A finite volume method for numerical grid generation

A novel method to generate body‐fitted grids based on the direct solution for three scalar functions is derived. The solution for scalar variables ξ, η and ζ is obtained with a conventional finite volume method based on a physical space formulation. The grid is adapted or re‐zoned to eliminate the residual error between the current solution and the desired solution, by means of an implicit grid‐correction procedure. The scalar variables are re‐mapped and the process is reiterated until convergence is obtained. Calculations are performed for a variety of problems by assuming combined Dirichlet–Neumann and pure Dirichlet boundary conditions involving the use of transcendental control functions, as well as functions designed to effect grid control automatically on the basis of boundary values. The use of dimensional analysis to build stable exponential functions and other control functions is demonstrated. Automatic procedures are implemented: one based on a finite difference approximation to the Cristoffel terms assuming local‐boundary orthogonality, and another designed to procure boundary orthogonality. The performance of the new scheme is shown to be comparable with that of conventional inverse methods when calculations are performed on benchmark problems through the application of point‐by‐point and whole‐field solution schemes. Advantages and disadvantages of the present method are critically appraised. Copyright © 1999 National Research Council of Canada.     

Quantification of oxygenated volatile organic compounds in seawater by membrane inlet-proton transfer reaction/mass spectrometry

The role of the ocean in the cycling of oxygenated volatile organic compounds (OVOCs) remains largely unanswered due to a paucity of datasets. We describe the method development of a membrane inlet-proton transfer reaction/mass spectrometer (MI-PTR/MS) as an efficient method of analysing methanol, acetaldehyde and acetone in seawater. Validation of the technique with water standards shows that the optimised responses are linear and reproducible. Limits of detection are 27 nM for methanol, 0.7 nM for acetaldehyde and 0.3 nM for acetone. Acetone and acetaldehyde concentrations generated by MI-PTR/MS are compared to a second, independent method based on purge and trap-gas chromatography/flame ionisation detection (P&T-GC/FID) and show excellent agreement. Chromatographic separation of isomeric species acetone and propanal permits correction to mass 59 signal generated by the PTR/MS and overcomes a known uncertainty in reporting acetone concentrations via mass spectrometry. A third bioassay technique using radiolabelled acetone further supported the result generated by this method. We present the development and optimisation of the MI-PTR/MS technique as a reliable and convenient tool for analysing seawater samples for these trace gases. We compare this method with other analytical techniques and discuss its potential use in improving the current understanding of the cycling of oceanic OVOCs.     

Beitr?ge zur Harnanalyse

Ohne Zusammenfassung     

Unusual coordination behavior of Cr3+ in microporous aluminophosphates

A CrAPO-5 molecular sieve has been investigated with X-ray absorption spectroscopy (EXAFS-XANES) as dehydrated material and after loading with water and ammonia to unravel the coordination geometries of Cr3+ in the framework of a microporous crystalline aluminophosphate, more particularly of the AFI-type. A comparison of the XANES data, a preedge analysis with crystal field multiplet calculations and EXAFS data, pointed toward the presence of framework Cr3+ which, on dehydration, takes on a distorted tetrahedral coordination state. Due to the 3d3 configuration of Cr3+, this unusual tetrahedral coordination environment strongly tends to transform into the more stable 6-fold coordination geometry by binding two extraframework water molecules during hydration. In the presence of ammonia, tetrahedral Cr3+ readily transforms into a 5-fold coordination geometry by binding one ammonia molecule. Therefore, depending on the environmental conditions, the Cr3+ ions can occur in a 4-, 5-, or 6-fold coordination. This observation underlines the flexibility of transition metal ions, such as Cr3+, to cope with unusual coordination geometries in inorganic hosts, making them interesting as potential active sites in heterogeneous catalysis.     

Simultaneous measurement of the ratio R=B(t --> Wb)/B(t --> Wq) and the top-quark pair production cross section with the D0 detector at sqrt(s) = 1.96 TeV

We present the first simultaneous measurement of the ratio of branching fractions, R=B(t --> Wb)/B(t --> Wq), with q being a d, s, or b quark, and the top-quark pair production cross section sigma(tt[over]) in the lepton plus jets channel using 0.9 fb(-1) of pp[over] collision data at sqrt(s)=1.96 TeV collected with the D0 detector. We extract R and sigma(tt[over]) by analyzing samples of events with 0, 1, and > or =2 identified b jets. We measure R=0.97(+0.09)/(-0.08)(stat+syst) and sigma(tt[over])=8.18(+0.09)(-0.84)(stat+syst) +/- 0.50(lumi) pb, in agreement with the standard model prediction.     

Catalytic Adventures in Space and Time Using High Energy X-rays

Very high energy X-rays (ca. >40 keV) have long offered great promise in providing great insight into the inner workings of catalysts; insights that may complement the battery of techniques available to researchers in catalysis either in the laboratory or at more conventional X-ray wavelengths. This contribution aims to critically assess the diverse possibilities now available in the high energy domain as a result of the maturation of third generation synchrotron facilities and to look forward to the potential that forthcoming developments in synchrotron source technology may offer the world of catalysis in the near future.