Arsenic hydrides detection

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. 

Tao et al. [658] have described a procedure in which antimony and arsenic were generated as hydrides and irradiated with ultraviolet light. The broad continuous emission bands were observed in the ranges about 240-750 nm and 220 - 720 nm, and the detection limits were 0.6 ng and 9.0 ng for antimony and arsenic, respectively. Some characteristics of the photoluminescence phenomenon were made clear from spectroscopic observations. The method was successfully applied to the determination of antimony in river water and seawater. The apparatus used in this technique is illustrated in Fig. 5.16. 

De Oliviera et al. [739] have described a technique for determining these elements based on the hydride generation technique. Detection limits are 1 xg/l for arsenic and antimony, and 0.5 pg/1 for selenium. 

Braman et al. [34] used sodium borohydride to reduce arsenic and antimony in their trivalent and pentavalent states to the corresponding hydrides. Total arsenic and antimony are then measured by their spectral emissions, respectively, at 228.8 nm and 242.5 nm. Limits of detection are 0.5 ng for antimony and 1 ng for arsenic, copper, and silver. Oxidants interfere in this procedure. 

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]. 

The manifold for hydride generation is shown in Fig. 12.7. The operating conditions are as follows forward power 1400W, reflected power less than 10W, cooling gas flow 12L nr1, plasma gas flow 0.12L nr1, injector flow, 0.34L m 1. The standard deviation of this procedure was 0.02pL 1 arsenic and the detection limit O.lpg L-1. Results obtained on a selection of standard reference sediment samples are quoted in Table 12.14. 

These methods were used to determine arsenic in certified sediments (Table 12.15). Conventional inductively coupled plasma atomic emission spectrometry is satisfactory for all types of samples, but its usefulness was limited to concentrations of arsenic greater than 5pg g-1 dry weight. Better detection limits were achieved using the flow-injection-hydride generation inductively coupled plasma technique in which a coefficient of variation of about 2% for concentrations of lOpg g 1 were achieved. 

The selective hydride generation-gas chromatographic method [121] using photoionization detection discussed in section 12.10.2.1 for the determination of arsenic III and arsenic V has been applied to the determination of down to 3.3pmol L 1 of antimony (Sb III, SbV) in sediments. 

Odanake et al. [1] have reported the application of gas chromatography with multiple ion detection after hydride generation with sodium borohydride to the determination of mono and dimethyl arsenic compounds, trimethyl arsenic oxide and inorganic arsenic in soil and sediments. Recoveries in spiking experiments were 100-102% (mono and dimethyl arsenic compounds and inorganic arsenic) and 72% (trimethyl arsenic oxide). 

Figure S.2 shows a schematic diagram of the automatic hydride/vapour-generator system designed by P.S. Analytical. This has been widely used to determine hydrideforming elements, notably arsenic, selenium, bismuth, tellurium and antimony, in a wide range of sample types. To provide a wide range of analyses on a number of matrices the chemistry must be very well defined and consistent. Goulden and Brooksbank s automated continuous-flow system for the determination of selenium in waste water was improved by Dennis and Porter to lower the detection levels and increase relative precision [10, 11]. The system described by Stockwell [9] has been specifically developed in a commercial environment using the experience outlined by Dennis and Porter.

Sowinski and Suffet 297) have used GC/MS to detect boron hydrides at trace levels, whereas Blum and Richter (298) have used capillary columns in the combined GC/MS of a series of phenylboronate derivatives. There have also been recent applications of GC/MS to the TMS derivatives of inorganic anions (299). The TMS derivatives of ammonium arsenates. 

B.6 Speciation of Arsenic Compounds by Ion-Exchange High-Performance Liquid Chromatography with Hydride Generation Atomic Fluorescence Detection. 

The most useful chemical species in the analysis of arsenic is the volatile hydride, namely arsine (AsH3, bp -55°C). Analytical methods based on the formation of volatile arsines are generally referred to as hydride, or arsine, generation techniques. Arsenite is readily reduced to arsine, which is easily separated from complex sample matrices before its detection, usually by atomic absorption spectrometry (33). A solution of sodium borohydride is the most commonly used reductant. Because arsenate does not form a hydride directly, arsenite can be analyzed selectively in its presence (34). Specific analysis of As(III) in the presence of As(V) can also be effected by selective extraction methods (35). 

Inorganic As(III) and As(V) were determined by atomic absorption spectrometry using the hydride technique. Total inorganic arsenic, As(III) + As(V), was measured after a prereduction reaction of As(V) to As(III) in acidic solution containing potassium iodide and ascorbic acid. For the selective hydride formation of As(III), samples were maintained at pH 5.0 during the hydride reaction (with 3% NaBH4, 1% NaOH) with a citrate-sodium hydroxide buffer solution (31). As(V) was determined by difference between total As and As(III). The detection limit of As(III) and As(V) was 0.1 nM. The selectivity of this method was checked by additions of As(III) and As(V) to lake water 95-100% recovery of As(III) and As(V) was found (32). 

Thomas and Sniatecki [51] also performed an analysis of trace amounts of arsenic species in natural waters using hydride generation IPC-ICP-MS. Six arsenic species were determined with detection limits in the range 1.0-3.0 fig l-1 and total arsenic was determined using hydride generation by atomic fluorescence detection. It was found that the predominant species present in bottled mineral water samples was always As(V) with very low levels of As(III). The authors described how the system required . .. further work using special chromatographic software. .. to improve the quantitative measurement at a natural level. ... 

The recommended procedure for the determination of arsenic and antimony involves the addition of 1 g of potassium iodide and 1 g of ascorbic acid to a sample of 20 ml of concentrated hydrochloric acid. This solution should be kept at room temperature for at least five hours before initiation of the programmed MH 5-1 hydride generation system, i.e., before addition of ice-cold 10% sodium borohydride and 5% sodium hydroxide. In the hydride generation technique the evolved metal hydrides are decomposed in a heated quartz cell prior to determination by atomic absorption spectrometry. The hydride method offers improved sensitivity and lower detection limits compared to graphite furnace atomic absorption spectrometry. However, the most important advantage of hydride-generating techniques is the prevention of matrix interference, which is usually very important in the 200 nm area. 

Jiminez de Bias et al. [32] have reported a method for the determination of total arsenic in soils based on hydride generation atomic absorption spectrometry and flow injection analysis. The method gave good recoveries and had a detection limit below 1 ig/l for an injection volume of 160 pi... 

Kimbrough and Wakakuwa [276,330] reported on an interlaboratory comparison study involving 160 accredited hazardous materials laboratories. Each laboratory performed a mineral acid digestion on five soils spiked with arsenic, cadmium, molybdenum, selenium and thallium. The instrumental detection methods used were inductively coupled plasma atomic emission spectrometry, inductively coupled plasma mass spectrometry, flame atomic absorption spectrometry, electrothermal atomic absorption spectrometry and hydride generation atomic absorption spectrometry. At most concentrations, the results obtained with inductively coupled plasma atomic emission spectrometry... 

Schramel [103] discusses the conditions for multi-element analysis of over 50 trace elements, giving detection limits. Wolnik [104] described a sample introduction system that extends the analytical capability of the inductively coupled argon plasma/polychromator to include the simultaneous determination of six elemental hydrides along with a variety of other elements in plant materials. Detection limits for arsenic, bismuth, selenium and tellurium range from 0.5 to 3 ng/ml and are better by at least an order of magnitude than those obtained with conventional pneumatic nebulisers, whereas detection limits for the other elements investigated remain the same. Results from the analysis of freeze-dried crop samples and NBS standard reference materials demonstrated the applicability of the technique. Results obtained by the analysis of a variety of plant materials are presented in Table 7.10. 

Magnuson, M.L., Creed, J.T. and Brockhoffl C.A. (1997) Speciation of arsenic compounds in drinking water by capillary electrophoresis with hydrodynamically modified electro-osmotic flow detected through hydride generation inductively coupled plasma mass spectrometry with a membrane gas-liquid separator./. Anal. At. Spectrom., 12, 689-695. 

The techniques used in the certification were based on hydride generation following either UV irradiation, GC or LC with ICPAES or QFAAS detection. Two techniques did not use hydride generation and were based on LC followed by QFAAS or ICPMS detection. The synthesis of pure calibrants or arsenic compounds has been necessary to enable a proper calibration to be carried out. All details on the techniques and calibrant preparation are described elsewhere (Quevauviller, 1998b). 

A number of techniques have been used for the speciation of arsenic compounds. The most important has been the formation of volatile hydrides of several species, separation by gas chromatography and detection by AAS. HPLC has been used to separate arsenic species. Several types of detectors have been studied for the determination of arsenic species in the column effluent. These have included AAS both off- and on-line, ICPAES and ICP-MS. An important comparative study of coupled chromatography-atomic spectrometry methods for the determination of arsenic was published (Ebdon et al., 1988). Both GC and HPLC were used as separative methods, and the detectors were FAAS, flame atomic fluorescence spectrometry (FAFS) and ICPAES. The conclusions were (1) that hydride generation and cryogenic trapping with GC-FAAS was the most... 

A novel HPLC-AAS interface based upon thermochemical hydride generation (THG) was developed for the determination of AB, AC and tetramethylarsonium cations, which had been separated by HPLC (Blais et al., 1990 Momplaisir et al., 1991). This has been described in Section 15.7. The detection limits of the three species were 13.3 ng (AB), 14.5 ng (AC) and 7.6ng (tetramethylarsonium cations). Advantages of this interface included low purchase and operating costs, low detection limits, and good reproducibility of results. The method was applied to determinations of arsenic species in seafoods and human urine. 

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