Atomic spectrometer, element interface

Introduction into a DC plasma requires rather more care and attention owing to its inherent design features. As the hydride is being introduced into the plasma, it is necessary to provide a controlled sheath of argon to contain the hydride and direct it into the plasma. This chimney effect significantly improves the sensitivity for hydride-forming elements. This interface has also formed the basis of an introduction system for mercury vapour into an atomic-fluorescence spectrometer as described by Godden and Stockwell [12]. 

Mass analysis is a relatively simple technique, with the number of ions detected being directly proportional to the number of ions introduced into the mass spectrometer from the ion source. In atomic mass spectrometry the ion source produces atomic ions (rather than the molecular ions formed for qualitative organic analysis) which are proportional to the concentration of the element in the original sample. It was Gray who first recognized that the inductively coupled plasma would make an ideal ion source for atomic mass spectrometry and, in parallel with Fassel and Honk, and Douglas and French developed the ion sampling interface necessary to couple an atmospheric pressure plasma with a mass spectrometer under vacuum. 

Multi-element determination of dissolved metals at ultratrace level may be performed by Inductively Coupled Plasma-Mass Spectrometry (ICP-MS). U.S. EPA s Methods 200.8 and 1638 present a methodology for measuring trace elements in waters and wastes by the above technique. Sample is acid digested and the solution is introduced by pneumatic nebulization into a radio-frequency plasma. The elements in the compounds are atomized and ionized. The ions are extracted from the plasma through a differentially pumped vacuum interface and separated by a quadrupole mass spectrometer by their mass to charge ratios. The mass spectrometer must have a resolution capability of 1 amu peak width at 5% peak height. 

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. 

Nygren, O., Nilsson, C.-A. and Freeh, W. (1988) On-line interfacing of a liquid chromatograph to a continuously heated graphite furnace atomic absorption spectrometer for element-specific detection. Anal. Chem., 60, 2204-2208. 

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. 

Trace element analyses are often required for the determination of toxic metals such as chromium, mercury and lead in environmental samples and for monitoring the workplace environment. Conventional methods requiring extraction and separation procedures are time consuming. However, recent developments in GC and HPLC interfaced to atomic absorption and plasma emission spectrometers have enabled on-line analyses to be carried out. Ideally, the GC or HPLC column should be connected directly to the spectrometer sample cell or sample area to avoid dilution and loss of resolution. In practice a short heated transfer line of stainless steel or silica is used which has an internal diameter smaller than the column i.d. 

Inductively coupled plasma has become the ionization method of choice for elemental mass spectrometry. It was initially developed as the excitation source for multi-element optical spectrometers, because at typical plasma temperatures of 5000-10,000°C virtually all elements on the periodic chart emit detectable light. Most molecules are also atomized at these temperatures, which makes inductively coupled plasma ideal for mass spectrometry monitoring of elemental composition as well. Fassell and co-workers introduced the first inductively coupled plasma interfaced to a mass spectrometer in 1980 (Houk et al., 1980). Elemental mass spectrometry normally requires only low-resolution analysers because unit mass resolution is typically required (i.e. the mass difference between elements, which is always equal to or greater than 1 Da). 

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. 

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