LEAFS determination and concentration of metals in Great Lakes ecosystem

A Laser-Excited Atomic Fluorescence Spectrometric (LEAFS) method for Tl determination has been extended to investigate the direct determination (without preconcentration nor acid digestion) of total Pb, for which the method validation was successfully achieved by using a standard reference material as well as many spike recoveries of digested and undigested unfiltered water samples. The method was applied to study total and dissolved Pb in many water columns collected from different stations in Lake Ontario. Dissolved Pb was found to be about twice as much as dissolved Tl, and total Pb about seven times higher than total Tl. Seventy five percent of Pb is in particulate form versus 11% for Tl. Also, a simple cold dissolution procedure using HNO(3) and HF (not a hot acid digestion) is proposed to "liquefy" sediments in a form suitable for LEAFS analysis and was used to analyze a sediment core, where pore water samples were also collected. The interaction dynamics of Tl within the natural environment of a water/pore water/sediment system from Lake Erie was assessed. The calculations of fluxes suggest a strong similarity between Tl and Cd geochemical transport. The paper also presents for the first time a genuine sediment pore water profile of Tl concentration, which ranged from sub- to 40 ng/l and which was directly determined by LEAFS.     

Release of137Cs from anoxic lacustrine sediment measurement and formulation

Low level measurements of¹³⁷Cx in lacustrine sediment and its pore water are possible to activity as low as 10 mBq. From this data, the flux of¹³⁷Cs through the sediment and to the bottom water can be estimated. The value of the diffusion coefficient in the pore water follows from separate radiotracer experiments.     

Surface tension as a function of temperature for some molten metals

Results are given for Sn, In, and Ge from the melting points up to 1700 C, for Pb up to 1400 C, for Tl up to 1100 C, for Bi up to 1300 C, and for Cd up to 600 C. In every case the surface tension is a linear function of temperature. Estimates are made of the critical temperatures of Cd and Ge. It is shown that deductions on the structure of the melts can be drawn from surface-tension data.     

226Ra, 228Ra and 210Pb Isotopes in Some Water Samples of Mines

A method for the determination of ²²⁶Ra, ²²⁸Ra and ²¹⁰Pb in water samples of mining regions by measuring the and intensities with the help of a liquid scintillation counter is presented. The high-energy part of the -particle spectrum emitted by ²¹⁰Bi is used for the determination of ²¹⁰Pb content in the samples. An attempt is also given to explain the radioactive disequilibrium between ²²⁶Ra and ²¹⁰Pb in the samples investigated.     

Kinetic Spectrophotometric Determination of Total Iron in Natural Water by Flow Injection Analysis Using On-Line Preconcentration

A new flow injection catalytic spectrophotometric method for on-line preconcentration and determination of total iron in natural water is described. The method is based on a combination of iron-catalyzed oxidation of diaminoditolyl by potassium bromate and the use of on-line preconcentration of iron onto 8-hydroxy-quinoline immobilized on silica gel. The corresponding calibration graph is linear over the range of 2.0–110ngmL^–1 for Fe(III) using a time-based technique for 5min preconcentration. The relative standard deviation of 11 measurements of 60ngmL^–1 Fe(III) was 0.67%. The method was applied to the determination of iron in natural water. The results obtained by the proposed method were compared with those obtained by ICP-AES. The t-test showed no significant differences between the two methods at a confidence level of 95%.     

Accurate determination of lead in wines by inductively coupled plasma mass spectrometry

Summary The capability of inductively coupled plasma mass spectrometry (ICP-MS) for Pb determinations in wine samples is studied. An evaluation is made of the signal behaviour in aqueous ethanolic medium. The effect of preliminary sample preparation on signal suppression or enhancement is investigated in conjunction with the ability of internal standardization to correct for it. As a result, an accurate and precise method of analysis is described in which the sample preparation is limited to a 10-fold dilution and external calibration is applied for quantitation. A detection limit of 0.2 g 1^–1 Pb in wine is achieved. The Pb content of ten different wines was found to range around 40 g 1^–1 with extreme values of 1.63 and 58.8 g 1^–1.     

Evidence of Ternary Inclusion Complexes Formation Using Factorial Design and Determination of Their Formation Constant

Evidence of the interaction among the [PbAc]⁺ and[PbEDTA]^-2 with the -cyclodextrin (-CD)is shown, using a 2⁴ factorial design. The factors used werethe [Pb(II)], [-CD], [Ac^-] and [EDTA] concentrationsat pH = 6.2. The statistical results indicate that the changes inchemical response for these species are associated to theinteraction among these factors. Spectrophotometric andelectrochemical studies were undertaken to assess the interactions.The equilibrium constants for inclusion complexes were determinedFor -CD-[PbAc]⁺ and -CD-[PbEDTA]^-2.     

Luminescence properties of acridine dyes in micellar sodium dodecyl sulfate solutions containing thallium ions

The effect of external heavy Tl^I ion on the luminescence properties of Trypaflavine, Acridine Yellow, and Acridine Orange solubilized in sodium dodecyl sulfate micelles was studied. An increase in the concentration of thallium ions results in a decrease in the intensity of prompt fluorescence, an increase in the intensity of delayed fluorescence, the appearance of phosphorescence at 20 °C, and a shortening of the triplet state lifetime of the dyes. The effective and micellar Stern—Volmer constants of fluorescence quenching of the dyes by thallium ions were determined. The effective and micellar quenching rate constants of triplet states of the dyes by Tl(i) ions and lifetimes of the triplet states of the dyes in the absence of thallium ions were calculated on the basis of kinetic measurements.     

Dehydration-dehydrogenation of 1- and 2-butanols on lanthanide oxide catalysts

Catalytic decomposition of 1- and 2-butanols on the rare earth oxides CeO₂, Pr₆O₁₁, and Me₂O₃ (Me=La, Sm, Eu, Dy, Ho and Yb) has been studied. Dehydration-dehydrogenation selectivity of these oxides was analyzed from the point of view of the fractional selectivity (S_F). For the decomposition of 2-butanol and the product distribution on the lanthanide oxides, preferential orientation to Hofmann olefin as well as a cis/trans ratio slightly higher than that of the equilibrium value is observed.

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1- 2- CeO₂, Pr₆O₁₁ Me₂O₃ (Me=La, Sm, Eu, Dy, Ho Yb). - (S_F). 2- , , / .

     

Kinetics of edta catalyzed oxidation of I? by Cr(VI)

The activity of various iron-containing ore catalysts during hydrogenation of Kansk-Achinsk lignite into liquid products in H-donor solvent (tetraline) has been studied. Ore samples contained pyrite, hematite and magnetite minerals. The most active appear to be pyrite samples. The catalytic effect of ore systems is, apparently, associated with the fact that during hydrogenation more active than tetraline H-donors are formed due to the hydrogenation of polycyclic aromatic molecules produced by thermal destruction of lignite.

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- H- . , , . , . , , , , , .

     

Gas phase thermolysis of phenylazoethane

The pyrolysis of phenylazoethane has been studied in a stirred-flow system using cyclohexene as carrier gas at sub-ambient pressures, in the temperature range of 380–416°C. The activation energy is examined in relation to the C–N bond dissociation energy and the heat of formation of the phenyldiazenyl radical.

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, - 380–416°C. C–N .

     

Destruction of organic materials by pressurized microwave digestion

Summary This paper describes the utility of pressurized microwave digestion (up to 85 bar) for a broad spectrum of organic materials (blood, urine, milk powder, tissues). The quality of the sample solution was tested by the determination of Pb, Cd and Cu (additionally Ni and Co in some of the matrices) by anodic stripping voltammetry (DPASV) and Hydride Generation AAS (HAAS) for As. It is clearly shown that no universal cooking recipe can be given. The necessary oxidation potential is very dependent on the type of organic matrix and therefore the use of acid combinations (HNO₃/HClO₄/H₂SO₄) is generally necessary to obtain adequate solution of the sample. In some cases the power of the microwave oven was not high enough to digest two samples simultaneously. (Significant differences in the ease of solution are shown in the digestion of one or two samples). Some important improvements for sample preparation, such as moistening the powdered material with water and mixing well with the acid used before closing the digestion vessel etc., are also given.Dedicated to Professor Dr. Wilhelm Fresenius on the occasion of his 80th birthday     

Solid-liquid equilibrium of the phenanthrene-fluorene system

The solid-liquid equilibrium of the phenanthrene-fluorene system was investigated by differential thermal analysis. Supplementary measurements were applied too: crystal decay temperature examination and melting point examination with a Boetius microscope. The investigated system forms a stable solution with a minimum at 58 mole% of phenanthrene and a temperature of 95.5°.

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Zusammenfassung Das fest-flüssig-Gleichgewicht des Systems Phenantren-Fluoren wurde durch die Differentialthermoanalyse untersucht. Als ergänzende Messungen wurden eingesetzt: die Untersuchung der Kristallzerfallstemperatur und die Prüfung des Schmelzpunktes mit dem Mikroskop nach Boetius. Das untersuchte System bildet eine stabile Lösung mit einem Minimum bei 59 Mol% Phenantren und einer Temperatur von 95.5°C.

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Résumé L'équilibre solide-liquide du système phénanthrène-fluorène a été étudié par analysethermique différentielle. Des essais complémentaires ont également été effectués: détermination de la température de disparition des cristaux et détermination du point de fusion au microscope suivant Boetius. Le système étudié forme une solution stable avec un minimum à 58 mol% de phénanthrène et une température de 95.5°.

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- -. . 5S .% 95.5°.

     

Determination of liquid vapour adsorption and desorption on and from solids by means of the derivatograph II

Studies of water adsorption and desorption on silica gel with a modified derivatograph are described. The dynamic gas chromatography step profile method was used to determine isotherms of adsorption and desorption from the TG curve. The obtained isotherms agree with those from other methods. The properties of surface liquid layers can be investigated by this method.

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Zusammenfassung Die Untersuchung der Adsorption und Desorption von Wasser an Silikagel mittels eines modifizierten Derivatographen wird beschrieben. Die dynamische gaschromatographische Stufenprofilmethode wurde zur Bestimmung der Ad- und Desorptionsisothermen aus den TG-Kurven herangezogen. Die erhaltenen Isothermen stimmen gut mit denen nach anderen Methoden bestimmten überein. Die Eigenschaften flüssiger Oberflächenschichten können mit dieser Methode untersucht werden.

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. . , . .

     

Iodometric determination of sulphate by a direct thermometric method

A thermometric method has been developed for the determination of sulphate after direct or indirect conversion to chromate. The chromate equivalent to sulphate is determined by direct injection enthalpimetry (DIE) using K1 as a reagent, by measuring the temperature change due to the exothermic reaction taking place. The temperature change is proportional to the concentration of sulphate originally present. The method is suitable for the determination of as low as 10^–4 M sulphate concentration, which means an increase in sensitivity of about tenfold in comparison with that of the thermometric method based on the reaction of sulphate with barium.

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Zusammenfassung Eine thermometrische Methode wurde zur Bestimmung von Sulfat nach direkter oder indirekter Umsetzung zu Chromat entwickelt. Das dem Sulfat äquivalente Chromat wurde mittels direkter Injektionsenthalpimetrie (DIE) unter Anwendung von KI als Reagenz bestimmt, indem die infolge der sich abspielenden exothermen Reaktion auftretende Temperaturänderung gemessen wurde. Die Temperaturänderung ist der Konzentration des ursprünglich vorhandenen Sulfats proportional.Die Methode eignet sich zur Bestimmung von Sulfatkonzentrationen in der Größenordnung von 10^–4 M, was eine etwa zehnfache Erhöhung der Empfindlichkeit im Vergleich zu jener der auf der Reaktion von Sulfat mit Barium beruhenden thermometrischen Methode bedeutet.

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Résumé On a mis au point une méthode thermométrique pour le dosage des sulfates, après conversion directe ou indirecte en chromate. Le dosage du chromate équivalent au sulfate s'effectue par enthalpimétrie d'injection directe en prenant l'iodure de potassium comme réactif et en mesurant les variations de température dues à la réaction exothermique qui se produit. La variation de température est proportionnelle à la concentration en sulfate initialement présent.La méthode se prête au dosage de concentrations en sulfate de l'ordre de 10^–4 M, ce qui signifie que la sensibilité est augmentée de dix fois comparativement à celle de la méthode thermométrique utilisant la réaction au sulfate de baryum.

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. , , , , , . . 10^–4 M, , .

     

Application of the microwave oven to the pretreatment of macrosamples in environmental radioactivity monitoring

In order to reduce the sample pretreatment in the measurements of - and -emitter radionuclides in environmental analysis, we present the application of the microwave oven to dry different environmental macrosamples such as vegetables, milk, meat, fish, soil and sediment. We have also studied this technique to evaporate water (rain water and seawater) and to optimize acid digestion of sediments. The results show that the microwave oven gives good results for drying environmental macrosamples, for evaporating water samples when applied in acid atack. With the porposed procedures, time of analysis shortened dramatically.     

Structure of amorphous Fe(III) hydroxides and their ageing products

X-ray analysis has revealed that at pH=7.5–12.0 similar amorphous Fe(III) hydroxides are formed. Their structural peruliarity is the presence of local regions with ordered arrangement of atoms typical for -FeOOH in the volume of primary particles. Ageing at pH=7.5 and 353 K leads to structure rearrangement to -Fe₂O₃.

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pH 7,5–12,0 Fe(III). , -FeOOH. pH 7,5 353 -Fe₂O₃.

     

Photolysis of alkylperoxy radicals frozen out from the gas phase

Photolysis of alkylperoxy radicals with 250 nm light has been studied and proposed for investigation of heterogeneous-homogeneous reactions by freezing out radicals from the gas phase and their ESR identification. Using amine decomposition reaction in the presence of O₂ as an example, we have shown that photodissociation of frozen peroxy radicals can be used to reduce the structure of initial alkyl radicals.

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- 250 . , .

     

An analysis of the possible causes of apparent compensation effects when investigating a substance under varying experimental conditions

The major causes leading to the apparent compensation effect (lgA=aE+b) at the thermal decomposition of one and the same substance in a series of experimental conditions (varying of the mass of the sample, of the heating rate, of disperseness, and at different distances from the equilibrium) were discussed. It was found that the appearance of a compensation effect at the study of the thermal decomposition of one and the same substance demonstrates the incorrect setup of the experiment, resulting in erroneous values calculated for the kinetic parameters.

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Zusammenfassung Die Hauptursachen, welche zum scheinbaren Kompensationseffekt (lgA=aE+b) der thermischen Zersetzung ein und derselben Substanz führen, wurden unter verschiedenen Versuchsbedingungen untersucht: unter Änderung der Probenmasse, der Aufheizgeschwindigkeit, der Dispersität und der Entfernung vom Gleichgewicht. Es wurde festgestellt, daß das Auftreten eines Kompensationseffekts bei der Untersuchung der thermischen Zersetzung ein und derselben Substanz auf die unrichtige Durchführung des Experiments hinweist, die zur Berechnung falscher Werte der kinetischen Parameter führt.

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Résumé On a étudié les causes principales de l'effet de compensation apparent (lgA=aE+ +b) lors de la décomposition thermique de la même substance dans différentes conditions expérimentales, en faisant varier notamment la masse du prélèvement, la vitesse du chauffage, la dispersion et l'écart à l'équilibre. On a trouvé que l'apparition d'un effet de compensation lors de l'étude de la décomposition thermique de la même substance résultait de l'exécution incorrecte de l'expérience qui mène à des valeurs fausses lors du calcul des paramètres cinétiques.

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, (lg A=aE+b) : , , , . , , .