Sensitivity GC detectors

The electron-capture detector (BCD) is probably the most sensitive GC detector presently available. However, like most high-sensitivity detectors, it is also very specific and will only sense those substances that are electron capturing (e.g., halogenated substances, particularly fiuorinated materials). 

The most sensitive GC detectors are sample-destructive. Thus, if there is a need for further sample investigation, effluent splitting becomes essential. In a typical situation, a small portion of the effluent is led into such a detector, while the remainder is trapped for additional physical or chemical studies. 

Several major advances that made GC a more attractive tool in blood hormone analysis took place during the last 10-15 years (a) development of more efficient, fast, and selective ways to purify plasma extracts, as based on the availability of various hpophilic gels and HPLC (b) availability of highly efficient capillary colunms to reduce the cases of co-elution of hormones with other mixture components (also, increasing detection sensitivity in most instances) and (c) a wider utilization of the mass spectrometer as a highly specific and sensitive GC detector. Several examples will now be shown to reinforce these points. 

Detectors in GC can be of low, medium, and high sensitivity highly sensitive GC detectors are of utmost importance to TEQA. 

The GC detector is the last major instrument component to discuss. The GC detector appears in Fig. 4.7 as the box to which the column outlet is connected. Evolution in GC detector technology has been as great as any other component of the gas chromatograph during the past 40 years. Among all GC detectors, the photoionization (PID), electrolytic conductivity (EICD), electron-capture (ECD), and mass selective detector (MSD) (or quadrupole mass filter) have been the most important to TEQA. The fact that an environmental contaminant can be measured in some cases down to concentration levels of parts per trillion (ppt) is a direct tribute to the success of these very sensitive GC detectors and to advances in electronic amplifier design. GC detectors manufactured during the packed column era were found to be compatible with WCOTs. In some cases, makeup gas must be introduced, such as for the ECD. Before we discuss these GC detectors and their importance to TEQA, let us list the most common commercially available GC detectors and then classify these detectors from several points of view. 

The electron capture detector is extremely sensitive, probably the most sensitive GC detector available (ca. 10-13 g/ml) and is widely used in the detection and analysis of halogenated compounds, in particular. 

Detectors. The function of the gc detector is to sense the presence of a constituent of the sample at the outlet of the column. Selectivity is the property that allows the detector to discriminate between constituents. Thus a detector selective to a particular compound type responds especially weU to compounds of that type, but not to other chemical species. The response is the signal strength generated by a given quantity of material. Sensitivity is a measure of the abiHty of the detector to register the presence of the component of interest. It is usually given as the quantity of material that can be detected having a response at twice the noise level of the detector. 

Reliable analytical methods are available for determination of many volatile nitrosamines at concentrations of 0.1 to 10 ppb in a variety of environmental and biological samples. Most methods employ distillation, extraction, an optional cleanup step, concentration, and final separation by gas chromatography (GC). Use of the highly specific Thermal Energy Analyzer (TEA) as a GC detector affords simplification of sample handling and cleanup without sacrifice of selectivity or sensitivity. Mass spectrometry (MS) is usually employed to confirm the identity of nitrosamines. Utilization of the mass spectrometer s capability to provide quantitative data affords additional confirmatory evidence and quantitative confirmation should be a required criterion of environmental sample analysis. Artifactual formation of nitrosamines continues to be a problem, especially at low levels (0.1 to 1 ppb), and precautions must be taken, such as addition of sulfamic acid or other nitrosation inhibitors. The efficacy of measures for prevention of artifactual nitrosamine formation should be evaluated in each type of sample examined. 

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. 

Coupled LC-LC can separate high-boiling petroleum residues into groups of saturates, olefins, aromatics and polar compounds. However, the lack of a suitable mass-sensitive, universal detector in LC makes quantitation difficult SFC-SFC is more suitable for this purpose. Applications of multidimensional HPLC in food analysis are dominated by off-line techniques. MDHPLC has been exploited in trace component analysis (e.g. vitamin assays), in which an adequate separation for quantitation cannot be achieved on a single column [972]. LC-LC-GC-FID was used for the selective isolation of some key components among the irradiation-induced olefinic degradation products in food, e.g. dienes and trienes [946],... 

The NO + 03 chemiluminescent reaction [Reactions (1-3)] is utilized in two commercially available GC detectors, the TEA detector, manufactured by Thermal Electric Corporation (Saddle Brook, NJ), and two nitrogen-selective detectors, manufactured by Thermal Electric Corporation and Antek Instruments, respectively. The TEA detector provides a highly sensitive and selective means of analyzing samples for A-nitrosamines, many of which are known carcinogens. These compounds can be found in such diverse matrices as foods, cosmetics, tobacco products, and environmental samples of soil and water. The TEA detector can also be used to quantify nitroaromatics. This class of compounds includes many explosives and various reactive intermediates used in the chemical industry [121]. Several nitroaromatics are known carcinogens, and are found as environmental contaminants. They have been repeatedly identified in organic aerosol particles, formed from the reaction of polycyclic aromatic hydrocarbons with atmospheric nitric acid at the particle surface [122-124], The TEA detector is extremely selective, which aids analyses in complex matrices, but also severely limits the number of potential applications for the detector [125-127],... 

A stream-splitter may be used at the end of the column to allow the simultaneous detection of eluted components by destructive GC detectors such as an FID. An alternative approach is to monitor the total ion current (TIC) in the mass spectrometer which will vary in the same manner as the response of an FID. The total ion current is the sum of the currents generated by all the fragment ions of a particular compound and is proportional to the instantaneous concentration of that compound in the ionizing chamber of the mass spectrometer. By monitoring the ion current for a selected mass fragment (m/z) value characteristic of a particular compound or group of compounds, detection can be made very selective and often specific. Selected ion monitoring (SIM) is more sensitive than TIC and is therefore particularly useful in trace analysis. 

The ideal HPLC detector should have the same characteristics as those required for GC detectors, i.e. rapid and reproducible response to solutes, a wide range of linear response, high sensitivity and stability of operation. No truly universal HPLC detector has yet been developed but the two most widely applicable types are those based on the absorption of UV or visible radiation by the solute species and those which monitor refractive index differences between solutes dissolved in the mobile phase and the pure mobile phase. Other detectors which are more selective in their response rely on such solute properties as fluorescence, electrical conductivity, diffusion currents (amperometric) and radioactivity. The characteristics of the various types of detector are summarized in Table 4.14. 

GC is coupled with many detectors for the analysis of pesticides in wastewater. At the present time the most popular is GC-MS, which will be discussed in more detail later in this section. The flame ionization detector (FID) is another nonselective detector that identifies compounds containing carbon but does not give specific information on chemical structure (but is often used for quantification because of the linear response and sensitivity). Other detectors are specific and only detect certain species or groups of pesticides. They include electron capture,nitrogen-phosphorus, thermionic specific, and flame photometric detectors. The electron capture detector (ECD) is very sensitive to chlorinated organic pesticides, such as the organochlorine compounds (OCs, DDT, dieldrin, etc.). It has a long history of use in many environmental methods,... 

Even though detectors used for GC are generally more sensitive and provide unique selectivity for many types of samples, the available HPLC detectors offer unique advantages in a variety of applications. In short, it is a good idea to recognize the fact that HPLC detectors are favored for some samples, whereas GC detectors are better for others. It should be noted that mass spectrometric detectors have been used effectively for both GC and HPLC. 

What does it mean to say that a GC detector is universal What does it mean to say that one GC detector is more sensitive and more selective than another ... 

GC detectors can be grouped into concentration-sensitive detectors and mass-sensitive detectors. The signal from a concentration-sensitive detector is related to the concentration of solute in the detector, which does not usually destroy the sample. Mass-sensitive detectors usually destroy the sample, and the signal is related to the rate at which solute molecules enter the detector. The response of a mass-sensitive detector is unaffected by make-up gas, while that of a concentration-sensitive detector will lower with make-up gas. A summary of some important characteristics of the GC detectors specifically used in drug residue analysis is presented in Table 23.1. 

MS detectors are unique among GC detectors because they deliver better quantitation of partially resolved peaks as well as improved confidence in peak identification. By their use, even chlorinated compounds like the coccidiostat clopidol can be determined with improved sensitivity and selectivity compared with traditional electron capture detection (20). The amount of the time needed to conduct GC-MS varies, depending upon confirmation or identification tasks. Sample preparation may take between 10 min and 24 h actual testing time may range from 30 min to 8 h, and evaluation between 1 and 40 h. 

The method of complete electrolysis is also important in elucidating the mechanism of an electrode reaction. Usually, the substance under study is completely electrolyzed at a controlled potential and the products are identified and determined by appropriate methods, such as gas chromatography (GC), high-performance liquid chromatography (HPLC), and capillary electrophoresis. In the GC method, the products are often identified and determined by the standard addition method. If the standard addition method is not applicable, however, other identification/determination techniques such as GC-MS should be used. The HPLC method is convenient when the product is thermally unstable or difficult to vaporize. HPLC instruments equipped with a high-sensitivity UV detector are the most popular, but a more sophisticated system like LC-MS may also be employed. In some cases, the products are separated from the solvent-supporting electrolyte system by such processes as vaporization, extraction and precipitation. If the products need to be collected separately, a preparative chromatographic method is use-... 

Mass Spectrometry. The use of a quadrupole mass spectrometer as a GC detector for nonmethane hydrocarbon analysis has come of age in recent years. Development of capillary columns with low carrier gas flows has greatly facilitated the interfacing of the GC and mass spectrometer (MS). The entire capillary column effluent can be dumped directly into the MS ion source to maximize system sensitivity. GC-MS detection limits are compound-specific but in most cases are similar to those of the flame ionization detector. Quantitation with a mass spectrometer as detector requires individual species calibration curves. However, the NMOC response pattern as represented by a GC-MS total ion chromatogram is usually very similar to the equivalent FID chromatogram. Consequently, the MS detector can... 

Assortment of Sensitive Detecting Systems. GC detectors (see Chapter 5) are relatively simple, highly sensitive, and possess rapid response. 

The GC detector has better sensitivity than many analytical techniques some detectors can sense 10 ltt g/sec,... 

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