氢化物负压发生和真空无火焰原子化器的原子吸收光谱法测定铋

在负压发生器中用1% NaBH_4将Bi(Ⅲ)还原为铋化氢后,向发生器中加入一定量的空气。用真空泵将铋化氢和空气的混合物同时吸入到真空电热石英管中,用原子吸收仪器测定。在原子化器内,加入空气中的氧与硼氢化钠分解产生的氢反应,生成水分子。因而消除了氢对测定铋的干扰。     

氢化物负压发生器—真空无火焰原子化器的原子吸收光谱法测定碲

在负压发生器中用1％NaBH_4将Te(Ⅳ)还原成碲化氢后,再加入2mL氧气,用真空泵将氧与碲化氢的混合物吸进电热真空石英管中,同时测定原子吸收光谱。加入的氧与硼氢化钠分解产生的氢反应生成水分子,消除了氢对碲的干扰。     

Optimization of the determination of selenium in marine samples by atomic absorption spectrometry: Comparison of a flameless graphite furnace atomic absorption system with a hydride generation atomic absorption system

A comparison has been made between a graphite furnace system based on nickel as a matrix stabilizing metal and an automated hydride generation system with a heated quartz cell. The effect of nickel as a matrix modifier was studied in pure selenite solutions as well as in biological matrixes by different charring temperatures. The suppression effect of different acids on the response of the analyte is reported and discussed. The use of an electrically heated quartz tube as an alternative to the argon hydrogen flame method unproved the selenium determination by hydride generation atomic absorption. The effect of hydrochloric acid to secure quantitative formation of selenium (IV) and the interference of copper in the response measurements have been studied. Further a comparison has been made between three different digestion procedures when the hydride generation atomic absorption system was applied. The results of the graphite furnace atomic absorption and the hydride generation atomic absorption were found to be equally accurate, but the graphite furnace technique gave better reproducibility.     

Arsenic determination in the ultratrace range by atomic absorption spectrometry after preconcentration of the hydride

Summary A method for the determination of extremely low levels of arsenic by hydride AAS is presented. It is based on hydride preconcentration in a quartz tube at liquid nitrogen temperatures under carefully evaluated and optimized experimental conditions, followed by rapid heating up to 100° C and measurement in a heated quartz cell. Under the given experimental conditions an absolute detection limit of 0.05 ng and a linear range up to 6 ng could be achieved, representing a 6.5-fold improvement of detection power in comparison to commercially available hydride systems.

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Arsenbestimmung im Ultraspurenbereich durch AAS nach Anreicherung des Hydrids

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On leave from Universidad de Antofagasta, Departamento de Quimica Analítica, Antofagasta, Chile. Taken in part from the Ph. D. thesis, University of Bonn     

氢化物负压发生,夹带氧气的真空无火焰原子吸收测量技术测定砷、锑、硒和锡

在负压氢化物发生器中用1％NaBH_4将砷、锑、硒和锡还原成氢化物后,加入一定量氧气,用真空泵将氧与氢化物的混合物吸入到电热石英管中,同时用原子吸收仪器测定。加入的氧与来自硼氢化钠分解产生的氢反应,生成气态水分子,因而消除了氢对测量元素的干扰。     

连续氢化物发生—电加热石英管—原子吸收光谱法实验系统

报道了连续氢化物发生－电加热石英管原子吸收光谱法实验系统。并以铅烷（ＰｂＨ４）发生为代表对氢化物发生器构型，残留液体积、原子化温度、石英管电加热区域长度、载气流速、测量波长选择泵速、进样管长度等诸多影响因素作了试验。     

Semi-automatic method for determination of total tin in rocks

Automatic equipment is used to generate tin hydride from sample solutions prepared by fusion of powdered rock with lithium metaborate followed by digestion with hydrofluoric and sulfuric acids. The evolved hydride is swept by argon into an electrically heated quartz tube atomizer. The atomic absorption of tin is measured at 224.6 nm. Oxalic acid and 1,10-phenanthroline are used to minimize interferences from iron, copper, and nickel. The detection limit of tin in the rock samples is 0.5 ppm. Results for reference rock samples agree closely with published values. A direct acid digestion procedure produces similar results for tin in many samples.     

Semi-automated method for the determination of bismuth in rocks

A rapid and accurate method for the determination of bismuth in rock samples is described. Automated equipment is used to generate bismuth hydride from solutions of rock samples prepared by digestion with a mixture of hydrofluoric and perchloric acids. The evolved hydride is carried to a heated quartz tube by a stream of argon, and the atomic absorption of bismuth recorded. Thiosemicarbazide and 1,10-phenanthroline are used as masking agents to minimize interferences from copper and nickel. As little as 20 ng Bi g^-1 can be determined; the average r.s.d. is 5.4%. Results obtained for six USGS standard rocks are in close agreement with the recommended values obtained by an isotope dilution technique.     

Determination of As(III) and total inorganic arsenic by on-line pretreatment in hydride generation atomic absorption spectrometry

Summary A method for the on-line prereduction of As(V) was developed in order to determine As(III) and As(V) with the same sensitivity by continuous flow hydride generation. In this procedure, the sample is continuously mixed with concentrated hydrochloric acid and a potassium iodideascorbic acid solution, flows through a heated PTFE-tube and is determined by hydride generation atomic absorption spectrometry in a heated quartz cell. The selective analysis of As(III) is carried out by continuous mixing of the sample with acetic acid and hydride generation. The method allows the rapid determination of inorganic arsenic species at concentrations down to 1 g/l. A manual sample preparation is not required.     

Flow injection electrochemical hydride generation of hydrogen selenide on lead cathode: critical study of the influence of experimental parameters.

A flow injection system for the determination of selenium by electrochemical hydride generation and quartz tube atomic absorption spectrometry is described. The generator consists of an electrolytic flow-through cell with a concentric arrangement and a packed cathode made of particulated lead. The influences of sample flow rate, carrier gas flow rate and electrolysis current on the hydrogen selenide generation have been critically studied. Both sample flow rate and electrolysis current play important roles in the efficiency of the hydride generation process. A characteristic mass of 2.4 ng and a concentration detection limit of 17 microg l(-1) were obtained for a sample volume of 420 microl.     

Determination of Bismuth in Geological Materials by Flow Injection Hydride Generation Atomic Absorption Spectrometry

Abstract

Flow injection analysis (FIA) has been applied to sample introduction in conjunction with automated hydride generation and AAS techniques for the determination of Bi in rock samples. The powdered rock sample is digested with a mixture of hydrofluoric, perchloric, and nitric acids. The evolved hydride is carried through to a heated quartz tube by a stream of argon, and the atomic absorption of Bi is measured at 223.2 nm.

Thiosemicarbazide and 1,10 - phenanthroline are used as masking agents to control interferences from Cu and Ni. The method permits the accurate determination of Bi in geological materials at levels as low as 10 ppb with an analysis rate of more than 50 digested samples per hour. Bi values on 13 international geological reference samples are reported.     

Determination of antimony by using a quartz atom trap and electrochemical hydride generation atomic absorption spectrometry

The analytical performance of a miniature quartz trap coupled with electrochemical hydride generator for antimony determination is described. A portion of the inlet arm of the conventional quartz tube atomizer was used as an integrated trap medium for on-line preconcentration of electrochemically generated hydrides. This configuration minimizes transfer lines and connections. A thin-layer of electrochemical flow through cell was constructed. Lead and platinum foils were employed as cathode and anode materials, respectively. Experimental operation conditions for hydride generation as well as the collection and revolatilization conditions for the generated hydrides in the inlet arm of the quartz tube atomizer were optimized. Interferences of copper, nickel, iron, cobalt, arsenic, selenium, lead and tin were examined both with and without the trap. 3σ limit of detection was estimated as 0.053 μg l^− 1 for a sample size of 6.0 ml collected in 120 s. The trap has provided 18 fold sensitivity improvement as compared to electrochemical hydride generation alone. The accuracy of the proposed technique was evaluated with two standard reference materials; Trace Metals in Drinking Water, Cat # CRM-TMDW and Metals on Soil/Sediment #4, IRM-008.     

Frequency-modulated simultaneous Atomic Absorption Spectrometry (FremsAAS): Determination of As,Se and Sb

The evaluation of accuracy and efficiency of the frequency-modulated simultaneous Atomic Absorption Spectrometry (FremsAAS) has been extended to an arrangement with EDL as light sources. Fundamental calibrations have been worked out for As, Se and Sb using a graphite furnace as well as hydride generation in combination with a heated quartz tube as atomization unit. The characteristic data are in good agreement with results obtained by conventional single-channel AAS instruments. Determinations in three standard reference materials with different complex matrices resulted in complete agreement with the certified values.     

Frequency-modulated simultaneous Atomic Absorption Spectrometry (FremsAAS): Determination of As, Se and Sb

The evaluation of accuracy and efficiency of the frequency-modulated simultaneous Atomic Absorption Spectrometry (FremsAAS) has been extended to an arrangement with EDL as light sources. Fundamental calibrations have been worked out for As, Se and Sb using a graphite furnace as well as hydride generation in combination with a heated quartz tube as atomization unit. The characteristic data are in good agreement with results obtained by conventional single-channel AAS instruments. Determinations in three standard reference materials with different complex matrices resulted in complete agreement with the certified values.     

Investigation of thallium hydride generation using in situ trapping in graphite tube by atomic absorption spectrometry

Thallium hydride was generated from aqueous solutions by merging sample and sodium tetrahydroborate reductant in a batch system. In situ preconcentration of volatile thallium hydride in a preheated graphite furnace coated with palladium, which was used as both the collection medium and atomizer, greatly improved the sensitivity for the determination of thallium by hydride generation atomic absorption spectrometry. The presence of tellurium can increase the generation efficiency of thallium hydride. The operating conditions were optimized. The calibration graph is linear up to 100 ng and the characteristic mass for thallium was 0.92 ng which is seventeen times lower than that obtained with the heated quartz tube atomizer.     

Speciation of major arsenic species in seawater by flow injection hydride generation atomic absorption spectrometry

Arsenic present at 1 microg L(-1) concentrations in seawater can exist as the following species: As(III), As(V), monomethylarsenic, dimethylarsenic and unknown organic compounds. The potential of the continuous flow injection hydride generation technique coupled to atomic absorption spectrometry (AAS) was investigated for the speciation of these major arsenic species in seawater. Two different techniques were used. After hydride generation and collection in a graphite tube coated with iridium, arsenic was determined by AAS. By selecting different experimental hydride generation conditions, it was possible to determine As(III), total arsenic, hydride reactive arsenic and by difference non-hydride reactive arsenic. On the other hand, by cryogenically trapping hydride reactive species on a chromatographic phase, followed by their sequential release and AAS in a heated quartz cell, inorganic As, MMA and DMA could be determined. By combining these two techniques, an experimental protocol for the speciation of As(III), As(V), MMA, DMA and nonhydride reactive arsenic species in seawater was proposed. The method was applied to seawater sampled at a Mediterranean site and at an Atlantic coastal site. Evidence for the biotransformation of arsenic in seawater was clearly shown.     

Stibine and bismuthine trapping in quartz tube atomizers for atomic absorption spectrometry — Method optimization and analytical applications

The compact trap-and-atomizer device was employed to trap stibine and bismuthine, and subsequently to volatilize collected analyte and atomize it for atomic absorption spectrometric detection. The device is actually the multiple microflame quartz tube atomizer (multiatomizer) with inlet arm modified to serve as the trap and to accommodate the oxygen delivery capillary employed for burning out hydrogen during the trapping step. The optimization of Sb and Bi collection in the device is presented based on a study of the influence of relevant experimental parameters on preconcentration efficiency of both analytes. The parameters studied were: (1) trap temperature during trapping and (2) hydrogen flow rate and (3) trap temperature during volatilization and (4) the stability of the trapped analyte species. Under optimized conditions, the preconcentration efficiency was 100% for both analytes. The trap-and-atomizer device can be replaced by the simple conventional externally heated quartz tube atomizer without any trap as demonstrated on the ultratrace antimony determination in groundwater reference material and mineral water samples. The interference of other hydride forming elements on Bi in-situ collection in the conventional externally heated quartz tube atomizer was investigated.     

Vapor generation and atom traps: Atomic absorption spectrometry at the ng/L level

Atom-trapping atomic absorption spectrometry is a technique that allows detection at the ng/L level for several analytes such as As, Se, Sb, Pb, Bi, Cd, In, Tl, Te, Sn and Hg. The principle involves generation of volatile species, usually hydrides, trapping these species on the surface of an atom trap held at an optimized temperature and, finally, revolatilizing the analyte species by rapid heating of the trap and transporting them in a carrier gas to a heated quartz tube, as commonly used with hydride generation AAS systems. A transient signal having, in most cases, a full width at half maximum of less than 1 s is obtained. The atom trap may be a quartz surface or a W-coil; the former is heated externally and the latter is heated resistively. Both collection and revolatilization temperatures are optimized. In some cases, the W-coil itself is used as an electrothermal atomizer and a heated quartz tube is then not needed. The evolution of these traps starts with the well-known Watling's slotted quartz tube (SQT), continues with atom trapping SQT and finally reaches the present traps mentioned above. The analytical figures of merit for these traps need to be standardized. Naturally, enhancement is on characteristic concentration, C₀, where the change in characteristic mass, m₀, can be related to trapping efficiency. Novel terms are suggested for E, enhancement factor; such as E_max, maximum enhancement factor; E_t, enhancement for 1.0 minute sampling and E_v, enhancement for 1.0 mL of sample. These figures will allow easy comparison of results from different laboratories as well as different analytes and/or traps.     

Determination of lead by continuous-flow hydride generation and atomic absorption spectrometry: Comparison of malic acid—dichromate,nitric acid—hydrogen peroxide and nitric acid—peroxodisulfate reaction matrices in combination with sodium tetrahydroborate

A continuous-flow hydride generator is combined with a heated quartz tube atomizeratomic absorption spectrometer system for the trace determination of lead. Malic acid K₂Cr₂O₇, HNO₃—H₂O₂ and HNO₃—(NH₄)₂S₂O₃ are all effective for plumbane generation by means of sodium tetrahydroborate. The relative merits of these systems are investigated in terms of sensitivity, efficiency of plumbane generation and interferences. The sensitivities (0.0044 absorbance) obtained under the recommended conditions for the three systems are 3.2, 1.7 and 1.1 ng Pb ml^-1, respectively, whereas plumbane generation efficiencies are 33%, 47% and >80%, respectively, for 1 μg Pb ml^-1. Silver, Au, Cu and Cd interfere seriously in all reaction systems. A dithizone extraction and back-extraction method is utilized to eliminate interfering ions, followed by reduction of the resulting solution in the peroxodisulphate system. The proposed method is applied to water samples and NBS 1566 oyster tissue.     

Speciation of major arsenic species in seawater by flow injection hydride generation atomic absorption spectrometry

Arsenic present at 1 μg L^–1 concentrations in seawater can exist as the following species: As(III), As(V), monomethylarsenic, dimethylarsenic and unknown organic compounds. The potential of the continuous flow injection hydride generation technique coupled to atomic absorption spectrometry (AAS) was investigated for the speciation of these major arsenic species in seawater. Two different techniques were used. After hydride generation and collection in a graphite tube coated with iridium, arsenic was determined by AAS. By selecting different experimental hydride generation conditions, it was possible to determine As(III), total arsenic, hydride reactive arsenic and by difference non-hydride reactive arsenic. On the other hand, by cryogenically trapping hydride reactive species on a chromatographic phase, followed by their sequential release and AAS in a heated quartz cell, inorganic As, MMA and DMA could be determined. By combining these two techniques, an experimental protocol for the speciation of As(III), As(V), MMA, DMA and non-hydride reactive arsenic species in seawater was proposed. The method was applied to seawater sampled at a Mediterranean site and at an Atlantic coastal site. Evidence for the biotransformation of arsenic in seawater was clearly shown.