Cold vapour atomic absorption spectroscopy

Agemian and Chau [55] have described an automated method for the determination of total dissolved mercury in fresh and saline waters by ultraviolet digestion and cold vapour atomic absorption spectroscopy. A flow-through ultraviolet digester is used to carry out photo-oxidation in the automated cold vapour atomic absorption spectrometric system. This removes the chloride interference. Work was carried out to check the ability of the technique to degrade seven particular organomercury compounds. The precision of the method at levels of 0.07 pg/1, 0.28 pg/1, and 0.55 pg/1 Hg was 6.0%, 3.8%, and 1.00%, respectively. The detection limit of the system is 0.02 pg/1. 

In 2002 extensive kinetic and product studies on the reactions of gaseous Hg with molecular and atomic halogens (X/X2 where X = Cl, Br) were performed at atmospheric pressure (750 1 Torr) and room temperature (298 1 K) in air and N2 [24]. Kinetics of fhe reactions with X/X2 were studied using both relative and absolute techniques. Cold vapour atomic absorption spectroscopy (CVAAS) and gas chromatography with mass spectroscopic detection (GC-MS) were the analytical methods applied. The measured rate constants for the reactions of Hg with CI2, Cl, Br2, and Br were (2.6 0.2) x IQ-i , (1.0 0.2) x 10" , < (0.9 0.2) x and (3.2 0.3) x 10 cm molecule s , respectively. Thus CI2 and Br2 are not important reactants in the troposphere for the CI2 and Br2 concentrations reported in literature [24]. 

An example is the determination of mercury in foodstuffs using cold vapour atomic absorption spectroscopy. The organic matter in foodstuffs is destroyed by wet oxidation. The mercury in solution is then reduced to the metallic state and released as a vapour in a stream of air. The quantity of mercury vapour in the air stream is measured by cold vapour atomic absorption spectroscopy. This part off the method is called the end determination. Often, as in this example, the end determination is equivalent to the analytical technique for the method. 

The primary method used to analyse for mercury is CVAAS (cold vapour atomic absorption spectroscopy). This has a sensitivity of parts per trillion for urine while determination of mercury in fish, shellfish, pharmaceuticals and foodstuffs has a sensitivity in the low parts per billion range, as has the analysis of mercury in samples of tissues and hair. Mercury levels in newly formed hair reflect those in blood the concentration however is about 250 times greater in hair. Once the mercury has interacted with the sulphur-containing proteins in hair it is essentially "fixed" and so provides an accurate monitor of exposure and accumulation. Analysis of the hair length can therefore be used to estimate the dates of contamination by mercury and also the peak blood levels achieved. 

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 detection systems used with HPLC can be broadly divided into three approaches photometry, plasma techniques (ICPAES, ICPMS), and cold vapour atomic absorption and fluorescence spectroscopy (CV-AAS, CV-AFS). The method with the lowest limits of detection (LOD) with sample introduction via a direct injection nebulizer used ICP-MS. An HPLC system coupled to atmospheric pressirre chemical ionization MS was used to identify methyl mercury spiked into a fish tissue CRM (DORM-1, NRCC). This type of system has a significant advantage over elemental detection methods because identification of the species present is based on their structure, rather than matching the analyte s retention time to that of a standard. 

The technique can be used with or without a flame. In the flameless technique several variations are possible, including a graphite furnace or cold vapour, all of which are more sensitive than flame photometry. Further details on atomic absorption spectroscopy are given in Chapter 27. 

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