Determination of arsenates

Discussion. Arsenates in solution are precipitated as silver arsenate, Ag3 As04, by the addition of neutral silver nitrate solution the solution must be neutral, or if slightly acid, an excess of sodium acetate must be present to reduce the acidity if strongly acid, most of the acid should be neutralised by aqueous sodium hydroxide. The silver arsenate is dissolved in dilute nitric acid, and the silver titrated with standard thiocyanate solution. The silver arsenate has nearly six times the weight of the arsenic, hence quite small amounts of arsenic may be determined by this procedure. 

Arsenites may also be determined by this procedure but must first be oxidised by treatment with nitric acid. Small amounts of antimony and tin do not interfere, but chromates, phosphates, molybdates, tungstates, and vanadates, which precipitate as the silver salts, should be absent. An excessive amount of ammonium salts has a solvent action on the silver arsenate. 

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A flow-injection system with electrochemical hydride generation and atomic absorption detection for the determination of arsenic is described. This technique has been developed in order to avoid the use sodium tetrahydroborate, which is capable of introducing contamination. The sodium tetrahydroborate (NaBH ) - acid reduction technique has been widely used for hydride generation (HG) in atomic spectrometric analyses. However, this technique has certain disadvantages. The NaBH is capable of introducing contamination, is expensive and the aqueous solution is unstable and has to be prepared freshly each working day. In addition, the process is sensitive to interferences from coexisting ions. 

DETERMINATION OF ARSENIC (As) IN NATURAL AND WASTE WATER USING HIDRIDE GENERATION ATOMIC FLUORESCENCE SPECTROMETRY... 

Discussion. The determination of arsenic in arsenic)III) compounds is based upon the following reaction ... 

The introduction of reversible redox indicators for the determination of arsenic(III) and antimony(III) has considerably simplified the procedure those at present available include 1-naphthoflavone, and p-ethoxychrysoidine. The addition of a little tartaric acid or potassium sodium tartrate is recommended when antimony(III) is titrated with bromate in the presence of the reversible... 

Although electrothermal atomisation methods can be applied to the determination of arsenic, antimony, and selenium, the alternative approach of hydride generation is often preferred. Compounds of the above three elements may be converted to their volatile hydrides by the use of sodium borohydride as reducing agent. The hydride can then be dissociated into an atomic vapour by the relatively moderate temperatures of an argon-hydrogen flame. 

The procedure followed describes methods for the determination of total levels, and in certain cases, available amounts of trace elements in soils. The determination of arsenic in soil by hydride generation AAS is included. 

Procedure. Follow the conditions recommended by the instrument manufacturers for the determination of arsenic by hydride generation. Typical instrumental... 

Analytical Methods Committee, Determination of Arsenic in Organic Materials, Society for Analytical Chemistry, London, 1960... 

Landsberger S, Swift G, and Neuhoff J (1990) Nondestructive determination of arsenic in urine by epithermal neutron activation analysis and Compton suppression. Biol Trace Elem Res 26-27 27-32. 

Onken B.M., Hossner L.R. Plant uptake and determination of Arsenic species in soil solution under flooded conditions. J Environ Qual 1995 24 373-381. 

Yamamoto et al. [6] conclude that their method was quite successful for the species-specific determination of arsenic and antimony in seawater. These methods, especially those for the determination of arsenic (III) and antimony (III), are quite satisfactory, as the method is almost free from interference of foreign ions. 

Haywood and Riley [14] have described a spectrophotometric method for the determination of arsenic in seawater. Adsorption colloid flotation has been employed to separate phosphate and arsenate from seawater [15]. These two anions, in 500 ml filtered seawater, are brought to the surface in less than 5 min, by use of ferric hydroxide (added as 0.1 M FeC 2 ml) as collector, at pH 4, in the presence of sodium dodecyl sulfate [added as 0.05% ethanolic solution (4 ml)] and a stream of nitrogen (15 ml/minutes). The foam is then removed and phosphate and arsenate are determined spectrophotometrically [16]. Recoveries of arsenate and arsenite exceeding 90% were obtained by this procedure. 

Afansev et al. [61] have described an extraction photometric method for the determination of arsenic at the xg/l range in seawater. This method uses diantipyrilmethane as the chromogene reagent. The coefficient of variation is... 

A UK standard official method [62] has been published for the spectropho-tometric determination of arsenic in sea water. The determination is effected by conversion to arsine using sodium borohydride which is added slowly to the acidified samples by a peristaltic pump. The liberated arsine is trapped in an iodine/potassium iodide solution and the resultant arsenate determined spectrophotometically as the arsenomolybdenum blue complex at 866 nm. The method is applicable down to 0.19 p,g arsenic. 

The neutron activation method for the determination of arsenic and antimony in seawater has been described by Ryabin et al. [66]. After coprecipitation of arsenic acid and antimony in a 100 ml sample of water by adding a solution of ferric iron (10 mg iron per litre) followed by aqueous ammonia to give a pH of 8.4, the precipitate is filtered off and, together with the filter paper, is wrapped in a polyethylene and aluminium foil. It is then irradiated in a silica ampoule in a neutron flux of 1.8 x 1013 neutrons cm-2 s 1 for 1 - 2 h. Two days after irradiation, the y-ray activity at 0.56 MeV is measured with use of a Nal (Tl) spectrometer coupled with a multichannel pulse-height analyser, and compared with that of standards. 

Amankwah and Fasching [4] have discussed the determination of arsenic (V) and arsenic (III) in estuary water by solvent extraction and atomic absorption spectrometry using the hydride generation technique. 

It has been reported that the differential determination of arsenic [36-41] and also antimony [42,43] is possible by hydride generation-atomic absorption spectrophotometry. The HGA-AS is a simple and sensitive method for the determination of elements which form gaseous hydrides [35,44-47] and mg/1 levels of these elements can be determined with high precision by this method. This technique has also been applied to analyses of various samples, utilising automated methods [48-50] and combining various kinds of detection methods, such as gas chromatography [51], atomic fluorescence spectrometry [52,53], and inductively coupled plasma emission spectrometry [47]. 

Yamamoto et al. [33] applied this technique to the determination of arsenic (III), arsenic (V), antimony (III), and antimony (V) in Hiroshima Bay Water. These workers used a HGA-A spectrometric method with hydrogen-nitrogen flame using sodium borohydride solution as a reductant. For the determination of arsenic (III) and antimony (III) most of the elements, other than silver (I), copper (II), tin (II), selenium (IV), and tellurium (IV), do not interfere in at least 30 000-fold excess with respect to arsenic (III) or antimony (III). This method was applied to the determination of these species in sea water and it was found that a sample size of only 100 ml is enough to determine them with a precision of 1.5-2.5%. Analytical results for surface sea water of Hiroshima Bay were 0.72 xg/l, 0.27 xg/l, and 0.22 xg/l, for arsenic (total), arsenic (III), and antimony (total), respectively, but antimony (III) was not detected. The effect of acidification on storage was also examined. 

Fujiwara et al. [94] found that, when present as a heteropolyacid complex, molybdenum(VI), germanium(IV), and silicon(IV) produced CL emission from the oxidation of luminol, and similar CL oxidation of luminol was observed for arsenic(V) and phosphorus(V) but with the addition of the metavanadate ion to the acid solution of molybdate. A hyphenated method was therefore proposed for the sensitive determination of arsenate, germanate, phosphate, and silicate, after separation by ion chromatography. The minimum detectable concentrations of arsenic(V), germanium(IV), phosphate, and silicon(IV) were 10, 50, 1, and 10... 

Up to 30% hydrogen can be added to the carrier gas stream of a helium microwave plasma torch, in the determination of arsenic, bismuth and tin. The argon torch accepts up to 20% hydrogen LOD about 2.5 pg Sn/L, with linear dynamic range over 3 orders of magnitude23. 

Devoto 115)has described an indirect procedure for the determination of 0.1 ppm arsenic in urine. The arsenomolybdic acid complex is formed and extracted from 1 ml of urine at pH 2 into 10 ml of cyclohexanone. The molybdenum in the complex is then measured. Before extracting the arsenic, phosphate in the urine is separated by extracting the phosphomolybdic acid complex at pH 1 into isobutyl acetate. The direct determination of arsenic in biological material and blood and urine is best done using a nitrous oxide-acetylene flame 116>. The background absorption by this flame is low at 1937 A, and interferences are minimized due to the high temperature of the flame. 

Sheppard, B. S., Heitkemper, D. T., and Gaston, C. M. (1994). Microwave digestion for the determination of arsenic, cadmium and lead in seafood products by inductively coupled plasma-atomic emission and mass spectrometry. Analyst 119 1683-1686. 

This technique has been applied to the determination of arsenic, selenium, organocompounds of arsenic, mercury and tin in soils, carbohydrates, total sulphur, arsenic, antimony, bismuth, selenium and organocompounds of mercury, tin and silicon in non-saline sediments, arsenic, bismuth, selenium or organotin compounds in saline sediments and arsenic and selenium in sludges. 

The determination of arsenic by atomic absorption spectrometry with thermal atomization and with hydride generation using sodium borohydride has been described by Thompson and Thomerson [117] and it was evident that this method could be modified for the analysis of soil. 

Cutter et al. [121] have described a method for the simultaneous determination of arsenic and antimony species in sediments. This method uses selective hydride generation with gas chromatography using a photoionization detector. 

Cutter [122] used a selective hydride generation procedure as a basis for the differential determination of arsenic and selenium species in sediments. Goulden et al. [123] also discuss the determination of arsenic and selenium in sediments by atomic absorption spectrometry. 

Goulden et al. [123] have described a semi-automated system for the determination of arsenic and selenium by hydride generation-industrively coupled plasma atomic-emission spectrometry. Sediments are brought into a solution by fusion with sodium hydroxide. 

Brzezinska-Paudyn et al. [124] compared results obtained in determinations of arsenic by conventional atomic emission spectrometry, flow-injection/hydride generation inductively coupled plasma atomic... 

These workers used an ARC 34000 inductively coupled plasma emission spectrometer with flow-injection hydride generation. The 189.04nm line (3nd order) was used for arsenic measurement. The flow-injection block and Buckler peristaltic pump, as described by Liversage et al. [125] were also used for the determination of arsenic by hydride generation. 

For the determination of arsenic by conventional inductively coupled plasma atomic emission spectrometry the samples were digested in closed Teflon vessels, similar to the technique described by Brzezinska et al. [126]. 

Cheam and Chau [128] used certified Great Lakes reference sediments for the determination of arsenic. 

The optimal reaction conditions for the generation of the hydrides can be quite different for the various elements. The type of acid and its concentration in the sample solution often have a marked effect on sensitivity. Additional complications arise because many of the hydrideforming elements exist in two oxidation states which are not equally amenable to borohydride reduction. For example, potassium iodide is often used to pre-reduce AsV and SbV to the 3+ oxidation state for maximum sensitivity, but this can also cause reduction of Se IV to elemental selenium from which no hydride is formed. For this and other reasons Thompson et al. [132] found it necessary to develop a separate procedure for the determination of selenium in soils and sediments although arsenic, antimony and bismuth could be determined simultaneously [133]. A method for simultaneous determination of As III, Sb III and Se IV has been reported in which the problem of reduction of Se IV to Se O by potassium iodide was circumvented by adding the potassium iodide after the addition of sodium borohydride [134], Goulden et al. [123] have reported the simultaneous determination of arsenic, antimony, selenium, tin and bismuth, but it appears that in this case the generation of arsine and stibene occurs from the 5+ oxidation state. 

All four dissolution procedures studied were found to be suitable for arsenic determinations in biological marine samples, but only one (potassium hydroxide fusion) yielded accurate results for antimony in marine sediments and only two (sodium hydroxide fusion or a nitricperchloric-hydrofluoric acid digestion in sealed Teflon vessels) were appropriate for determination of selenium in marine sediments. Thus, the development of a single procedure for the simultaneous determination of arsenic, antimony and selenium (and perhaps other hydride-forming elements) in marine materials by hydride generation inductively coupled plasma atomic emission spectrometry requires careful consideration not only of the oxidation-reduction chemistry of these elements and its influence on the hydride generation process but also of the chemistry of dissolution of these elements. 

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