Cold mercury vapour generation samples

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 characteristics of the separator and its associated equipment used for hydride and cold mercury vapour generation are dictated by the state of the sample. 

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... 

Cold vapour generation is the term exclusively reserved for mercury. Mercury in a sample is reduced to elemental mercury by tin (II) chloride (eqn 27.2) ... 

Lee SH, Jung KH, Lee DH. 1989. Determination of mercury in environmental samples by cold-vapour generation and atomic-absorption spectrometry with a gold-coated graphite furnace. Talanta 36(10) 999-1003. 

In analogy to sample introduction by hydride generation, mercury trace analysis is possible 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. 

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]. 

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. 

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