent and adsorbate concentrations have been studied. The Cation Exchange Capacity values for particular deposits drop in the following order: Jelšovy potok > Kopernica > Lieskovec > Lastovce > Dolná Ves. Bentonites irradiated samples with 390 kGy have shown higher specific surface and higher values of the adsorption capacity. Distribution coefficients have been determined for bentonite-cesium solution system as a function of contact time and adsorbate and adsorbent concentration. The data have been interpreted in terms of Langmuir isotherm. The uptake of Cs has been rapid and the adsorption of cesium has increased with increasing metal concentrations. The adsorption percentage has decreased with increasing of metal concentrations. Adsorption of Cs has been suppressed by presence of Ca²⁺ more than Na⁺ cation. Sorption experiments carried out show that the most suitable materials intended for use as barriers surrounding a canister of spent nuclear fuel are bentonites of the Jelšovy potok and Kopernica deposits.     

Preliminary study to prepare a reference material of styrene metabolites – mandelic acid and phenylglyoxylic acid – in human urine

 A preliminary batch of the reference material was prepared by freeze-drying pooled urine samples obtained from healthy persons occupationally exposed to styrene. Tests for homogeneity and stability were performed by determining urine concentrations of mandelic (MA) and phenylglyoxylic acids (PGA). The urinary MA and PGA concentrations were followed over an 8-month period using high performance liquid chromatography (HPLC). No changes of the concentration values were found. Pure PA and PGA from Merck and Fluka, respectively, were used for traceability purposes, because certified or standard reference materials for MA and PGA do not exist. Control material ClinChek-Urine Control (Recipe) was analysed simultaneously. The mean values of MA and PGA compared well with the means of control samples and fell within the control range. The certified values and their uncertainties were evaluated from the results of interlaboratory comparisons, homogeneity (277.0 ± 7.4 mg L⁻¹ for MA and 148.0 ± 4.7 mg L⁻¹ for FGA) and stability tests. The values are unweighted arithmetical averages of accepted results and their uncertainties are combined uncertainties enlarged by coefficient k=1, evaluated from the standard uncertainties of the interlaboratory comparison, homogeneity and stability tests. Received: 17 September 2002 Accepted: 1 November 2002 Acknowledgement This work was supported by the Internal Grant Agency of Ministry of Health of the Czech Republic (Grant NJ/6784–3). Presented at CERMM-3, Central European Reference Materials and Measurements Conference: The function of reference materials in the measurement process, May 30–June 1, 2002, Rogaška Slatina, Slovenia Correspondence to I. Šperlingová     

A new method of evaluation of element pollutant mobility in sediments

The application of a strong chelating agent for the screening test of element mobility in sedimentary systems was investigated. Single-step and sequential extraction procedures were applied to four sediment samples collected from an industrially polluted region of Eastern Slovakia. A sequential extraction procedure (SEP), recommended by the Institute for Reference Materials and Measurements (IRMM), was applied and used as a reference extraction method. A single-step extraction with 0.05 mol dm⁻³ ethylenediaminetetraacetic acid (EDTA) was adapted for sediments when extraction conditions were optimised. The extraction efficiency of the single-step procedure was compared with that of SEP. The contents of elements extracted by Na2EDTA were in good agreement with the sum of the first three steps of the SEP for Fe, Mn, and Co. Na₂EDTA can therefore be considered capable to extract the majority of elements associated with the reducible sedimentary phase — bound to Fe and Mn oxides in the regional geological conditions of the monitored region. Thus, Na₂EDTA extraction of Fe and Mn can serve as an economical, time-saving supplementary test for the IRMM procedure. This paper is dedicated to the memory of Erika Krakovská Presented at the XVIIIth Slovak Spectroscopic Conference, Spišská Nová Ves, 15–18 October 2006.     

Study of the chemical properties of gravitation dust sediments

The chemical properties of the gravitation dust sediment particles depend on their source. Two samples of the gravitation dust sediment have been investigated. The first sample, collected in locality Košice – Vel’ká Ida, near by U.S. Steel Ltd. (a metallurgy plant), represents the metallurgy industry pollutants. The second sample, collected in Košice city, represents the urban dust. Dust sediments particles create a non-homogeneous system. For this reason, the particles size distribution has been studied. On the base of the obtained experimental results one sample was divided into two approximately same mass fractions. The mineralogical composition of the dust particles matrix was determined by DTA, XRD, and SEM-EDS analyses. The total content of the chosen trace risk elements was defined by various AAS methods. The physical–chemical forms of elements in the dust sediment are characterised by different mobility and biotoxicity. The single-step extraction was used for the isolation of various element forms. 1 mol · dm⁻³ NH₄NO₃, 0.05 mol · dm⁻³ EDTA, and 2 mol · dm⁻³ HNO₃ were used as extraction reagents. The content of the elements in extracts was determined by the FAAS method.     

In memoriam

Prof. Ing. Zdeněk Šolc, CSc (21 September 1931–30 September 2006) Prof. Zdeněk Šolc was born in 1931. After finishing his university studies, he joined the University of Pardubice where he remained for more than 50 years. He started to work at the Department of Physical Chemistry. His main fields of interest were: preparation of monocrystals, crystallization from solutions, measuring of physical and chemical properties of solutions. In the 1960's he turned to inorganic technology, studying inoranic pigments and he moved to the Department of Inorganic Technology. In this vast area of science, he achieved his greatest successes, and pigments became his ever-lasting passion up to the end of his life. The research in the field of crystallisation was oriented to development of liquid crystals for use in temperature indication, and materials for integrated circuits; besides that a school of inorganic pigments was formed (M. Trojan, Z. Šolc, D. Brandová) whose main orientation is mixed oxide materials for use in ceramics and enamels. A predominant part of the mentioned research activities was pursued at KAnT in 1990–1996, when the Department was headed by Professor Ing. Zdeněk Šolc. Most of Prof. ŠolcŠs projects were focused on the reactivity of inorganic pigments and powder materials, research of their high-temperature syntheses and rating of their physical and chemical properties. He applied mainly simultaneous thermal analytical techniques: thermogravimetry, differential thermal analysis using dynamic measuring conditions and quasi-isothermal and quasi-isobaric ones, moreover emanation thermal analysis and thermal conductivity measurements. Prof. Zdeněk Šolc was a creative scientist. He published more than 50 scientific papers in international journals and wrote 10 textbooks. He was the author of almost 100 lectures of conferences held in the Czech Republic and foreign countries. He had a silent but a very kind personality and he will be missed very much both by the local and the international communities. Requiescat in pace     

Effect of gamma-irradiation on adsorption properties of Slovak bentonites

One of the basic prerequisites for the use of bentonite as engineering barrier in deep geological repositories for radioactive waste and spent nuclear fuel is their stability against ionizing radiation stemming from radionuclides present in radioactive waste and spent nuclear fuel. The aim of this study was to compare the changes in the adsorption properties of selected Slovak bentonites in relation to uranium fission products (¹³⁷Cs and ⁹⁰Sr), prior to and after irradiation of bentonites with a ⁶⁰Co γ-source and specifying the changes in the structure of Slovak bentonites induced by γ-radiation. The changes in irradiated natural forms of Slovak bentonites and the changes in their natrified analogues and fractions with different grain sizes were studied from five Slovak deposits: Jelšovy potok, Kopernica, Lastovce, Lieskovec and Dolná Ves. The EPR spectra of bentonites from deposits Jelšovy potok and Lieskovec with absorbed doses of 10⁴ and 10⁵ Gy γ-rays showed no changes in the structure of the studied Slovak bentonites. The changes, which in terms of structure destabilization can be considered insignificant, occurred only in bentonites with absorbed doses of γ-radiation as much as 1 MGy. The absorbed dose of 1 MGy γ-radiation did not have an effect on the adsorption of cesium on every studied bentonite. Changes that can also be regarded as insignificant occurred only during strontium adsorption, especially on Fe–bentonite from deposit Lieskovec and Ca–Mg–bentonite from deposit Jelšovy potok, when an increase in the adsorption capacity occurred. Attention should be paid in further research of this topic which would require carrying out experiments on bentonite samples with absorbed doses higher by several orders of magnitude.     

Sol-gel Preparation of Rutile Type Solid Solution in TiO2-RuO2 System

The preparation of rutile type solid solutions in (TiO₂)_x -(RuO₂)_1−x system in the 0≤x ≤0.7 concentration range is described. The single phase solid solutions are formed by controlled nanocrystallization of amorphous gels prepared by the sol-gel method. The kinetics of this crystallization process has been analyzed. It was found that the crystallization does not correspond to the Johnson-Mehl-Avrami model and it can be described by the two-parameter Šesták-Berggren kinetic model. This revised version was published online in August 2006 with corrections to the Cover Date.     

Effect of addition of ameliorative materials on the distribution of As,Cd, Pb,and Zn in extractable soil fractions

The effects of lime, limestone, and zeolite addition on the availability of As, Cd, Pb, and Zn in three contaminated soils were investigated in a pot experiment after four vegetation periods of spring wheat, spring barley, and oat. The results showed different responses of extractable element portions to soil amendment when 0.01 mol dm⁻³ aqueous CaCl₂ was applied as a soil extraction agent. Substantial differences were evident among the investigated elements as well as among the individual soil treatments. Except natural zeolite, the ability of ameliorative materials to redistribute cadmium and zinc from a soil solution into less mobile but labile soil fractions was observed. The lead availability was less affected and the extractability of arsenic even increased in some of the treated pots. Moreover, the availability of arsenic was more affected by different characteristics of experimental soils than by individual soil treatments. It was found that these treatments can be applied neither for multicontaminated nor for all the soil types. The soil treatments had a lower effect on the less mobile soil fractions. Presented at the XVIIIth Slovak Spectroscopic Conference, Spišská Nová Ves, 15–18 October 2006.     

Effect of gamma irradiation on trichromatic values of spices

The effect of γ-irradiation on trichromatic color values L*, a*, and b* was determined in black pepper, oregano, and allspice samples irradiated at average doses from 5 kGy to 30 kGy. Trichromatic values a* measured in methanol extracts of treated spices immediately after the irradiation process were significantly changed, but the subsequent storage of allspice and oregano caused much more distinctive alteration of these color values than the irradiation itself. Additionally, the differences in redness between the reference (non-irradiated) allspice and oregano samples and samples treated by γ-radiation gradually disappeared during the storage period. On the contrary, the post-irradiation storage of black pepper samples did not reveal any changes of a* values. Presented at the XVIIIth Slovak Spectroscopic Conference, Spišská Nová Ves, 15–18 October 2006.     

Mobility of important toxic analytes in urban dust and simulated air filters determined by sequential extraction and GFAAS/ICP-OES methods

The modified BCR three-step sequential extraction procedure has been applied to homogenized urban dust samples and to simulated air filters loaded with the prepared urban dust via the wet deposition procedure. This work has been focused on comparative study of the distribution of trace elements in both samples and evaluation of the factors influencing the reliability of results with respect to the proposed extraction procedure. Extracted chemical fractions were analyzed by ICP-OES and GFAAS depending on the concentration levels of investigated trace elements As, Cd, Cr, Mn, Ni, and Pb, selected according to their adverse effect on the human health. Statistically evaluated results indicate significant differences between the extracted portions of analytes in urban dust and simulated air filters, where the mobility of some analytes in simulated air filters was higher than that in urban dust samples. The impact of surfactant Triton X-100 (0.05 vol. %) on the extraction procedure was also investigated. Presented at the XVIIIth Slovak Spectroscopic Conference, Spišská Nová Ves, 15–18 October 2006.     

The Effect of an Electric Field on Reaction Fronts in Autocatalytic Systems

The effects of applying a constant electric field E to an ionic autocatalytic reaction with a general power p (p≥1) are discussed through a consideration of the equations for the corresponding travelling waves. It is shown that, when the ratio of diffusion coefficients D of autocatalyst and substrate is less than some value D₀ (which depends on p), the effect of a negative electric field is to increase the wave speed of the reaction front over its field-free value. This is in contrast to previous results for cubic autocatalysis (p=2) [J.H. Merkin and H. Ševčíková. J. Math. Chem. 25 (1999) 111.] for D>D₀, where the effect is to decrease the wave speed. This feature, seen in the numerical solutions of the travelling wave equations, is confirmed by an expansion for small E and in an asymptotic analysis for p large     

Application of non-isothermal cure kinetics on the interaction of poly(ethylene terephthalate) — Alkyd resin paints

Samples of paint (P), reused PET (PET-R) and paint/PET-R mixtures (PPET-R) were evaluated using DSC to verify their physical-chemical properties and thermal behavior. Films from paints and PPET-R are visually similar. It was possible to establish that the maximum amount of PET-R that can be added to paint without significantly altering its filming properties is 2%. The cure process (80–203°C) was identified through DSC curves. The kinetic parameters, activation energy (E _a) and Arrhenius parameters (A) for the samples containing 0.5 to 1% of PET-R, were calculated using the Flynn-Wall-Ozawa isoconversional method. It was observed that for greater amounts of PET-R added, there is a decrease in the E _a values for the cure process. A Kinetic compensation effect (KCE), represented by the equation InA=−2.70+0.31E _a was observed for all the samples. The most suitable kinetic model to describe this cure process is the autocatalytic Šesták-Berggreen, model applied to heterogeneous systems.     

Crystallization kinetic of fluoro- zirconate glasses by non-isothermal analysis

Fluoride glasses have been extensively studied due to their high transparency in the infrared wavelength. The crystallization kinetics of these systems has been studied using DTA and DSC techniques. Most of the experimental data is frequently investigated in terms of the Johnson-Mehl-Avrami (JMA) model in order to obtain kinetic parameters. In this work, DSC technique has been used to study the crystallization of fluorozirconate glass under non-isothermal conditions. It was found that JMA model was not fit to be applied directly to these systems, therefore, the method proposed by Málek has been applied and the Šesták-Berggren (SB) model seems to be adequate to describe the crystallization process. This revised version was published online in July 2006 with corrections to the Cover Date.     

Effect of selenium oxidation state on cadmium translocation in chamomile plants

Syntheses and spectral characteristics of cadmium(II) compounds (CdSeO₄, CdSeO₃, and Cd(NCSe)₂(nia)₂) containing selenium in oxidation states (VI), (IV), and (-II) are described. In Cd(NCSe)₂(nia)₂, nicotinamide (nia) and selenocyanate anions are bonded to Cd atom as N-donor monodentate ligands. Nicotinamide is coordinated through the ring nitrogen atom. The effects of these selenium compounds as well as Cd(NCS)₂(nia)₂ on the growth and Cd accumulation in roots and shoots of hydroponically cultivated chamomile plants (cultivar Lutea) were studied. In the applied concentration range (12–60 μmol dm⁻³) Cd(NCS)₂(nia)₂ affected neither the length nor the dry mass of roots and shoots. Other compounds applied at 24 μmol dm⁻³ and 60 μmol dm⁻³ significantly reduced dry mass of roots and shoots. Selenium oxidation state in the cadmium compounds affected Cd accumulation in plant organs as well as Cd translocation within the plants, which was reflected in the values of bioaccumulation (BAF) and translocation factors (S/R). Cd amount accumulated by shoots was lower than that in the roots. The highest BAF values determined for Cd accumulation in shoots were obtained with CdSeO₄. Substitution of S with Se in the Cd(NCX)₂(nia)₂ (X = Se or S) caused an increase of Cd translocation into the shoots. Presented at the XVIIIth Slovak Spectroscopic Conference, Spišská Nová Ves, 15–18 October 2006.     

Modification and characterization of montmorillonite fillers used in composites with vulcanized natural rubber

Parent Ca-montmorillonite (Jelšovy Potok, Slovakia, Ca-JP) and Na-montmorillonite Kunipia-F (Japan, Na-KU) were ion-exchanged with octadecyltrimethylammonium (ODTMA) cations. Characteristics of the samples were studied by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (IR) and thermogravimetry (TG). Surface areas were measured by sorption of N₂ and ethyleneglycol monoethyl ether. Scanning electron microscopy photographs (SEM) were used to characterize the texture of samples. The XRD patterns show that, upon intercalation, the basal spacing of montmorillonite is expanded and corresponds to the pseudotrimolecular arrangement of organic cations in the interlayers. The IR spectra of organically modified montmorillonite show C-H stretching and bending bands of both CH₃ and CH₂ groups in the 3000–2800 cm⁻¹ and 1500–1400 cm⁻¹ region, respectively. Modification of montmorillonite by organic cations decreased the hydrophilicity of their mineral surface and adsorbed water evaporated at lower temperatures. The SEM photographs reveal a tendency towards lump formation and agglomeration of the ODTMA-montmorillonite particles. The modification introducing organic moiety lead to a substantial decrease in the surface area of both montmorillonites; however, it remained remarkably high, being at the level typical for silica. Completely characterized fillers were used to prepare rubber compositions with enhanced physical properties, as described in Hrachová et al. (2008).     

Coupling of microwave induced plasma optical emission spectrometry with HPLC separation for speciation analysis of Cr(III)/Cr(VI)

Feasibility and limitations of direct coupling of high performance liquid chromatographic (HPLC) separation to microwave induced plasma (MIP)-optical emission spectrometry (OES) for elementspecific detection was tested and compared to inductively coupled plasma (ICP)-optical emission spectrometric detection on the basis of the Cr(III)/Cr(VI) speciation analysis of water samples. Coupling was performed by a hydraulic high pressure nebulizer (HHPN) radiative-heating/watercooling interface which provides about 20 % and 80 % aerosol yield in the case of helium and argon carrier gases, respectively. Desolvation efficiency of aqueous solutions was approximately 80 %. Applying the ion-pair HPLC separation, the organic eluents and reagents in the MIP cause a 50–75 % signal suppression for Cr(VI) and 25–50 % for Cr(III). In a pure aqueous solution the MIP Cr(VI) signal was by 20 % lower than that of Cr(III). These effects were lower using the ICP source, but they cannot be neglected. Easily ionizable matrix elements (Na, Ca) can cause 70 % signal suppression in the MIP, and 20 % in the ICP. Therefore, species dependent calibration is required in both cases. In the case of HPLC detection by MIP-OES, the detection limit was 13 ng for Cr(III), and 18 ng for Cr(VI). Using the ICP-OES detection, the detection limit was 0.2 ng for Cr (III) and 0.4 ng for Cr (VI). The linear dynamic ranges in both cases were two orders of magnitude. Presented at the XVIIIth Slovak Spectroscopic Conference, Spišská Nová Ves, 15–18 October 2006.