Trace determination of Tl, Cu, Pb, Cd, and Zn in specimens of the limnic environment using isotope dilution mass spectrometry with thermal ionization

Within the framework of the German Environmental Specimen Bank program, Tl, Cu, Pb, Cd and Zn were determined in homogenized materials from the limnic environment using Isotope Dilution Mass Spectrometry (IDMS) with thermal ionization. The analytical procedures which were developed for the trace metal analysis of bioindicator and sediment samples are described in detail. Results obtained in bream, mussels (Dreissena polymorpha) and sediments of Lake Constance/Estuary of Constance in the sampling years 1981, 1985, 1988, 1990, 1992 and 1993 are discussed and compared with those of bream from the lakeland district of Born-hoeved/Lake Belau and from the River Saar as well as from reference materials.     

Comparison of short range interactions in nematic liquid crystals A 2H-NMR study of 5CB-d19 as a solute

Previous studies using dideuterium as a solute have demonstrated the importance for orientation of the interaction between the solute molecular quadrupole moment and the average electric field gradient present in liquid crystals. With the aim of learning about additional orientational mechanisms, we have studied the temperature dependence of the ²H-NMR spectra of the liquid crystal 5CB-d₁₉ as the solute in three liquid crystal mixtures: 55 wt % 1132/EBBA, 56·5 wt % 1132/EBBA and 70 wt % 5CB/EBBA. In these mixtures, the contribution from the environment to the average electric field gradient at the ²H nucleus of dideuterium is zero. The spectra of 5CB-d₁₉ in the mixtures 55 wt % 1132/EBBA and 56·5 wt % 1132/EBBA are equivalent, but are different from those in 70 wt % 5CB/EBBA. The spectra of 5CB in 55 wt % 1132/EBBA and 70 wt % 5CB/EBBA are analysed using two different models for the short range potential, and param eters of the models are used to compare the potentials in the different mixtures. For a given spectral splitting of the chain C₁ deuteron, the reduced short range potential is the same in all three mixtures studied. The spectral differences observed are a consequence of different nematic-isotropic phase transition temperatures combined with the effect of trans/gauche-isomerization in the hydrocarbon chain.     

Pretransitional electro-optic response of 6CB liquid crystal in the isotropic phase

In this work, the electro-optic response of a 6CB liquid crystal layer is studied using a sensitive differential technique. The layer is held at a temperature just above the nematic to isotropic phase transition. Transverse magnetic (p) polarized light incident on the cell is coupled to guided modes in the liquid crystal layer using prism coupling. The modes manifest themselves as sharp dips in the reflectivity as the angle of incidence is scanned. When a low frequency sinusoidal voltage is applied to the cell, the resonant mode shapes and excitation angles are altered at a frequency which is twice that of the applied field, resulting in a modulation of the reflectivity for a given angle of incidence. By synchronous observation of the modulated signal, a differential signal is recorded. Comparing the data with modelling generated from multilayer optics theory, two effects are then quantified. The first of these is an induced birefringence, varying quadratically with applied voltage, which is well understood and can be expressed in terms of Landau-de Gennes theory. The second is a field induced perturbation in the imaginary part of the optical permittivity, δε_i, which implies a modification of the light scattering properties of the liquid crystal. The measurement of the latter effect is, as far as we know, a novel one, being only made possible by the remarkable sensitivity of the synchronous differential technique.     

Kinetic model for hydrocarbon-assisted particulate boron combustion

A kinetic model is presented to describe the high temperature (1800 K < T < 3000 K) surface oxidation of particulate boron in a hydrocarbon combustion environment. The model includes a homogeneous gas-phase B/O/H/C oxidation mechanism consisting of 19 chemical species and 58 forward and reverse elementary reactions, multi-component gas-phase diffusion, and a heterogeneous surface oxidation mechanism consisting of ‘elementary’ adsorption and desorption reaction steps. Thermochemical and kinetic parameters for the surface reactions are estimated from available experimental data and/or elementary transition state arguments. The kinetic processes are treated using a generalized kinetics code, with embedded sensitivity analysis, for the combustion of a one-dimensional (particle radius), spherical particle. Model results are presented for the oxidation of a 200 μm boron particle in a JP-4/air mixture at ambient temperatures of 1400 K and 2000 K. These results include temperature and gas-phase species profiles as a function of radial distance and particle burning rates. © 1994 John Wiley & Sons, Inc.     

Analysis of the structure of an amorphous sediment obtained upon decomposition of potassium oxofluroniobate in water

An amorphous sediment was prepared by the decomposition of potassium oxofluoroniobate K_{2 ? x} Nb₄O₃(O, F)₃F in water. For this sediment, the atomic radial distribution function was analyzed with the use of a fragment model, which allows one to interpret expanded coordination spheres as being formed by first several strongest diffusion maxima. These spheres carry the most reliable information on the structure. It is shown that the amorphous sediment consists of the randomly packed Nb(O,F)₆-octahedra with interatomic distances close to those observed in the ordered region in the N-Nb₂O₅ structure. During decomposition in water, the initial K_{2 ? x} Nb₄O₃(O, F)₃F phase loses KF-layers, whereas Nb₆ clusters with metal bonds are destroyed.     

LIDAR mapping of ozone-episode dynamics in Paris and intercomparison with spot analyzers Supplementary material available at http://link.springer.de/journals/apb

Continuous mapping of an ozone episode in Paris in June 1999 has been performed using a differential absorption lidar system. The 2D ozone concentration vertical maps recorded over 33 h at the Champ de Mars are compiled in a video clip that gives access to local photochemical dynamics with unprecedented precision. The lidar data are compared over the whole period with point monitors located at 0-, 50-, and 300-m altitudes on the Eiffel Tower. Very good agreement is found when spatial resolution, acquisition time, and required concentration accuracy are optimized. Sensitivity to these parameters for successful intercomparison in urban areas is discussed. Received: 11 February 2002 / Published online: 14 March 2002     

SECOND BEST TAXES AND QUOTAS IN NITROGEN REGULATION

This paper investigates second best policies to regulate nitrogen leaching. When the policy maker controls the total nitrogen use, an overall tax is superior to an action equivalent overall quota. When the goal is to regulate the expected level of nitrogen leaching, expected profit of a risk neutral farmer is greater under an overall tax than under an overall quota under a reasonable condition. The welfare ranking of action equivalent taxes and quotas for a risk averse farmer is generally ambiguous. In the numerical analyses, overall taxes turned out to be superior to overall quotas with both targets, despite a very high value of absolute risk aversion, 0.01. These results suggest that an overall tax is probably a superior policy to an overall quota to regulate expected total nitrogen use or expected nitrogen leaching for risk neutral and most of risk averse farmers.