Spectrophotometric catalytic determination of ultra-trace amounts of selenium based on the reduction of resazurin by sulphide

A sensitive catalytic method for determining ng ml^? concentration of selenium is described. The method is based on the catalytic action of Se(IV) on the reduction of resazurin by sulphide, monitored spectrophotometrically at 605 nm. The linearity range of the calibration graph is dependent on the concentration of sulphide. The variables affecting the rate of the reaction were investigated and the optimum conditions were established. The method is simple, rapid, precise, sensitive and widely applicable. As low as 8.0 × 10^?4 μg ml^?1 of selenium can be determined. The relative standard deviation of seven determination of 10 ng Se was 0.7%. The determination of Se(IV) in the presence of Se(VI) and the determination of total selenium are also described.     

Determination Of SE(IV) in the Presence of SE(VI) at NG ML− Concentration Levels by a Kinetic Spectrophotometric Method

ABSTRACT

The catalytic effect of Se(IV) on the reduction reaction of thionine(TN) by sulfide ion is used for determination of trace amounts of selenium(IV) ion by a kinetic-spectrophotometric method. This new method is simple and highly sensitive. The reaction was monitored spectrophotometrically by measuring the decrease in absorbance of the reaction mixture at 598 nm. The fixed time method was used for the first 45s from initiation of the reaction. Under the optimum conditions, in the concentration range of 2-90 ng ml^? of selenium(IV), a quite linear regression equation (r = 0.9984, n = 14) was obtained. The experimental detection limit of the method (S/N = 3) was 1.3 ng ml^?. The relative standard deviation of ten replicate measurements is 2.51% for a 40 ng ml^? solution of selenium. The proposed method is used to the study of selenium (IV,VI) speciation in water at ng ml^? levels. This method was extended for the determination of selenium in real samples.     

2-(α-pyridyl)thioquinaldinamide: a novel fluorimetric reagent in inorganic trace analysis. : Part 2. A simple selective determination of selenium(IV) at Ultratrace Levels

The very sensitive fluorimetric determination of selenium(IV) is based on its oxidation of the non-fluorescent 2-(α-pyridyl)thioquinaldinamide in slightly acidic solution (0.05–0.15 M sulphuric acid). The excitation and emission wavelengths are 350 nm and 500 nm, respectively. Linear calibration graphs are obtained for different ranges of selenium concentration between 0.01 ng ml^?1 and 0.5 μg ml^?1. Over sixty ions either do not interfere or can be masked in the determination of 1 ng ml^?1 Se(IV). The method is applied successfully to various synthetic mixtures and to a native sulphur sample. The reaction is fast and the fluorescent system is stable for 24 hours.     

Kinetic spectrophotometric determination of trace amounts of selenium based on the catalytic reduction of maxilon blue-SG by sulfide

A simple and sensitive catalytic spectrophotometric method was developed for the determination of trace amounts of selenium. The method is based on the catalytic effect of selenium in form Se(IV) on the reduction of Maxilon Blue-SG by sodium sulfide. Indicator reaction is followed spectrophotometrically by measuring the absorbance change at λ_max=654 nm and constant temperature (30.0±0.1 °C) by fixed time method. Selenium could quantitatively be determined in the range 0.004-0.200 μg ml⁻¹ Se(IV) with a detection limit of 0.205 ng ml⁻¹ Se(IV). All of the variables that affected the reaction rate were investigated and established optimum conditions to give maximum sensitivity. The R.S.D.s of the method (N=12) for the Se(IV) concentrations of 0.004, 0.016, 0.040 and 0.160 μg ml⁻¹ are between 2.27 and 0.32%, respectively, and depended on Se(IV) concentration. The interference effect of various anion and cations on the Se(IV) determination was also fully studied. The selectivity of catalytic reaction was greatly improved with the use of the strong cation exchange resin. The developed kinetic-catalytic reaction was applied to the determination of selenium in real samples as Antioxidant-S, Selsun (which is a healthcare product for the treatment of dandruff) and analytical grade sodium metabisulfite, and in spring water samples without any pre-concentration. The acceptable recoveries were obtained by the method for appropriate standard Se(IV) additions. The method is simple, practical and suitable for using in small laboratories owing to its precision, sensitivity and relative selectivity.     

Spectrofluorimetric kinetic determination of selenium (IV) by flow injection analysis in cationic micellar medium

A sensitive catalytic kinetic spectrofluorimetric method for determining ng ml(-1) of selenium by flow injection analysis has been developed. The method, based on the catalytic effect of Se (IV) on the reduction of resorufin by sulphide, in the presence of cetylpyridinium chloride, is monitored spectrofluorimetrically (lambda(ex)=480 nm; lambda(em)=583 nm). The linearity range of the calibration graph is dependent on the concentration of sulphide. The variables affecting the rate of the reaction were investigated. The method is simple, rapid, precise, sensitive, and widely applicable. The limit of detection is 1 ng ml(-1) Se (IV), and the calibration range is 5-1000 ng ml(-1). Sampling rate is 60 samples h(-1), and the relative standard deviation of 12 determinations of 100 ng ml(-1) Se was 0.76%. The determination of Se (IV) in the presence of Se (VI) and total selenium is described. The method was applied to the determination of Se in selenium tablets, and several synthetic samples.     

Kinetic Spectrophotometric Determination of Vanadium (V) Based on its Inhibitory Effect on the Thionine – Ascorbic Acid Reaction

ABSTRACT

A simple and sensitive kinetic method for the determination of vanadium(V) based on its inhibitory effect on the reduction of thionine by ascorbic acid at pH=5 is described. The reaction rate is monitored spectrophotometrically by measuring the decrease in absorbance of thionine at 598 nm after a fixed time (10 min). The calibration graph is linear in the range of 10 ? 120 ng ml^?1 of vanadium(V) and the detection limit is 6 ng ml^?1. The relative standard deviation (RSD) for 80 ng ml^?1 of V(V) was 0.96% (n=10). The method was successfully applied to the determination of vanadium in a certified reference sample.     

Kinetic-Spectrophotometric Determination of Traces of Osmium by Its Catalytic Effect on the Oxidation of Pyrogallol Red by Hydrogen Peroxide

Abstract

A Kinetic-spectrophotometric method for the determination of ultra-trace amounts of osmium(VIII) is described. It is based on the catalytic action of osmium(VIII) on the oxidation of pyrogallol red with hydrogen peroxide, yielding a colorless product in neutral medium. The reaction is followed spectrophotometrically by measuring the rate of change in absorbance at 540 nm and 30°C. Os(VIII) in the range 0.005 -100 ng.ml^?1 can be determined. The proposed method is hardly subject to interferences. The relative standard deviation is 1.5% for 1 ng.ml^?1 of Os(VIII). The kinetic parameters of the catalyzed and uncatalyzed reactions are reported. The detection limit is 1 pg.ml^?1.     

Atomic absorption spectrometric determination of selenium with carbon furnace atomization

A Varian Techtron model 63 carbon rod atomizer is used for the atomic absorption spectrometric determination of nanogram quantities of selenium. The pronounced interferences from the matrices in biological digests can be obviated by isolating selenium from sample matrices by precipitation with ascorbic acid. The precision of the determination is improved by incorporating 5000 μg Ni ml^?1 in the analytical solutions. Selenium at μg g^?1 and sub-μg g^?1 levels in a variety of biological samples can be determined. The detection limit is 25 ng Se g^?1.     

Kinetic-Spectrophotometric Determination of Molybdenum(VI) Based on Its Catalytic Effect on the Thionine-Hydrazine Reaction

Abstract

A kinetic method for the determination of trace amounts of Mo(VI) (0.05-4 μg ml^?1) based on its catalytic effect on the reduction of thionine by hydrazine monochloride in strongly acidic media is reported. The reaction is monitored spectrophotometrically by measuring the decrease in absorbance of thionine at 605 nm after a fixed time (5 min.). The detection limit of the method is 23 ng ml^?1 and the relative standard deviation (RSD) for 0.05 μg ml^?1 of Mo(VI) is 1.2% (n=7). The method is almost free from interferences, especially from large amounts of tungsten. The procedure was successfully applied to the determination of trace amounts of molybdenum in steel.     

Pervaporation as a Separation Technique for Direct Determination of Volatile Selenium Species by Atomic Fluorescence Spectrometry

Abstract

This paper reports for the first time a suitable way to determine methylated selenium compounds using the new approach of pervaporation coupled to atomic fluorescence spectrcmetry (PV-AFS).

The method developed allows direct extraction, separation, preconcentration and determination of dimethylselenium (DMSe) and dimethyldiselenium (DMDSe) from slurry samples. Under the optimum conditions, the detection limits (LODs) were found to be 0.66 ng and 0.39 ng for DMSe and DMDSe, respectively, the precision being about 6–9 % for 10 ng mL as selenium concentration. The linearity ranges were from the LOD to 0.7 μg mL^?1 for DMSe and from the LOD to 0.4 μg mL^?1 for DMDSe (as Se). The pervaporation efficiencies were 55 ± 1 % and 85 ± 5 % for DMSe and DMDSe, respectively. The proposed method was successfully applied to determine methylated selenium species in sewage sludge, garlic and oyster samples. The concentrations found were from 0.07 to 1.42 μg g^?1.

As no certified reference materials are available for these analytes, validation was carried out by recovery studies in these matrices, and the results showed that the proposed method performed satisfactorily.     

Flow injection spectrophotometric determination of trace amounts of selenium

A simple, rapid and sensitive flow injection spectrophotometric method for determination of selenium (0.005-1.5 mug ml(-1)) is described. The method is based on the catalytic effect of Se(IV) on the reduction reaction of thionine (TN) with sulphide ion, monitored spectrophotometrically at 598 nm. The detection limit is 5 ng ml(-1) the relative standard deviation for eight replicate measurements is 1.1% for 1 mug ml(-1) of selenium. The sampling rate is 25-30 samples h(-1). The procedure was applied successfully to the determination of selenium in real samples.     

Flow Injection Catalytic Determination of Vanadium using the Indicator Reaction between Victoria Blue B and Bromate and A Citric Acid Activator

ABSTRACT

A flow injection catalytic method is proposed for determination of trace vanadium based on its catalytic action on a new indicator reaction between Victoria blue B (VBB) and potassium bromate in the presence of citric acid as an activator and in dilute sulfuric acid medium. The reaction is monitored spectrophotometrically by measuring the decrease in absorbance of VBB injected at the maximum absorption wavelength of 618 nm. The detection limit is 0.5 ng ml^?1 and is independent of the initial valence state of vanadium. The relative standard deviation is 1.5% obtained from 11 standard solutions each containing 40 ng ml^?1 of vanadium. The sampling rate is about 15 samples per hour. This method is very simple and has been applied to the determination of trace vanadium in some natural waters with recoveries of 93-103%.     

Integrated Retention/Spectrophotometric Detection Method for the Determination of Formaldehyde

Abstract

An integrated-sensor method for the determination of formaldehyde based on retention of the reaction product of the analyte with p-rosaniline and sulfite in a flow-cell packed with Dowex 1-X-8 anion exchange resin was developed. The method has a good selectivity with a detection limit of 0.3 μg ml^?1 (1 ml sample) or 75 ng ml^?1 (2 ml sample), and a linear range between 1–30 μg ml^?1. The relative standard deviations (n = 11) were 2.8 and 1.3% for 2 and 20 μg ml^?1 formaldehyde, respectively. Depending on the working conditions, the sampling frenquency ranged between 10 and 18 h^?1. The method was applied to the determination of formaldehyde in well water.     

Square-wave cathodic adsorptive stripping voltammetric determination of trace amounts of 2-mercaptobenzimidazole in water samples

A sensitive, simple and reproducible square-wave cathodic adsorptive stripping voltammetric method is developed for the determination of 2-mercaptobenzimidazole (MBIM) in different water samples using a static mercury drop electrode (SMDE) as a working electrode. The solution conditions and instrumental parameters were optimized for the determination of MBIM by square-wave cathodic adsorptive stripping voltammetry. This method is based on a sensitive adsorptive reduction peak of the MBIM at ?0.532 V vs. Ag/AgCl reference electrode in a Britton-Robinson buffer at pH 10.0. The linear concentration range was 20–600 ng ml^?1 when using 0.0 V as the accumulation potential. The detection limit of the method was calculated to be 8.41 ng ml^?1. The precision was excellent with relative standard deviations (n = 20) of 2.30%, 1.71%, 2.25% and 1.33% at MBIM concentrations of 40, 90, 200 and 500 ng ml^?1, respectively. The proposed voltammetric method is used for the determination of MBIM in different spiked water samples.     

Cyclodextrin Enhanced Spectrofluorimetric Determination of Melatonin in Pharmaceuticals and Urine

ABSTRACT

Melatonin forms a 1:1 inclusion complex with methyl-β-cyclodextrin with an association constant of 139 ? 30 M^?1 at 20 °C. The effect of several cyclodextrins and derivatives on the fluorescence spectra of melatonin was studied with a great increase of fluorescence signal when methyl-β-cyclodextrin was employed. Optimal conditions of the method were: [methyl-β-cyclodextrin] = 0.01 M and temperature 20 °C; the pH does not affect the luminescence emission. The linear dynamic range (LDR) was 50-3000 ng ml^?1 and a limit of detection of 10 ng ml^?1 of melatonin was obtained with a relative standard deviation (RSD) of 0.77% (at 0.3 μg ml^?1 level). This simple method was satisfactorily applied to the determination of melatonin in pharmaceutical preparations and urine.     

Highly Sensitive Determination of Traces of Co(II) in Pharmaceutical and Urine Samples Using Kinetic–Spectrophotometric Method

Abstract

A high sensitive, accurate and simple kinetic method has been developed for determination of trace of Co(II) ions, based on its strongly catalytic effect in the reaction oxidation of disodium-6-hydroxy-5-[(4-sulfophenyl)azo]-2-naphtalenesulfonic acid (artificial color, Sunset Yellow FCF, E110 in text selected as SY) by hydrogen peroxide in borate buffer at pH of 9.5, by monitoring the rate of disappearance of SY. Reaction rate was monitored spectrophotometrically, at λ_max of the SY at 478.4 nm. The optimum operating conditions regarding reagents concentration and temperature were established. The tangent method was adopted for constructing the calibration curve, which was found to be linear over the concentration range 1.18–17.67 ng ml^?1 and 17.67–58.90 ng ml^?1 of Co(II). The limit of detection (3σ) is 0.15 ng ml^?1, and limit of quantification (10σ) is 0.5 ng ml^?1. The effects of the other ions on the reaction rate were determined for an assessment of the selectivity of the method. The developed kinetic procedure was successfully applied for the determination of Co(II) in pharmaceutical and urine samples. The unique features of this procedure are that the determination can be performed at room temperature, and the analysis time is short. The newly developed method is high sensitive, simple, inexpensive and efficient for use in the analysis of a large number of samples.     

Sensitivity enhancement using nanometer silica particles on the surface of a quartz cell in mercury and selenium determination by vapor generation atomic absorption spectrometry

The sensitivity of on-line vapor generation atomic absorption spectrometry of mercury and selenium was improved by using a new atom trap technology. The inner wall of a T-shaped quartz tube was coated with nanometer SiO₂ so increase the residence time of the analyte atoms in the light path. The linear range of the calibration plots thus was increased to a range from 5.0 to 150 ng mL^?1 for mercury, and from 4.5 to 100 ng mL^?1 for selenium. The detection limits are 0.9 ng mL^?1 for Hg and 1.0 ng mL^?1 for Se which is a 2-fold improvement. The technique was applied to the determination of Hg and Se in herbs and hair.     

Nanometer‐sized alumina packed microcolumn solid‐phase extraction combined with field‐amplified sample stacking‐capillary electrophoresis for the speciation analysis of inorganic selenium in environmental water samples

In this paper, a new method of nanometer‐sized alumina packed microcolumn SPE combined with field‐amplified sample stacking (FASS)–CE‐UV detection was developed for the speciation analysis of inorganic selenium in environmental water samples. Self‐synthesized nanometer‐sized alumina was packed in a microcolumn as the SPE adsorbent to retain Se(IV) and Se(VI) simultaneously at pH 6 and the retained inorganic selenium was eluted by concentrated ammonia. The eluent was used for FASS–CE–UV analysis after NH₃ evaporation. The factors affecting the preconcentration of both Se(IV) and Se(VI) by SPE and FASS were studied and the optimal CE separation conditions for Se(IV) and Se(VI) were obtained. Under the optimal conditions, the LODs of 57 ng L^?1 (Se(IV)) and 71 ng L^?1 (Se(VI)) were obtained, respectively. The developed method was validated by the analysis of a certified reference material of GBW(E)080395 environmental water and the determined value was in a good agreement with the certified value. It was also successfully applied to the speciation analysis of inorganic selenium in environmental water samples, including Yangtze River water, spring water, and tap water.     

Determination of trace selenium in biological material by preconcentration and x-ray emission spectrometry

Selenium is determined in the ng g^?1 to μg g^?1 range in biological and environmental samples. A wet digestion procedure was optimized with respect to volatility losses and recovery yields, by using ⁷⁵Se metabolically incorporated into rat organs. Selenium is preconcentrated from the digestion liquid by a two-step reduction with 4 M HCl and ascorbic acid. The colloidal selenium formed is adsorbed on activated carbon and filtered on a Nucleopore membrane for measurement by energy-dispersive x-ray fluorescence. Almost complete recovery was obtained, and the detection limit was 20 ng, corresponding to 10 ng g^?1 for a 2-g sample. Biological reference materials were analyzed with satisfactory results, and the accuracy of the method was good.     

Differential Pulse Voltammetric Determination of Selenocystine Using Selenium‐gold Film Modified Electrode

Differential pulse voltammetric determination of selenocystine (SeC) using selenium‐gold film modified glassy carbon electrode ((Se‐Au)/GC) is presented. In 0.10 mol?L^?1 KNO₃ (pH 3.20) solution, SeC yields a sensitive reduction peak at ?740 mV on (Se‐Au)/GC electrode. The peak current has a linear relationship with the concentration of SeC in the range of 5.0×10^?8–7.0×10^?4 mol?L^?1, and a 3σ detection limit of SeC is 3.0×10^?8 mol?L^?1. The relative standard deviation of the reduction current at SeC concentration of 10^?6 mol?L^?1 is 3.88% (n=8) using the same electrode, and 4.19% when using three modified electrodes prepared at different times. The content of SeC in the selenium‐enriched yeast and selenium‐enriched tea is determined. The total selenium in ordinary or selenium‐enriched tea is determined by DAN fluorescence method. The results indicate that in selenium‐enriched yeast about 20% of total selenium is present as SeC and in selenium‐enriched tea SeC is the major form of selenoamino acids. The total selenium content in selenium‐enriched tea soup is 0.09 μgSe/g accounting by 7% compared with that in selenium‐enriched tea. Hence, only a little amount of selenium is utilized by drinking tea, and most selenium still stay in tealeaf. Uncertainty are 22.4% and 16.1% for determination of SeC in selenium‐enriched yeast and selenium‐enriched tea by differential pulse voltammetry (DPV) on (Se‐Au)/GC electrode, respectively.