Hydride Generation and Cold Vapour Technique

In analogy to sample introduction by hydride generation, it is also possible to perform mercury trace and isotope analysis by reducing Hg compounds to the metal using the cold vapour technique or the determination of iodine at the ultratrace level (after oxidation with 70 % perchloric acid of iodide to iodine) via the gas phase. 

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Hydride Generation and Cold Vapour Technique Coupled to an Inductively Coupled Plasma Source... 

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. 

Figure 95 A FIA system adapted for hydride generation and cold vapour techniques (Perkin Elmer Corp.)...

Initially hydride generation and cold vapour techniques were developed for the quantitative determination of the hydride-forming elements and mercury by atomic absorption spectrometry (Chapters, Sections 6.2 and 6.3), but nowadays these methods are also widely used in plasma atomic emission spectrometry. In the hydride generation technique, hydride-forming elements are more efficiently transported to the plasma than by conventional solution nebulization, and the production and excitation of free atoms and ions in the hot plasma is therefore more efficient. Spectral interferences are also reduced when the analyte is separated from the elements in the sample matrix. Both continuous (FIA) and batch approaches have been used for hydride generation. The continuous method is more frequently used in plasma AES than in AAS. Commercial hydride generation systems are available for various plasma spectrometers. 

A flame AAS (FAAS) detector can monitor the GC effluent continuously to provide on-line analysis. However, as the gas flow rates for the flame are quite high, the residence time in the flame is short, and this can adversely affect the detection limits. Detection limits in the microgram range are usually achieved. Improved detection limits can be obtained if the additional techniques of hydride generation or cold vapour mercury detection are used as described in Section 4.6. 

Hydride and cold-vapour techniques represent a special combination of chemical separation and pre-enrichment with AAS determination, resulting in higher powers of detection for elements with volatile hydrides, eg, As, Bi, Se, Sb, Hg. Recent literature on vapour generation has been reviewed by Hill et al. (1991). Some examples of the use of hydride generation for the analysis of plant material are given by Muse et al. (1989), Leuka et al. (1990) and Ainsworth and Cooke (1990). Hydride generation can also be used with ICP-EAS (see below) and applications have been reviewed (Nakahara, 1991). 

The techniques dealt with in this chapter are discussed in terms of similarities. For this reason, hydride generation and cold mercury vapour generation are addressed first, notwithstanding the limited scope of this technique as regards analytes — scope that can... 

To implement an easy and automated means for chemical vapour generation procedures (hydride generation for arsenic, selenium, etc., and cold vapour mercury), which allows for a reduction on the interferences caused by first-row transition metals (such as copper and nickel). FI methods may be readily coupled with almost all the atomic-based spectroscopic techniques (including graphite furnace atomisers). 

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. 

At the present time there are no ETA—AAS methods that can compete with the cold vapour technique for Hg or with hydride generation methods for Sb and Te. Another attractive method for Sb and Te is low pressure microwave induced plasma (MIP) emission spectroscopy [138]. Using low-temperature ashing and solvent extraction as preparation, physiological concentrations of both elements ([Pg.376]

Because the hydride and cold vapour generation techniques have so far been used mainly with liquid and dissolved samples, all aspects related to the variables influencing the process and the characteristics of the ensuing methods, among others, have been established in the light of a liquid entering the separator. Most such aspects also affect solid samples and are thus worth some comment, as are those that are exclusive to them — all briefly as this technique has scarcely been applied to solid samples. 

Detection of extremely low levels of metals may be possible by the use of hyphenated techniques such as hydride generation, ICP-OES/graphite furnace, ultrasonic nebuliser and cold vapour trap for Hg, and by utilising the axial viewing mode of the ICP-OES could achieve results close to ICPMS levels. Table 7.14 shows a brief list of metals and methods that are commonly considered for food analysis. 

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. 

AAS determinations based on hydride and cold vapour generation, electrothermal atomization with graphite furnaces have also been used successfully with FI systems to improve the overall performance of these techniques. Special requirements on the atomization-detection systems for hydride and cold vapour generation will be discussed in Chapter 5, and for the graphite furnace, in Chapter 4. 

Because MIPs are formed at low temperatures, liquid samples cannot be introduced because they extinguish the plasma, even small amounts of organic vapour. However, the on-line coupling of HPEC to MIP-OES has been described for the speciation of mercury and arsenic compounds. Continuous cold vapour (CV) or hydride generation (HG) techniques were used as interfaces between the exit of the HPEC column and the MIP, held in a surfatron at reduced pressure [24]. 

It should be pointed out that few elements are present in most natural waters at concentrations where flame spectroscopic techniques are directly applicable. Those that are include calcium, magnesium, sodium, potassium, and, in some samples and if conditions are very carefully optimized, manganese, iron, and aluminium. Zinc, and sometimes cadmium, may be determined directly by AFS. Mercury and hydride-forming elements may be determined if cold vapour and hydride generation sample introduction techniques are employed, as discussed in... 

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). 

The techniques discussed in this chapter vary in automatability and frequency of use. Thus, while automatic hydride and cold mercury vapour generation are implemented in laboratory-constructed or commercially available dynamic equipment that is straightforward, easy to operate and inexpensive, automating laboratory headspace modes and solid-phase microextraction is rather complicated and commercially available automated equipment for their implementation is sophisticated and expensive. Because of its fairly recent inception, analytical pervaporation lacks commercially available equipment for any type of sample however, its high potential and the interest it has aroused among manufacturers is bound to result in fast development of instrumentation for both solid and liquid samples. This technique, which is always applied under dynamic conditions, has invariably been implemented in a semi-automatic manner to date also, its complete automatization is very simple. 

The benefit of sample preparation techniques using microwave acid digestion and bomb combustion is that the sample is totally enclosed during the decomposition. These methods remove matrix interference and generate aqueous solutions, which can be analysed using ICP-OES. Sub-trace concentrations can be detected when hyphenated attachments are used, e.g. ultrasonic nebuliser, hydride generation or continuous cold vapour method. These methods are essential where trace levels of toxic elements are present that need to be identified and quantified. 

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. 

Recent improvements in FAAS include the addition of a flow injection sample delivery system. This allows for automatic dilution and reagent addition, and also provides for automated cold vapour or hydride generation needed for As, Se and Hg (e g., Saraswati et al., 1995). Other new techniques are improving the sensitivity of FAAS. A slotted silica tube placed in the flame improves the sensitivity 8 fold forCd and c. 3 fold forCu, Pb, and Zn. Experimental application of graphite tubes in the flame can improve Pb sensitivity 50 fold (Alvarado Jaffe, 1998). 

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