Innovative characterization, monitoring and sensor technologies for environmental radioactivity at USDOE sites

The mission of the U. S. Department of Energy Office of EnvironmentalManagement (EM) is to clean up its contaminated sites from the past productionof nuclear weapons. Within EM, the Office of Science and Technology (OST)is responsible for providing a full range of science and technology resourcesneeded to support resolution of EM cleanup and long-term environmental stewardshipproblems. This responsibility includes implementation of a technology developmentpathway from basic research to development, demonstration, and deploymentof scientific and technological solutions needed by DOE sites. One OST Programis the Characterization, Monitoring, and Sensor Technology Crosscutting Program(CMST-CP), which aims to provide innovative technologies (i.e., faster, better,cheaper, and/or safer) for environmental characterization and monitoring.This paper describes several technologies that CMST-CP has supported for developmentwith significant benefits realized or projected over the baseline characterizationand monitoring practices. Examples of these technologies include mapping ofsubsurface radioactivity using Cone Penetrometer and drilling techniques;a Rapid Liquid Sampler for Sr, Ra, Tc, and Cs using 3M Empore Rad Disks;Long-Range Alpha Detectors; a Compact High Resolution Spectrometer; BetaScintfor determination of Sr in soil; Laser-Induced Fluorescence Imaging techniquesfor mapping U on surfaces; the Environmental Measurements While Drilling System;and the Expedited Site Characterization methodology.     

Mechanism of isotope exchange of dihydrogen with liquid water catalyzed by hydroxide ions

In the analysis of the reaction between dissolving hydrogen and aqueous alkali hydroxide solutions the interaction of hydrogen with the molecular ion (H₃O₂)^– should be studied. This interaction is analyzed by the interacting bonds method. The activation energy (E_a) is estimated.

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, (H₃O₂)^–. . (E_a).

     

New instruments and methods for enthalpimetric analysis and calibration

A review is given of recently developed instruments used in thermometric analysis and new methods of direct injection enthalpimetry.In the past two years, several types of Tronac (Orem, Utah) and Setaram (Lyon, France) calorimeters have been developed. A new mixing cell construction led to development of a flow instrument for automated thermometric analyses (Technicon, Tarrytown N. Y.). A new type of Hungarian instrument, Ditermanal (Orion, Budapest) permits arbitrary analyses.At the Technical University in Brno, small table twin isoperibol instruments allowing the direct analyses of solid samples have been developed. The use of PTC thermistors and a calibration device improved the accuracy of measurements.Many new methods of silicate and lime analysis, water determination, etc. have been elaborated.

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Zusammenfassung Eine Übersicht über die zur thermometrischen Analyse eingesetzten, entwickelten Instrumente und neuen Methoden der Direkt-Injektion Enthalpimetrie wird gegeben.In den zwei vergangenen Jahren wurden verschiedene Kalorimetertypen TRONAC (Orem, Utah) und SETARAM (Lyon, France) entwickelt. Eine neue Mischzellenkonstruktion ermöglichte es ein Durchflussinstrument für automatische thermometrische Analysen (TECHNICON, Tarrytown, N. Y.) zu entwickeln. Ein neuer ungarischer Instrumententyp, DITERMANAL (ORION, Budapest), ermöglicht die Durchführung von Schiedsanalysen.An der Technischen Universität Brno wurden kleinen Zwillings-Isoperibol-Tisch Instrumente entwickelt, welche auch die direkten Analysen fester Proben ermöglichen. Der Einsatz von PTC-Thermistoren und einer Eichvorrichtung erhöhte die Messgenauigkeit.Viele neue Methoden der Silikat- und Kalkanalyse, Wasserbestimmungen usw. wurden erarbeitet.

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Résumé On passe en revue les instruments récemment mis au point et utilisés en analyse thermométrique ainsi que les nouvelles méthodes d'enthalpimétrie par injection directe.Dans les deux dernières années, divers types de calorimètres ont été mis au point: TRONAC (Orem, Utah) et SETARAM (Lyon, France). La réalisation d'une nouvelle cellule de mélange a permis de mettre au point un appareil à flux pour les analyses thermométriques automatiques (TECHNICON, Tarrytown, N. Y.). Un nouveau type d'instrument hongrois, DITERMANAL (ORION, Budapest) permet d'effectuer des analyses arbitrales.A l'université technique de Brno de petites tables instruments jumeaux isopériboliques permettant aussi d'effectuer des analyses directes des corps solides ont été réalisés. L'application de thermistors PTC et un dispositif pour l'étalonnage augmentent l'exactitude des mesures.Des méthodes nouvelles nombreuses pour l'analyse des silicates, des pierres calcaires, de l'eau, etc., ont fait l'objet d'études.

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, . (, ) (, ). (H, , -). (, ) . , . . , , .

     

Rapid Separation of Plutonium in Environmental Samples Using an Anion Exchange Resin Disk

A rapid analytical method of Pu in environmental samples by alpha-ray spectrometry and high-resolution inductively coupled plasma mass spectrometer (HR-ICP-MS) using a 3M Empore anion exchange resin disk for solid phase extraction has been developed. A trace amount of Pu was quantitatively adsorbed with an Empore anion exchange resin disk (47 mm diam.) at a flow rate of 150–200 ml/min from 8M HNO₃ sample solution. The disk was washed with 10 ml of 8M HNO₃ and 12 ml of 9M HCl and then the Pu was quantitatively eluted with 15 ml of 1M HNO₃/0.03M ascorbic acid solution. The time needed to separate Pu from the sample solution with the present method was about 20 minutes. The separated Pu was determined with alpha-ray spectrometry and HR-ICP-MS. The present method was applied to the determination of Pu in the certified reference material (IAEA-135) and the environmental soil sample. The analytical results were almost in good agreement with the literature values.     

Calorimetric studies of aluminosilicate catalysts heats and entropies of cumene adsorption on cation substituted metakaolinite

Differential heats of cumene adsorption at 293 K on Ca-, Sr- and Ba-substituted metakaolinites at surface coverages up to 0.1 have been measured on a Calvet microcalorimeter. The presence of two energetically different adsorption centers are shown to be determined by the nature of the exchanged cation; the adsorption heats decrease in the sequence Ba, Sr, Ca, Mg.

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293 Ca-, Sr, Ba- 0.1. . , Ba, Sr, Ca, Mg.

     

Kinetics of phase transformations in Cu-Al and Cu-Zn-Al alloys

The non-isothermal kinetics of the solid-state reactions taking place in Cu-Al and Cu-Zn-Al alloys were studied by DTA and X-ray measurements. It was found that the degree of conversion, which represents the change in the reacting system, is a function of the area increase in the DTA peak. The kinetic analysis shows that DTA is a useful method for the study of formal kinetic laws. From thef() functions, conclusions on the mechanism of the phase transformations can be drawn.

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Zusammenfassung Die nicht-isotherme Kinetik von in Cu-Al und Cu-Zn-Al-Legierungen verlaufenden Festkörperreaktionen wurden mittels DTA und Röntgenmessungen untersucht. Es wurde festgestellt, daß die Zunahme der Fläche des DTA-Peaks abhängig von dem die Veränderungen im Reaktionssystem repräsentierenden Konversionsgrad ist. Die kinetische Analyse zeigt, daß die DTA eine nützliche Methode zur Untersuchung der formalen kinetischen Gesetzmäßigkeiten ist. Aus den Functionenf() können Schlußfolgerungen hinsichtlich des Mechanismus der Phasenübergänge gezogen werden.

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, Cu-Al Cu-Zn-Al. , , , . . f() .

     

Kinetics of reduction of magnesium sulfate by carbon oxide

The thermodynamic analysis and the results of thermogravimetric investigation of the reduction of magnesium sulfate by carbon oxide are reported.The isothermal experiments were carried out in the temperature range 640 to 675°. A shrinking-core model was found to fit the reaction rate. An activation energy of 209.7±8.6 kJ/mol was obtained.

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Zusammenfassung Es wird über thermodynamische Analyse und Resultate einer thermogravimetrischen Untersuchung der Reduktion von Magnesiumsulfat mit Kohlendioxid berichtet. Die isothermen Experimente wurden im Temperaturbereich 640 bis 675° durchgeführt. Zur Erklärung der Reaktionsgeschwindigkeit wurde eine Shrinking-Modell gefunden. Es wurde eine Aktivierungsenergie von 209.7±8.6 kJ/mol erhlten.

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. 640–675°. , . 209,7±8,6 /.

     

Electronic influence of water adsorbed on ZnO in H2 and Co oxidation

In this paper we calculate the effect of surface OH/OH^– on the simultaneous adsorption of H₂ and O₂ on ZnO. A quantitative comparison between H₂ and CO oxidation rates shows that the two mechanisms are similar for the same water recovery on ZnO.

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OH/OH^– H₂ O₂ ZnO. H₂ CO , ZnO.

     

Oxidative polymerization of durene and diphenyl oxide in the presence of palladium(II) and heteropolyacids

The possibility of obtaining tetramers from durene or diphenyl oxide in the presence of H₅PMo₁₀V₂O₄₀, a reversible oxidant, and palladium acetate as catalyst is demonstrated.

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— H₅PMo₁₀V₂O₄₀ .

     

Thermal decomposition of Cr(III) complexes with urea and thiourea

The thermal decompositions of Cr(III) complexes with urea and thiourea were investigated. The courses of the decompositions were found to be anion- and ligand-dependent. Suggestions for a mechanism of decomposition of these complexes are presented. The final product of decomposition of the complexes investigated was chromium(III) oxide (Cr₂O₃).

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Zusammenfassung Die thermische Zersetzung der Komplexe von Cr(III) mit Karbamid und Thiokarbamid wurde untersucht. Der Verlauf der Zersetzung wurde für Anionen- und Liganden-abhängig gefunden. Vorstellungen über eine mechanische Zersetzung dieser Komplexe werden gegeben. Das Endprodukt der Zersetzung der untersuchten Komplexe war jeweils Chrom(III)oxid (Cr₂O₃).

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Résumé On a étudié la décomposition thermique des complexes du chrome(III) avec l'urée et la thiourée. On a trouvé que le processus de la décomposition dépend de l'anion et du ligand. On propose un mode de décomposition mécanique pour ces complexes. Le produit final de la décomposition des complexes étudiés est l'oxyde de chrome(III), Cr₂O₃.

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Cr (111) . , . . (111) (Cr₂O₃).

     

Distribution of components in the rare earth ammonia synthesis catalysts and effect of additives

The distribution of components in the HG-1 ammonia catalyst promoted by rare earth oxide (successfully developed by the authors) was analyzed by electron microprobe photography. The results enable us to explain the effect of additives upon the activity as well as the remarkably high lifetime of catalyst.

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HG-1, ( ) , . , .

     

Some peculiarities of coke formation and burning on catalysts for reforming

Presence of two maxima on the DTA curves of coked catalysts is attributed to the metal-catalyzed oxidation of less polymerized coke in a higher temperature region.

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.

     

Kinetics and mechanism of the oxidation of bis(acetylacetonato)-cobalt(II) by cumene hydroperoxide in the presence of pyridine

Stoichiometric reaction of bis(acetylacetonato) cobalt(II) with cumene hydroperoxide in chloroform solutions containing added pyridine has been studied by the PMR method.

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() Co(II) , .

     

Solid state reaction between dichromates and oxalates

The thermal investigation of the reaction taking place between dichromates and oxalates in the solid state has been done taking two systems of potassium dichromate-potassium oxalate and sodium dichromate-sodium oxalate. The techniques employed include thermogravimetry, differential thermal analysis, infrared spectroscopy and X-ray diffraction studies. The results indicate a stoichiometric reaction of dichromate and oxalate in 11 ratio to give the corresponding chromate as the sole product.

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Zusammenfassung Anhand der Systeme Kaliumdichromat-Kaliumoxalat bzw. Natriumdichromat-Natriumoxalat wurde eine thermische Untersuchung der Festkörperreaktion zwischen Dichromaten und Oxalaten durchgeführt. Dazu wurden thermogravimetrische, dififerentialthermoanalytische, IR-spektroskopische und Röntgendiffraktionsverfahren angewendet. Im Ergebnis zeigte sich eine stöchiometrische Reaktion von Dichromat und Oxalat im Verhältnis 11, die das entsprechende Chromat als einziges Produkt liefert.

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, , — — . , 11 .

     

Studies of vanadium catalysts for sulfur dioxide oxidation by51V-NMR

Studies of the⁵¹V-NMR spectra of a series of industrial catalysts and systems modelling the active catalyst component indicate that the catalyst composition depends on the preparation method and during thermal treatment the support interacts with the active component. The local environment of vanadium is being formed in the process of catalytic reactions.

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⁵¹V , -I-4, , : KVO₃, KVO₃–SiO₂, KVO₃–K₂SO₄ , , . .

     

Catalytic oxidation of carbon monoxide by oxygen and nitrogen oxides on a copper-chromium oxide catalyst

The kinetics of CO oxidation by O₂, NO and NO₂ has been studied on a Cu–Cr-oxide catalyst. A comparison with the kinetics of the CO–N₂O interaction has been made. In all cases the reaction rate is described by the equation:r=k p _CO ¹ P _0x ⁰ . The oxidation of CO has been studied in the presence of different oxidants in the reaction mixture.

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CO , . CO . CO . CO .

     

Measurement of the rate constant of hydrogen atoms with carbon monoxide in tubular and jet stirred open reactors

The reaction of hydrogen atoms with carbon monoxide has been studied in discharge flow systems with a new method of detection of atoms. The results obtained with tubular and jet stirred open reactors agree with those of other authors working in transient conditions and with more sophisticated techniques.

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. , , , .

     

Thermal and infrared spectrum analyses of natural and synthetic andersonites

The thermal decompositions of natural and synthetic andersonites were studied. Two partly overlapping dehydration steps and three partly overlapping decarbonation steps were observed. The second dehydration and the first decarbonation steps also partly overlap. During decarbonation, the gradual formation of sodium diuranate and monoclinic and hexagonal phases in the Na₂U₂O₇-CaUO_4–x system was proved. The results were correlated with measured infrared spectra using site and factor group analysis and X-ray structure analysis. The chemical formula inferred for natural andersonite, Na₂Ca[UO₂(CO₃)₃] 5.6H₂O, agrees with that proposed for its synthetic analogue.

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Zusammenfassung Die thermische Zersetzung von natürlichem und synthetischem Andersonit wurde untersucht. Sie umfasst zwei teilweise überlappende Entwässerungs- und drei teilweise überlappende Decarboxylierungsstufen. Der zweite Entwässerungs- und der erste Decarboxylierungsschritt überlagern einander ebenfalls teilweise. Während der Decarboxylierung wird die allmähliche Bildung von Natriumdiuranat und monoklinen und hexagonalen Phasen des Systems Na₂U₂C₇-CaUO_4–x nachgewiesen. Die Ergebnisse wurden mit den gemessenen IR-Spektren unter Benutzung der site- und Faktor-Gruppenanalyse sowie Röntgenbeugungsuntersuchungen korreliert. Die für natürlichen Andersonit abgeleitete Formel Na₂Ca[UO₂(CO₃)₃].5,6H₂O stimmt mit der für synthetischen Andersonit vorgeschlagenen überein.

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. . . , Na₂U₂O₇-CaUO_4–x. . Na₂Ca[UO₂(CO₃)₃] 5,6₂, ** , .

     

Oxidation of 2,6-xylenol by Co(III) chelates in toluene

A simple reaction scheme and kinetic data are presented for the oxidation of 2,6-xylenol by Co(III) chelates in toluene.

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2,6- Co(III) .

     

Differential-thermal and thermogravimetric analysis of some gagates from Bulgaria

The thermal behaviour of three gagates (Bulgaria) was investigated by DTA and TG. The characteristic endo- and exoeffects and the sequence of the thermal stabilities are established.

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Zusammenfassung Das thermochemische Verhalten von drei Gagaten (Bulgarien) wurde mittels DTA und TG untersucht. Die charakteristischen endo- und exothermen Effekte und die Reihenfolge der thermischen Stabilitäten wurden ermittelt.

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