Detector, atomic spectrometer application

The calibration of atomic spectrometers can be handled much easier than that of conventional IC detectors using the large dynamic range of ICP techniques. Those simple off-line calibrations had been used for ICP-AES and ICP-MS in on-line preconcentration applications. With its ability to decide between isotopes the ICP-MS is well suited for isotope dilution analysis (IDMS), a calibration tool which increases the accuracy, the results and saves time due to reduced calibration work. The use of IDMS in combination with on-line coupling methods allows a significant speedup of the usually to IDMS applied time consuming separation processes. 

As noted earlier, USNs have been employed for sample insertion into atomic spectrometers suoh as flame atomio absorption spectrometry (FAAS) [9,10], electrothermal atomic absorption speotrometry (ETAAS) [11], atomic fluorescence spectrometry (AFS) [12,13], induotively ooupled plasma-atomic emission spectrometry (ICP-AES) [14,15], inductively coupled plasma-mass spectrometry (ICP-MS) [16,17] and microwave induced plasma-atomic emission spectrometry (MIP-AES) [18,19]. Most of the applications of ultrasonic nebulization (USNn) involve plasma-based detectors, the high sensitivity, selectivity, precision, resolution and throughput have fostered their implementation in routine laboratories despite their high cost [4]. 

The widespread use of USNn for sample insertion in atomic spectrometers is apparent from the number of reported applications. As noted earlier, the atomic techniques benefiting to the greatest extent from USN are plasma-based techniques [4,19]. By contrast, FAAS- and ETAAS-based detectors have scarcely been used with USNn [9-11]. 

The association of a spectrometer with a liquid chromatograph is usually to aid in structure elucidation or the confirmation of substance identity. The association of an atomic absorption spectrometer with the liquid chromatograph, however, is usually to detect specific metal and semi-metallic compounds at high sensitivity. The AAS is highly element-specific, more so than the electrochemical detector however, a flame atomic absorption spectrometer is not as sensitive. If an atomic emission spectrometer or an atomic fluorescence spectrometer is employed, then multi-element detection is possible as already discussed. Such devices, used as a LC detector, are normally very expensive. It follows that most LC/AAS combinations involve the use of a flame atomic absorption spectrometer or an atomic spectrometer fitted with a graphite furnace. In addition in most applications, the spectrometer is set to monitor one element only, throughout the total chromatographic separation. 

During the last decade, research efforts in the field of LC-MS have changed considerably. Technological problems in interfacing appear to be solved, and a number of interfaces have been found suitable for the analysis of flavonoids. These include TSP, continuous-flow fast-atom bombardment (CF-FAB), ESI, and APCI. LC-MS is frequently used to determine the occurrence of previously identified compounds or to target the isolation of new compounds (Table 2.11). LC MS is rarely used for complete structural characterization, but it provides the molecular mass of the different constituents in a sample. Then, further structural characterization can be performed by LC-MS-MS and MS-MS analysis. In recent years, the combination of HPLC coupled simultaneously to a diode-array (UV-Vis) detector and to a mass spectrometer equipped with an ESI or APCI source has been the method of choice for the determination of flavonoid masses. Applications of LC-MS (and LC-MS-MS) in flavonoid... 

S. Euan, H. Pang and R. S. Houk, Application of generalized standard additions method to inductively coupled plasma atomic emission spectroscopy with an echelle spectrometer and segmented-array charge-coupled detectors, Spectrochim. Acta, Part B, 50(8), 1995, 791-801. 

HPLC units have been interfaced with a wide range of detection techniques (e.g. spectrophotometry, fluorimetry, refractive index measurement, voltammetry and conductance) but most of them only provide elution rate information. As with other forms of chromatography, for component identification, the retention parameters have to be compared with the behaviour of known chemical species. For organo-metallic species element-specific detectors (such as spectrometers which measure atomic absorption, atomic emission and atomic fluorescence) have proved quite useful. The state-of-the-art HPLC detection system is an inductively coupled plasma/MS unit. HPLC applications (in speciation studies) include determination of metal alkyls and aryls in oils, separation of soluble species of higher molecular weight, and separation of As111, Asv, mono-, di- and trimethyl arsonic acids. There are also procedures for separating mixtures of oxyanions of N, S or P. 

It is worth stressing that everything that has ever been published on the application of AAS to food analysis can be done at least as well with HR-CS AAS. Since the same flames and burners, and the same type of electrothermal atomizers, are used in both systems, and only the spectrometer part from the radiation source to the detector has been re-designed, it is much more appropriate to talk about the improvements brought about by this change, and about the simplifications and the additional features that have become available this way. 

Both Q and SF mass spectrometers are scanning (sequential) analyzers and multiisotope analysis can be achieved at the expense of the measurement sensitivity and precision. The sequential measurement of m/z at different points within a time-dependent concentration proble of a transient signal can result in peak distortions and quantisation errors commonly referred to as spectral skew. The alternative is TOF-MS which features the ability to produce a complete atomic mass spectrum in less than 50 xs and thus allows very brief transient signals to be recorded with high bdelity. This is especially useful in the on-line isotope ratio determination. However, a 10-fold loss in sensitivity of a TOF-ICP-MS instrument in comparison with the latest Q instruments often creates an obstacle for the wider application of TOF-ICP-MS as a detector in the CE of metallobiomolecules in biological samples. 

Besides the universal detector systems, for example electron capture, flame ionisation and thermal conductivity usually coupled with gas chromatographic columns, various other detectors are now being used to provide specific information. For example, the gas chromatograph/mass spectrometer couple has been used for structure elucidation of the separated fractions. The mechanics of this hybrid technique have been described by Message (1984). Other techniques used to detect the metal and/or metalloid constituents include inductively coupled plasma spectrometry and atomic absorption spectrometry. Ebdon et al. (1986) have reviewed this mode of application. The type and mode of combination of the detectors depend on the ingenuity of the investigator. Krull and Driscoll (1984) have reviewed the use of multiple detectors in gas chromatography. 

The majority of applications in atomic spectrometry involve the use of the flame AAS detector. A detailed review of the field is given by Valcarcel and Gallego [35] and Tyson [36]. FI liquid-liquid extractions are implemented for different objectives including preconcentration, interference removal and indirect determination of anions and organic analytes. The coupling of FI liquid-liquid extraction systems to a flame AA spectrometer pose no major difficulties, occasional entrainment of traces of aqueous phase into the detector usually will not produce noticeable effects, while the presentation of the analyte to the detector in an organic solvent extract may create 2-3 fold extra sensitivity enhancements for many elements compared to sample introduction in the aqueous phase. However, a few points discussed below are to be noted to produce an optimized interfacing. 

The main application of the MIP atomic emission spectrometer has been as a detector for GC, where it is more commonly known as an AED. 

Simple, low-dispersion monochromators or even interference filters are used for most flame emission applications since few atomic line spectral interferences are expected as a result of the limited population of the higher-lying excited states. For high-temperature sources such as ICPs, higher-dispersion spectrometers are typically used. Instruments set up to do simultaneous multielemental analysis can use direct readers with PMT detection. However, most modern detections systems for this type of source for simultaneous multielemental analysis employ a high-dispersion eschelle grating spectrometer and an array detector such as a CCD or CID. 

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