Atomic spectrometer, element specific detector

Transient signals are typically obtained in atomic spectrometry when samples are introduced by flow injection techniques or when the spectrometer is used as an element-specific detector in hyphenated techniques. Inductively coupled plasma mass spectrometry has nowadays become the detection technique of choice for multielement-specific detection in speciation as it allows multielemental... 

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. 

Comparison of graphite furnace atomic absorption and inductively coupled argon plasma emission spectrometers as element-specific detectors for liquid chromatography... 

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. 

A primary source is used which emits the element-specific radiation. Originally continuous sources were used and the primary radiation required was isolated with a high-resolution spectrometer. However, owing to the low radiant densities of these sources, detector noise limitations were encounterd or the spectral bandwidth was too large to obtain a sufficiently high sensitivity. Indeed, as the width of atomic spectral lines at atmospheric pressure is of the order of 2 pm, one would need for a spectral line with 7. = 400 nm a practical resolving power of 200 000 in order to obtain primary radiation that was as narrow as the absorption profile. This is absolutely necessary to realize the full sensitivity and power of detection of AAS. Therefore, it is generally more attractive to use a source which emits possibly only a few and usually narrow atomic spectral lines. Then low-cost monochromators can be used to isolate the radiation. 

Table 3.4 compares detection limits with secondary fluorescers to the results with the RMF method and 15-kV broadband excitation [16,17]. Four different fluorescence analyzers were tested (units A, B, C, and D), and the results were corrected for differences in performance for the energy-dispersive spectrometers employed on each unit. Unit A used a chromium anode tube, and unit B used a tungsten anode tube. Unit A was a commercial, general-purpose instrument. Unit B was specifically designed for atmospheric aerosol analysis, where closer coupling between the tube, fluorescer, sample, and detector could be employed with some sacrifice of insensitivity to specimen-positioning errors. Table 3.5 lists the x-ray tube operating conditions required for Table 3.4. For medium- to high-atomic-number elements, the secondary fluorescer method provides detection limits equivalent to the RMF element, but requires much higher x-ray tube power. For light elements.

CE)] with a sensitive and element-specific atomic detector (usually an atomic absorption, emission or mass spectrometer) have become fundamental tools for speciation analysis, as can be seen in a special journal issue devoted to such application. Some of the hyphenated techniques available for spedes-selective analysis in biological and environmental materials are schematically shown in Figure 1.12. The choice of hyphenated technique depends primarily on the objective of the research. Speciation analysis in environmental and/or biological samples faces two main challenges because of the usually low concentrations of the analytes (below 1 pgg ) and the complexity of the matrix itself. 

Common gas chromatographic detectors that are not element- or metal-specific, atomic absorption and atomic emission detectors that are element-specific, and mass spectrometric detectors have all been used with the hydride systems. Flame atomic absorption and emission spectrometers do not have sufficiently low detection limits to be useful for trace element work. Atomic fluorescence [37] and molecular flame emission [38-40] were used by a few investigators only. The most frequently employed detectors are based on microwave-induced plasma emission, helium glow discharges, and quartz tube atomizers with atomic absorption spectrometers. A review of such systems as applied to the determination of arsenic, associated with an extensive bibliography, is available in the literature [36]. In addition, a continuous hydride generation system was coupled to a direct-current plasma emission spectrometer for the determination of arsenite, arsenate, and total arsenic in water and tuna fish samples [41]. 

Fig. 4.7 Schematic drawing of an atomic absorption spectrometer Light of a particular wavelength, absorbed by a specific element, is focused upon an atomized sample and the amount of that light that is absorbed is measured by the detector. The amount of light missing is proportional to the amount of a specific element in the atomized sample...

The gas chromatograph may be interfaced with atomic spectroscopic instruments for specific element detection. This powerful combination is useful for speci-ation of different forms of toxic elements in the environment. For example, a helium microwave induced plasma atomic emission detector (AED) has been used to detect volatile methyl and ethyl derivatives of mercury in fish, separated by GC. Also, gas chromatographs are interfaced to inductively coupled plasma-mass spectrometers (ICP-MS) in which atomic isotopic species from the plasma are introduced into a mass spectrometer (see Section 20.10 for a description of mass spectrometry), for very sensitive simultaneous detection of species of several elements. 

The basic function of the mass spectrometer is to measure the mass-to-charge ratios of analyte ions, and the various designs of mass spectrometers have been described in detail in the literature. The HPLC-MS system has four main components consisting of a sample inlet, an ion source, a mass analyzer, and finally an ion detector. The sample introduction system vaporizes the HPLC column effluent. The ion source produces ions from the neutral analyte molecules in the vapor phase. Several designs of ion sources have been used over the past years including electrospray ionization (ESI), atmospheric pressure chemical ionization (APCI), thermospray ionization (TSP), continuous flow fast atom bombardment (FAB), and atmospheric pressure photoionization (APPI). The inductively coupled plasma (ICP) is a hard ionization source and is used specifically for the detection of metals and metals in adducts or in organometallic compounds. Generally, ICP-MS is used for elemental speciation analysis with HPLC, which has been described elsewhere in... 

The inductively coupled plasma (ICP) atomic emission spectrometer (AES) is used for the high-sensitivity detection of metals in dissolved samples. Applications include metals analysis of polymers, additives, catalysts, and other components on polymers and plastic formulations as well as advanced composite materials. The operating principle is essentially the same as in ICP-MS, instrument with the main difference being the detector. While the ICP-MS detector is a quadruple mass spectrometer which detects elements by their mass, the ICP-AES uses a detector based on the specific energy frequency emitted by each element in the plasma. 

Chromatography has as its basis the transformation of a complex multi-component sample into a time-resolved, separated analyte stream, usually observed in the analog differential signal mode. The chromatographic sample is thus distinctive in that analytes are changing in nature and with time. An essential feature of chromatographic instrumentation is a detector for qualitative and quantitative determination of the components resolved by the column this should respond immediately and predictably to the presence of solute in the mobile phase. An important class of solute properly detectors are those giving Selective , or Specific information on the eluates. Spectral property detectors such as the mass spectrometer, the infrared spectrophotometer and the atomic emission spectrometer fall into this class. Such detectors may be element selective , structure or functionality selective or property selective . 

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