Detection methods/detectors

As CE continues to evolve, it is not surprising to see a concomitant development of optical detection methods. Detector innovations have been required to keep up with smaller diameter capillaries, faster separations, parallel capillary systems, and microfluidic-based electrophoretic formats. In parallel to these changes, more flexible and higher performance imaging detectors, UV light sources, and clever applications of these advances continue to push the envelope in terms of light-based detection forCE. 

Further, peak overlap results in nonlinear detector response vs concentration. Therefore, some other detection method must be used in conjunction with either of these types of detection. Nevertheless, as can be seen from Figure Ilf, chiroptical detection can be advantageous if there is considerable overlap of the two peaks. In this case, chiroptical detection may reveal that the lea ding and tailing edges of the peak are enantiomerically enriched which may not be apparent from the chromatogram obtained with nonchiroptical detection (Fig. He). 

Physical detection methods are based on inclusion of substance-specific properties. The most commonly employed are the absorption or emission of electromagnetic radiation, which is detected by suitable detectors (the eye, photomultiplier). The / -radiation of radioactively labelled substances can also be detected directly. These nondestructive detection methods allow subsequent micropreparative manipulation of the substances concerned. They can also be followed by microchemical and/or biological-physiological detection methods. 

It is generally necessary to multiply the response obtained from a detection method by a response factor to convert the response into a useful value. For instance, the response of a fluorescence detector would be multiplied by an appropriate factor (y to obtain the concentration of the particular toxin present, or by a different factor (f ) to calculate the toxicity. Since the specific toxicities of the various toxins - the ratios of toxicity to concentration - vary over a broad range, the f and f for a given toxin will generally be different, often greatly so. Furthermore, the f may vary for the different toxins, and the f may also vary. In an analysis, multiplication by the appropriate factor is straightforward because the various components of interest are resolved and the response for each can be multiplied by the appropriate response factor, f or f, for each toxin. Assays, however, present a dilemma. Because the components are not resolved and only one response is obtained, only one response factor can be used. The potential accuracy of an assay is therefore limited principally by the range of response factors to the... 

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 widely regarded approach to accomplish the determination of as many pesticides as possible in as few steps as possible is to use MS detection. MS is considered a universally selective detection method because MS detects all compounds independently of elemental composition and further separates the signal into mass spectral scans to provide a high degree of selectivity. Unlike GC with selective detectors, or even atomic emission detection (AED), GC/MS may provide acceptable confirmation of the identity of analytes without the need for further information. This reduces the need to re-inject a sample into a separate GC system (usually GC/MS) for pesticide confirmation. Through the use of selected ion monitoring (SIM), efficient ion-trap or quadrupole devices, and/or tandem mass spectrometry (MS/MS), modern GC/MS instruments provide LODs similar to or lower than those of selective detectors, depending on the analytes, methods, and detectors. 

Perhaps the most revolutionary development has been the application of on-line mass spectroscopic detection for compositional analysis. Polymer composition can be inferred from column retention time or from viscometric and other indirect detection methods, but mass spectroscopy has reduced much of the ambiguity associated with that process. Quantitation of end groups and of co-polymer composition can now be accomplished directly through mass spectroscopy. Mass spectroscopy is particularly well suited as an on-line GPC technique, since common GPC solvents interfere with other on-line detectors, including UV-VIS absorbance, nuclear magnetic resonance and infrared spectroscopic detectors. By contrast, common GPC solvents are readily adaptable to mass spectroscopic interfaces. No detection technique offers a combination of universality of analyte detection, specificity of information, and ease of use comparable to that of mass spectroscopy. 

The overall performance of a separation method is intrinsically linked to that of the detector used as part of the system. A detector is a device that monitors, in the dimensions of space or time, the presence of the components of a mixture that has been subjected to a chromatographic process. The detection methods provide evidence concerning the quality of the separation and serve especially to increase sensitivity and selectivity. The quantitative aspects of chromatographic analyses are dependent upon the detector capabilities. 

Many IC techniques are now available using single column or dual-column systems with various detection modes. Detection methods in IC are subdivided as follows [838] (i) electrochemical (conductometry, amper-ometry or potentiometry) (ii) spectroscopic (tJV/VIS, RI, AAS, AES, ICP) (iii) mass spectrometric and (iv) postcolumn reaction detection (AFS, CL). The mainstay of routine IC is still the nonspecific conductometric detector. A significant disadvantage of suppressed conductivity detection is the fact that weak to very weak acid anions (e.g. silicate, cyanide) yield poor sensitivity. IC combined with potentiometric detection techniques using ISEs allows quantification of selected analytes even in complex matrices. The main drawback... 

An ion mobility spectrometer consists of a sample-introduction device a drift tube where ionisation and separation of ions takes place and a detector. Ionisation sources of choice include radioactive sources (e.g. a 63Ni foil), photoionisation methods, corona-spray ionisation, flame ionisation and corona discharge. The most common detection method used to measure the... 

The concept of peak capacity is rather universal in instrumental analytical chemistry. For example, one can resolve components in time as in column chromatography or space, similar to the planar separation systems however, the concept transcends chromatography. Mass spectrometry, for example, a powerful detection method, which is often the detector of choice for complex samples after separation by chromatography, is a separation system itself. Mass spectrometry can separate samples in time when the mass filter is scanned, for example, when the mass-to-charge ratio is scanned in a quadrupole detector. The sample can also be separated in time with a time-of-flight (TOF) mass detector so that the arrival time is related to the mass-to-charge ratio. 

In soil analysis, HPLC is used much like GC in that soil is extracted and the extract, after suitable cleanup and concentration, is analyzed. One major difference between them is that HPLC does not require the components to be in the gaseous phase. They must, however, be soluble in an eluent that is compatible with the column and detector being used. A second difference is that both a syringe and an injector are used to move the sample into the eluent and onto the column. Detection is commonly by UV absorption, although RI, conductivity, and mass spectrometry are also commonly used. Conductivity or other electrical detection methods are used when analysis of ionic species in soil is carried out [3,78],... 

Several kinds of detection systems have been applied to CE [1,2,43]. Based on their specificity, they can be divided into bulk property and specific property detectors [43]. Bulk-property detectors measure the difference in a physical property of a solute relative to the background. Examples of such detectors are conductivity, refractive index, indirect methods, etc. The specific-property detectors measure a physico-chemical property, which is inherent to the solutes, e.g. UV absorption, fluorescence emission, mass spectrum, electrochemical, etc. These detectors usually minimize background signals, have wider linear ranges and are more sensitive. In Table 17.3, a general overview is given of the detection methods that are employed in CE with their detection limits (absolute and relative). 

Three different detection methods (gas chromatography with electron capture, mass spectrometric and atomic emission detectors) have been compared for the determination of polychlorobiphenyls in highly contaminated marine sediments [74], Only atomic emission detection in the chlorine-selective mode provided excellent polychlorobiphenyl profiles without interferences. However, the lower sensitivity of the atomic emission detector, compared to the other two detectors required a 10 to 20g sample size for most analyses. 

Since different lamps and windows are available, this detection method can often be selective for only some of the components present in the sample. Its ability to detect small concentrations is especially good for aromatic hydrocarbons and inorganics. It is a nondestructive detector. 

Many separation and detection methods applied in combination with liquid chromatography (LC) that are described in the literature for the determination of surfactants are not specific to the detection of these compounds at trace levels. Even ultraviolet (UV) spectra obtained from diode array detectors often give only limited information. Furthermore, non-reproducible retention behaviour as well as coelution interference effects are frequently observed during the separation of surfactant-containing extracts. This is recognised, however, only in those cases where specific detection methods such as mass spectrometry (MS) are applied. 

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