Mercury cold vapour determination

While the sensitivity enhancement is highly beneficial, care is needed with the technique to avoid interferences.2 Ions which complex mercury, such as sulfide3 and halides, may interfere with the rate of reduction to Hg. Interference may also be encountered from any volatile organic compounds in the sample which happen to absorb at the wavelength used (253.6 nm). Invariably a water trap is built into the apparatus to avoid problems caused by condensation in the atom cell.2 

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Figure 1 Apparatus for cold vapour mercury determination by AAS...

The success achieved in cold vapour mercury determinations prompted a number of investigators to examine the scope for conversion of other elements to... 

A) Cold vapour technique. This procedure is strictly confined to the determination of mercury,45 which in the elemental state has an appreciable vapour pressure at room temperature so that gaseous atoms exist without the need for any special treatment. As a method for determining mercury compounds the procedure consists in the reduction of a mercury(II) compound with either... 

MDHS 14 General method for the gravimetric determination of respirable and total dust MDHS 15 Carbon disulphide MDHS 16 Mercury vapour in air Laboratory method using hopcalite adsorbent tubes, and acid dissolution with cold vapour atomic absorption spectrometric analysis MDHS 17 Benzene in air Laboratory method using charcoal adsorbent tubes, solvent desorption and gas chromatography MDHS 18 Tetra alkyl lead compounds in air Continuous on-site monitoring method using PAC Check atomic absorption spirometry... 

Mercury was determined after suitable digestion by the cold vapour atomic absorption method [40]. Lead was determined after digestion by a stable isotope dilution technique [41-43]. Copper, lead, cadmium, nickel, and cobalt were determined by differential pulse polarography following concentration by Chelex 100 ion-exchange resin [44,45], and also by the Freon TF extraction technique [46]. Manganese was determined by flameless atomic absorption spectrometry (FAA). 

Reduction to metallic mercury was used by an overwhelming proportion of the participants, with stannous chloride as reductant in all but one case in which sodium borohydride was used. In all cases but four, the participants used cold-vapour atomic absorption for final determination. This makes comparison of detection techniques difficult, but the good results ob-... 

This method consists of suspending for a standard time 70 mussels (Mytilus edulis), each of a standard weight, in a plastic coated wire cage 2 m below the surface. Mercury in the mussels was determined by cold vapour atomic... 

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. 

Jurka and Carter [50] have described an automated determination of down to O.lpg L 1 mercury in river sediment samples. This method is based on the automated procedure of El-Awady [51] for the determination of total mercury in waters and waste waters in which potassium persulphate and sulphuric acid were used to digest samples for analysis by the cold vapour technique. These workers proved that the use of potassium permanganate as an additional oxidizing agent was unnecessary. 

Elements such as As, Se and Te can be determined by AFS with hydride sample introduction into a flame or heated cell followed by atomization of the hydride. Mercury has been determined by cold-vapour AFS. A non-dispersive system for the determination of Hg in liquid and gas samples using AFS has been developed commercially (Fig. 6.4). Mercury ions in an aqueous solution are reduced to mercury using tin(II) chloride solution. The mercury vapour is continuously swept out of the solution by a carrier gas and fed to the fluorescence detector, where the fluorescence radiation is measured at 253.7 nm after excitation of the mercury vapour with a high-intensity mercury lamp (detection limit 0.9 ng I l). Gaseous mercury in gas samples (e.g. air) can be measured directly or after preconcentration on an absorber consisting of, for example, gold-coated sand. By heating the absorber, mercury is desorbed and transferred to the fluorescence detector. 

Typical cold vapour generation AAS system used for mercury determination. The same system can be used with a flame in place of the Pyrex tube to allow the determination of hydride -forming elements. 

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. 

The certification procedure for seven trace metals (Ba, Ca, Li, Mg, Mn, Na and Sr) in the certified reference material FEBS-1 (National Research Council Canada, Institute for National Measurement Standards, Ottawa, Canada) based on fish otolith matrix by isotope dilution - ICP-MS in comparison to ICP optical emission spectrometry and X-ray fluorescence analysis, is described by Sturgeon et al4X The isotope dilution technique is also employed for species analysis in biological systems,46 e.g., for the determination of mercury species in tuna material,54 or in aquatic systems using cold vapour ICP-MS.55... 

Gaseous and volatilised analytes can also be easily determined by FAAS and ETAAS. For example, the determination of several elements by the formation of covalent volatile hydrides e.g. arsenic, selenium) and cold vapour generation (mercury and cadmium) is feasible with good analytical sensitivity (see Section 1.4.1.1). 

O. Ertas and H. Tezel, A validated cold vapour-AAS method for determining mercury in human red blood cells, J. Pharm. Biomed. Anal., 36(4), 2004, 893-897. 

E. Ramalhosa, S. Rio Segade, E. Pereira, C. Vale and A. Duarte, Simple methodology for methylmercury and inorganic mercury determinations by high-performance liquid chromatography-cold vapour atomic fluorescence spectrometry. Anal. Chim. Acta, 448(1-2), 2001, 135-143. 

G. A. Zachariadis and J. A. Stratis, Optimisation of cold vapour atomic absorption spectrometric determination of mercury with and without amalgamation by subsequent use of complete and fractional factorial designs with univariate and modified simplex methods, J. Anal. At. Speetrom., 6(3), 1991, 239-245. 

Kuwae et al. [138] have described a rapid determination of mercury in soils by high-frequency induction heating (rf) followed by cold vapour atomic absorption spectrometry. The mercury released from the sample is absorbed in stannous chloride-hydroxylamine prior to atomic absorption spectrometry. Recovery of 99.4 to 99.8% mercury was obtained by this method from portions of sample containing between 0.025-0.15 p,g of mercury. 

Nicolson [139] has described a rapid thermal decomposition technique for the atomic absorption determination of mercury in soils. In this method, air is used to sweep mercury vapour from the heated (650-750 °C) sample onto gold foil. In the second stage, heating of the gold foil releases mercury vapour into a cold vapour atomic absorption spectrometer. 

Cold vapour (or flameless) atomic absorption spectrometry is the method of choice for the determination of mercury in soils [136-147]. Ure and Shand [ 141 ]... 

Cold vapour atomic absorption spectrometry and atomic fluorescence spectrometry (253 nm emission) have been applied to the determination of down to 0.01 mg/kg of mercury in soils and sediments [ 144],... 

Sakamoto et al. [148] have shown that the differential determinations of different forms of mercury in soil can be accomplished by successive extraction and cold vapour atomic absorption spectrometry. 

Bandyopadhyay and Das [151] extracted mercury from soils with the liquid anion exchanger Aliquat-336 prior to determination by cold vapour atomic absorption spectrometry. 

Hon et al. [34] describe a simple piece of equipment for the determination of down to 80 pg/1 of mercury by AAS using a static cold vapour procedure. In this method [35], the sample was digested with the sulfuric acid, a measured portion pipetted into the reduction vessel, and the vessel immediately capped. The reductant, comprising 1% stannous chloride, was introduced. The evolved elemental mercury in the headspace was then introduced into the absorption cell by water displacement. Maximum sensitivity is obtained when the volume of the displaced air is equal to the internal volume of the absorption cell, and the mercury solution is 9 M in sulfuric acid. The peak absorbance at 253.7 nm exhibited a marked decline for hydrochloric acid concentrations above 1.5 M and for nitric acid concentrations above 3 M. The calibration graph obtained for mercury(II) in 9M sulfuric acid is linear from 0 to 17ng/ml, and the sensitivity is 0.08 ng/ml. A windowless absorption cell can also be used with a narrower linear calibration range. 

Bloom, N. and Fitzgerald, W.F. (1988) Determination of volatile mercury species at the picogram level by low-temperature gas chromatography with cold-vapour atomic fluorescence detection. Anal. Chim. Acta, 208, 151-161. 

Jian, W. and McLeod, C.W. (1992) Rapid sequential determination of inorganic mercury and methylmercury in natural waters by flow-injection-cold vapour-atomic fluorescence spectrometry. Talanta, 39, 1537-1542. 

Welz, B., D.L. Tsalev, and M. Sperling. 1992. On-line microwave sample pretreatment for the determination of mercury in water and urine by flow-injection cold-vapour atomic absorption spectrometry. Anal. Chim. Acta 261 91-103. 

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