Characterization of an Irish Sea radioactively contaminated marine sediment core by radiometric and mass spectrometric techniques

Summary A radioactively contaminated marine sediment core stemming from Irish Sea has been characterized by radiometric and mass spectrometric techniques as for ²³⁷Np, ²⁴¹Am, ²³⁹Pu, ²⁴⁰Pu, ²⁴¹Pu, ¹³⁷Cs and ¹⁵⁴Eu. The data obtained with independent methods in the framework of a QA/QC program as compared with the source term discharges, as well as with those reported in literature, are in good agreement.     

O− and OH− chemical ionization of some fatty acid methyl esters and triacylglycerols

O^? and OH^? react with fatty acid methyl esters (FAMES) under chemical ionization conditions both as Bronsted bases to form [M - H]^? and as nucleophiles to form the carboxylate ion RCOO^?. O^? shows a much greater tendency to react as a nucleophile than does OH^?. The [M - H]^? ions fragment by elimination of CH³OH, with unsaturation in certain positions in the fatty acid hydrocarbon chain promoting this elimination for unknown reasons. The reaction of O^? and OH^? with triacylglycerols leads to [M - H]^?, characteristic of the molecular mass, and to carboxylate ions characteristic of the fatty acid(s) present in the lipid. The presence of the three ester functions in the lipids greatly enhances the formation of carboxylate ions compared to the FAMES.     

Preparation of 125I-Lanreotide and its biodistribution in murine model of melanoma

Lanreotide, a somatostatin analogue, was radioiodinated with ¹²⁵I to explore the possibility of using ¹²³I labeled lanreotide as a diagnostic radiopharmaceutical for tumors overexpressing somatostatin (SST) receptors. Radioiodination was carried out with ¹²⁵I using chloramine T as the oxidant. The labeling yield was >90%. Characterization of ¹²⁵I-Lanreotide was carried out by paper electrophoresis as well as HPLC. ¹²⁵I-Lanreotide was purified by chromatography using a C18 Sep-Pak column. Radiochemical purity of the purified ¹²⁵I-Lanreotide thus obtained was >99%. Significant tumor uptake of ¹²⁵I-Lanreotide was observed in C57BL/6 mice bearing melanoma.     

Measurement of absolute intensity of 1001 keV gamma-ray of 234mPa

The sorption behavior of ²³⁵U fission fission products ⁹⁹Mo and ¹³²Te was studied through batch and dynamic experiments when they were dissolved in 1 to 7M HNO₃ solutions. It was found that ⁹⁹Mo is always totally adsorbed on hydrated SnO₂, while ¹³²Te is rather weakly adsorbed, therefore they can be separated from each other although ¹³²Te in the solution still remains contaminated with other radionuclides as well as ⁹⁹Mo does in the solid.     

Volumes of mixing and theP * effect: Part II. Mixtures of alkanes with liquids of different internal pressures

The Flory theory of solution thermodynamics is used to predict exess volumes for systems containing a series of n-alkanes mixed with liquids of higher P^* parameter and internal pressure, i.e., cyclopentane, cyclohexane, carbon tetrachloride, benzene and dioxane as well as of lower P^*, i.e., decamethyltetrasiloxane. Trends of V ^E , e.g. changes of sign with alkane carbon number are well predicted and indicate the importance of the P^* contribution in V ^E . Mixtures of hexane isomers with liquids of much higher P^* typically have large excess enthalpies through zero as an S-shaped curve against composition which is negative on the side of the high P^* component. This behaviour is interpreted as arising from increasingly large negative P^* contributions in V ^E .     

Thermodynamic study of the interaction of Co(II)-Schiff base complexes with phosphines

The equilibrium constants and the thermodynamic parameters for the interaction of CoL^x (L¹ = 5-OMe-salabza, L² = salabza, L³ = 5-Br-salabza and L⁴ = 5-NO₂-salabza) as acceptors, with phosphines (PBu₃, PPh₂Me) as donors in dichloromethane were studied. This was performed by using UV-Vis spectrophotometry titration for 1:1 adduct formation of the selected complexes at various temperatures (T = 283–298 K). The trend of the adduct formation of the Co(II) complexes with a given phosphine donor decreases as CoL¹ > CoL² > CoL³ > CoL⁴. The stability of the resulting adducts with different Co(II)-schiff base complexes found to decrease in the order PBu₃ > PPh₂Me.     

Regional characteristics of naturally occurring radionuclides in surface sediments of Chinese deserts and the Keum River area of Korea

Naturally occurring radionuclides (NORN) such as ⁴⁰K, ²²⁶Ra and ²³²Th from 44 surface sediment samples collected from four desert regions of Chinese were determined to investigate the regional characteristics of the source areas of Asian dust. The radionuclides for 41 surface sediment samples collected from seven sites of the Keum River area in Korea were also determined to compare the regional characteristics with the Chinese desert area. The specific activities (SA) and the specific activity ratios (SAR) of the radionuclides were investigated for distinguishing the source region of Asian dust. The SA of ²²⁶Ra and ²³²Th as well as the SAR of ²²⁶Ra/⁴⁰K and ²³²Th/⁴⁰K were found to be useful to characterize source area and tracing Asian dust.     

Evaluation of methane negative ion chemical ionization mass spectra of polycyclic aromatic hydrocarbons and related compounds

Negative ion chemical ionization (NICI) mass spectra with methane as reagent gas and the ion abundance ratios of the negative to the positive base peak for 51 polycyclic aromatic hydrocarbons and related compounds were measured and evaluated for highly sensitive detection and isomer differentiation. Either [M ? H]^?, M^?˙ or MH^? was the base peak, except for one compound with [M ? H₂]^?˙ as its base peak. The numbers of compounds with [M ? H]^?, M^?˙ or MH^? as their base peaks were 17, 26 and 7, respectively. Many of the compounds with [M ? H]^? as the base peak had an aliphatic part in their structure. The average value of N/P (negative/positive ion abundance ratio at the base peaks) was < 1. Many of the compounds with M^?˙ as the base peak had a relatively high electron affinity. A correlation between electron affinities and ion abundances was found. In most cases, the N/P ratios were > 1, and even reached 400 in benzo [a] pyrene. Many of the compounds with MH^? as their base peaks had a phenyl group, in which cases the N/P ratios were < 1. In the case of compounds with 18 or fewer carbon atoms, in particular, it was easy to distinguish isomers by comparing their NICI mass spectra. The N/P values served as a guideline in sensitive detection. Nine compounds achieved an N/P of ≥50.     

Influence of natural sorbents on the immobilization of spent ion exchange resins in cement

Summary Leach characteristics of ¹³⁷Cs and ⁶⁰Co radionuclides from spent mix bead ion exchange resins and both ordinary Portland cement and cement mixed with two kind of natural sorbents (bentonite and clinoptilolite) have been studied using the International Atomic Energy's (IAEA) standard leach method. The waste immobilization performance of low-level wastes in natural sorbent mixtures was determined. The solidification matrix was a standard Portland cement mixed with 290-350 (kg/m³) spent mix bead exchange resins, with or without 1-10% of bentonite or/and clinoptilolite. The leaching rates from the cement-bentonite matrix were measured after 300 days as ⁶⁰Co: (1.20-9.72) ^. 10^-5 cm/d and ¹³⁷Cs: (1.00-9.22) ^. 10^-4 cm/d. From the leaching data, the apparent diffusivity of cobalt and cesium in cement-bentonite or/and clinoptilolite matrix with a waste load of 350 kg/m³ of spent mix bead exchange resin was calculated as ⁶⁰Co: (1.0-5.9) ^. 10^-6 cm²/d and ¹³⁷Cs: (0.48-2.4) ^. 10^-4 cm²/d. The compressive strength of these samples is determined according to the ASTM standards.     

Decomposition of meta- and para-phenylphenol during ozonation process

The decomposition of meta-phenylphenol (m-PP) and para-phenylphenol (p-PP) in a heterogeneous gas-liquid system using ozone was investigated. The influence of different reaction parameters such as ozone and PP isomers concentration as well as pH and temperature of the reaction mixture on the PP decay rate was determined. The second-order rate constants for the direct reaction of molecular ozone, determined in a homogeneous system, were (5.85 ± 0.35) × 10² M^?1 s^?1 and (8.90 ± 0.33) × 10² M^?1 s^?1 for m-PP and p-PP, respectively. The rate constants for the reaction of m-PP and p-PP with ozone increased with increasing pH. The reaction rate constants with ozone were found to be (1.75 ± 0.02) × 10⁹ M^?1 s^?1 and (1.86 ± 0.02) × 10⁹ M^?1 s^?1 for m-PP and p-PP anions, respectively.     

Advanced oxidation processes for decolorization of aqueous solution containing acid red G azo dye

Some investigations concerning the decolorization of Acid Red G azo dye by photooxidation with hydrogen peroxide were performed. The influences of pH, oxidant concentration, and the presence of Fe²⁺ or other metal ions (Co²⁺, Cu²⁺, Ni²⁺, Mn²⁺) as potential catalysts, were investigated. The best results were obtained in the presence of ferrous ions in acid and neutral media. The other ions are not as effective as Fe²⁺ for dye decolorization. Co²⁺ and Cu²⁺ ions have a catalytic action, at low concentration, within a wide range of pH. Ni²⁺ and Mn²⁺ ions have no catalytic effect in photooxidation with hydrogen peroxide at acid Ni²⁺ and Mn²⁺ ions have no catalytic effect in photooxidation with hydrogen peroxide at acid pH values, but show a weak action in alkaline media.     

133Cs NMR Spectroscopic Investigation of the Interaction of 133Cs+ with Monovalent Cations in Aqueous Solution

¹³³Cs NMR spectroscopy was used to study the interaction of ¹³³Cs⁺ with monovalent cations in aqueous solution. The interaction between ¹³³Cs⁺ and the cations causes a repulsive polarization in the electron environment of ¹³³Cs⁺, which is detected by a change in its resonance frequency. The resulting ¹³³Cs chemical shift seemed to be dependent on the activities and the single-ion enthalpies and entropies of hydration of the cations. The hydration cospheres of an ion are the barriers through which ¹³³Cs⁺ must pass in order to come into contact with the cation. These hydration cosphere barriers can be related to the single-ion enthalpy and entropy of hydration of the cation. The experiments revealed that ¹³³Cs⁺ is not nearly as sensitive a probe as ¹²⁹Xe, presumably due to its more tightly bound hydration cospheres. However, ¹³³Cs NMR was moderately successful in predicting trends in the chemical shift behavior induced by the cations studied.     

Effect of gamma and electron-beam irradiation on the anisotropy of electric properties of indium selenide

The generation and distribution of radiation defects in single-crystal samples of indium selenide with an electron number density of 5 × 10¹⁴−1 × 10¹⁶ cm⁻³ during irradiation with γ-rays (doses of 10⁷ and 10⁸ R) and 25-MeV electrons (fluences of 10¹⁵ particle/cm²) was studied, as well as the behavior of the mobility.     

The diffusion of H+ and Ni2+ ions in an inorganic cation-exchange matrix

The kinetics of sorption on zirconium hydrophosphates with various water contents was studied. The self-diffusion coefficients of Ni²⁺ and H⁺ and the effective diffusion coefficients of Ni²⁺ ions corresponding to the exchange Ni²⁺ → H⁺ were determined. The self-diffusion coefficients of ions in samples with an 85% water content were as high as 4.17 × 10^?11 m²/s (Ni²⁺) and 5.06 × 10^?10 m²/s (H⁺). Water loss caused by drying the sorbents resulted in a decrease in the rate of ion exchange.     

Seasonal variation of 129I species in the Baltic Proper

Iodine speciation plays a significant role in iodine volatilizing into atmosphere from the seas, as well as serving as a biological indicator. Despite this importance, the data on iodine species revealed inconclusive evidence of what factors controlling speciation transformation. We here present new data on profiles of ¹²⁹I speciation in the Baltic Proper during November 2009. Along with the two earlier investigations (August 2006 and April 2007), an assessment of seasonal variation of ¹²⁹I species is presented. The results show that, due to the anoxic nature of Baltic Proper, presence of ¹²⁹IO₃ ^? in the Baltic Proper does not follow an obvious seasonal cycle, as the case with ¹²⁹I^?. Concentrations of ¹²⁹I^? in the Baltic Proper exhibit higher values in summer than the other two seasons (spring and winter), which might be associated with degrading of organic matter and release from sediment to water column that is more pronounced during summer. ¹²⁹I^? in surface water from the three seasons does not reflect the release function from the reprocessing facilities during the period April 2007 to November 2009. Consequently variability of ¹²⁹I^? in surface seawater of the Baltic Proper depends, to some extent, on local physical as well as biochemical conditions.     

Thermodynamic characteristics of ion-exchange sorption of Co2+ cations on Na-vermiculite

The exchange of Na⁺ ions of vermiculite for Co²⁺ cations is measured by sorption-analytical and microcalorimetric methods. The previously revealed growth of the equilibrium constant with a rise in the degree of filling θ of vermiculite exchange sites with Co²⁺ cations is confirmed. This result is explained by the segregation of Co²⁺ and Na⁺ cations being exchanged in separate interlayer regions of vermiculite. The negative heats of exchange of Na⁺ cations for Co²⁺ cations are associated with the energy consumption for the rearrangement of the segregated interlayer regions in vermiculite. The positive entropy changes resulting from the exchange indicate the formation of a more disordered Co-Na-layered “cake” in comparison with the initial Na-form vermiculite. A decrease in the integral molal free-energy change ΔG _m of the mixed form of the mineral is determined by the entropy factor. It is shown that, as θ increases, the ΔG _m(θ) dependence passes from a positive to a negative range of values. This pattern of the curve may be interpreted as a gradual phase transition from the Na-form to the mixed Co-Na-segregated form. The first derivatives of the enthalpy and entropy changes with respect to the degree of filling θ exhibit distinct maxima at θ ～ 0.20 as a result of the transition from the ideal mixing of Co²⁺ and Na⁺ cations being exchanged to their segregation.     

A study of the behavior of cadmium and zinc microquantities in sorption and coprecipitation processes in tetrahydrofuran solutions

The sorption of ¹⁰⁹Cd and ⁶⁵Zn microquantities with NaX and NaA zeolites in the presence of divalent lanthanides (Ln²⁺) (Ln=Tm, Dy, and Nd) from tetrahydrofuran (THF) solutions was studied. It was found that in contrast to ¹³⁷Cs⁺, ¹⁰⁹Cd and ⁶⁵Zn, as well as ⁸⁵Sr²⁺ microquantities were sorbed by zeolites very poorly: ∼99% of the species remained in solution. The distribution coefficients (K _d ) of ¹⁰⁹Cd and ⁶⁵Zn were ∼0.3 and ∼0.4 ml/g, respectively. When Tm²⁺ was used as a reducer, it partially oxidized in solution to Tm³⁺ to form precipitates of the composition TmI₃·3THF. A study of the co-crystallization of ¹⁰⁹Cd and ⁶⁵Zn, as well as ⁸⁵Sr²⁺ microquantities with the TmI₃·3THF solid phase in the presence of Tm²⁺ from THF solutions showed that in contrast to ⁸⁵Sr²⁺, ¹⁰⁹Cd and ⁶⁵Zn microquantities co-crystallized with the TmI₃·3THF solid phase. The co-crystallization coefficients (D) for ¹⁰⁹Cd and ⁶⁵Zn depended on the ratio Tm³⁺/Tm²⁺ in solution and increased with its increasing. The assumption was made that in the presence of Tm²⁺, ¹⁰⁹Cd²⁺ and ⁶⁵Zn²⁺ form M⁺ ions, which quickly react with M²⁺ ions to form dimers of the composition M₂ ³⁺ (M=Cd and Zn).     

Preparation of Ce-Zr-O solid solution

A single phase solid solution of Ce-Zr-O can be made by using NH₄HCO₃ solution as precipitating agent. The influence of preparation conditions, such as pH, Zr⁴⁺/(CO₃ ^2-+HCO₃ ^-) and Ce³⁺/Zr⁴⁺ ratio on the formation of the solid solution were investigated. The results show that a single phase Ce-Zr-O solid solution can be formed only under a narrow window of preparation conditions, indicating that some compounds are formed in the precipitating process. The compound may contain Ce³⁺, Zr⁴⁺, CO₃ ^2-, HCO^3-, and OH^-. The solid solution so prepared can be described as Ce_0.37Zr_0.63O₂. This revised version was published online in August 2006 with corrections to the Cover Date.     

The chemistry and kinetic behavior of Cu-Cr-As/B wood preservatives. I. Fixation of chromium on wood

The kinetic behavior of CrO₃ in its reaction with wood has been elucidated. Various reactions take place between CrO₃ and the lignin and cellulose in wood. CrO₃ reacts with cellulose in a two-step reaction: the first step is an adsorption of Cr^VI onto the cellulose to form Cr^VI/cellulose activated complexes. The second step is a Cr^VI → Cr^III reduction taking place on the cellulose surface. The Cr^III formed is only physically adsorbed to the cellulose or very weakly bound as small amounts of Cr^III can be released into the reaction medium. The Cr^VI adsorbed by cellulose appears mainly to be reduced to Cr^III. The reaction of Cr^VI with lignin has been shown to be the composition of the three successive reaction of Cr₂O₇^2?, HCrO₄^?, and CrO₄^2? with the guaiacyl units of lignin. Insoluble and stable Cr^VI/lignin complexes in which chromium maintains its hexavalent oxidation state are formed. Rate constants and energies of activation for all the reactions have been determined. The fixation of CrO₃-derived compounds on wood has been explained as the combination of the various reactions investigated. The results indicate that 60% of Cr is fixed irreversibly to the lignin of wood as Cr^VI and 40% is weakly bound, probably just precipitated, on the cellulose surface as Cr^III of which small amounts can be released in a water medium. The complex Cr^VI and Cr^III species forming complexes with the guaiacyl units have been identified.