Microwave digestion of fish tissue for selenium determination by differential pulse polarography

In KIO(3)NH(3)NH(4)Cl medium, the selenium complex Se(O)SO(2-)(3), resulted from the reaction of selenite and sulphite in acid solution, gave a catalytic wave, which was applied to the determination of selenium in fish by differential pulse polarography. The sample was decomposed using the HNO(3)/H(2)SO(4)/H(2)O(2) digestion mixture in a closed PTFE digestion vessel with microwave heating. The detection limit was 0.06 mug/dm(3). The calibration curve was linear up to 8 mug/dm(3). Selenate present was reduced with hot hydrochloric acid to selenite. The recoveries of the selenite and selenate in two spiked samples investigated ranged from 91 to 104%. The NIES CRM No. 6 mussel was analyzed and the results obtained agreed well with the reference value (reference value: 1.5 mug/g; found: 1.43 +/- 0.05 mug/g). The results obtained by differential pulse polarography were in good agreement with those found by hydride generation atomic absorption spectrometry.     

Performance of the Orion 97-70 total residual chlorine electrode at low concentrations and its application to the analysis of cooling waters

The performance characteristics of the Orion 97-70 total residual chlorine electrode have been determined and the electrode has been found to give a near-theoretical response down to chlorine concentrations in the range 1-5 mug/1. Within-batch relative standard deviations are about 6-8% at concentrations above 50 mug/1. and 10-15% at lower levels. The method is virtually free from interferences (only strong oxidizing agents such as permanganate interfere) but large variations in salinity affect the calibration by changing the conditional standard potential. The best performance at low concentrations (<50 mug/1.) is achieved only if the manufacturer's recommended procedure is changed, namely by using a more dilute iodide reagent, stirring constantly, adding the iodide reagent before the buffer solution and using chloramine-T as a standard.     

Malachite green as a reagent for detection and spectrophotometric determination of chromium(VI)

A sensitive and inexpensive method of spectrophotometric determination of chromium(VI), based on the absorbance of its complex with malachite green and acetic acid at pH 2.5 is reported. The complex shows a molar absorptivity of 8 x 10(4) l.mole(-1) cm(-1) at 560 nm, using malachite green and acetic acid as reference solution. The effect of time, temperature, pH and reagent concentration is studied and optimum operating conditions are established. Beer's law is applicable in the concentration range 2.0-22.8 mug/ml chromium(VI). The resin beads act as a catalyst and as little as 1.6 mug of chromium(VI) is detected in the resin phase as compared to 4.1 mug in the solution phase. The standard deviation in the determinations is +/-0.40 mug/ml for a 10.35 mug/ml solution.     

Comparison of ultrasound-assisted extraction and microwave-assisted digestion for determination of magnesium, manganese and zinc in plant samples by flame atomic absorption spectrometry

In this paper, a sample preparation method based on acid extraction of magnesium, manganese and zinc from plant tissue by means of high intensity probe ultrasonication is described. Acid extracts obtained upon sonication were directly nebulised into an air-acetylene flame for fast metal determination by atomic absorption spectrometry. Parameters influencing extraction such as sonication time, ultrasound amplitude, sample mass, particle size, extractant composition and volume were fully optimised. Optimum conditions for metal extraction were as follows: a 3-min sonication time, a 30% ultrasonic amplitude, a 0.1-g sample mass, a particle size less than 50 mum, a 0.3% m/v HCl concentration in the extractant solution and a 5-ml extractant volume. Six plant samples used in the human diet were analysed, the concentration range of the three metals approximately being in the range of 1500-3000 mug g(-1) for Mg, 30-735 mug g(-1) for Mn and 20-45 mug g(-1) for Zn. Limits of detection corresponding to the ultrasound-assisted extraction method were 0.10, 1.26 and 0.65 mug g(-1) for Mg, Mn and Zn, respectively. Between-batch precision, expressed as R.S.D., was about 0.5, 1.5 and 1% for Mg, Mn and Zn, respectively. Analytical results for the three metals by ultrasound-assisted extraction and microwave-assisted digestion showed a good agreement, thus indicating the possibility of using mild conditions for sample preparation instead of intensive treatments inherent with the digestion method. The advantages and drawbacks of ultrasound-assisted extraction in respect to the microwave-assisted digestion are discussed.     

Preconcentration and flame atomic absorption spectrometry determination of cadmium in mussels by an on-line continuous precipitation-dissolution flow system

A rapid, sensitive, accurate and precise flame atomic absorption method is described for the determination of cadmium in mussels. The method is based on the continuous precipitation of cadmium as an ion pair between tetraiodocadmate and quinine and dissolution of the precipitate with ethanol. The metal can be preconcentrated 32-fold using 15 ml of sample solution by using a time-based technique at a sampling flow rate of 3.0 ml min(-1). The proposed method allows the determination of cadmium in the range 0.25-5.5 mug g(-1). The precision (relative standard deviation) obtained for different amounts of cadmium is in the range 1.5-4.7% at the 0.25-5.0 mug g(-1) level. The method demonstrates high tolerance to interferences, and the data obtained are in agreement with the certified value of a selected reference material. This procedure was applied to the determination of cadmium in mussel samples from estuaries in Galicia (Spain).     

Stable isotope dilution-mass spectrometry for determining total selenium levels in plants, soils and sewage sludges

Quantitation of selenium in plants, soils and sludges was achieved by isotope dilution-mass spectrometry using a benchtop instrument. Samples for analysis were spiked with (76)Se isotope solution. Plant material was digested on a heating block at 150 degrees C using a mixture of nitric acid and hydrogen peroxide. Selenium in soils and sludges was released by treatment with nitric acid followed by digestion with nitric and hydrofluoric acids. Selenium in the digests was reduced to Se(IV) with hydrochloric acid and derivatised with nitro-1, 2-phenylenediamine to 5'-nitropiazselenol. Analysis by gas chromatography-mass spectrometry using selected ion monitoring was validated using certified reference materials (CRMs) and gave results within the certified range with a low standard deviation. The CRMs plant (Chinese cabbage leaves) and soil (Chinese soil) were found to contain (+/-95% confidence limits) 0.091(+/-0.007) mug g(-1) and 1.67(+/- 0.04) mug g(-1)Se respectively. The certified values were 0.083(+/-0.008) mug g(-1) and 1.56(+/-0.12) mug g(-1) respectively. The selenium content of four different freely drained acid Scottish soils under grasslands was in the range 0.5-0.8 mug g(-1) air-dried soil. Sewage sludges were found to contain measurably more selenium than the soils, and samples of three sludges taken from sites in the UK contained between 1.1 and 3.5 mug g(-1) dry matter.     

Determination of micro amounts of oxygen in silicon by inert-gas fusion

A chromatographic inert-gas fusion method using an Ni-Sn fusion bath and helium as carrier gas has been developed for determining micro amounts of oxygen in silicon. With the Ni-Sn bath, the oxygen determination can be done at lower temperatures (1650-1700 degrees ) in a heated graphite crucible than in an empty crucible (with no molten metal bath) in which the sample is directly in contact with the carbon. Four samples can be analysed in succession in a single crucible with a relatively short time for oxygen extraction (5 min). Careful control of experimental conditions, and the use of a water-cooled quartz tube and a small unshielded graphite crucible have resulted in a lower blank (0.1 mug of oxygen), and better reproducibility, enabling oxygen in silicon to be determined down to 1 ppm. A calibration curve for determining oxygen in single crystals of silicon by measuring the infrared absorption at 9 mum has been constructed and gives results agreeing with those obtained by alpha-particle activation analysis.     

Column-switching high-performance liquid chromatographic analysis of carbamazepine and its principal metabolite in human plasma with direct sample injection using an alkyl-diol silica (ADS) precolumn

In this paper, the on-line coupling of solid-phase extraction, based on a restricted-access support with high-performance reverse phase chromatography for the analysis of carbamazepine (CBZ) and carbamazepine-10,11-epoxide (CBZ-E) in human plasma samples is described. A precolumn packed with 25 mum C(18) alkyl-diol support is used for direct plasma injection. Using column-switching techniques, the analytes were enriched on the precolumn by a 5 mM phosphate buffer (pH 7) with 2% of methanol solution at a flow-rate of 0.8 ml min(-1), while proteins and endogenous hydrophilic substances in plasma were washed off to waste. The enriched analytes were then back-flushed onto the analytical C(18) column, separated by a mixture of 10 mM phosphate buffer (pH 7) acetonitrile (70:30 v/v) solution at a flow-rate of 1.0 ml min(-1) and detected by the ultraviolet absorbance set at 212 and 285 nm and without transfer loss. Linear calibration graphs were obtained for sample injection volumes of 50 (0.2-4.0 of mug of CBZ ml(-1) and 0.1-5.0 mug of CBZ-E ml(-1), respectively), and 20 mul (5.0-20.0 mug of CBZ ml(-1)); in either case the r-value was >0.9963. Recoveries from spiked plasma samples were quantitative for both analytes and the coefficients of variation were below 3.83%. The lowest samples concentrations that can be quantified with acceptable accuracy and precision was 0.2 mug CBZ ml(-1) and 0.1 mug CBZ-E ml(-1) when a sample volume of 50 mul was injected. Concentrations of 0.08 and 0.05 mug ml(-1) of CBZ and CBZ-E were considered the limit of detection for a signal-to-noise ratio of 3. Furthermore, the developed column-switching method was successfully applied to the determination of CBZ and CBZ-E in plasma samples of patients submitted to CBZ therapy.     

Colour reaction of free chlorine with p-amino-N,N-diethylaniline in the presence of alcohol and its analytical application

A simple, precise, rapid-colour-forming and stable spectrometric method has been developed for determining free chlorine in water. p-Amino-N,N-diethylaniline reacts with free chlorine almost instantaneously in the presence of alcohol to form a red oxidized product with absorption maximum at 513 nm. Beer's law is obeyed in the free chlorine concentration range of 0-2 microg ml(-1). The molar absorptivity is 1.79 x 10(4) l mol(-1) cm(-1), limit of detection 0.0036 microg ml(-1), relative standard deviation 1.51%, and amount of free chlorine 7 microg. The colour reaction rate and absorbance are independent of temperature in the range 3-45 degrees C and the stable absorptivity lasts for at least 1 h. The method is satisfactory for the determination of free chlorine in aqueous solution.     

Extraction and spectrophotometric determination of titanium(IV) with alizarin and fluoride

The characteristics of the mixed-ligand titanium(IV)-fluoride-alizarin complex, including the optimum conditions of formation and extraction into methyl isobutyl ketone, are described. A simple and sensitive procedure for spectrophotometric determination of titanium has been developed. At pH 9.5-10.3 titanium reacts with alizarin in the presence of fluoride to form a red-violet complex that is completely extractable into methyl isobutyl ketone, and has its absorption maximum at 513 nm. The molar absorptivity at 513 nm is 7.0 x 10(4)l.mole(-1).cm(-1). Beer's law is obeyed up to 22 mug of titanium in 30 ml of solution. The method has been used for the determination of titanium in an oxide mixture and aluminium alloy samples.     

Novel rapid decomposition and dissolution method for silicates using a mixed potassium metaborate/potassium carbonate flux

A novel method for the rapid dissolution of fused silicates in mineral acid is described. Fusion with 2.5 g of a KBO(2)-K(2)CO(3) (3:2, w/w) mixture in a platinum crucible at 1000 degrees C will decompose 0.1 g of silicate samples such as basalt rock, glass sand and powdered glass in 10 min, and the cooled fusion cakes can be completely dissolved by 20 ml of 3 N mineral acids such as hydrochloric, nitric and sulfuric acids in less than 1 min at about 50 degrees C. Fusion with 5.0 g of a KBO(2)-K(2)CO(3) (3:2, w/w) mixture can completely decompose 0.1 g of chrome refractory in 20 min and the cooled melt can be dissolved by 80 ml of 3 N hydrochloric or sulfuric acids in less than 30 s.     

Preconcentration of iron (III), cobalt (II) and copper (II) nitroso-R complexes on tetradecyldimethylbenzylammonium iodide-naphthalene adsorbent

Iron, cobalt and copper form coloured water soluble anionic complexes with disodium 1-nitroso-2-naphthol-3-6-disulphonate (nitroso R-salt). The anionic complex is retained quantitatively as a water insoluble neutral ion associated complex (M-nitroso R-TDBA) on tetradecyldimethylbenzylammonium iodide on naphthalene (TDBA(+)I(-)-naphthalene) packed column in the pH range of: Fe(III): 3.1-6.5, Co: 3.4-8.5 and Cu 5.9-8.0 when their solutions are passed individually over this adsorbent at a flow rate of 0.5-5.0 ml/min. The solid mass consisting of an ion associated metal complex along with naphthalene is dissolved out of the column with 5 ml dimethylformamide/chloroform and metals are determined spectrophotometrically. The absorbance is measured at 710 nm for iron, 425 nm for cobalt and 480 nm for copper. Beers law is obeyed in the concentration range 9.2-82 mug of iron, 425 nm for cobalt cobalt and 3.0-62 mug of copper in 5 ml of final DMF/CHCl(3) solution. The molar absorptivities are calculated to be Fe: 7.58 x 10(3), Co: 1.33 x 10(4) and Cu: 4.92 x 10(4)M(-1)cm(-1). Ten replicate determinations containing 25 mug of iron, 9.96 mug of cobalt and 3.17 mug of copper gave mean absorbances 0.677, 0.450 and 0.490 with relative standard deviations of 0.88, 0.98 and 0.92%, respectively. The interference of large number of metals and anions on the estimations of these metals has been studied. The optimized conditions so developed have been employed for the trace determination of these metals in standard alloys, waste water and fly ash samples.     

Determination of serum selenium by hydride generation flame atomic absorption spectrometry

Serum is rapidly digested with a mixture of nitric and perchloric acids at a temperature of 180 +/- 10 degrees C, and hydrochloric acid is used to reduce selenium(VI) to selenium(IV). Selenium is determined by hydride generation flame atomic absorption spectrometry. The results show that this method has the advantages of being sensitive, accurate, rapid and simple. After the serum is digested and diluted, 4.0 ml is taken for the determination. The characteristic concentration, detection limit, variation coefficient, recovery rate and linear range are 2.93 mug 1(-1), 1.55 mug l(-1), 1.6-5.0%, 97.3-99.2% and 0.0-320.0 mug l(-1) respectively. Serum at 4 degrees C and in frozen state can be preserved for at least 7 and 14 days, respectively.     

Fast determination of calcium, magnesium and zinc in honey using continuous flow flame atomic absorption spectrometry

A procedure is described for the rapid determination of calcium, magnesium and zinc in honey with no previous mineralization stage. The samples are dissolved in a solution containing dilute hydrochloric acid and a lanthanum salt, and then directly introduced into the flame atomic absorption spectrometer by means of a simple continuous-flow manifold. The computer-controlled system performs an automatic on-line dilution of the solutions, in this way decreasing matrix effects due to the organic matter content and allowing analytical signals within the linear response range to be obtained. Calibration is carried out against aqueous standards. Reproducibilities for calcium and magnesium measurements in the honey samples are close to +/-3%. The detection limit for zinc is 0.2 mug g(-1), the reproducibility obtained for a honey sample containing 1.7 mug g(-1) zinc being +/-5.2%. The results agree with those obtained by means of a lengthy mineralization-based procedure, the main advantages of the non-conventional methodology reported being automation, saving of time and a decrease in the contamination risk.     

Comparison of four microwave digestion methods for the determination of selenium in fish tissue by using hydride generation atomic absorption spectrometry

Four microwave digestion methods of fish tissue for selenium determination by hydride generation atomic absorption spectrometry were compared, in which potassium hexacyanoferrate(III) was chosen as a masking agent for eliminating matrix interferences. The results showed that the methods employing HNO(3)/H(2)O(2), HNO(3)/K(2)S(2)O(8)/H(2)O(2) and HNO(3)/H(3)PO(4)/H(2)O(2) digestion media were unreliable. However, the decomposition using the digestion media of HNO(3)/H(2)SO(4)/H(2)O(2) enabled adequate digestion of fish tissue and retention of selenium in a state amenable for determination. Therefore, the digestion procedures with HNO(3)/H(2)SO(4)/H(2)O(2) media are proposed for the determination of selenium in fish tissue by hydride generation atomic absorption spectrometry. The recoveries of the spiked samples investigated ranged from 90 to 102%. The result obtained from analyzing the NIES CRM No. 6 mussel was in good agreement with the reference value (reference value: 1.5 mug/g; found: 1.45 +/- 0.05 mug/g). The limit of detection for selenium was 0.03 mug/g dry mass for a 100 mg sample. The contents of selenium in local fish species investigated ranged from 0.49 to 2.90 mug/g, and the relative standard deviation for the determination of selenium was less than 8%.     

Simultaneous determination of manganese and selenium in serum by electrothermal atomic absorption spectrometry

A method for determination of manganese and selenium in serum by simultaneous atomic absorption spectrometry (SIMAAS) is proposed. The samples (30 mul) were diluted (1+3) to 1.0% v/v HNO(3)+0.10% w/v Triton X-100 directly in the autosampler cups. A total of 20 mug Pd+10 mug Mg(NO(3))(2) was used as chemical modifier. The pyrolysis and atomization temperatures for the simultaneous heating program were 1200 and 2300 degrees C, respectively. The addition of an oxidant mixture (15% w/w H(2)O(2)+1.0% v/v HNO(3)) and the inclusion of a low temperature pyrolysis step (400 degrees C) attenuated the build-up of carbonaceous residues onto the integrated platform. An aliquot of 15 mul of the reference or sample solution was introduced into the graphite tube and heated at 80 degrees C; subsequently, 10 mul of oxidant mixture+10 mul of chemical modifier was introduced over that aliquot and the remaining heating program steps were executed. This strategy allowed at least 250 heating cycles for each THGA tube without analytical signal deterioration. The characteristic masses for manganese (6 pg) and selenium (46 pg) were estimated from the analytical curves. The detection limits were 6.5 pg (n=20, 3delta) for manganese and 50 pg (n=20, 3delta) for selenium. The reliability of the entire procedure was checked with the analysis of serum from Seronormtrade mark Trace Elements in Serum (Sero AS) and by addition and recovery tests (97+/-9% for manganese and 96+/-7% for selenium) using five serum samples.     

Rapid decomposition and dissolution of silicate rocks by fusion with lithium tetraborate and lithium sulphate

Fusion with 1.0 g of Li(2)B(4)O(7)Li(2)SO(4) (2:1) mixture in a platinum crucible at 1000 degrees will decompose 0.1 g of silicate rock in less than 10-15 min, and the cooled fusion cake can be completely dissolved by 20 ml of 1.2M hydrochloric acid at 90-100 degrees in approximately 5 min.     

Catalytic isomerization of quadricyclane using fourier transform near-infrared absorption spectroscopy: diffusion, conversion, and temperature effect

By using Fourier transform near-infrared (NIR) absorption spectroscopy, the kinetic behaviors of quadricyclane isomerization, as catalyzed by anhydrous CuSO(4) in chloroform mixture with and without agitation, are presented. Given the acquired NIR spectra, the concentration decay of quadricyclane with the reaction time is determined with the aid of partial least-squares analysis. When the mixture is not agitated, the diffusion coefficients in chloroform are evaluated to be (3.8 +/- 0.1) x 10(-5) cm(2) s(-1) at 27 degrees C and (4.4 +/- 0.1) x 10(-5) cm(2) s(-1) at 39 degrees C. In the size-dependent experiments of the catalyst, the one-site and two-site coordinated conversion rate constants are further determined to be (8.5 +/- 5.9) x 10(-6) s(-1) A(-1) and (2.2 +/- 0.8) x 10(-8) s(-1) A(-2), respectively, at 27 degrees C and (1.3 +/- 0.8) x 10(-5) s(-1) A(-1) and (1.92 +/- 0.01) x 10(-6) s(-1) A(-2), respectively, at 39 degrees C. A denotes the total catalyst surface area per unit effective volume of solvent. Accordingly, the activation energies for one-site and two-site coordination are evaluated to be 24.8 and 286.2 kJ mol(-1), respectively. The reaction is dominated by one-site coordination (1:1 complex) between the reactant and the catalyst. Unless temperature increases, the two-site coordinated reaction may be ignored. In contrast, when analogous experiments are performed in the stirred solution, the diffusion factor is ignored but the conversion rate constants rise due to the increase of collision frequency. For instance, the one-site and two-site coordinated rate constants are increased to (1.7 +/- 1.4) x 10(-5) s(-1) A(-1) and (1.27 +/- 0.06) x 10(-5) s(-1) A(-2) at 39 degrees C. The two-site coordinated reaction rate is enhanced by a factor of 10. Thus, isomerization may proceed via both 1:1 and 1:2 coordination between the reactant and the catalyst. The Arrhenius plot yields the corresponding activation energies to be 24 +/- 3 and 275 +/- 3 kJ mol(-1). The activation energies remain constant, no matter whether the solution is agitated or not.     

Colour reaction of platinum(II) with 5-(4-nitrophenylazo)-8-(p-toluenesulphonamido)-quinoline and its analytical applications

A simple, rapid and sensitive spectrophotometric method has been developed for the determination of platinum. 5-(4-Nitrophenylazo)-8-(p-toluenesulphonamido)quinoline (NPTSQ) reacts with platinum(II) almost instantaneously in alkaline solution to form a violet-red 1:2 complex with an absorption maximum at 640 nm. Beer's law is obeyed over the concentration range 0-1 mug/ml platinum. The molar absorptivity is 1.37 x 10(5) 1.mole(-1).cm(-1). The method has been used for the determination of microamounts of platinum in catalysts and anode slime.     

Colorimetric determination of macrolide antibiotics using ferric ion

Macrolide antibiotics such as erythromycin, oleandomycin, spiromycin, and tylosin are found to react with Fe(3+) in the presence of an acetic acid-sulfuric acid mixture to form a colored product having a useful absorption band at 592 nm. Troleandomycin forms only a weakly colored product upon reaction. The molar absorptivity is about 2900 1 mol(-1) cm(-1) for erythromycin and the detection limit is 5 mug ml(-1). This colorimetric method permits the analysis of fermentation broths containing either erythromycin or tylosin without a separation step.