Acid-digestion, Ashing and Extraction Procedures

The actual analytical methods will be detailed in the appropriate chapters, but here we will just comment on the techniques involved. 

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Total decomposition of the sample, the purpose of which is to release fluorine from inorganic or organic matrixes and convert it to fluoride ions, is usually a prerequisite for determining the amount of total fluorine. Commonly used procedures involve oxygen bomb combustion in a closed bomb [176,180], open ashing [181,182], alkali hydroxide or alkali carbonate fusion [151,183-187], pyrohydroly-sis [187-191], acid extraction [192,193] and microwave acid digestion [194-196]. 

A number of procedures for the determination of metals and biological samples call for the extraction of the metal with an organic chelating agent in order to remove interferences and concentrate the metal to enable detection of low levels. The urine or blood sample may be first subjected to wet ashing to enable extraction of the metal. Beryllium from an acid-digested blood or urine sample may be extracted by acetylacetone into methylisobutyl ketone prior to atomic absorption analysis. Virtually all of the common metals can be determined by this approach using appropriate extractants. 

Oliver [190] recommends the dissolution of the polymer if possible (see above) but in other cases a wet ashing procedure was used. The sample was heated with 2—3 ml of concentrated sulphuric acid and then hydrogen peroxide added drop-wise until the organic matter was destroyed. Twenty elements were determined in a 2% solution of polymer. Polymers may be dispersed in an organic solvent and trace metals removed by leaching with an appropriate aqueous solution, preferably the procedure should be repeated more than once to ensure complete extraction. To determine antimony in fire-retardant polypropylene, the sample was dispersed in xylene and extracted with 6M hydrochloric acid under reflux [191]. The filtered acid layer was combined with two further extracts prior to aspiration into the air/acetylene flame and measurement at 217.6 nm. Martinie and Schilt [45] reported that nylon would dissolve completely in perchloric/nitric acid digestion but potentially explosive problems were encountered in the dissolution of Amberlite resins and rubber. 

The dry-ashing plus acid digestion of tea leaves (Section 1.1) and the available phosphorus extraction (Section 1.3) are contrasting procedures in regard to the acceptable precision of the determination. In one the sample is weighed to 0.1 mg ( 0.02%), whereas in the other the 5 cm3 scoop used for measuring soil, may introduce a variation of 0.2 g ( 4%). You may like to think about this. Is the sample measuring procedure appropriate for the purpose of the analysis in each case ... 

The freeze dried or lyophilised samples of excreta can be digested at low temperatures (170-210°C) for 15-20 min with a minimal acid mixture of nitric and perchloric (1 2). Though this procedure can not destroy the organic matter completely, it should be at least as effective as the mineral acid extraction procedures described for excreta samples (Riner et al.. 1974). Maurer (1977) also found better results by extracting the specimens with a mixture of nitric (65%). hydrochloric acid (25%) and water (3 27 20) compared to those obtained by dry ashing. 

By the mid-1970s, most analytical procedures for CDU analysis used either wet ashing (mineral acid) or high temperatures (>400° C) to digest the organic matrix of urine, followed by cadmium chelation with APDC or DDTC solutions and extraction with MIBK. The resulting aliquots were analyzed by flame or graphite-furnace AAS (Kjellstrom 1979). 

Thallium has been determined in 10 ml of ashed serum or in urine by extracting with sodium diethyldithiocarbamate into MIBK n°). More recently, Savory and co-workers 1131 described a wet digestion procedure for 50 ml of urine or 5 ml of serum in which the thallium is separated by extracting the bromide into ether, evaporating the ether and then taking up in dilute acid for aspiration. As little as 0.1 ppm is determined in urine. Curry et al.114) determined less than 1 ng of thallium in 200 /d of urine by using the tantalum sample boat technique. The sample in the boat is dried by holding the boat 1 cm from the flame and then it is inserted into the flame where it is vaporized. A similar procedure is used for >3 ng of thallium in 50-100/al of blood, except that the blood is preashed with 3 drops of nitric acid. Since the tantalum boat method is susceptible to interelement interferences, the method of standard additions is used for calibration. 

Lopez Garcia et al. [2] have described a rapid and sensitive spectrophotometric method for the determination of boron complex anions in plant extracts and waters which is based on the formation of a blue complex at pH 1 - 2 between the anionic complex of boric acid with 2,6-dihydroxybenzoic acid and crystal violet. The colour is stabilised with polyvinyl alcohol. At 600 nm the calibration graph is linear in the range 0.3-4.5 xg boron per 25 ml of final solution, with a relative standard deviation of 2.6% for xg/l of boron. In this procedure to determine borate in plant tissues, the dried tissue is treated with calcium hydroxide, then ashed at 400 °C. The ash is digested with 1N sulfuric acid and heated to 80 °C, neutralized with cadmium hydroxide and then treated with acidic 2,6-dihydroxybenzoic acid and crystal violet, and the colour evaluated spectrophotometrically at 600 nm. Most of the ions present in natural waters or plant extracts do not interfere in the determination of boron complex anions by this procedure. Recoveries of boron from water samples and plant extracts were in the range of 97 -102%. 

According to Stoeppler et al. [15], severe errors up to a factor of two may result from ETA—AAS analysis of biological materials without some form of sample pretreatment. The approaches that will be discussed here are (a) the use of diluent solutions to minimise matrix and molecular absorption interferences (b) partial decomposition techniques in which metals are extracted from proteins with acids (c) dissolution of tissue samples without complete oxidation (d) complete oxidation procedures such as dry ashing, wet digestion at ambient and elevated pressures, and low temperature ashing with reactive gases at low pressures. 

Princi (1947), Smith et al. (1955), Smith and Kench (1957), and Tsuchiya (1967) used colorimetric procedures similar to those described in the CDB section above to estimate CDU concentrations. In these methods, urine (50 ml) is reduced to dryness by heating in a sand bath and digested (wet ashed) with mineral acids. Cadmium then is complexed with dithiazone, extracted with chloroform and quantified by spectrophotometry. These early studies typically report reagent blank values equivalent to 0.3 pg Cd/I, and CDU concentrations among nonexposed control groups at maximum levels of 10 pg Cd/I—erroneously high values when compared to more recent surveys of cadmium concentrations in the general population. 

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