Exploration of the potential application of plutonium isotopes in source identification of sandstorm in the atmosphere of Beijing

Plutonium (Pu) is an anthropogenic radionuclide which mainly derived from atmospheric nuclear tests in the environment. In this study, the Pu isotopes (²³⁹Pu and ²⁴⁰Pu) in aerosol samples collected during the sandstorm and non-sandstorm period were measured by accelerator mass spectrometry (AMS) and the behavior of Pu was studied. The activity concentrations of ²³⁹Pu and ²⁴⁰Pu in the aerosol samples of Beijing were ranged from 0.62 nBq/m³ to 99.6 nBq/m³ for ²³⁹Pu and 3.51 nBq/m³ to 60.23 nBq/m³ for ²⁴⁰Pu, respectively. ²³⁹Pu and ²⁴⁰Pu concentrations exhibited a remarkable seasonal variation trend, with the higher results showed in spring, and the relatively lower concentrations in winter. The observed higher concentration of ²³⁹Pu and ²⁴⁰Pu detected in sandstorm samples further indicated Pu was closely related to the occurrence of sandstorms. The global fallout characteristics of ²⁴⁰Pu/²³⁹Pu atom ratios (average 0.20, ranging from 0.16 to 0.27) in aerosol samples indicating that global fallout was the major source of Pu in the atmosphere. Using aluminum (Al) as an indicator of soil resuspension, significant positive correlation between ²³⁹Pu and Al (r² = 0.934), ²⁴⁰Pu and Al (r² = 0.525) revealed that soil resuspension was a primary source of atmospheric Pu in Beijing. These results implied that the combination of ²³⁹Pu, ²⁴⁰Pu and Al could be used as the potential tracer of sandstorm.     

Standard enthalpy of formation of lithium diphosphate

Lithium carbonate (Li₂CO₃) and ammonium dihydrogen phosphate (NH₄H₂PO₄) were used for synthesizing lithium diphosphate (Li₄P₂O₇). The purity of the latter compound was checked up by X-ray diffraction. The heat of dissolution of (Li₄P₂O₇) in phosphoric acid solution was measured in a C-80 SETARAM calorimeter. Many dilution and mixing processes in acid solutions of several concentrations (w/w) H₃PO_4, were also realized in the calorimeter in order to get the standard enthalpy of formation of this product. Two thermochemical cycles were investigated and the obtained values for the enthalpy of formation are: (−3383.4 and −3147) kJ · mol⁻¹. The former one is in better agreement with literature data.     

Thermodynamic characterization of the melting of a series of polyesteramides

The changes in enthalpy, entropy and volume upon melting have been determined by dilatometric and differential scanning calorimetry measurements for four polyesteramides of the type:

$\text{-[-}\text{COφCONH(CH}{}_2\text{)}{}_{\mathrm{n}}\text{}\text{NHCOφCOO(CH}{}_2\text{)}{}_{\mathrm{m}}\text{}\text{O}\text{-]-}{}_{\mathrm{x}}$

with the following values for n and m; 6-6, 12-2, 12-6 and 12-12. The changes in each state function vary quite regularly with the number of CH₂ groups/repeating unit. A comparison is made between experimental data on the entropy of fusion and theoretical predictions. There is emphasis on the influence on the thermodynamics of melting of the rigidity of the -OCO-φ-CONH- residues and, in particular, of the persistence in the molten state of many interchain hydrogen bonds.     

The role of hyaluronan in the structure and function of the biomatrix of connective tissues

This review focuses on the only polysaccharide compartment of the biomatrix of connective tissues: hyaluronan. This pure polysaccharide is present in the largest amount and highest concentration in three connective tissues of the adult vertebrate body: the vitreus of the eye, the synovial fluid of the joint, and the dermis of the rooster comb. The molecular properties, weight average molecular weight, polydispersity, and elastoviscous properties of hyaluronan, as well as its distribution in these biomatrices, are presented. The differences and similarities in the biological function of this polysaccharide in the biomatrix are discussed. The effect of aging on the hyaluronan content of the vitreus, synovial fluid, and the dermis of human skin is also presented.

Thermal decomposition of rhombohedral double carbonates of dolomite type

DTA and TG studies in air were carried out for hydrothermally prepared rhombohedral double carbonates of dolomite type, CaMg(CO₃)₂, CaMn(CO₃)₂, CdMg(CO₃)₂, CdMn(CO₃)₂ and CdZn(CO₃)₂. The solid decomposition products in air have been compared to those obtained under hydrothermal conditions with CO₂ pressure. The dolomite [CaMg(CO₃)₂] decomposes in two stages both in air as well as under high CO₂ pressure. The other carbonates studied, follow a single stage decomposition in air and a two stage decomposition under hydrothermal condition. In air, the manganese containing carbonates CaMn(CO₃)₂ and CdMn(CO₃)₂, decompose to form mixed oxides of CaMnO₃ and CdMnO₃ respectively, while CdMg(CO₃)₂ and CdZn(CO₃)₂ decompose to their respective two mono oxides.

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Zusammenfassung Mittels DTA und TG in Luft werden die hydrothermisch hergestellten rhomboedrischen Doppelkarbonate (Dolomittyp) CaMg(CO₃)₂, CaMn(CO₃)₂, CdMg(CO₃)₂, CdMn(CO₃)₂ und CdZn(CO₃)₂ untersucht. Die in Luft erhaltenen festen Zersetzungsprodukte wurden mit denen verglichen, die unter hydrothermischen Bedingungen mit CO₂-Druck entstehen. Dolomit zersetzt sich sowohl in Luft als auch unter hohem CO₂-Druck in zwei Schritten. Die übrigen untersuchten Karbonate zersetzen sich in Luft in einem, unter hydrothermischen Bedingungen in zwei Schritten. In Luft zersetzen sich die magnesiumhaltigen Karbonate CaMn(CO₃)₂ und CdMn(CO₃)₂ unter Bildung der Mischoxide CaMnO₃ und CdMnO₃, während aus CdMg(CO₃)₂ und CdZn(CO₃)₂ jeweils die entsprechenden beiden Monoxide entstehen.

     

Study of kinetics and mechanism of the acid dissociation of copper(II) complex of novel C-functionalized macrocyclic dioxotetraamines

The kinetics of the acid dissociation of copper(II) complexes of novel C-functionalized macrocyclic dioxotetraamines has been studied by means of a stopped-flow spectrophotometer. The acid dissociation rate follows the law V_d = C_comkK₁K₂H ²/(1+K₁H+K₁K₂H ²). From the experimental facts we have obtained, the dissociation kinetics are interpreted by a mechanism involving the negatively charged carbonyl oxygen of the complex being rapidly protonated in a pre-equilibrium step, the rate-determining step being intramolecular hydrogen (enolic tautomer) migration (to imine nitrogen). The dissociation rate reached a plateau in the strongly acidic solution. By means of temperature coefficient method, ΔH ^φ, ΔS ^φ of the pre-equilibrium step and ΔH ^≠, ΔS^≠ of the rate-determining step were obtained. The results of 13-membered macrocyclic dioxotetraamines have been discussed. The influence of the substituents to the acid dissociation rates has also been discussed. The Bronsted type linear free energy relationships do also exist in these C-functionalized dioxotetraamine copper(II) complexes.     

Kinetics of the thermal decomposition of dinitramide

The kinetic regularities of the heat release during the thermal decomposition of liquid NH₄N(NO₂)₂ at 102.4–138.9 °C were studied. Kinetic data for decomposition of different forms of dinitramide and the influence of water on the rate of decomposition of NH₄N(NO₂)₂ show that the contributions of the decomposition of N(NO₂)₂ ⁻ and HN(NO₂)₂ to the initial decomposition rate of the reaction at temperatures about 100 °C are approximately equal. The decomposition has an autocatalytic character. The analysis of the effect of additives of HNO₃ solutions and the dependence of the autocatalytic reaction rate constant on the gas volume in the system shows that the self-acceleration is due to an increase in the acidity of the NH₄N(NO₂)₂ melt owing to the accumulation of HNO₃ and the corresponding increase in the contribution of the HN(NO₂)₂ decomposition to the overall rate. The self-acceleration ceases due to the accumulation of NO₃ ⁻ ions decreasing the equilibrium concentration of HN(NO₂)₂ in the melt. For Part 2, see Ref. 1. Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 3, pp. 395–401 March 1998.     

Asymptotic behavior of the RHF energy of the PPP model of alternant cyclic polyenes

The large N expansion of the restricted Hartree–Fock (RHF) exchange energy per atom E(N) of the Pariser–Parr–Pople (PPP) model of cyclic polyenes (annulenes) C_NH_N is derived in detail. We explicitly derive the coefficients E₀ and E₁ of the asymptotic expansion: E(N)=E₀+E₁ ln N/N²+O(N⁻²), N→∞, in the very simple case of half-filling and no bond alternation. The exchange energy per atom in the infinite chain can be written as E_ex=(2/π²)∑^∞_j=1{[γ_∞(2j−1)]/[(2j−1)²]}, where γ_∞ is the two-electron repulsion integral in the infinite chain. On the other hand, the second coefficient E₁ giving a finite-size correction is found to be 1/2b, where b is the bond length. This value of E₁ differs slightly from that of a linear chain with periodic boundary conditions because the distance between sites depends upon the radius of the ring, i.e., upon N. © 1998 John Wiley & Sons, Inc. Int J Quant Chem 66 : 397–407, 1998     

Polarographic Behaviour and Determination of Kinetic Parameters of Lead-Pamoate Complex in Dimethyl Sulfoxide

The polarography of lead ion in dimethyl sulfoxide (DMSO) was investigated in the DMSO concentration range 0–80 vol.%. The complex species identified were Pb₂(DMSO)⁴⁺₃, Pb(DMSO)²⁺₃ and Pb(DMSO)²⁺₆ in [DMSO]<10 vol.%, 10< [DMSO]<43 vol.% and [DMSO]>43 vol.%, respectively. In the presence of pamoic acid, the reduction of lead ion in DMSO was two-electron reversible diffusion-controlled at pH≤6.0, but it became irreversible at pH>6.0. The complex species identified was Pb(D_m)₂(P_m)₃(OH)^6? at pH>6.0. The rate constants of electro-reduction and electro-oxidation, activation energies were determined. The hydrolysis constants of lead ion in dimethyl sulfoxide concentration 40–70 vol.% at pH 4.5–6.0 were found to be of the order of 10^?6. The stability constants of the Pb(DMSO)²⁺₃ and Pb(DMSO)²⁺₀ were also determined to be of the orders of 10¹ and 10⁵, respectively.     

Influence of heating rate on kinetic quantities of solid phase thermal decomposition

Thermogravimetric analyses of thermal decomposition (pyrolysis, thermal dissociation and combustion) of 9 different samples were carried out in dynamic conditions at different heating rates. The kinetic parameters (E, A and k_m) of thermal decomposition were determined and interrelations between the parameters and heating rate q were analyzed. There were also relations between Arrhenius and Eyring equations analyzed for thermal decomposition of solid phase. It was concluded that Eyring theory is an element, which interconnects used thermokinetic equations containing Arrhenius law and suggests considering kinetic quantities in way relative to 3 kinetic constants (E, A and k_m). Analysis of quantities other than km (i.e. E, A, Δ⁺H, Δ⁺S) in relation to heating rate is an incomplete method and does not lead to unambiguous conclusions. It was ascertained that in ideal case, assuming constant values of kinetic parameters (E and A) towards heating rate and satisfying both Kissinger equations, reaction rate constant k_m should take on values intermediate between constants (k_m)₁ and (k_m)₂ determined from these equations. Whereas behavior of parameters E and A towards q were not subjected to any rule, then plotting relation k_m vs. q in the background of (k_m)₁ and (k_m)₂ made possible classification of differences between thermal decomposition processes taking place in oxidizing and oxygen-free atmosphere.     

Kinetics of decomposition of alkylammonium salts

The thermogravimetric curves of di-n-propylammonium, di-iso-propylammonium, di-n-butylammonium and di-iso-butylammonium chlorides showed similar profiles, characterized by mass loss in only one stage, corresponding to decomposition of compounds. The following thermal stability order was obtained: [Bu₂ ⁿNH₂]Cl>[Pr₂ ⁿNH₂]Cl>[Pr₂ ⁱNH₂]Cl>[Bu₂ ⁱNH₂]Cl. The values of activation energy for non-isothermal data obtained by Ozawa and Coats-Redfern integral methods were in agreement and stability order obtained by thermogravimetry were reproduced in both methods. The decomposition reactions of [Pr₂ ⁿNH₂]Cl, [Pr₂ ⁱNH₂]Cl and [Bu₂ ⁱNH₂]Cl were better described by A3 model and [Bu₂ ⁿNH₂]Cl by A2 model. This revised version was published online in August 2006 with corrections to the Cover Date.     

Benefits of near-infrared spectroscopy for characterization of selected organo-montmorillonites

The potential of near infrared (NIR) spectroscopy in characterization of organically modified clay minerals is introduced. Selected organo-clays, possibly perspective fillers in clay polymer nanocomposites, were prepared from Na-montmorillonite and different surfactants containing octylammonium chain(s), hexadecylammonium chain(s) or a benzene ring with or without a reactive double bond. Based on the stretching (ν) and bending (δ) vibrations observed in the middle IR (MIR) region, the first overtone (2νXH) and combination (ν + δ)XH modes of XH groups (X = O, C, N) are identified. The effect of larger alkylammonium cations on the vibrations of Si-O and OH bonds in montmorillonite layers is observed. The changes in the intensity of the (ν + δ)H₂O band near 5250 cm⁻¹ allows for comparison of the amount of water adsorbed on the montmorillonite surface. The water content decreases with the size of the organic cation reflecting increasing hydrophobicity of the montmorillonite surface. The NIR region shows the 2νCH₃ and 2νCH₂ bands in the 5900-5500 cm⁻¹ region, an upward shift is observed for the complex band due to 2νCH(Ar) of aromatic benzene ring. The NIR spectra are extremely useful in identification of NH₂⁺, NH⁺ and vinyl groups, which are difficult to recognize in the MIR spectra of organo-clays due to overlapping with other absorption bands. The intense bands corresponding to overtones and combination vibrations of NH₃⁺ and NH₂⁺ groups are found in the 6600-6050 cm⁻¹ and 5000-4600 cm⁻¹ regions, the (ν + δ)NH⁺ is unambiguously identified near 4750 cm⁻¹. The characteristic band assigned to 2νCH₂ in H₂CC is detected near 6130 cm⁻¹.     

Synthesis and Spectroscopic Characterization of Silver(I) Complexes of Selenones

Silver(I) complexes of selenones, [LAgNO₃] and [AgL₂]NO₃ (where L is imidazolidine-2-selenone or diazinane-2-selenone and their derivatives) have been prepared and characterized by elemental analysis, IR and NMR (¹H, ¹³C and ¹⁰⁷Ag) spectroscopy. An upfield shift in the C=Se resonance of selenones in ¹³C NMR and a downfield shift in N-H resonance in ¹H NMR are consistent with selenium coordination to silver(I). In ¹⁰⁷Ag NMR, the AgNO₃signal is deshielded by 450-650 ppm on coordination to selenones. Greater upfield shifts in ¹³C NMR were observed for [LAgNO₃] compared to [AgL₂]NO₃complexes, whereas the opposite trend was observed for ¹H and¹⁰⁷Ag NMR chemical shifts.     

Stereoselective formation of ansa-metallocenes in reactions of radical-anionic salts of acenaphthylene with lanthanide and calcium halides

ansa-Metallocenes (⁵:⁵-C₂₄H₁₆)M(THF)₂ (M = Sm (1), Yb (2), Ca (3)) and (⁵:⁵-C₂₄H₁₆)MI(THF) (M = Dy (8), Er (9), Tm (10), Lu (11)) were prepared in 50—90% yields by the in situ reactions of two equivalents of potassium acenaphthylenide K⁺C₁₂H₈ ^– with MI₂ or MI₃, respectively. Complexes 2 and 3 were also obtained by direct reduction of acenaphthylene with ytterbium and calcium naphthalenides, respectively. An ESR signal of the acenaphthylene radical anion, which was observed upon dissolution of compound 2 in THF, indicates that the [C₂₄H₁₆]^2– ansa-ligand dissociated into two [C₁₂H₈]^·– radical anions. Hydrolysis of complex 2 in benzene afforded 1,1",3,3"-tetrahydro-3,3"-biacenaphthylene (4) and 3,3",4,4"-tetrahydro-3,3"-biacenaphthylene (5). The reaction of complex 2 with ZrCl₄ and the reaction of compound 3 with Me₃SiCl proceeded with the cleavage of the C—C bond between two acenaphthylene fragments of the [C₂₄H₁₆]^2– ansa-ligand to produce (²-C₁₂H₈)ZrCl₂(THF)₃ (6) and bis(trimethylsilyl)acenaphthene (Me₃Si)₂C₁₂H₈ (7), respectively. Compounds 1—3, 6, 7, and 11 were characterized by ¹H and ¹³C NMR spectroscopy. The temperature dependence of the ¹H NMR spectrum of compound 11 in tetrahydrofuran is indicative of the dynamic exchange of the solvent molecules in the coordination sphere of the Lu atom. After cooling of the solution to 210 K, the dynamic process was terminated as evidenced by the nonequivalence of the ¹H signals of two acenaphthylene fragments. According to the X-ray diffraction data for complex 11, dimerization of two acenaphthylene radical anions at the Lu atom gave rise to the rac-ansa-metallocene structure. In compound 11, the Lu atom is ⁵-coordinated by two five-membered rings of the acenaphthylene ligands and also by the I atom and the THF molecule. The coordination environment about the Lu atom is a distorted tetrahedron. The average distance between the lutetium atom and the carbon atoms of the five-membered rings is 2.623 .     

Synthesis, characterization and solution behaviour of phosphoryl complexes of tin tetrafluoride

The preparation and characterization of a series of octahedral complexes [SnF₄L₂] (L = (Me₂N)₃PO (1), L = (R₂N)₂P(O)F; R = Me (2); Et (3) or L = R₂NP(O)F₂; R = Me (4); Et (5)) are described. These new adducts have been characterised by multinuclear (¹⁹F, ³¹P and ¹¹⁹Sn) NMR, IR spectroscopy and elemental analysis. The NMR data particularly the ¹⁹F NMR spectra showed that the complexes exist in solution as mixtures of cis and trans isomers. The solution behaviour of the complexes studied by variable temperature NMR in the presence of excess ligand indicated that, unlike in the SnCl₄ analogues, the ligand exchange at room temperature is slow for 1–3 and fast only for 4 and 5. The metal–ligand exchange barriers in [SnF₄L₂] and [SnCl₄L₂] systems were estimated and compared. The results indicate that in addition to the difference in the Lewis acidity between SnF₄ and SnCl₄ the nature of the substituents (fluorine atoms) on the phosphorus atom of the ligand can contribute considerably to the lability of the complex obtained.     

Graphical representation of the state of orientation of polymer systems

The orientation distribution function for noncrystalline structural units in polymer systems cannot be determined completely from any experimental source; only the second and/or fourth moments of the distribution function, i.e., the second and/or fourth orders of the generalized orientation factors F_lm^j, can be evaluated. It is there-fore necessary to estimate the distribution function from F_2m^j and F_4m^j. In this paper, a graphical representation of the state of orientation is first discussed in terms of plots of F₄₀^j against F₂₀^j for several types of distribution functions for uniaxial orientation. These are three types of extreme concentration of the distribution at particular polar angles θ₀ given by θ₀ = 0, 0<θ₀<π/2, and θ₀ = π/2; five types of rather realistic distributions having single maxima at θ_j = 0, θ₀, π/2 and double maxima at θ_j = 0, π/2, and a single minimum at θ_j = θ₀; and four types of more realistic distributions including Kratky's floating rod model in an affine matrix. Second, estimation of the distribution function for uniaxial orientation from F₄₀^j and F₂₀^j is discussed quantitatively in terms of the mean-square error by three approximation methods: (a) expansion of the distribution function in finite series of spherical harmonics through the fourth order, (b) approximation of the distribution function as a composite of two components, random orientation and a particular orientation distribution given by N_a (cos²θ_j)^a, N_a being a constant, and (c) approximation of the distribution function by N_a (cos²θ_j)^a alone. It is concluded that when the orientation distribution is sharp, estimation by the second method of approximation gives a smaller error than the first.     

Study of the spectrum of cherenkov light

It is pessible to study experimentally Cherenkov light spectra in a liquid scintillation spectrometer with colour filters. Cherenkov light spectra of⁶⁰Co,¹⁹⁸Au,¹¹⁵Cd,¹⁴³Ce,¹⁴⁰La,³²P,⁸⁶Rb,⁷⁶As,⁴²K and an external standard were studied in a Packard 3375 type liquid scintillation spectrometer, using 11 various Kodak Wratten filters. The absorption maxima of the filters ware in the 410–796 nm interval.     

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.     

Radiochemical characterization of spring waters in Balaton Upland, Hungary, estimation of radiation dose to members of public

Hungary is rich in spring waters. A survey studying the naturally occurring alpha emitter radionuclides in 30 frequently visited and regularly consumed spring waters was conducted out in the Balaton Upland region of Hungary.²²⁶Ra, ²²⁴Ra, ²³⁴U, ²³⁸U and ²¹⁰Po activity concentrations were determined by using alpha spectrometry after separation from matrix elements. Average concentration (mBq L^{− 1}) of ²²⁶Ra, ²²⁴Ra, ²³⁴U, ²³⁸U and ²¹⁰Po in the spring waters is varied from 2.1 to 601, from < 1.1 to 65.4, from 3.9 to 741.9, from < 0.44 to 274.3 and from 2 to 15.2 respectively. In most cases radioactive disequilibrium was observed between uranium and radium isotopes. The doses for the analyzed samples of spring water are in the range 3.59–166.73 μSv y^{− 1} with an average 18.2 μSv y^{− 1} .This is well below the 100 μSv y^{− 1} reference level of the committed effective dose recommended by WHO. Only one water sample had a dose higher than 100 μSv y^{− 1}, mainly due to the contribution from radium (²²⁶Ra, ²²⁴Ra) and ²¹⁰Po isotopes. This study provides important information for consumers and authorities about their internal radiological exposure risk from spring water intake.