Selective electron-capture

The structure-selective, electron-capture detector (ECD) is the second aost widely used ionization detector [115-118]. It owes Buch of its popularity to its unsurpassed sensitivity to a wide range of toxic and biologically active coapounds. Consequently, it is widely used in trace analysis for the detemination of pesticides, herbicides and industrial chemicals in the... 

Janev, R. K., Phaneuf, R. A Tawara H. and Shirai, T. (1993) Recommanded cross sections for state-selective electron capture in collisions of C6+and 08+ ions with atomic hydrogen, At. Data and Nucl. Data Tables, 55, pp. 201-232. 

Nota and Improta [813] determined cyanide in coke oven waste water by gas chromatography. The method is based on treatment of the sample with bromine and direct selective determination of the cyanogen bromide by gas solid chromatography using a BrCN selective electron capture detector. No preliminary treatment of the sample to remove interferences is necessary in this method, and in this sense it has distinct advantages over many of the earlier procedures. Bromine also oxidises thiocyanate to cyanogen bromide. Previous treatment of the sample with aqueous formaldehyde destroys thiocyanate and prevents its interference. 

Electron-Ion and Ion-Ion Recombination Processes, M. R. Flannery Studies of State-Selective Electron Capture in Atomic Hydrogen by Translational Energy Spectroscopy, H. B. Gilbody Relativistic Electronic Structure of Atoms and Molecules, I. P. Grant The Chemistry of Stellar Environments,... 

Besides the universal FID-detector, the selective electron capture (ECD), nitrogen-selective thermionic (NPD) and flame photometric (FPD) detectors have been used for the measurement of PAH, and nitrogen or sulfur containing heterocyclic analogs respectively (Wakeham (26), Willey et al. (29)). 

Reaction of polyoxyethylene and polyoxypropylene compounds with hydrogen bromide produces mono- and dibromoethane and mono- and dibromopropane, which are easily measured by gas chromatography. Less often, HI is used in place of HBr, giving the corresponding iodoethane and iodopropane compounds. Depending on the product, it may also be possible to determine the hydrophobe component by GC. When coupled with appropriate initial isolation steps, this reaction may even be used for trace analysis, especially if the halogen-selective electron capture detector is used (58-60). A technique for specific determination of AE in wastewater in the parts per billion range is based on GC determination of the alkyl bromides with mass selective detection (61). 

An electron capture detector is relatively insensitive to nonhalogenated compounds, providing the additional selectivity. 

Selectivity Because it combines separation with analysis, gas chromatography provides excellent selectivity. By adjusting conditions it is usually possible to design a separation such that the analytes elute by themselves. Additional selectivity can be provided by using a detector, such as the electron capture detector, that does not respond to all compounds. 

For carrying out of given researches method of synthetic pyrethroids determination in air has been developed. Chromatographic behaviour is investigated and optimum conditions of the synthetic pyrethroids analysis with application of capillary column with stationary phase DB-5 and electron-capture detector are selected. 

Several methods are available for the analysis of trichloroethylene in biological media. The method of choice depends on the nature of the sample matrix cost of analysis required precision, accuracy, and detection limit and turnaround time of the method. The main analytical method used to analyze for the presence of trichloroethylene and its metabolites, trichloroethanol and TCA, in biological samples is separation by gas chromatography (GC) combined with detection by mass spectrometry (MS) or electron capture detection (ECD). Trichloroethylene and/or its metabolites have been detected in exhaled air, blood, urine, breast milk, and tissues. Details on sample preparation, analytical method, and sensitivity and accuracy of selected methods are provided in Table 6-1. 

The presence of heteroatoms usually provides a convenient feature for improving selectivity by employing selective detection mechanisms. GC may then use flame photometric detection (FPD) for S and P atoms and to a certain extent for N, Se, Si etc. thermoselective detection (TSD) and nitrogen-phosphorus detection (NPD) for N and P atoms electron capture detection (ECD) for halogen atoms (E, Cl, Br, and 1) and for systems with conjugated double bonds and electron-drawing groups or atomic emission detection (AED) for many heteroatoms. 

On the other hand, if only specific GC detectors, e.g. the electron capture, nitrogen-phosphorus or flame photometric detectors, are tested, the argument of lack of GC method sensitivity is not acceptable. In most cases mass spectrometric detectors provide the sensitivity and selectivity needed. Unfortunately, tandem mass spectrometry (MS/MS) or MS" detectors for GC are still not widely used in official laboratories, and therefore these techniques are not always accepted for enforcement methods. 

For multi-analyte and/or multi-matrix methods, it is not possible to validate a method for all combinations of analyte, concentration and type of sample matrix that may be encountered in subsequent use of the method. On the other hand, the standards EN1528 andEN 12393 consist of a range of old multi-residue methods. The working principles of these methods are accepted not only in Europe, but all over the world. Most often these methods are based on extractions with acetone, acetonitrile, ethyl acetate or n-hexane. Subsequent cleanup steps are based on solvent partition steps and size exclusion or adsorption chromatography on Florisil, silica gel or alumina. Each solvent and each cleanup step has been successfully applied to hundreds of pesticides and tested in countless method validation studies. The selectivity and sensitivity of GC combined with electron capture, nitrogen-phosphorus, flame photometric or mass spectrometric detectors for a large number of pesticides are acceptable. 

A survey of the literature with a key phrase tissue residue analysis yielded a distribution of separation and detection techniques as outlined in Table 2. LC with either UV or fluorescence detection was the most common separation and detection technique, representing 61% of the citations. The results are an indication of the maturity of LC as a common, well-understood technique. The second most commonly used technique cited in the literature (13%) was GC with either a mass-selective or electron capture detector. GC is also a mature technology and a good choice owing to the... 

Gas chromatography with electron capture and/or mass-selective detection... 

Visible wavelength spectrophotometry Mass selective detection Nitrogen-phosphorus detection Electron capture detection UV detection... 

Universal and selective detectors, linked to GC or LC systems, have remained the predominant choice of analysts for the past two decades for the determination of pesticide residues in food. Although the introduction of bench-top mass spectrometers has enabled analysts to produce more unequivocal residue data for most pesticides, in many laboratories the use of selective detection methods, such as flame photometric detection (FPD), electron capture detection (BCD) and alkali flame ionization detection (AFID) or nitrogen-phosphorus detection (NPD), continues. Many of the new technologies associated with the on-going development of instrumental methods are discussed. However, the main objective of this section is to describe modern techniques that have been demonstrated to be of use to the pesticide residue analyst. 

The most common final separation techniques used for agrochemicals are GC and LC. A variety of detection methods are used for GC such as electron capture detection (BCD), nitrogen-phosphorus detection (NPD), flame photometric detection (FPD) and mass spectrometry (MS). For LC, typical detection methods are ultraviolet (UV) detection, fluorescence detection or, increasingly, different types of MS. The excellent selectivity and sensitivity of LC/MS/MS instruments results in simplified analytical methodology (e.g., less cleanup, smaller sample weight and smaller aliquots of the extract). As a result, this state-of-the-art technique is becoming the detection method of choice in many residue analytical laboratories. 

A technique known as selective electron capti sensitization has been used to increase the response of the BCD weakly electron-capturing compounds [117]. In this mode a standard electron-capture detector is used with a supply of makeup gas doped with a specific sensitizing reagent such as oxygen nitrous oxide. In this way the BCD functions as an ion-aoleculSj... 

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