Vapour generation flame atomic

Figure S.4 shows a calibration graph of arsenic concentrations obtained by using a Perkin Elmer 2100 atomic-absorption system bnked to a P.S. Analytical hydride/vapour generator (PSA 10.003). An electrically heated tube has been used in this work and the spectral source was an electrodeless discharge lamp. Alternatively, a flame-heated tube can be used.

Diemer, J. and Heumann, K.G. (1997) Bromide/bromate speciation by NTI-IDMS and ICP-MS coupled with ion exchange chromatography. Fresenius J. Anal. Chem., 357,74-79. Duan, YX., Wu, M., Jin, Q.H. and Hieftje, G.M. (1995) Vapour generation of nonmetals coupled to microwave plasma-torch mass-spectrometry. Spectrochim. Acta B, 50,355-368. Ebdon, L., Hill, S. and Jones, R (1987) Interface system for directly coupled high performance liquid chromatography-flame atomic absorption spectrometry for trace metal determination./. Anal. At. Spectrom., 2, 205-210. 

A surprising addition has recently been made to the list of elements which may be usefully determined by vapour generation techniques, namely cadmium.5 Sodium tetraethylborate was used to produce a volatile cadmium species, with citrate being used to mask interference from nickel and copper. Using an argon-diluted hydrogen diffusion flame as atomizer, the detection limit by AFS was 20 ng l-1. 

Maintaining the quality of food is a far more complex problem than the quality assurance of non-food products. Analytical methods are an indispensable monitoring tool for controlling levels of substances essential for health and also of toxic substances, including heavy metals. The usual techniques for detecting elements in food are flame atomic absorption spectroscopy (FAAS), graphite furnace atomic absorption spectrometry (GF AAS), hydride generation atomic absorption spectrometry (HG AAS), cold vapour atomic absorption spectrometry (CV AAS), inductively coupled plasma atomic emission spectrometry (ICP AES), inductively coupled plasma mass spectrometry (ICP MS) and neutron activation analysis (NAA). 

CV-AAS, Cold Vapour Atomic Absorption Spectrometry ETA-AAS, Electrothermal Atomization Atomic Absorption Spectrometry FAAS, Flame Atomic Absorption Spectrometry FIG-AAS, Flydride Generation Atomic Absorption Spectrometry ICP-AES. Inductively Coupled Plasma Atomic Emission Spectrometry ID-MS, Isotopic Dilution Mass Spectrometry HR-ICP-MS, Magnetic Sector High Resolution Inductively Coupled Plasma Mass Spectrometry NAA, Neutron Activation Analysis Q-ICP-MS, Quadrupole Inductively Coupled Plasma Mass Spectrometry Z-ETA-AAS, Zeeman Electrothermal Atomization Atomic Absorption Spectrometry... 

A number of methods have been described for improving the sensitivity of conventional FAAS in order to allow the analysis without resorting to more expensive techniques. Best known of these techniques are hydride generation, cold vapour, semi-flame (Delves cup, tantalum boat), and slotted tube atom trap (STAT) methods. 

In AAS, FIA has been applied to hydride generation and cold vapour techniques, microsampling for flame atomic absorption, analysis of concentrated solutions, addition of buffers and matrix modifiers, dilution by mixing or dispersion, calibration methods, online separation of the matrix and analyte enrichment, and indirect AAS determinations. 

A novel technique of atomisation, known as vapour generation via generation of the metal hydride, has been evolved, which has increased the sensitivity and specificity enormously for these elements [5-7,9]. In these methods the hydride generator is linked to an atomic absorption spectrometer (flame graphite furnace) or inductively coupled plasma optical emission spectrometer (ICP-OES) or an inductively coupled plasma mass spectrometer (IPC-MS). Typical detection limits achievable by these techniques range from 3 pg/1 (arsenic) to 0.09 pgd (selenium). 

Although electrothermal atomisation methods can be applied to the determination of arsenic, antimony, and selenium, the alternative approach of hydride generation is often preferred. Compounds of the above three elements may be converted to their volatile hydrides by the use of sodium borohydride as reducing agent. The hydride can then be dissociated into an atomic vapour by the relatively moderate temperatures of an argon-hydrogen flame. 

The technique of flame emission spectroscopy is used to determine the concentration of Ba, K, and Na ions by measuring the intensity of emission at a specific wavelength by the atomic vapour of the element generated from calcium acetate i.e., by introducing its solution into a flame. 

We have already seen in Chapter 2 that choice of atomizer system to be used may have a dramatic effect upon sensitivity, and thus upon signal-to-noise ratio. It is necessary to choose not only between flames, electrothermal atomization (ETA), and cold vapour and hydride generation techniques (which are discussed in Chapter 6), but sometimes also between different flames. Those elements which tend to form thermally stable oxides, such as Al, Ti, Si, Zr, may only be determined in a hotter, reducing nitrous oxide-acetylene flame. They cannot be determined with useful sensitivity in the air-acetylene flame. Some elements, Ba and Cr for example, may be determined in air-acetylene, but are more efficiently atomized in nitrous oxide-acetylene. 

The direct introduction of atomic vapour into the AAS flame can also be seen as an equipment variation [148, 152], Here, the evaporation of the steel samples can be carried out with the help of the glow-discharge lamp [148] or an aerosol generator with a low current d.c.-arc discharge [152]. Another example is the combination of gas chromatography and AAS [92], where AAS is used as an element detector. 

Several types of atomization cell are available flame, graphite furnace, hydride generation and cold vapour. Flame is the most common. In the premixed laminar flame, the fuel and oxidant gases are mixed before they enter the burner (the ignition site) in an expansion chamber. The more commonly used flame in FAAS is the air-acetylene flame (temperature, 2500 K), while the nitrous oxide-acetylene flame (temperature, 3150K) is used for refractory elements, e.g. Al. Both are formed in a slot burner positioned in the light path of the HCL (Fig. 27.4). 

The methods officially used in the wine trade transactions are summarized in Table 8.1. Generally, the OIV methods are officially adopted in the European Union without significant technical changes. The methods reported are mainly colorimetric, titrimetric, or use Atomic Emission Spectroscopy (AES, e.g. Flame Spectrophotometry), Atomic Absorption Spectroscopy (AAS), Hydride Generation-AAS (HG-AAS), Electrothermal-AAS (ET-AAS) and Vapour Atomic Flourescence Spectrophotometry (VAF). 

Hydride generation AAS (HGAAS) and cold vapour AAS (CVAAS) are special combinations of chemical separation and enrichment with AAS. In HGAAS the analyte is transformed to a volatile hydride, stripped off by an inert gas and atomized in a quartz tube, flame-in tube etc. About ten elements (As, Se, Bi, Sb etc.) can be determined by this technique. The accuracy and detection limits depend on the proper isolation of the hydride. CVAAS is the universally acknowledged most sensitive method for determination of Hg. The generation of elemental mercury vapour is similar to the hydride generation however the quartz cell may not be heated and this gives the name of the method. 

Hydride generation is a common method for the detection of metalloids such as As, Bi, Ge, Pb, Sb, Se, Sn and Te, although other vapours, e.g. Hg or alkylated Cd, may also be determined. This technique improves the sensitivity of the analysis substantially. Since the sample is in the gas phase, the sample transport efficiency is close to 100%. The hydrides atomize readily in the flame, although this approach is usually used in conjunction with a quartz T-piece in the atom cell. Methods have been developed that trap the hydrides on the surface of a graphite tube for use with ETAAS. This leads to preconcentration and further improvements in detection limit. 

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