Simultaneous determination of chromium(VI) and chromium(III) by flame atomic absorption spectrometry with a chelating ion-exchange flow injection system

Summary Simultaneous Determination of Chromium(VI) and Chromium(III) by Flame Atomic Absorption Spectrometry with a Chelating Ion-Exchange Flow Injection System A simple method is described for the simultaneous determination of chromium(VI) and chromium(III) in a flow injection system comprising chelating ion-exchange and flame atomic absorption spectrometry. Sampling rates for 2001 and 1 ml sample volumes were 120 and 60 h^–1 (240 and 120 speciations per hour), respectively. Typical relative standard deviations were 0.52% for Cr(VI) (0.50g ml^–1 and 0.67% for Cr(III) (0.10,g ml^–1) and the corresponding limits of detection were 85 ng ml^–1, and 16 ng ml^–1, respectively.On leave from University of Belgrade.     

Fourth-derivative spectrophotometric determination of neodymium in mixed rare earths with methyl thymol blue and cetylpyridinium chloride

A sensitive and selective method is described for the determination of neodymium in mixed rare earths using fourth-derivative spectrophotometry. The method is based on the absorption spectra of 4f electron transitions of the complex of neodymium with methyl thymol blue and cetylpyridinium chloride. The influence of various instrumental parameters and reaction conditions for maximum colour development are investigated. The calibration curve is linear over the range 0–3.5 g ml^–1 neodymium. The relative standard deviation for determination of 1.4 g ml^–1 neodymium (n = 7) is 1.6%. The detection limit (signal-to-noise ratio = 3) is 0.2 g ml^–1.     

Determination of medecamycin by adsorptive stripping voltammetry with an activated electrode

The adsorptive and electrochemical behaviors of medecamycin were investigated on a glassy carbon electrode (GCE) pretreated by anodic oxidation at +1.8 V for 5 min in 0.025 mol l^–1 NH₃-NH₄Cl (pH 8.6) solution. An adsorptive stripping voltammetric method for the determination of medecamycin at the pretreated glassy carbon electrode has been developed. Medecamycin was accumulated in NH₃-NH₄Cl buffer (pH 9.0) at a potential of –0.7 V (vs. saturated calomel electrode (SCE)) for a certain time, and then determined by second-order differential anodic stripping voltammetry. The second-order differential anodic stripping peak current at +0.72 V was proportional to the concentration of medecamycin in the range 2.0 g ml^–1 to 50.0 g ml^–1. The detection limit (three times the signal-to-noise) was 1.0 g ml^–1 and the relative standard deviation of the results was 3.28% for eight successive determinations of 10.0 g ml^–1 medecamycin. This method has been applied to the direct determination of medecamycin in commercial tablets and spiked urine samples with satisfactory results.     

Catalytic-fluorimetric determination of EDTA and iron(III) by flow injection analysis

Summary In this paper the authors report on several methods for the direct determination of EDTA and indirect determination of iron(III), based on the inhibition effect of EDTA on the catalytic action of copper (II) on the oxidation of 2,2-dipyridyl ketone hydrazone by hydrogen peroxide and on the decrease of this inhibition effect in the presence of Fe(III), respectively. These methods allow the determination of EDTA in the ranges of 0.4–2.0 g · ml^–1 and 0.2–1.0 g · ml^–1 for the normal and reversed FIA modes, respectively, and of 40–240 ng · ml^–1 for Fe(III) by reversed FIA.

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Katalytisch-fluorimetrische Bestimmung von EDTA und Eisen(III) durch FließinjektionsanalyseInhibitionsmethoden

Zusammenfassung Verfahren zur direkten Bestimmung von EDTA sowie zur indirekten Bestimmung von Eisen(III) werden beschrieben. Sie beruhen auf der Inhibitorwirkung von EDTA auf den katalytischen Effekt von Kupfer(II) bei der Oxidation von 2,2-Dipyridylketonhydrazon mit Wasserstoffperoxid bzw. auf der Schwächung dieser Inhibitorwirkung in Gegenwart von Eisen(III). Es ist mit diesen Methoden möglich, EDTA im Bereich von 0,4–2,0 g/ml (normale FIA) bzw. 0,2–1,0 g/ml (umgekehrte FIA) und Eisen im Bereich von 40–240 ng/ml (umgekehrte FIA) zu bestimmen.

     

Characterization of airborne particulates by laser microprobe mass analysis

Summary Laser microprobe mass analysis (LAMMA) was applied to characterize aerosol particles collected and separated from 16m to 0.06m by a low pressure cascade impactor. Positive ion LAMMA spectra showed characteristic molecular peaks such as PbCl⁺, a series of Si₂O⁺–Si₂O₄ ⁺ and NaAl₂Si₂O₂ ⁺–NaAl₂Si₂O₅ ⁺, and TiO⁺ in 0.06–0.12m, 0.5–1m and 4–8m fraction, respectively. In the negative ion LAMMA spectra, it was observed that the fragment peaks of sulfate ions were deficient above 2m and those of nitrate ions were deficient under 2m. LAMMA allows remarkable insights into the chemical nature of aerosol particles.

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Charakterisierung luftgetragener Teilchen durch Laser-Microprobe-Massenspektrometrie

Zusammenfassung Laser-Microprobe-Spektrometrie (LAMMS) wurde zur Analyse atmosphärischen Aerosols herangezogen, welches im Korngrößenbereich zwischen 16m und 0.06m mit einem Niederdruckkaskadenimpaktor fraktioniert gesammelt wurde. Positive LAMMS-Spektren zeigten charakteristische molekulare Peaks, wie etwa PbCl⁺, eine Serie von Si₂O⁺–Si₂O₄ ⁺ und NaAl₂Si₂O₂ ⁺–NaAl₂Si₂O₅ ⁺, sowie TiO⁺ in der 0,06–0,12-m,- 0,5–1–m- bzw. 4–8-m-Fraktion. In den negativen LAMMS-Spektren konnten über 2m keine Fragmentpeaks für Sulfationen, unter 2m. keine für Nitrationen beobachtet werden. LAMMS ermöglicht eine bemerkenswerte Einsicht in die chemische Natur von Aerosolteilchen.

     

Simultaneous determination of aluminium and iron in glasses,phosphate rocks and cement using first- and second-derivative spectrophotometry

First- and second-derivative spectrophoto-metric methods for the simultaneous determination of aluminium and iron in their mixtures are described. The methods are based on the colored complexes formed by aluminium and iron with hematoxylin in the presence of cetyltrimethylammonium bromide as a surfactant. The zero-crossing method has been utilized to measure the first- and second-derivative value of the derivative spectrum. Aluminium (0.05–1 gml^-1) could be determined in the presence of iron (0.09–1.6 gml^-1) and vice versa. The detection limits of aluminium and iron are 0.01 and 0.09 gml^-1, respectively in the first-derivative mode and 0.014 and 0.1 gml^-1 in the second-derivative mode. The proposed method has been applied to the simultaneous determination of aluminium and iron in glasses, phosphate rocks, cement and magnesite alloy.     

Determination of trace amounts of morpholine and its thermal degradation products in boiler water by HPLC

Summary Morpholine and its amine-type thermal degradation products present in boiler feed water and steam condensate were derivatised with N-succinimidyl-p-nitrophenylacetate. These pre-column derivatives were determined by high-performance liquid chromatography with UV detection at 280 nm. The analytical column was Supelco-sil-ODS with an isocratic mobile phase. Morpholine and its breakdown products were monitored in the range 0.01–10 g ml^–1 with a relative standard deviation of 0.4–3.0%. Chromatographic analysis of boiler feed water and steam condensate samples collected from a boiler servicing a petroleum refinery is described.     

Cyclodextrin-based optosensor for determination of tryptophan

A flow-through optosensor for tryptophan is described. The sensor is developed in conjunction with a flow-injection analysis system and uses immobilized -cyclodextrin as the sensing agent. The detection limit for tryptophan was 4ng ml^–1. The RSD for determination of 1 g ml^–1 of tryptophan was 2.8%.     

Spectrophotometric determination of vanadium(IV) in the presence of vanadium(V) using Br-PADAP

In the present paper, a simple and sensitive method is proposed for vanadium(IV) determination in the presence of vanadium(V). This is based on the oxidation of vanadium(IV) present in the sample to vanadium(V) by addition of iron(III) cation, followed by a complexation reaction of iron(II) with the spectrophotometric reagent 2-(5-bromo-2-pyridylazo)-5-diethylaminophenol (Br-PADAP). The iron(II) reacts with Br-PADAP immediately, forming a stable complex with a large molar absorptivity. The vanadium(IV) determination is possible, with a calibration sensitivity of 0.549 g ml^–1, for an analytical curve of 18.8 ng ml^–1 to 2.40 g ml^–1, molar absorptivity of 2.80 × 10⁴ 1 mole^–1 cm^–1 and a detection limit of 5.5 ng ml^–1. Selectivity was increased with the use of EDTA as a masking agent. The proposed method was applied for the vanadium(IV) determination in the presence of several amounts of vanadium(V). The results revealed that 200 g of vanadium(V) do not interfere with determination of 5.00 g of vanadium(IV). The precision and the accuracy obtained were satisfactory (R. S. D.<2%).     

Spectrofluorimetric determination of nucleic acids as 8-hydroxyquinoline/ yttrium ternary complexes

The formation of nucleic acids/8-hydroxyquinoline/yttrium(III) ternary complexes and their fluorescent properties have been studied. The nucleic acids studied include native and thermally denatured calf thymus DNA, fish sperm DNA and yeast RNA. In the range of pH 7.6–8.5, controlled by NH₃-NH₄C1 buffer, ternary complexes are formed that fluoresce at different wavelengths with different nucleic acids. Based on the fluorescence reactions, sensitive spectrofluorimetric methods for nucleic acids are proposed. In optimal conditions, the calibration curves were linear in the range 0.5–4.0 gml^–1 for calf thymus DNA, 0.5–2.5 g ml^–1 for fish sperm DNA and 0.5–4.0 g ml^–1 for yeast RNA. The limits of determination (3 ) were 0.030 g ml^–1 for calf thymus DNA, 0.020 g ml^–1 for fish sperm DNA and 0.090 g ml^–1 for yeast RNA. Corresponding to the interferences of coexisting substances, six synthetic samples were constructed and the results of determination were satisfactory.     

Spectrophotometric determination of mercury with 5,10,15,20-tetrakis(3-chloro-4-sulfophenyl)porphine by flow injection analysis

5,10,15,20-tetrakis(3-chloro-4-sulfophenyl)porphine (m-Cl-TPPS₄) was synthesized and used for the Spectrophotometric determination of mercury by flow injection analysis. A pseudo-first-order reaction kinetic mechanism was proposed with a rate constant of 0.8 min^–1 for Hg(II) withm-Cl-TPPS₄ in the presence of 8-hydroxyquinoline in a medium of 1.0M acetic acid and sodium acetate buffer solution (pH 6.22). In the optimum conditions of reaction temperature (85 ° C), stopped-flow time (60 s) and sampling volume (100 l), the method's relative standard deviation was 0.82% (n = 12) at 5.0 g ml^–1 mercury, with a linear range of 0–12.0 g ml^–1 and an analytical frequency of 60h^–1. The detection limit (3) was 0.025 g ml^–1. Interference studies showed that most metal ions co-existing with Hg²⁺ could be tolerated at 100-fold excess levels, but Zn²⁺, Cu²⁺ and Mn²⁺ needed to be masked. The method has been applied to the analysis of water samples with satisfactory results.     

Differential pulse voltammetric methods for the simultaneous estimation of uranium-iron and uranium-cadmium mixtures in solution

Differential pulse voltammetric methods have been developed for the simultaneous estimation of the constituents of uranium-iron and uranium-cadmium mixtures in solution. A mixture of 1M H₃PO₄–1M KH₂PO₄ (with a pH1.5), was found to be the most ideal supporting electrolyte for both methods, among many that were evaluated for their suitability. In uranium-iron mixtures the calibration for iron was found to be linear up to 150 g ml^–1 (r²=0.9986), while that of uranium up to 500 g ml^–1 (r²=0.999). Iron at 6.7 g ml^–1 level could be determined in the presence of 800 fold uranium (wt/wt) without significant interference. Uranium at 21 g ml^–1 level could be analyzed with 5-fold iron (wt/wt). This upper limit of iron was due to the precipitation of iron as phosphate. In the case of uranium — cadmium mixtures, cadmium calibration for cadmium was found to be linear up to 1300 g ml^–1 (r²=0.9993). Concentration levels of 4.6 g ml^–1 Cd could be determined at a 500-fold excess (wt/wt) of uranium. Uranium calibration was linear up to 500 g ml^–1 (r²=0.999) and 21 g ml^–1 uranium could tolerate up to a 1000-fold excess of cadmium (wt/wt). Both procedures could tolerate 10 g ml^–1 levels of metal ions, such as chromium, copper, manganese, molybdenum and vanadium.     

Spectrophotometric and derivative spectrophotometric determination of palladium(II) using pyridopyridazine dithione in the presence of non-ionic surfactant

Pyridopyridazine dithione (PPD) was synthesized as a new sensitive and selective reagent for spectrophotometric and derivative spectrophotometric determination of palladium(II). In aqueous and micellar medium, PPD forms 1:4 complexes having molar absorptivities of 4.68 × 10⁴ and 5.74 × 10⁴lmol^–1 cm^–1 at 570 and 615 nm, respectively. Beer's law was obeyed up to 2.2 and 2.5 g ml^–1 with detection limits of 0.2 and 0.1g ml^–1. The relative standard deviations for 1.23g ml^–1 were 2.6 and 1.3%, in the absence and presence of Triton X-100. In fourth-derivative mode, the regression equation, linear range, detection limit and RSD for 0.075 g ml^–1 wereD ₄ = 4.3C + 1.5 × 10^–3, 0.013 – 0.23 g ml^–1, 3.7 ng ml–1 and 0.78%, respectively. The ionization constants of the reagent and stability constants of the complexes were evaluated. The method is free from interference by most common metal ions and anions. The method was applied for determination of palladium in activated charcoal.     

Platinum concentration in silicone breast implant material and capsular tissue by ICP-MS

Inductively coupled plasma-mass spectrometry (ICP-MS) was used to determine the concentration of platinum (Pt) in silicone breast implant gel (range, 0.26–48.90 g g^–1 Pt; n=15), elastomer (range, 3.05–28.78 g g^–1 Pt; n=7), double lumen (range, 5.79–125.27 g g^–1 Pt; n=7), foam (range, 5.79–8.36 g g^–1 Pt; n=2), and capsular tissue (range, 0.003–0.272 g g^–1 Pt; n=15). The results show that very high levels of Pt are present in the encasing elastomer, double lumen, and foam envelope materials. Silicone breast implants can be a source of significant Pt exposure for individuals with these implants.     

β-Naphthoquinone sulfonate as electrochemical labelling reagent for high-sensitivity LC analysis of drugs in biological fluids

Summary A new sensitive, high-performance liquid chromatography (HPLC) method using electrochemical detection (ECD) is reported for the determination of 21 amphetamine-like compounds such as amphetamine, methamphetamine, methoxyphenamine, phentermine, ephedrine, mescaline, STP and methylenedioxyamphetamine, in biological fluids. Primary and secondary amines in biological specimens were easily labelled with -naphtho-quinone-4-sulfonate (BNQS) at 60°C for 30 min. Hydrodynamic voltamograms of BNQ-derivatives showed a maximum response at an applied potential of around zero V (against Ag/AgCl) in reducing model. BNQ derivatives of amines were analyzed by HPLC using a reducing ECD at zero V (Ag/AgCl). Separation was on a Bondasphere C18 with mobile phase: acetonitrile-methanol-0.01 M H₂SO₄. Good separations of twenty one amphetamine-analogs were obtained. Only 50 l of biological fluid containing those drugs at a concentration of over 1 g ml^–1 were needed direct for determination with good accuracy. When extraction was carried out prior to the labelling reaction, the detection limits were much improved to less than 10 ng ml^–1.This method was successfully applied to determination of methamphetamine in hair.     

Determination of fission product ruthenium by isotope dilution mass spectrometry

Isotope dilution mass spectrometry using enriched isotope⁹⁶Ru as a spike was applied to the determination of ruthenium as a fission product. Ruthenium in the solution was oxidized to RuO₄ by Ce/IV/ and separated from coexisting metal elements by distillation. Silica-gel technique was employed to enhance ion current of ruthenium in the mass spectrometric measurement. The lower detection limit was 0.005 g ml^–1 and the relative standard deviations /n=3/ for 1.2 and 0.05 g ml^–1 of ruthenium were 0.2 and 0.5%, respectively.     

Determination of pyrimethanil and kresoxim-methyl in soils by headspace solid-phase microextraction and gas chromatography-mass spectrometry

A method using headspace solid-phase microextraction (HS-SPME) then gas chromatography–mass spectrometry with selected ion monitoring (GC–MS, SIM) has been developed for determination of trace amounts of the fungicides pyrimethanil and kresoxim-methyl in soil and humic materials. Both fungicides were extracted on to a fused-silica fibre coated with 85 m polyacrylate (PA). Response-surface methodology was used to optimise the experimental conditions. For soil samples the linear dynamic range of application was 0.004–1.000 g g^–1 for pyrimethanil and 0.013–1.000 g g^–1 for kresoxim-methyl. The detection limits were 0.001 g g^–1 and 0.004 g g^–1 for pyrimethanil and kresoxim-methyl, respectively. HP-SPME–GC–MS analysis was highly reproducible—relative standard deviations (RSD) were between 6.7 and 12.2%. The method was validated by analysis of spiked matrix samples and used to investigate the presence of pyrimethanil and kresoxim-methyl above the detection limits in soil and humic materials.     

Thorium in man and environment uptake and clearance

The intake and tissue distribution of thorium (^{2 3 2}Th) was studied in an urban (Bombay) population in India. From the analysis of 16 whole diet samples, the average daily intake through food was found to be 2 g (range 0.8–4.3 g·d^–1). The estimated intake through drinking water and inhalation comes out to be 0.03 and 0.02 g per day. From the analysis of human autopsy tissue samples it is observed that the concentration ranges in lungs and bone are 1.5–16 g/kg and 0.2–9.0 g/kg fresh weight respectively. The average urinary concentration is 12 ng/1 (range 7–22 ng/l for 10 samples). Among the different body tissues, pulmonary lymph nodes were found to contain the highest concentration (geometric mean 53.4 g/kg, range 31.4–85.5 g/kg for 6 samples). Analysis of the samples was done by the neutron activation technique. 311.8 keV gamma photons of^{2 3 3}Pa which is the activation product of^{2 3 2}Th, were counted after chemical separation. A 54 cm³ intrinsic Ge detector coupled to 1024-channel analyser was used. Using the average lung content and the daily average intake values of thorium through inhalation, the clearance half-time from lung was estimated.     

Alternative spectrophotometric determination of niobium and tantalum with o-hydroxyhydroquinonephthalein in cationic surfactant micellar media

Summary The alternative and simultaneous spectrophotometric determination of niobium and tantalum was examined by using the colour development between o-hydroxyhydroquinonephthalein (Qnph) and niobium or tantalum in the presence of hexadecyltrimethylammonium chloride (HTAC) in strong acidic media. Beer's law was obeyed up to 10.0 g of niobium and up to 18.0 g of tantalum in a final volume of 10.0 ml. The apparent molar absorption coefficients for niobium and tantalum were 2.18×10⁵ and 2.09×10⁵ l mol^–1 cm^–1 with Sandell's sensitivities of 0.00042 g/cm² niobium at 520 nm and 0.00085 g/cm² tantalum at 510 nm, respectively. The alternative assay of niobium and tantalum was possible by using two methods: Method A — masking method with oxalic acid, Method B — acid adjusting-method using 50% sulfuric acid. These methods were 2–6-times more sensitive than other methods.Application of xanthene derivatives in analytical chemistry. Part XC. Part LXXXIX see ref [1]     

A new spectrophotometric method for the determination of hydrazine in environmental samples

Summary Hydrazine is determined spectrophotometrically by using veratraldehyde (3,4-dimethoxybenzaldehyde) as a new reagent. The reaction is based on the condensation of veratraldehyde with hydrazine in acidic medium. The resulting yellow coloured condensation product has maximum absorption at 410 nm. The colour system obeys Beer's law in the range of 0.065 to 0.3 g/ml of hydrazine. Molar absorptivity and Sandell's sensitivity are found to be 6.72×10⁴ l mol^–1 cm^–1 (±100) and 0.0004 g cm^–2, respectively. The method is successfully applied for the determination of hydrazine in polluted water, biological samples, in isoniazide tablets and in air. It is compared with other reported spectrophotometric methods and is found to be of comparable sensitivity.