PubMed · 15689897
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Michele Jonsson Funk, Vicky A LeGrys. 2005. Testing diagnostic tests: why size matters.. https://doi.org/10.1016/j.jpeds.2004.10.054
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In autumn 2001, a full-scale test road was built with municipal solid waste incineration (MSWI) bottom ash at the Dåvamyran landfill, Umeå, Northern Sweden. Leachates were collected from asphalted sections with either bottom ash or gravel as filling material. In this research, 12 months of ash leachate sampling were evaluated with respect to emissions of contaminants such as trace metals and chlorides (Cl). The usefulness of regression models describing trace metal mobility from bottom ash was also tested as predictive tools for reusability applications of MSWI bottom ash. Cl, Cu, and Cr had the highest mobility (considering leachate concentrations) in the ash leachate, though concentrations of Cl and Cu decreased during the sampling period (Cl from 10,000 to 600 mg l(-1); Cu from 1600 to 500 microg l(-1)). An increased mobility of Cr during the autumns (about 3-4 times higher compared to the summer) was noted with a maximum value of nearly 70 microg l(-1) during autumn 2001. Pb showed a very low mobility over the entire year with leachate concentrations of around 3-4 microg l(-1). Chemical equilibrium calculations using Minteq indicated that several Cu minerals were oversaturated in the leachate, thus mineral precipitation could be responsible for declining amounts of Cu in the leachate. Adsorption to iron oxides was found to be a probable explanation for the low mobility of Pb. A reasonably good agreement between regression models and field values were achieved for Ni, Pb, Zn, and Cu, while the models for Cd and Cr were less promising. Even though a large part of the variation (R2=61-97%) in the leaching experiment could be explained by only pH and L/S, field data were much more scattered than expected from field pH.
We have performed density functional theory calculations on an oxo-iron porphyrin catalyst with chloride as an axial ligand and tested its reactivity toward propene. The reactions proceed via multistate reactivity on competing doublet and quartet spin surfaces. Close-lying epoxidation and hydroxylation mechanisms are identified, whereby in the gas phase the epoxidation reaction is dominant, while in environments with a large dielectric constant the hydroxylation pathways become competitive. By contrast to reactions with thiolate as an axial ligand all low-lying pathways have small ring-closure and rebound barriers, so it is expected that side products and rearrangements will be unlikely with Fe=O(porphyrin)Cl, whereas with Fe=O(porphyrin)SH some side products were predicted. The major differences in the electronic configurations of Fe=O(porphyrin)Cl and Fe=O(porphyrin)SH are due to strong mixing of thiolate orbitals with iron 3d orbitals, a mixing which is much less with chloride as an axial ligand. Predictions of the reactivity of ethylbenzene-h (12) versus ethylbenzene-d (12) are made.
A new design of miniaturised separation device for performing isotachophoresis (ITP) has been produced. The device contains a simple arrangement of channels comprising a single separation channel with a 'double T' injection geometry. The device was produced in poly(methyl methacrylate) and incorporates an on-column conductivity detector. A new electrolyte system was developed to enable the rapid determination of chloride to be made. This electrolyte system uses a leading ion of 3.5 mM nitrate at pH 3.0 with 0.5 mM indium(III) added as a complexing agent. Use of this electrolyte system with the new separation device allowed chloride samples to be analysed in under 100 s, with a limit of detection (LOD) calculated to be 2.2 mg l(-1).