Application of hydride generation to the determination of trace concentrations of arsenic by inductively-coupled plasma atomic emission spectrometry

A method is described for the determination of traces of arsenic, based on sodium tetrahydroborate reduction of arsenic and introduction of the arsine formed to a relatively low-powered (1.6 kW) inductively-coupled plasma where the arsenic atomic emission is generated, Inter-element interference effects are described; many can be eliminated by addition of potassium iodide to the sample solutions, but the standard additions method is recommended for accurate arsenic determination. Potassium iodide is also used for prereducing arsenic(V) to arsenic(III). The method has a detection limit of 0.1 ng As ml^-1 and the linear calibration range spans nearly four orders of magnitude. The proposed method is applied to the determination of ng ml^-1 levels of arsenic in waste waters.     

Determination of arsenic by hydride generation with a long absorption cell for atomic absorption spectrometry

A method is described for the determination of arsenic involving hydride generation and atomic absorption spectrometry with an improved long graphite-tube furnace capable of considerably higher temperatures than the conventional quartz-tube heaters. Arsine is generated with sodium tetrahydroborate, held in a nitrogen-cooled trap and then swept with helium into an alumina tube (19 cm long) placed within the graphite furnace. The optimum conditions for determination of arsenic are given. The detection limit is 0.2 ng ml^?1 with RSD of 2–3%. Results for various NBS Standard Reference Materials agreed well with expected values and were as follows: orchard leaves, 10 ± 1 μg g^?1; tomato leaves, 0.28 ± 0.03 μg g^?1; bovine liver, 0.046 ± 0.005 μg g^?1.     

Determination of arsenic in steel and cast iron by hydride-generation atomic absorption spectrometry

A procedure is described for the determination of arsenic in steel and cast iron by atomic absorption spectrometry after hydride generation with sodium tetrahydroborate. The samples are decomposed with a nitric/perchloric acid mixture. The data are evaluated directly against acidic standard solutions of arsenic(V). The limit of detection is about 1 μg g^?1 and the precision is better than 4% for concentrations exceeding 10 μg g^?1.     

A simple and sensitive continuous hydride generation system for the determination of arsenic and selenium by atomic absorption and atomic fluorescence spectrometry

The development and optimization of a continuous hydride generation system for atomic absorption spectrometry (a.a.s.) and atomic fluorescence spectrometry (a.f.s.) is described. Sodium tetrahydroborate(III) solution and sample solution are delivered by two small peristaltic pumps to a gas/liquid separator. The evolved hydrides are swept to a miniature argon/hydrogen diffusion flame burning on a borosilicate glass tube. Detection limits (2σ) obtained for arsenic are 0.8 ng ml^-1 by a.a.s. and 0.34 ng ml^-1 by a.f.s., and for selenium 0.5 ng ml^-1 by a.a.s. and 0.13 ng ml^-1 by a.f.s. Linear working ranges are typically 1–100 ng ml^-1 with a typical measurement time of 1 min per sample or standard.     

Ultra-trace arsenic and mercury speciation and determination in blood samples by ionic liquid-based dispersive liquid-liquid microextraction combined with flow injection-hydride generation/cold vapor atomic absorption spectroscopy

A simple, fast, and sensitive method for speciation and determination of As (III, V) and Hg (II, R) in human blood samples based on ionic liquid-dispersive liquid-liquid microextraction (IL-DLLME) and flow injection hydride generation/cold vapor atomic absorption spectrometry (FI-HG/CV-AAS) has been developed. Tetraethylthiuram disulfide, mixed ionic liquids (hydrophobic and hydrophilic ILs) and acetone were used in the DLLME step as the chelating agent, extraction and dispersive solvents, respectively. Using a microwave assisted-UV system, organic mercury (R-Hg) was converted to Hg(II) and total mercury amount was measured in blood samples by the presented method. Total arsenic content was determined by reducing As(V) to As(III) with potassium iodide and ascorbic acid in a hydrochloric acid solution. Finally, As(V) and R-Hg were determined by mathematically subtracting the As(III) and Hg(II) content from the total arsenic and mercury, respectively. Under optimum conditions, linear range and detection limit (3σ) of 0.1–5.0 µg L^?1 and 0.02 µg L^?1 for As(III) and 0.15–8.50 µg L^?1 and 0.03 µg L^?1 for Hg(II) were achieved, respectively, at low RSD values of < 4% (N = 10). The developed method was successfully applied to determine the ultra-trace amounts of arsenic and mercury species in blood samples; the validation of the method was performed using standard reference materials.     

Molecular emission cavity analysis : Part 29. Determination of Tin after Conversion to its Volatile Hydride

Tin(II) and tin(IV) (each 0–40μg ml^?1) are determined after reduction with sodium tetrahydroborate to volatile tin hydride, and collection in a cold trap. The SnO emission stimulated in an oxy-cavity placed in a hydrogen/nitrogen flame is measured at 408 nm. The detection limit is 80 ng ml^?1 tin (II) in a 1-ml sample. The depressive effects of some cations are eliminated by EDTA.     

Synthesis hexagonal ß-Ni(OH)2 nanosheets for use in electrochemistry sensors

A new method for the determination of inorganic arsenic species (As(III) and As(V)) was developed by dispersive liquid-liquid microextraction (DLLME) separation and graphite furnace atomic absorption spectrometry (GFAAS) detection. In the pH range of 3–5, As(III) complexes with ammonium pyrrolidinedithiocarbamate (APDC) and then can be extracted into carbon tetrachloride droplets formed by injecting the binary solution of carbon tetrachloride (extraction solvent) and methanol (dispersive solvent) into the sample solution. As(V) is not extracted at the same pH conditions and remained in the aqueous phase. After extraction and phase separation by centrifugation, the enriched As(III) in the sedimented phase was determined by GFAAS. Total inorganic arsenic was determined after reduction of As(V) to As(III) with sodium thiosulfate and potassium iodide, and As(V) was calculated by difference. Under optimized conditions, the detection limits of this method for As(III) were 36 ng L^?1 with an enrichment factor of 45, and the relative standard deviation (R.S.D.%) was 3.1% (n?=?11, c?=?1.0 ng mL^?1). The method has been applied to the speciation of As(III) and As(V) in natural water samples with satisfactory results.     

Speciation analysis of inorganic arsenic by a multisyringe flow injection system with hydride generation-atomic fluorescence spectrometric detection

In this study, a new technique by hydride generation-atomic fluorescence spectrometry (HG-AFS) for determination and speciation of inorganic arsenic using multisyringe flow injection analysis (MSFIA) is reported. The hydride (arsine) was generated by injecting precise known volumes of sample, a reducing sodium tetrahydroborate solution (0.2%), hydrochloric acid (6 M) and a pre-reducing solution (potassium iodide 10% and ascorbic acid 0.2%) to the system using a multisyringe burette coupled with one multi-port selection valve. This solution is used to pre-reduce As(V) to As(III), when the task is to speciate As(III) and As(V). As(V) is determined by the difference between total inorganic arsenic and As(III). The reagents are dispensed into a gas-liquid separation cell. An argon flow delivers the arsine into the flame of an atomic fluorescence spectrometer. A hydrogen flow has been used to support the flame. Nitrogen has been employed as a drier gas (Fig. 1).Several variables such as sample and reagents volumes, flow rates and reagent concentrations were investigated in detail. A linear calibration graph was obtained for arsenic determination between 0.1 and 3 μg l⁻¹. The detection limit of the proposed technique (3σ_b/S) was 0.05 μg l⁻¹. The relative standard deviation (R.S.D.) of As at 1 μg l⁻¹ was 4.4 % (n = 15). A sample throughput of 10 samples per hour was achieved. This technique was validated by means of reference solid and water materials with good agreement with the certified values. Satisfactory results for speciation of As(III) and As(V) by means of the developed technique were obtained.     

Determination of selenomethionine by high performance liquid chromatography-direct hydride generation-atomic absorption spectrometry

A simple, reliable, trace determination of selenomethionine (Semet) based on a direct hydride generation atomic absorption spectrometric method was developed using sodium tetrahydroborate (0.3% in 0.2% NaOH) and hydrochloric acid (3 M). The method excluded any chemical pretreatment prior to hydride generation (HG). The optimized HG system was successfully coupled with the HPLC system. The detection limit (3σ of blank; n=5), reproducibility (R.S.D. of three successive analyses/day, performed on three different days), and repeatability (R.S.D. of three successive analyses) of the method were 1.08 ng ml⁻¹, 9.8% for 9.04 ng ml⁻¹ and 2.1–9.5% for 30.0–1.27 ng ml⁻¹ Semet as Se (standards prepared in Milli-Q water). Calibration graph was linear up to 30 ng ml⁻¹. This HPLC-HG-AAS method is very promising and successfully determined Semet (spiked) in human urine.     

The determination of traces of arsenic in water by arsine generation and radiometric analysis

A tracer method based on the concentration-dependent distribution principle has been developed for trace arsenic determination. Standard and sample arsenic solutions labelled with a fixed amount of radioactive arsenic-74 are isolated by arsine generation with sodium borohydride followed by absorption in potassium iodide—iodine solution. The separated arsenic(III) is then extracted with equal but limited amounts of zinc diethyldithiocarbamate in chloroform and determined radiometrically by the concentration-dependent distribution principle. The method is practically free from interferences, and arsenic in aqueous solution as low as 0.5 ng ml^-1 can be determined. Results for natural and environmental water samples are compared with results obtained by the arsine generation-atomic absorption technique.     

Biomethylation and biotransformation of arsenic in a freshwater food chain: Green alga (chlorella vulgaris)→shrimp (neocaridina denticulata)→killifish (oryzias iatipes)

Tolerance, bioaccumulation, biotransformation and excretion of arsenic compounds by the fresh–water shrimp (Neocaridina denticulata) and the killifish (Oryzias latipes) (collected from the natural environment) were investigated. Tolerances (LC₅₀) of the shrimp against disodium arsenate [abbreviated as As(V)], methylarsonic acid (MAA), dimethylarsinic acid (DMAA), and arsenobetaine (AB) were 1.5, 10, 40, and 150μg As ml^?1, respectively. N. denticulata accumulated arsenic from an aqueous phase containing 1 μg As ml^?1 of As(V), 10 μg As ml^?1 of MAA, 30 μg As ml^?1 of DMAA or 150 μg As ml^?1 of AB, and biotransformed and excreted part of these species. Both methylation and demethylation of the arsenicals were observed in vivo. When living N. denticulata accumulating arsenic was transferred into an arsenic–free medium, a part of the accumulated arsenic was excreted. The concentration of methylated arsenicals relative to total arsenic was higher in the excrement than in the organism. Total arsenic accumulation in each species via food in the food chain Green algae (Chlorella vulgaris) → shrimp (N. denticulata) → killifish (O. latipes) decreased by one order of magnitude or more, and the concentration of methylated arsenic relative to total arsenic accumulated increased successively with elevation in the trophic level. Only trace amounts of monomethylarsenic species were detected in the shrimp and fish tested. Dimethylarsenic species in alga and shrimp, and trimethylarsenic species in killifish, were the predominant methylated arsenic species, respectively.     

Determination of Arsenic and Phosphorus in Doped Polysilicon Layers

Abstract

The method is based on polysilicon dissolution with a water-hydrofluoric-nitric acid etchant mixture followed by matrix volatilization as hexafluorosilicic acid. Losses of arsenic through volatilization are avoided by its oxidation with permanganate. Phosphorus is determined by the molybdenum blue method with direct addition of a mixed reagent to the residue. Spectrophotometric evaluation at 882 nm provides a detection limit of 10 ng P ml^?1 with a precision better than 3%. Arsenic is determined by reducing As(V) to electroactive As(III) on addition of sulphite in 2 M hydrochloric acid. Differential-pulse polarography of this solution provides a precision of 2% and a detection limit of 20 ng As ml^?1.     

Hydride generation atomic fluorescence spectrometric determination of As, Bi, Sb, Se(IV) and Te(IV) in aqua regia extracts from atmospheric particulate matter using multivariate optimization

A highly sensitive and simple method, based on hydride generation and atomic fluorescence detection, has been developed for the determination of As, Bi, Sb, Se(IV) and Te(IV) in aqua regia extracts from atmospheric particulate matter samples. Atmospheric particulates matter was collected on glass fiber filters using a medium volume sampler (PM1 particulate matter). Two-level factorial designs have been used to optimise the hydride generation atomic fluorescence spectrometry (HG-AFS) procedure. The effects of several parameters affecting the hydride generation efficiency (hydrochloric acid, sodium tetrahydroborate and potassium iodide concentrations and flow rates) have been evaluated using a Plackett-Burman experimental design. In addition, parameters affecting the hydride measurement (delay, analysis and memory times) have been also investigated. The significant parameters obtained (sodium tetrahydroborate concentration, sodium tetrahydroborate flow rate and analysis time for As; hydrochloric acid concentration and sodium tetrahydroborate flow rate for Se(IV); and sodium tetrahydroborate concentration and sodium tetrahydroborate flow rate for Te(IV)) have been optimized by using 2ⁿ + star central composite design. Hydrochloric acid concentration and sodium tetrahydroborate flow rate were the significant parameters obtained for Sb and Bi determination, respectively. Using a univariate approach these parameters were optimized. The accuracy of methods have been verified by using several certified reference materials: SRM 1648 (urban particulate matter) and SRM 1649a (urban dust). Detection limits in the range of 6 × 10⁻³ to 0.2 ng m⁻³ have been achieved. The developed methods were applied to several atmospheric particulate matter samples corresponding to A Coruña city (NW Spain).     

Determination of Inorganic Arsenic Species by Electrochemical Hydride Generation Atomic Absorption Spectrometry with Selective Electrochemical Reduction

A new direct procedure for the determination of inorganic arsenic species was developed by electrochemical hydride generation atomic absorption spectrometry （EcHG-AAS） with selective electrochemical reduction. The determination of inorganic arsenic species is based on the fact that As（Ⅲ） shows significantly higher absorbance at low electrolytic currents than As（Ⅴ） in 0.3 mol·L^-1 H2SO4. The electrolytic current used for the determination of As（Ⅲ） without considerable interferences of As（Ⅴ） was 0.4 A, whereas the current for the determination of As（Ⅲ） and As（Ⅴ） was 1.2 A. For equal concentrations of As（Ⅲ） and As（Ⅴ） in a sample, the interferences of As（Ⅴ） during the As（Ⅲ） determination were smaller than 5%. The absorbance for As（Ⅴ） could be calculated by subtracting that for As（Ⅲ） measured at 0.4 A from the total absorbance for As（Ⅲ） and As（Ⅴ） measured at 1.2 A, and then the concentration of As（Ⅴ） can be obtained by its calibration curve at 1.2 A. The methodology developed provided the detection limits of 0.3 and 0.6 ng·mL^-1 for As（Ⅲ） and As（Ⅴ）, respectively. The relative standard deviations were of 3.5% for 20 ng·mL^-1 As（Ⅲ） and 3.2% for 20 ng·mL^-1 As（Ⅴ）. The method was successfully applied to determination of soluble inorganic arsenic species in Chinese medicine.     

Dual‐column capillary microextraction (CME) combined with electrothermal vaporization inductively coupled plasma mass spectrometry (ETV‐ICP‐MS) for the speciation of arsenic in human hair extracts

In this work, dual‐column capillary microextraction (CME) system consisting of N‐(2‐aminoethyl)‐3‐aminopropyltrimethoxysilane (AAPTS)‐silica coated capillary (C1) and 3‐mercaptopropyl trimethoxysilane (MPTS)‐silica coated capillary (C2) was developed for sequential separation/preconcentration of arsenite [As(III)], arsenate [As(V)], monomethylarsonic acid [MMA(V)] and dimethylarsinic acid [DMA(V)] in the extracts of human hair followed by electrothermal vaporization inductively coupled plasma mass spectrometry (ETV‐ICP‐MS) detection with iridium as permanent modifier. Various experimental parameters affecting the dual‐column microextraction of different As species had been investigated in detail. It was found that at pH 9, As(V) and MMA could be quantitatively retained by C1 and only As(III) could be quantitatively retained by C2. With the aid of valve switching, As(V)/MMA(V) retained on C1 and As(III) retained on C2 could be sequentially desorbed by 10 µl of 0.01 mol l^?1 HNO₃ [for As(V)], 0.1 mol l^?1 HNO₃ [for MMA(V)] and 0.2 mol l^?1 HNO₃‐3% thiourea (m/v) [for As(III)], respectively, the eluents were immediately introduced into the Ir‐coated graphite tubes for further ETV‐ICP‐MS detection. With two‐step ETV pyrolysis program, Cl^? in the sample matrix could be in situ removed, and the total As in the human hair extracts or digested solution could be interference‐free, determined by ETV‐ICP‐MS. DMA(V) in the human hair extracts was obtained by subtraction of total As in the human hair extracts from other three As species. Under the optimized conditions, the detection limits (3 σ) of the method were 3.9 pg ml^?1 for As(III), 2.7 pg ml^?1 for As(V), 2.6 pg ml^?1 for MMA(V) and 124 pg ml^?1 for total As with the relative standard deviations less than 7.0% (C = 0.1 ng ml^?1, n = 7), and the enrichment factor was 286, 262 and 260 for As(III), As(V) and MMA(V), respectively. The developed method was successfully applied for the speciation of arsenic in the extracts of human hair. Copyright © 2009 John Wiley & Sons, Ltd.     

Determination of As(III) and As(V) in water samples by flow injection online sorption preconcentration coupled to hydride generation atomic fluorescence spectrometry

A method was developed for the determination of arsenite [As(III)] and arsenate [As(V)] in water samples using flow injection online sorption coupled with hydride generation atomic fluorescence spectrometry (HG-AFS) using a cigarette filter as the sorbent. Selective determination of As(III) was achieved through online formation and retention of the pyrrolidine dithiocarbamate arsenic complex on the cigarette filter, but As(V) which did not form complexes was discarded. After reducing As(V) to As(III) using L-cysteine, total arsenic was determined by HG-AFS. The concentration of As(V) was calculated by the difference between As(III) and total arsenic. The analytes were eluted from the sorbent using 1.68 mol L^?1 HCl. With consumption of 22 mL of the sample solution, the enrichment factor of As(III) was 25.6. The detection limits (3σ/k) and the relative standard deviation for 11 replicate determinations of 1.0 ng mL^?1 As(III) were found to be 7.4 pg mL^?1 and 2.6%, respectively.     

Sorption of arsenic,antimony and bismuth on glycolmethacrylate gels with bound thiol groups for direct sampling in electrothermal atomic absorption spectrometry

Batch sorption of arsenic, antimony and bismuth from solutions in 1 M sulphuric acid has distribution coefficients of 10⁴–10⁵. Quantitative sorption on the hydrophilic methacrylate gel containing thiol groups (Spheron Thiol) is possible within 60 min for bismuth or arsenic and 120 min for antimony. Conditions for the electrothermal atomization of arsenic sorbed on Spheron Thiol and injected into the graphite tube as a suspension are optimized. The sensitivities possible are 3.2 ng As ml^-1, 13 ng Sb ml^-1 and 2.8 ng Bi ml^-1; the coefficient of variation for 10 ng of As is 4%. Complete recovery of 40 ng As ml^-1 added to solutions of 5% KCI or 5% MgCl₂ and to river water was obtained.     

Evaluation of atomic fluorescence spectrometry as a sensitive detection technique for arsenic speciation

The potential of coupling anion-exchange high-performance liquid chromatography, hydride generation and atomic fluorescence spectrometry (HPLC–HG–AFS) for arsenic speciation is considered. The effects of hydrochloric acid and sodium tetrahydroborate concentrations on signal-to-background ratio, as well as argon and hydrogen flow rates, were investigated. Detection limits for arsenite, dimethylarsinic acid (DMA), monomethylarsonic acid (MMA) and arsenate were 0.17, 0.45, 0.30 and 0.38 μg l⁻¹, respectively, using a 20-μl loop. Linearity ranges were 0.1–500 ng for As(III) and MMA (as arsenic), and 0.1–800 ng for DMA and As(V) (as arsenic). Arsenobetaine (AsB) was also determined by introducing an on-line photo-oxidation step after the chromatographic separation. In this case the limits of detection and linear ranges for the different species studied were similar to the values obtained previously for As(V). The technique was tested with a human urine reference material and a volunteer's sample. © 1998 John Wiley & Sons, Ltd.     

Determination of arsenic in glycerine by flow injection,hydride generation and inductively-coupled plasma/atomic emission spectrometry

The determination of low concentrations of arsenic in glycerine is investigated with flow injection for the introduction of analyte and tetrahydroborate reagent for arsine generation, separation in a vapor-liquid flow cell, and inductively-coupled plasma/atomic emission spectrometry (i.c.p./a.e.s.). Peak areas are used to quantify arsenic in the concentration range 0.12–3.0 μg ml^?1. Peak areas for prepared standards exhibited average deviations of about 1.4% for this concentration range. The slope and intercept for a least- squares fit of area (nanocoulombs) vs. concentration (μg ml^?1) were 10.9 ± 0.17 and 0.46 ± 0.3, respectively.     

Determination of lead by hydride generation atomic absorption spectrometry in the presence of nitroso-R salt

A method is described for the determination of lead by hydride generation atomic absorption spectrometry in the presence of nitroso-R salt (1-nitroso-2-naphthol-3,6-disulphonic acid, disodium salt). The method is superior in sensitivity to those using peroxodisulphate, dichromate or hydrogen peroxide as oxidants. A characteristic concentration (0.0044 absorbance) of 0.8 ng ml^?1 and a relative standard deviation of 3.8% for 20 ng ml^?1 Pb were obtained. The proposed method has been applied successfully to the determination of lead in certified reference materials.