Flow injection determination of selenium by successive retention of Se(IV) and tetrahydroborate(III) on an anion-exchange resin and hydride generation electrothermal atomization atomic absorption spectrometry with in-atomizer trapping: Part 1. Method development and investigation of interferences

A sample solution was passed at 20 ml min⁻¹ through a column (150×4 mm²) of Amberlite IRA-410Stron anion-exchange resin for 60 s. After washing, a solution of 0.1% sodium borohydride was passed through the column for 60 s at 5.1 ml min⁻¹. Following a second wash, a solution of 8 mol l⁻¹ hydrochloric acid was passed at 5.1 ml min⁻¹ for 45 s. The hydrogen selenide was stripped from the eluent solution by the addition of an argon flow at 150 ml min⁻¹ and the bulk phases were separated by a glass gas–liquid separator containing glass beads. The gas stream was dried by passing through a Nafion® dryer and fed, via a quartz capillary tube, into the dosing hole of a transversely heated graphite cuvette containing an integrated L’vov platform which had been pretreated with 120 μg of iridium as trapping agent. The furnace was held at a temperature of 250°C during this trapping stage and then stepped to 2000°C for atomization. The calibration was performed with aqueous standards solution of selenium (selenite, SeO₃²⁻) with quantification by peak area. A number of experimental parameters, including reagent flow rates and composition., nature of the gas–liquid separator, nature of the anion-exchange resin, column dimensions, argon flow rate and sample pH, were optimized. The effects of a number of possible interferents, both anionic and cationic were studies for a solution of 500 ng 1⁻¹ of selenium. The most severe depressions were caused by iron (III) and mercury (II) for which concentrations of 20 and 10 mg  1⁻¹ caused a 5% depression on the selenium signal. For the other cations (cadmium, cobalt, copper, lead,. magnesium, and nickel) concentrations of 50–70 mg 1⁻¹ could be tolerated. Arsenate interfered at a concentration of 3 mg⁻¹, whereas concentrations of chloride, bromide, iodide, perchlorate, and sulfate of 500–900 mg l⁻¹ could be tolerated. A linear response was obtained between the detection limit of 4 ng 1⁻¹, with a characteristic mass of 130 pg. The RSDs for solutions containing 100 and 200 ng 1⁻¹ selenium were 2.3% and 1.5%, respectively.     

Flow injection hydride generation electrothermal atomic absorption spectrometric determination of toxicologically relevant arsenic in urine

Analytical procedure for the determination of toxicologically relevant arsenic (the sum of arsenite, arsenate, monomethylarsonate and dimethylarsinate) in urine by flow injection hydride generation and collection of generated inorganic and methylated hydrides on an integrated platform of a transverse-heated graphite atomizer for electrothermal atomic absorption spectrometric determination (ETAAS) is elaborated. Platforms are pre-treated with 2.7 μmol of zirconium and then with 0.10 μmol of iridium which serve both as an efficient hydride sequestration medium and permanent chemical modifier. Arsine, monomethylarsine and dimethylarsine are generated from diluted urine samples (10–25-fold) in the presence of 50 mmol L⁻¹ hydrochloric acid and 70 mmol L⁻¹ l-cysteine. Collection, pyrolysis and atomization temperatures are 450, 500, 2100 and 2150 °C, respectively. The characteristic mass, characteristic concentration and limit of detection (3σ) are 39 pg, 0.078 μg L⁻¹ and 0.038 μg L⁻¹ As, respectively. The limits of detection in urine are ca. 0.4 and 1 μg L⁻¹ with 10- and 25-fold dilutions. The sample throughput rate is 25 h⁻¹. Applications to several urine CRMs are given.     

Electrochemical hydride generation atomic absorption spectrometry for determination of cadmium

An electrolytic hydride generation system for determination of another hydride forming element, cadmium, by catholyte variation electrochemical hydride generation (EcHG) atomic absorption spectrometry is described. A laboratory-made electrolytic cell with lead-tin alloy as cathode material is designed as electrolytic generator of molecular hydride. The influences of several parameters on the analytical signal have been evaluated using a Plackett-Burman experimental design. The significant parameters such as cathode surface area, electrolytic current, carrier gas flow rate and catholyte concentration have been optimized using univariate method. The analytical figures of merit of procedure developed were determined. The calibration curve was linear up to 20 ng ml⁻¹of cadmium. The concentration detection limit (3σ, n = 8) of 0.2 ng ml⁻¹ and repeatability (relative standard deviation, n = 7) of 3.1% were achieved at 10.0 ng ml⁻¹. It was shown that interferences from major constituents at high concentrations were significant. The accuracy of method was verified using a real sample (spiked tap water) by standard addition calibration technique. Recovery of 104% was achieved for Cd in the spiked tap water sample.     

Flow injection-hydride generation atomic absorption spectrometric determination of selenium, arsenic and bismuth

A simple and robust flow injection system which permits low sample and reagent consumption is described for rapid and reliable hydride generation atomic absorption spectrometric determination of selenium, arsenic and bismuth. The system, which composed of one peristaltic pump and one four channel solenoid valve, used water as the carrier streams for both sample and NaBH₄ solution. Rapid off-line pre-reduction of the analytes was achieved by using hydroxylamine hydrochloride for selenium and a mixture of potassium iodide and ascorbic acid for arsenic and bismuth. Transition metal interference was eliminated with the addition of thiourea and EDTA into the NaBH₄ solution and significant sensitivity enhancement was observed for selenium in the presence of thiourea in the reductant solution. Under optimised conditions, the method achieved detection limits of 0.2 ng mL⁻¹ for Se, 0.5 ng mL⁻¹ for As and 0.3 ng mL⁻¹ for Bi. The method was very reproducible, achieving relative standard deviations of 6.3% for Se, 3.6% for As and 4.7% for Bi, and has a sample throughput of 360 h⁻¹. Successful application of the method to the quantification of selenium, arsenic and bismuth in a certified reference river sediment sample is reported.     

Speciation of inorganic arsenic by electrochemical hydride generation atomic absorption spectrometry

A simple procedure was developed for the speciation of inorganic arsenic by electrochemical hydride generation atomic absorption spectrometry (EcHG–AAS), without pre-reduction of As(V). Glassy carbon was selected as cathode material in the flow cell. An optimum catholyte concentration for simultaneous generation of arsine from As(III) and As(V) was 0.06 mol l⁻¹ H₂SO₄. Under the optimized conditions, adequate sensitivity and difference in ratio of slopes of the calibration curves for As(III) and As(V) can be achieved at the electrolytic currents of 0.6 and 1 A. The speciation of inorganic arsenic can be performed by controlling the electrolytic currents, and the concentration of As(III) and As(V) in the sample can be calculated according to the equations of absorbance additivity obtained at two selected electrolytic currents. The calibration curves were linear up to 50 ng ml⁻¹ for both As(III) and As(V) at 0.6 and 1 A. The detection limits of the method were 0.2 and 0.5 ng ml⁻¹ for As(III) and As(V) at 0.6 A, respectively. The relative standard deviations were of 2.1% for 20 ng ml⁻¹ As(III) and 2.5% for 20 ng ml⁻¹ As(V). The method was validated by the analysis of human hair certified reference material and successfully applied to speciation of soluble inorganic arsenic in Chinese medicine.     

Determination of major antimony species in seawater by continuous flow injection hydride generation atomic absorption spectrometry

The capabilities and limitations of the continuous flow injection hydride generation technique, coupled to atomic absorption spectrometry, for the speciation of major antimony species in seawater, were investigated. Two pre-concentration techniques were examined. After continuous flow injection hydride generation and collection onto a graphite tube coated with iridium, antimony was determined by graphite furnace atomic absorption spectrometry. The low detection limits obtained (∼5 ng l⁻¹ for Sb(III) and ∼10 ng l⁻¹ for Sb(V) for 2.5 ml seawater samples) permitted the determination of Sb(III) and total antimony in seawater with the use of selective hydride generation and on-line UV photooxidation. The number of samples that can be analyzed is about 15 per hour for Sb(III) determinations and 10 per hour for total antimony determinations. The analysis of seawater samples showed that Sb(V) was the predominant species, even in the presence of important biological activity.     

顺序注射氢化物发生-原子荧光光谱法同时测定中草药中铋和汞

建立了一种顺序注射氢化物发生-原子荧光光谱法测定中草药中的Bi和Hg的方法,讨论了共存离子的干扰情况。在最佳实验条件下,Bi和Hg的检出限分别为0.0057μg/L和0.0197μg/L,加标回收率为93.4%~104.7%,相对标准偏差小于4.3%,被测中草药试样中共存的离子对Bi和Hg的测定没有干扰。方法可用于中草药试样中Bi和Hg的同时测定。     

Determination of As(III) and total inorganic arsenic by flow injection hydride generation atomic absorption spectrometry

A simple procedure was developed for the direct determination of As(III) and As(V) in water samples by flow injection hydride generation atomic absorption spectrometry (FI–HG–AAS), without pre-reduction of As(V). The flow injection system was operated in the merging zones configuration, where sample and NaBH₄ are simultaneously injected into two carrier streams, HCl and H₂O, respectively. Sample and reagent injected volumes were of 250 μl and flow rate of 3.6 ml min⁻¹ for hydrochloric acid and de-ionised water. The NaBH₄ concentration was maintained at 0.1% (w/v), it would be possible to perform arsine selective generation from As(III) and on-line arsine generation with 3.0% (w/v) NaBH₄ to obtain total arsenic concentration. As(V) was calculated as the difference between total As and As(III). Both procedures were tolerant to potential interference. So, interference such as Fe(III), Cu(II), Ni(II), Sb(III), Sn(II) and Se(IV) could, at an As(III) level of 0.1 mg l⁻¹, be tolerated at a weight excess of 5000, 5000, 500, 100, 10 and 5 times, respectively. With the proposed procedure, detection limits of 0.3 ng ml⁻¹ for As(III) and 0.5 ng ml⁻¹ for As(V) were achieved. The relative standard deviations were of 2.3% for 0.1 mg l⁻¹ As(III) and 2.0% for 0.1 mg l⁻¹ As(V). A sampling rate of about 120 determinations per hour was achieved, requiring 30 ml of NaBH₄ and waste generation in order of 450 ml. The method was shown to be satisfactory for determination of traces arsenic in water samples. The assay of a certified drinking water sample was 81.7±1.7 μg l⁻¹ (certified value 80.0±0.5 μg l⁻¹).     

Determination and interference studies of bismuth by tungsten trap hydride generation atomic absorption spectrometry

The determination of bismuth requires sufficiently sensitive procedures for detection at the μg L⁻¹ level or lower. W-coil was used for on-line trapping of volatile bismuth species using HGAAS (hydride generation atomic absorption spectrometry); atom trapping using a W-coil consists of three steps. Initially BiH₃ gas is formed by hydride generation procedure. The analyte species in vapor form are transported through the W-coil trap held at 289 °C where trapping takes place. Following the preconcentration step, the W-coil is heated to 1348 °C; analyte species are released and transported to flame-heated quartz atom cell where the atomic signal is formed. In our study, interferences have been investigated in detail during Bi determination by hydride generation, both with and without trap in the same HGAAS system. Interferent/analyte (mass/mass) ratio was kept at 1, 10 and 100. Experiments were designed for carrier solutions having 1.0 M HNO₃. Interferents such as Fe, Mn, Zn, Ni, Cu, As, Se, Cd, Pb, Au, Na, Mg, Ca, chloride, sulfate and phosphate were examined. The calibration plot for an 8.0 mL sampling volume was linear between 0.10 μg L⁻¹ and 10.0 μg L⁻¹ of Bi. The detection limit (3 s/m) was 25 ng L⁻¹. The enhancement factor for the characteristic concentration (C_o) was found to be 21 when compared with the regular system without trap, by using peak height values. The validation of the procedure was performed by the analysis of the certified water reference material and the result was found to be in good agreement with the certified values at the 95% confidence level.     

Use of a surfactant in the determination of arsenic by flow injection hydride generation atomic absorption spectrometry

The possible benefits of the addition of an anionic surfactant, didodecyldimethylammonium bromide, in the determination of arsenic, by flow injection hydride generation atomic absorption spectrometry using a flame-heated quartz tube atomizer, were studied in the light of previous reports concerning the effects of surfactants on chemical vapor generation procedures. Concentrations of arsenic between 5 and 30 μg l⁻¹ were used. Calibrations in the presence and absence of the surfactant in the sample solution were not significantly different, either for the case where vesicles were formed in the presence of the analyte or where they were preformed in the surfactant solution and then added to the analyte. The surfactant had no effect on recoveries in the presence of copper, nickel or bismuth. The addition of the surfactant to the acid carrier and/or borohydride streams had no effect. It is proposed that there may be a greater role for surfactants in the improvement of the processes by which the hydride is transferred to the bulk gas phase than has been attributed in previous reports on this subject.     

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.     

On-line elimination of spectral interference of iron matrix in the flame atomic absorption determination of zinc by anion-exchange separation

A flow injection analysis (FIA) system has been developed for the flame atomic absorption spectroscopic (FAAS) determination of zinc in iron matrix. The spectral line interference of iron at 213.859 nm was eliminated by on-line separation using a micro-column of strong anion-exchange resin (Dowex 1-X8). The zinc chloro complexes were retained from 2 M HCl solution while most of the iron chloro complexes were passed to waste. For a 2% iron solution, matrix removal efficiency was 98.2% which means that positive spectral line interference of iron at the Zn line was reduced from 0.42 to 0.008 μg ml⁻¹ Zn. The optimized flow injection system can handle up to 48 samples with good precision (less than 3.5% relative standard deviation (R.S.D.)) in the working range of 0.075-2.2 μg ml⁻¹ Zn. Comparative analysis of a certified reference material and synthetic sample solutions containing traces of Zn in 2% Fe by the proposed method and by graphite furnace atomic absorption spectroscopy (GFAAS) showed no evidence of analytical bias at the 95% confidence level.     

Determination of bismuth in metallurgical materials using a quartz tube atomizer with tungsten coil and flow injection-hydride-generation atomic absorption spectrometry

A method for the determination of bismuth in metallurgical materials using hydride generation coupled with a merging zones flow system and atomic absorption spectrometry using a quartz tube atomizer with tungsten coil is proposed. The parameters related to the bismuthine generation, the flow injection system and the use of a tungsten coil were studied and the optimized system shows a wide calibration range and good stability over time, without losses in sensitivity. The analytical curve is linear from 10 to 750 μg l⁻¹ of Bi with R0.999. A detection limit of 1.9 ng Bi and an analytical frequency of 60 determinations per hour were obtained. Five metallurgical reference materials were analyzed with the proposed method after their acid dissolution. The results obtained were in good agreement with certified or recommended values, and the relative standard deviations were lower than 5%.     

A novel analytical system involving hydride generation and gold-coated W-coil trapping atomic absorption spectrometry for selenium determination at ng l level

A novel analytical technique was developed where gaseous hydrogen selenide formed by sodium tetrahydroborate reduction is transported to and trapped on a resistively heated gold-coated W-coil atom trap for in situ preconcentration. Gold coating on W-coil was prepared by using an organic solution of Au. The atom trap is held at 165 °C during the collection stage and is heated up to 675 °C for revolatilization; analyte species formed are transported to an externally heated quartz T-tube where the atomization takes place and the transient signal is obtained. The carrier gas consisted of 112.5 ml min^− 1 Ar with 75 ml min^− 1 H₂ during the collection step and 112.5 ml min^− 1 Ar with 450 ml min^− 1 H₂ in the revolatilization step. The half width of the transient signal obtained is less than 0.5 s. The RSD for the measurements was found to be 3.9% (n = 11) for 0.10 µg l^− 1 Se using peak height measurements.     

顺序注射氢化物发生-原子荧光光谱法同时测定硒和砷的研究

建立了一种顺序注射氢化物发生-原子荧光光谱法测定试样中Se和As的方法,同时讨论了共存离子的干扰情况.在最佳实验条件下,Se和As的检出限分别为0.16和0.095 μg/L,加标回收率为92.4%～104.7%.     

Determination of essential metals in complete diet feed by flow injection and flame atomic absorption spectrometry

A prior study of different sample pre-treatments for the determination of metallic elements in complete diet feeds was performed in order to choose the most suitable for these samples. The studied pre-treatment were: acid extraction (lixiviation), wet digestion (on microwave oven) and dry ashing mineralization (calcination). Lixiviation (acid extraction) with hydrochloric acid was selected due to its accuracy, fast and simple pre-treatment procedure. Due of the different levels of concentration of the metallic elements in the samples, the same manifold was used but with small variations. Copper (with on-line pre-concentration by chelating Chelex-100 resin), calcium (with on-line dilution) and iron determination gave suitable accuracy and precision and required a little time for analysis. Five different samples were analyzed by flow injection and the results were contrasted with dry ashing mineralization in batch procedure and with the labeled contents.     

Design and application of a novel integrated electrochemical hydride generation cell for the determination of arsenic in seaweeds by atomic fluorescence spectrometry

An integrated electrochemical hydride generation cell, mainly composed of three components (a gas liquid separator, a graphite tube cathode and a reticulate Pt wire anode), was laboratory constructed and employed for the detection of arsenic by coupling to atomic fluorescence spectrometry. This integrated cell was free of ion-exchange membrane and individual anolyte, with the virtues of low-cost, easy assembly and environmental-friendly. Using flow injection mode, the sample throughput could come to 120 h⁻¹ attributed to the small dimension of the cathode chamber. The operating conditions for the electrochemical hydride generation of arsenic were investigated in detail and the potential interferences from oxygen or various ions were also evaluated. Under the optimized conditions, no obvious oxygen quenching effects were observed. The limit of detection of As (III) for the sample blank solution was 0.2 ng mL⁻¹ (3σ) and the relative standard deviation was 3.1% for nine consecutive measurements of 5 ng mL⁻¹ As (III) standard solution. The calibration curve was linear up to 100 ng mL⁻¹. The accuracy of the method was verified by the determination of arsenic in the reference materials GBW08517 (Laminaria Japonica Aresch) and GBW10023 (Porphyra crispata) and the developed method was successfully applied to determine trace amounts of arsenic in edible seaweeds.     

Determination of toxic and non-toxic arsenic species in urine by microwave assisted mineralization and hydride generation atomic absorption spectrometry

Flow injection — microwave oven — hydride generation — atomic absorption spectroscopy (FI-MO-HG-AAS) has been optimized for the determination of the total and toxic arsenic in urine with and without persulfate, respectively. With microwave oven assisted digestion of urine with 5% (w/v) K₂S₂O₈ and 5% (w/v) NaOH all arsenicals completely can be converted to arsenate, which is determined by HG-AAS to give the total concentration of the six species present in urine. The detection limits of 4–6 g l^–1, the relative standard deviation of 3–7% and the high sample throughput make the methods suitable for rapid routine on-line determination. Application of the proposed procedures to the analysis of urine from people on a diet rich in seafood revealed a significant increase in total urinary arsenic due to the rapid excretion of organoarsenicals. Efficient decomposition and quantitative recovery of all arsenic species in spiked urine is achieved by using 5% K₂S₂O₈ in 5% NaOH at 4.6 ml min^–1, microwave power of 700 W and a 1.5 m coil.     

Determination of Te in soldering tin using continuous flowing electrochemical hydride generation atomic fluorescence spectrometry

An electrochemical hydride generation system was developed for the detection of Te by coupling an electrochemical hydride generator with atomic fluorescence spectrometry. Since TeH₂ is unstable and easily decomposes in solution, a reticular W filament cathode was used in the present system. The TeH₂ generated on the cathode surface was effectively driven out by sweeping gas from the cathode chamber. In addition, a low temperature electrochemical cell (10 °C) was applied to reduce the decomposition of TeH₂ in solution. The limit of detection (LOD) was 2.2 ng ml^− 1 and the relative standard deviation (RSD) was 3.9% for nine consecutive measurements of standard solution. This method was successfully employed for determination of Te in soldering tin material.     

Arsenic in marine tissues — The challenging problems to electrothermal and hydride generation atomic absorption spectrometry

Analytical problems in determination of arsenic in marine tissues are addressed. Procedures for the determination of total As in solubilized or extracted tissues with tetramethylammonium hydroxide and methanol have been elaborated. Several typical lyophilized tissues were used: NIST SRM 1566a ‘Oyster Tissue’, BCR-60 CRM ‘Trace Elements in an Aquatic Plant (Lagarosiphon major)’, BCR-627 ‘Forms of As in Tuna Fish Tissue’, IAEA-140/TM ‘Sea Plant Homogenate’, NRCC DOLT-1 ‘Dogfish Liver’ and two representatives of the Black Sea biota, Mediterranean mussel (Mytilus galloprovincialis) and Brown algae (Cystoseira barbata). Tissues (nominal 0.3 g) were extracted in tetramethylammonium hydroxide (TMAH) 1 ml of 25% m/v TMAH and 2 ml of water) or 5 ml of aqueous 80% v/v methanol (MeOH) in closed vessels in a microwave oven at 50 °C for 30 min. Arsenic in solubilized or extracted tissues was determined by electrothermal atomic absorption spectrometry (ETAAS) after appropriate dilution (nominally to 25 ml, with further dilution as required) under optimal instrumental parameters (pyrolysis temperature 900 °C and atomization temperature 2100 °C) with 1.5 μg Pd as modifier on Zr–Ir treated platform. Platforms have been pre-treated with 2.7 μmol of zirconium and then with 0.10 μmol of iridium which served as a permanent chemical modifier in direct ETAAS measurements and as an efficient hydride sequestration medium in flow injection hydride generation (FI-HG)–ETAAS. TMAH and methanol extract 96–108% and 51–100% of As from CRMs. Various calibration approaches have been considered and critically evaluated. The effect of species-dependent slope of calibration graph or standard additions plot for total As determination in a sample comprising of several individual As species with different ETAAS behavior has been considered as a kind of ‘intrinsic element speciation interference’ that cannot be completely overcome by standard additions technique. Calibration by means of CRMs has given only semi-quantitative results. The limits of detection (3σ) were in the range 0.5–1.2 mg kg^− 1 As dry weight (wt.) for direct ETAAS analysis of extracts in both TMAH and MeOH. Within-run precision (RSD%) was 5–15% and 7–20% for TMAH and MeOH extracts at As levels 4–50 mg kg^− 1 dry wt., respectively.