Entrapment of Humic Acid in a Sol-Gel Matrix—A New Tool for Sorption Studies

Humic substances are natural complexed mixtures of organic compounds originated from the decomposition of plant and animal residues. These compounds are ubiquitous in soils, sediments, surface waters and groundwaters. They contain both hydrophobic and hydrophilic moieties, able to interact with hydrophobic organic contaminants and with heavy metals. These sorption interactions play a crucial role in contaminants fate and transport and their understanding and quantification are essential for modeling and predictions. However, sorption analyses frequently suffer from experimental problems. A novel idea presented in this study is to use sol-gel as an inert matrix to immobilize (entrap) specific, well defined, humic molecules which then be used in sorption studies. We developed a successful procedure for the immobilization of humic acid (HA) in a sol-gel matrix. After gelation and drying, the doped gel was crushed and washed several times, yielding a very stable product. It was then used in a series of batch experiments, studying the sorption of several polycyclic aromatic hydrocarbons (PAHs) with Aldrich HA. The sorption coefficients (K _oc) obtained with the immobilized HA were highly correlated with the values expected based on the hydrophobicity of the contaminants. We concluded that the entrapped HA retained its original properties and that it was accessible to the external contaminants through the pore network.     

Photo-Induced Reactions between Glyoxal and Hydroxylamine in Cryogenic Matrices

In this paper, the photochemistry of glyoxal–hydroxylamine (Gly–HA) complexes is studied using FTIR matrix isolation spectroscopy and ab initio calculations. The irradiation of the Gly–HA complexes with the filtered output of a mercury lamp (λ > 370 nm) leads to their photoconversion to hydroxyketene–hydroxylamine complexes and the formation of hydroxy(hydroxyamino)acetaldehyde with a hemiaminal structure. The first product is the result of a double hydrogen exchange reaction between the aldehyde group of Gly and the amino or hydroxyl group of HA. The second product is formed as a result of the addition of the nitrogen atom of HA to the carbon atom of one aldehyde group of Gly, followed by the migration of the hydrogen atom from the amino group of hydroxylamine to the oxygen atom of the carbonyl group of glyoxal. The identification of the products is confirmed by deuterium substitution and by MP2 calculations of the structures and vibrational spectra of the identified species.     

A Modification of an Algorithm by Golub and Plemmons for Large Linear Least Squares in the Context of Doppler Positioning

This paper considers the solution of the geodetic Doppler multi-stationadjustment, i.e. the problem of computing the positions of severalstations observing the Doppler shift on radio frequencies emittedby several artificial satellites passing over the horizon. Amodification of an algorithm due to Golub and Plemmons, forsolving large linear least-squares problems where the observationmatrix has a block dual angular form, is proposed in this framework.This modification is shown to reduce substantially both datatransfer between the tracking stations and the main computingcentre, and the total computational effort required to obtainthe solution of the problem. Preliminary numerical results arediscussed and some further comments presented.     

Fission yields at different fission-product kinetic energies for thermal-neutron-induced fission of 239Pu

At the recoil spectrometer “Lohengrin” of the Institut Laue-Langevin in Grenoble, the yields of the light fission products from the thermal-neutron-induced fission of ²³⁹Pu were measured as a function of A, Z, the kinetic energy E and the ionic charge states q. The nuclear charge and mass distributions summed over all ionic charge states were determined for different light fissionproduct kinetic energies between 93 and 112 MeV. The proton odd-even effect which was measured to be (11.6 ± 0.6)% causes considerable fine structure in the yields. The average kinetic energy of even-Z elements in the light fission-product group is 0.3 ± 0.1 MeV larger than for odd-Z elements. The neutron odd-even effect is (6.5 ± 0.7)%. The comparison with previously published data ¹) for thermal-neutron-induced fission of ²³⁵U reveals a correlation between the proton odd-even effect in the yield and in the kinetic energy of the elements. The dependence of the proton odd-even effect on the fragmentation is very similar for ²³⁵U and ²³⁹Pu when it is considered as a function of the nuclear charge of the heavy fission products. The isobaric variances σ_z². for thermal-neutron fission of ²³⁵U and ²³⁹Pu coincide at all kinetic energies if the influence of the proton odd-even effect is averaged out. This supports the hypothesis that the magnitude of σ_z² is determined only by quantum-mechanical zero-point fluctuations. The influence of the spherical shells Z = 50 and N = 82 on the fragmentation is discussed.     

Flow equations for the spin-boson problem

Using continuous unitary transformations recently introduced by Wegner [1], we obtain flow equations for the parameters of the spin-boson Hamiltonian. Interactions not contained in the original Hamiltonian are generated by this unitary transformation. Within an approximation that neglects additional interactions quadratic in the bath operators, we can close the flow equations. Applying this formalism to the case of Ohmic dissipation at zero temperature, we calculate the renormalized tunneling frequency. We find a transition from an untrapped to trapped state at the critical coupling constant α _c =1. We also obtain the static susceptibility via the equilibrium spin correlation function. Our results are both consistent with results known from the Kondo problem and those obtained from mode-coupling theories. Using this formalism at finite temperature, we find a transition from coherent to incoherent tunneling atT ₂ ^* ≈2T ₁ ^* , whereT ₁ ^* is the crossover temperature of the dynamics known from the NIBA.     

Bifurcations of Poiseuille flow between parallel plates: Three-dimensional solutions with large spanwise wavelength

The spatial dynamics approach is applied to the analysis of bifurcations of the three-dimensional Poiseuille flow between parallel plates. In contrast to the classical studies, we impose time periodicity as well as spatial periodicity with period 2/ in the streamwise direction. However, we make no assumptions on the behavior in the spanwise direction, except the uniform closeness of the bifurcating solution to the basic flow. In an abstract setting it is shown how the dimension of the critical eigenspace of the spatial dynamics analysis can be uniquely determined from the classical linear stability problem. For the three-dimensional Poiseuille problem we are able to find all relevant coefficients from the analysis of the purely two-dimensional problem. Moreover, we are able to analyze precisely the influence of a spanwise pressure gradient and the associated spanwise mass flux. The study of the reduced problem shows that there are two different kinds of solutions (spirals and ribbons) which are 2p/ periodic in the spanwise direction, as in the Couette-Taylor problem, and both of them bifurcate in the same direction.     

Time response of a coupled atoms-cavity system

We study the time response of a quantum optical system to a step excitation. The system is composed of a collection of N two-level atoms coupled to a single mode of the electromagnetic field of an optical cavity. The size of the step excitation is not limited to the low-intensity regime. Before the system reaches steady state there is an oscillatory exchange of energy between the atoms and the cavity. We compare the experimental results quantitatively with theoretical calculations and with previous transmission spectroscopy measurements.     

BaIr0,67Be0,33O3: Eine stabilisierte kubische Form von BaIrO3

Inhaltsübersicht. Es ist gelungen, ein durch BeO stabilisiertes Bariumoxoiridat der Zusammensetzung BaIr_0,67Be_0,33O₃ in der Kristallform eines kubischen Perowskits mit kleiner Elementarzelle erstmals darzustellen. Raumgruppe O¹_h–Pm3m, a = 4,1009 Å, Z = 1. Ir⁵⁺ und Be² + besetzen die Oktaederposition des Perowskits statistisch. BaIr_0,67Be_0,33O₃: A Stabilized Cubic Form of BaIrO₃ For the first time it was possible to prepare a new barium-oxoiridate of the formula BaIr_0,67Be_0,33O₃, stabilized by BeO. It crystallizes in a small cubic unit cell of the perovskite type. Space group O¹_h–Pm3m; a = 4.1009 Å; Z = 1. Ir⁵⁺ and Be²⁺ occupy the octahedra positions of the perovskite structure statistically.