Detection methods, selection

The pump-probe concept can be extended, of course, to other methods for detection. Zewail and co-workers [16,18, 19 and 2Q, 93] have used the probe pulse to drive population from a reactive state to a state that emits fluorescence [94, 95, 96, 97 and 98] or photodissociates, the latter situation allowing the use of mass spectrometry as a sensitive and selective detection method [99, 100]. 

Plasma atomic emission spectrometry is also employed as a detection method for gc (see Plasma technology). By monitoring selected emission lines a kind of selective detection based on elemental composition can be achieved (see Spectroscopy). 

All the usual detection methods are naturally suitable for the detection of such substances (Fig 2) In addition, however, it is also possible to detect the ) -radiation they produce The selectivity of the detection is, thus, increased This, however,... 

The attributes required of a method usually include good sensitivity, low hmits of detection, and selectivity. It must be recognized that while low limits of detection will usually require good sensitivity, the latter, in itself, does not guarantee low limits of detection since these are often determined by the levels of interfering materials present and not the absolnte sensitivity of the technique. Low limits of detection allow the analyte to be determined at levels at or below those considered to be harmful or prescribed by legislation or at which it is found in a particular... 

Alternatively, LC is used for the separation and quantification of PAHs using both UV and fluorescence detection. The analytes are identified based on their relative retention times and UV and/or fluorescence emission spectra. For UV detection an efficient cleanup is a prerequisite since this detection method is not very selective (almost universal for PAHs), and hence it also responds to many coeluting compounds. Due to the high specificity of fluorescence detection for most PAHs, this LC detection method is less susceptible to potential interferences. As in the case of GC the apphcation of internal standard(s) is mandatory since solvents have to be evaporated during the cleanup, which may result in partial losses of some of the more volatile analytes. 

Its principles include polar extraction with acetone-water (2 1, v/v), homogeneous partitioning of the target molecules into an organic solvent, GPC cleanup on Bio-Beads, fractionation by adsorption column chromatography on silica gel (Si02) deactivated with 1.5% water and finally GC with various selective detection methods (NPD, BCD, FPD). 

There are several factors involved in defining the limitations of an analytical method. Selecting the right method for defining these limitations can be as important as the actual definitions. Factors that must be taken into consideration in defining detection and quantification limits are ... 

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. 

Sample preparation consists of homogenization, extraction, and cleanup steps. In the case of multiresidue pesticide analysis, different approaches can have substantially different sample preparation procedures but may employ the same determinative steps. For example, in the case of soil analysis, the imidazolinone herbicides require extraction of the soil in 0.5 M NaQH solution, whereas for the sulfonylurea herbicides, 0.5M NaOH solution would completely decompose the compounds. However, these two classes of compounds have the same determinative procedure. Some detection methods may permit fewer sample preparation steps, but in some cases the quality of the results or ruggedness of the method suffers when short cuts are attempted. For example, when MS is used, one pitfall is that one may automatically assume that all matrix effects are eliminated because of the specificity and selectivity of MS. 

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. 

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. 

For method tryout, run a control sample and two fortifications from each site. One fortification should be done at the LOQ and the other at the highest expected residue level, perhaps 1000 x LOQ. If the recoveries are within the acceptable range of 70-120% and there are no interferences, proceed with the method validation. If interferences are present which prevent quantitation of the analyte, try additional cleanup steps with SPE or use a more selective detection method such as liquid chromatography/mass spectrometry (LC/MS). 

From the above-given condensed review of the EEP detection methods one can infer that none of these methods can independently satisfy all the requirements specified for the study of heterogeneous processes involving the EEP participation. To our opinion, the application of semiconductor sensors for detection of EEPs can be provided by a combination of required qualities. The sensors are highly sensitive, miniature, can be operated within wide ranges of gas temperatures and pressures, and are made of simple devices. At the same time, a series of problems arise connected with the preliminary preparation of sensors and improving their selectivity. These and other questions of general nature will be considered in the section that follows. 

There are methods available to quantify the total mass of americium in environmental samples. Mass spectrometric methods provide total mass measurements of americium isotopes (Dacheux and Aupiais 1997, 1998 Halverson 1984 Harvey et al. 1993) however, these detection methods have not gained the same popularity as is found for the radiochemical detection methods. This may relate to the higher purchase price of a MS system, the increased knowledge required to operate the equipment, and the selection by EPA of a-spectrometry for use in its standard analytical methods. Fluorimetric methods, which are commonly used to determine the total mass of uranium and curium in environmental samples, have limited utility to quantify americium, due to the low quantum yield of fluorescence for americium (Thouvenout et al. 1993). 

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... 

The guanine radical cations (G +) are detected by their reactions with water, which leads after treatment with piperidine or ammonia to selective strand cleavage [14]. A similar charge detection method was used by J.K. Barton, G.B. Schuster and I. Saito as described in their articles in this volume. The cleavage products were separated and quantified by gel electrophoresis. A typical example is shown in Fig. 7 where the GGG unit acts as a thermodynamic sink for the positive charge, and the efficiency of the charge transfer can be measured by the product ratio Pggg/Pg-... 

Undoubtedly, the technique most suited to tackle polyatomic multichannel reactions is the crossed molecular beam (CMB) scattering technique with mass spectrometric detection and time-of-flight (TOF) analysis. This technique, based on universal electron-impact (El) ionization coupled with a quadrupole mass filter for mass selection, has been central in the investigation of the dynamics of bimolecular reactions during the past 35 years.1,9-11 El ionization affords, in principle, a universal detection method for all possible reaction products of even a complex reaction exhibiting multiple reaction pathways. Although the technique is not usually able to provide state-resolved information, especially on a polyatomic... 

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