Sensitive spectrofluorimetric determination of zinc at ultra-trace levels

An ultra-trace method based on the reaction of zinc with salicylthiocarbohydrazone (SATCH) and Triton X-100 as a non-ionic surfactant was developed for the fluorimetric determination of zinc at the picogram level. The reaction is carried out in the pH range 4.4–4.7 in an aqueous ethanolic medium [52% (v/v) ethanol]. The influence of the reaction variables is discussed. The detection limit is 10 pg ml^?1 and the range of application is 0.01–500 μg l^?1, with an optimum range of 0.04–400 μg l^?1. The relative standard deviations are 0.68% (0.01–0.1 μg l^?1 of zinc), 0.41% (0.1–1.0 μg l^?1 of zinc), 0.64% (1–10 μg l^?1 of zinc), 0.82% (10–100 μg l^?1 of zinc) and 0.15% (100–500 μg l^?1 of zinc). The method is highly sensitive and selective in the presence of Cd^II and Hg^II. The effect of interferences from other metal ions and anions was studied; the masking action is discussed. The advantages of the proposed method include its high sensitivity, simplicity and selectivity.     

Automated method for the determination of boron in water by flow-injection analysis with in-line preconcentration and spectrophotometric detection

A sensitive, automated method for the determination of boron in water samples is described, involving flow injection with on-line ion-exchange preconcentration and spectrophotometric detection of the azomethine-H—boron complex. The method is applicable to various water samples and is free from interferences, even in coloured samples. Detection limits of 5 μg l^?1 at 20 samples h^?1 and 1 μg l^?1 at 10 samples h^?1 with relative standard deviations of < 10% at 1–10 μg l^?1 and < 5%at 10–200 μg l^?1 levels of boron were achieved. The recoveries for spiked natural water samples ranged from 96 to 101%. The method compares favourably with inductively coupled plasma atomic emission spectrometry.     

Determination of molybdenum at μ l−1 levels by catalytic spectrophotometric flow injection analysis

A flow injection analytical method based on the catalytic action of molybdenum on the oxidation of iodide by hydrogen peroxide in acidic medium is proposed. The triiodide formed is measured spectrophotometrically at 350 nm. Molybdenum is determined in natural water samples without preconcentration at a sampling rate of 90 h^?1 with 200-μl sample injections. The detection limit is 0.7 μ l^?1 and the calibration curve is linear over the range 1–1000 μ l^?1. The relative standard deviation is 0.83% for 50 μ l^?1 molybdenum and 1.9% for 13 μ l^?1 molybdenum.     

Continuous-flow extraction of organophosphorus pesticides coupled on-line with high-performance liquid chromatography

A continuous-flow extraction system coupled on-line with a high-performance liquid chromatograph with an ultraviolet detector is used to study the extraction of three organophosphorus pesticides (fenthion, azinphos methyl and diazinon) from aqueous samples with n-heptane as the organic solvent. Diazinon was not extracted significantly. The influence on the extraction of different parameters (coil length, flow rate and phase volume ratio) were studied. The calibration graphs are linear for 0.5–7 mg l^?1 and 8–20 mg l^?1 foor azinphos methyl where the percentage extraction (E%) is 90% and 70%, respectively, and up to 4 mg l^?1 for fenthion, where the E% is 33%. The detection limits and the relative standard deviations are 0.04 and 0.09 mg l^?1, and 3.4 and 5.3%, for azinphos methyl fenthion, respectively. Other pesticides and related compounds were found not to interfere. The sample throughput of this method was 15 h^?1.     

Flow-injection spectrophotometric determination of fluoride based on alizarin fluorine blue in the presence of sodium dodecyl sulphate

The stopped-flow reagent-injection method proposed for the spectrophotometric determination of fluoride with lanthanum (III)/alizarin fluorine blue in the presence of sodium dodecyl sulphate at pH 4.6 (λ_max=574 nm) provides a linear calibration graph for 0.08–1.2 mg l^?1 fluoride. The relative standard deviation (n=10) was 0.2% at 0.60 mg l^?1 fluoride. The sampling rate was 60 h^?1. The method is applied to sea and bottled mineral waters with satisfactory results.     

Direct determination of lead in blood by electrothermal atomic absorption spectrometry with L'vov platform and matrix modification

An electrothermal atomic-absorption procedure with the L'vov platform and a simple five- or ten-fold sample dilution with a matrix-modifier solution containing diammonium hydrogenphosphate, Triton X-100 and nitric acid, is described for the direct determination of relatively low levels of lead in heparinized blood. The graphite-furnace parameters and matrix-modifier composition are optimized. Sensitivity, imprecision, accuracy and detection limit are reported. Results obtained by standard addition for ten human blood samples (30–400 μg l^?1 lead) were confirmed by an extraction/flame atomic-absorption reference method. Differences in mean lead values ranged from 2 to 31 μg l^?1 with 5.1% mean relative difference. The mean relative standard deviations for consecutive and between-day determinations were 4.6 and 9%, respectively. Accuracy was verified by analyzing six bovine-blood standards certified for lead in the range 70–1100 μg l^?1; deviations of found concentrations from expected values ranged from 0 to 44 μg l^?1 with 4.3% mean relative error. Recovery experiments done with human blood gave 104% (90–121%) of the added lead. The method offers several advantages for routine application in comparison with the extraction/flame atomic-absorption procedure.     

Spectrofluorimetric determination of trace amounts of thorium

A spectrofluorimetric method, based on the formation of a fluorescent complex with salicyladehyde carbohydrazone, is optimized for the determination of thorium (20–800 μg l^?1) at “pH” 1.3–1.7. The relative standard deviation is 2.7% for 100 μg Th l^?1. The method is applied to synthetic mixtures containing various amounts of thorium and to the determination of thorium in monazite samples.     

Flow-injection spectrophotometric determination of aluminium in water with pyrocatechol violet

Optimum conditions for the adaptation of the spectrophotometric pyrocatechol violet method for aluminium to a flow-injection system are described. The detection limit is 3 μg Al l^?1 and calibration graphs are linear up to 3 or 10 mg l^?1 (with 200-μl or 10-μl injection loops, respectively). The relative standard deviation is 〈 2% at 0.1 mg Al l^?1. Potential interferences of 40 common inorganic ions and of 20 organic substances, including fulvic acid, are reported. With the use of conventional masking agents and predigestion of samples with high organic content, the method is suitable for determining total aluminium in natural waters.     

Preconcentration and Spectrophotometric Determination of Chromium (VI) and Total Chromium in Drinking Water by the Sorption of Chromium Diphenylcarbazone with Surfactant Coated Alumina

Abstract

A simple and inexpensive method for determining chromium (VI) in drinking water by spectrophotometry after preconcentration with sodium dodecyl sulphate (SDS) coated alumina column is described. Chromium(VI) is reacted with diphenylcarbazide (DPC) and the Cr-DPC complex is quantitatively adsorbed onto a SDS coated alumina column from 800 ml of sample solution. The complex is then eluted with a 8 ml mixture of methanol, acetone and hydrochloric acid and determined by spectrophotometry. Total chromium can be determined after oxidation of chromium (III) to chromium (VI) by KMnO₄. The relative standard deviation (10 replicate analyses) at the 10 μg l^?1 of chromium (VI) and 10 μg l^?1 of total chromium were 3.5% and 3.4% and corresponding limits of detection (based on 3 σ) were 0.040 μg l^?1 and 0.033 μg l^?1, respectively.     

Determination of total phosphorus in waters with amperometric detection by coupling of flow-injection analysis with continuous microwave oven digestion

For the determination of total phosphorus in waters by flow-injection analysis, a continuous microwave oven decomposition with subsequent amperometric detection of orthophosphate is proposed. The percentage digestion was examined for two different decomposition reagents and by varying the pH of the carrier and the length and diameter of the digestion coil. With potassium peroxodisulphate decomposition the recoveries of phosphorus vary from 91 to 100% for organic phosphorus compounds, and with perchloric acid decomposition the recoveries vary from 60 to 70% for inorganic polyphosphates. Calibration graphs are linear for up to 30 mg P l^?1, the determination limit is 0.1 mg P l^?1 and the precision of the method is 3% (relative standard deviation) (n = 5) at 5 mg P l^?1. The sampling rate is 20 h^?1. Good recoveries of phosphorus after addition to domestic waste water sample are obtained.     

Fluorimetric determination of anionic surfactants by extraction as safranine-T ion-pairs

A simple and rapid method is proposed for the spectrofluorimetric determination of anionic surfactants. It is based on formation of an ion-pair at pH 2 with safranine-T and its subsequent extraction into chloroform. Fluorescence intensity is increased by a factor of about 5 with respect to that of the reagent. The calibration graph is linear in the concentration range 0.015–0.40 mg l^?1 dodecyl sulfate; the relative standard deviation is 5.6% at 0.22 ml l^?1 surfactant. The method is applied to determine anionic surfactants in city waste-waters, giving recoveries close to 100%.     

Determination of total tin in silicate rocks by graphite furnace atomic absorption spectrometry

A method is described for the determination of total tin in silicate rocks utilizing a graphite furnace atomic absorption spectrometer with a stabilized-temperature platform furnace and Zeeman-effect background correction. The sample is decomposed by lithium metaborate fusion (3 + 1) in graphite crucibles with the melt being dissolved in 7.5% hydrochloric acid. Tin extractions (4 + 1 or 8 + 1) are executed on portions of the acid solutions using a 4% solution of trioctylphosphine oxide in methyl isobutyl ketone (MIBK). Ascorbic acid is added as a reducing agent prior to extraction. A solution of diammonium hydrogenphosphate and magnesium nitrate is used as a matrix modifier in the graphite furnace determination. The limit of detection is > 10 pg, equivalent to > 1 μg l^?1 of tin in the MIBK solution or 0.2–0.3 μg g^?1 in the rock. The concentration range is linear between 2.5 and 500 μg l^?1 tin in solution. The precision, measured as relative standard deviation, is < 20% at the 2.5 μg l^?1 level and < 7% at the 10–30 μg l^?1 level of tin. Excellent agreement with recommended literature values was found when the method was applied to the international silicate rock standards BCR-1, PCC-1, GSP-1, AGV-1, STM-1, JGb-1 and Mica-Fe. Application was made to the determination of tin in geological core samples with total tin concentrations of the order of 1 μg g^?1 or less.     

Biamperometric Determination of Tetracycline in Pharmaceuticals

Abstract

A fast, reliable, and low cost biamperometric flow‐injection method, with an error of 1.3% and an analytical throughput of 55 samples h^?1, for determination of tetracycline hydrochloride in pharmaceuticals capsules is proposed. The analytical curve was linear (r=0.998) in the range 10 to 50 mg l^?1 using Fe(CN)₆ ^3? and NaOH solutions as reagent and carrier stream/supporting electrolyte, respectively. A relative standard deviation of 1.6% (10 sequential injections of 30.0 mg l^?1) was verified with detection and quantification limits of 0.6 and 3.4 mg l^?1, respectively.     

Square‐Wave Voltammetry Determination of Aspartame in Dietary Products Using a Boron‐Doped Diamond Electrode

Abstract

The use of square‐wave voltammetry in conjunction with a cathodically pretreated boron‐doped diamond electrode for the analytical determination of aspartame in dietary products is described. In this determination, the samples were analyzed without previous treatment in a 0.5 mol l^?1 H₂SO₄ solution. A single oxidation peak at a potential of 1.6 V vs. Ag/AgCl (3.0 mol l^?1 KCl) with the characteristics of an irreversible reaction was obtained. The analytical curve was linear in the aspartame concentration range 9.9×10^?6 to 5.2×10^?5 mol l^?1 with a detection limit of 2.3×10^?7 mol l^?1. The relative standard deviation (n=5) obtained was smaller than 0.2% for the 1.0×10^?4 mol l^?1 aspartame solution. The proposed method was applied with success to the determination of aspartame in several dietary products and the results were similar to those obtained using an HPLC method at 95% confidence level.     

Determination of cobalt in plant digests by adsorption stripping voltammetry

The procedure involves adsorption of cobalt onto a static mercury drop as its dimethylgloximate complex (pH 9.3, adsorption potential ?0.70 V, adsorption time 2 min), followed by a d.c. cathodic scan, effecting reduction at ?1.15 V (SCE). Of the dominant electroactive trace elements in plants (Mn, Fe, Zn), only zinc interfered; it was masked by nitrolotriacetic acid (2 × 10^?4 M). The detection limit is 0.01 μg l^?1 cobalt in the digest; the relative standard deviation is 2.5% at 0.75 μg l^?1. Calibration is linear in the range 0–6.0 μg l^?1 cobalt. Results obtained by the voltammetric method, by electrothermal atomic absorption spectrometry and neutron activation analysis are compared for seven pasture samples containing 0.1–0.2 mg kg ^?1 cobalt. The activation method provides validation for the same preparation and voltammetric results.     

Determination of boron in water by flow injection/inductively coupled plasma emission spectrometry

A method is described involving flow injection and inductively coupled plasma emission spectrometry for the determination of boron (0.5–25 mg l^?1) in water at a sampling rate of 320 h^?1. An 11-ml capacity cloud chamber, with a tangential aerosol outlet, was used to introduce the nebulized sample to the plasma. The sample volume injected was 300 μl. The relative standard deviation for peak height was 3% for 10 mg l^?1 of boron at a carier flow-rate of 3.5 ml min^?1. The wash-out between samples was improved by using the 11-ml cloud chamber rather than a conventional 110-ml chamber.     

The determination of gold by anodic stripping voltammetry

A method is described for the routine determination of gold as its chloride or cyanide complex by anodic stripping voltammetry at a glassy carbon electrode coupled to a microprocessor-controlled voltammeter. The preferred supporting electrolyte is 0.1 M HCl/0.32 M HNO₃, with plating at ?200 mV or ?1200 mV (vs. Ag/AgCl). The stripping peak potentials range from 830 to 1150 mV (vs. Ag/AgCl) depending on concentration and plating time. Precision (percent relative standard deviation) is better than 5 % for a range of concentrations between 5 μg l^?1 and 1000 μg l^?1. The detection limit is about 5 μg l^?1 for a 5-min plating period. Interferences from Cu, Hg, Ag and other electroactive species are overcome by preliminary extraction with diethyl ether.     

Application of microwave-assisted micellar extraction combined with solid-phase microextraction and high-performance liquid chromatography with UV detection for the determination of organochlorine pesticides in different mud samples

Abstract

A sequential injection analysis method for the simultaneous spectrophotometric determination of phosphate and silicate has been developed. The method is based on the different reaction rates of the heteropolymolybdate formation reactions. Concentrations within the range 0.026—0.485 mmol P l^?1 and 0.125—2.848 mmol Si l^?1 have been determined at a frequency of 30 samples per hour. An R.S.D. of 2.1% was obtained for 0.162 mmol P l^?1 and of 1.1% for 1.424 mmol Si l^?1. The method was found to be suitable for the determination of phosphate and silicate in wastewater.     

Flow-injection technique for the determination of low levels of phosphorus in natural waters

An inexpensive flow-injection instrument for determining low concentrations of dissolved reactive phosphorus in natural waters is reported. The unique feature is the use of an inexpensive detector consisting of a flow cell and a simple photometer that incorporates a super-bright light-emitting diode as the source and a photodiode as the detector. The tin(II) chloride-molybdate method was optimized using a modified simplex optimization method. Silicate interference up to 5 mg Si l^?1 was removed by addition of 0.10% (w/v) tartaric acid. Using the tartaric acid-modified optimized reagents, a detection limit of 0.6 μg P l^?1 was achieved. The method was linear over the range 0–100 μg P l^?1 with an excellent precision (r.s.d. 2.9% at 2.0 and 0.5% at 50 μg P l^?1). An in-line pre-concentration anion-exchange column was used to obtain an even lower detection limit of 0.1 μg P l^?1 and applied to the analysis of real samples.     

Flow-injection spectrophotometric determination of palladium in catalysts and dental alloys with 2-(5-bromo-2-pyridylazo)-5-(N-propyl-N-sulfopropyl-amino)aniline

2-(5-Bromo-2-pyridylazo)-5-(N-propyl-N-sulfopropylamino)aniline rapidly forms a water-soluble complex with palladium in an acetate-buffered medium at pH 3.2.The molar absorptivity of the complex is 9.84×10⁴l mol^?1 at 612 nm. The calibration graph is linear over the range of 10–100 μg l^?1 palladium; the detection limit is 2 μg l^?1 and the relative standard deviation is 0.6% for 100 μg l^?1 palladium. The sample throughput is 50 h^?1. Divalent transition metals (Fe, Ni, Co) do not interfere at levels from 2 to 10 mg l^?1. Interference from copper is prevented by adding 10^?3 M EDTA solution to the carrier stream. Palladium in solutions of catalysts and dental alloys can be determined selectively, sensitively and rapidly.