Shoji Motomizu

Spectrophotometric determination of phosphate in river waters with molybdate and malachite green

On the basis of the coloration formed with molybdate and malachite green in aqueous solution, trace amounts of phosphate were determined. The molar absorptivity was 7.8 × 104 l mol–1 cm–1 at 650 nm. The absorbance of the reagent blank was about 0.02, and its relative standard deviation was less than 10%. The recommended concentration range of phosphorus was 0.1–5 µg and the limit of detection was 0.01 µg of phosphorus. The sample solution was acidified with sulphuric acid and heated in a water-bath above 90 °C for 40 min, and subsequently it was coloured with molybdate and malachite green. The colour was stabilised by adding poly(vinyl alcohol). The method was applied to the determination of parts per billion (109) amounts of phosphorus in river and tap waters; the relative standard deviation was less than 4% and the recovery was 95–101%.

Determination of trace heavy metals in herbs by sequential injection analysis-anodic stripping voltammetry using screen-printed carbon nanotubes electrodes

A method for the simultaneous determination of Pb(II), Cd(II), and Zn(II) at low microg L(-1) concentration levels by sequential injection analysis-anodic stripping voltammetry (SIA-ASV) using screen-printed carbon nanotubes electrodes (SPCNTE) was developed. A bismuth film was prepared by in situ plating of bismuth on the screen-printed carbon nanotubes electrode. Operational parameters such as ratio of carbon nanotubes to carbon ink, bismuth concentration, deposition time and flow rate during preconcentration step were optimized. Under the optimal conditions, the linear ranges were found to be 2-100 microg L(-1) for Pb(II) and Cd(II), and 12-100 microg L(-1) for Zn(II). The limits of detection (S(bl)/S=3) were 0.2 microg L(-1) for Pb(II), 0.8 microg L(-1) for Cd(II) and 11 microg L(-1) for Zn(II). The measurement frequency was found to be 10-15 stripping cycle h(-1). The present method offers high sensitivity and high throughput for on-line monitoring of trace heavy metals. The practical utility of our method was also demonstrated with the determination of Pb(II), Cd(II), and Zn(II) by spiking procedure in herb samples. Our methodology produced results that were correlated with ICP-AES data. Therefore, we propose a method that can be used for the automatic and sensitive evaluation of heavy metals contaminated in herb items.

Determination of total and dissolved amount of iron in water samples using catalytic spectrophotometric flow injection analysis.

A flow injection spectrophotometric method has been developed for the determination of dissolved and total amounts of iron in tap and natural water samples. The method for the determination of iron employs a sample acidification step in order to decompose iron hydroxide and iron-complexes into free iron, Fe(III) and Fe(II). The amounts of free iron were detected using a catalytic action of Fe(III) and Fe(II) on the oxidation of N,N-dimethyl-p-phenylenediamine in the presence of hydrogen peroxide. Increase in absorbance of oxidized product was detected spectrophotometrically at 514 nm. The proposed method allows 0.02 and 0.06 microg l(-1) of LOD and LOQ, respectively, with relative standard deviation (RSD) below 2%. The accuracy and the precision of the method were evaluated by the analysis of the standard reference material, river water. The developed method was successfully applied to real water samples.

Trace and ultratrace analysis methods for the determination of phosphorus by flow-injection techniques.

Trace (< or =1 mg/l or 30 microM) and ultratrace (< or =1 microg/l or 30 nM) analysis methods for phosphorus determination by flow-injection analysis are reviewed. Most of the methods cited in this review are fundamentally based on the reaction of orthophosphate with molybdate to form heteropoly acids, such as molybdenum yellow and molybdenum blue, and some of the methods are based on the formation of such secondary reactions as ion associates and their aggregates with bulky cations, such as cationic dyes and quaternary ammonium ions. The heteropoly acids themselves can be measured by spectrophotometry, and the ion associate formed with a cationic dye, Malachite Green (MG), can be measured based on the coloration of MG. Light scattering detection methods can be used for measuring the aggregates of ion associates formed with bulky cations. Highly sensitive detection of phosphorus can be accomplished by fluorophotometry; Rhodamine B (RB) and its analogues react with molybdophosphate to form ion associates, which shows fluorescence quenching of RB: LOD is about 5 nM. The detection method based on the chemiluminescence of luminal oxidized with molybdophosphoric acids is probably the most sensitive of all the detection methods reported so far: LOD of the method is as low as 1nM. The LOD of the molybdenum blue method can be improved by using a liquid core waveguide: LOD is 0.5 nM.

Speciation of arsenic(III) and arsenic(V) by inductively coupled plasma-atomic emission spectrometry coupled with preconcentration system

A novel and simple flow-based method was developed for the simultaneous determination of As(III) and As(V) in freshwater samples. Two miniature columns with a solid phase anion exchange resin, placed on two 6-way valves were utilized for the solid-phase collection/concentration of arsenic(III) and arsenic(V), respectively. As(III) could be retained on the column after its oxidation to As(V) species with an oxidizing agent. The collected analytes were then sequentially eluted by 2M nitric acid and introduced into ICP-AES. Potassium permanganate was examined as potential oxidizing agent for conversion of As(III) to As(V). The standard deviation of the analytical signals (peak height) for the replicate analysis (n=5) of 0.5mugl(-1) solution were 3 and 5% for As(III) and As(V), respectively. The limit of detection (3sigma) for both As(III) and As(V) were 0.1mugl(-1). The proposed system produced satisfactory results on the application to the direct analysis of inorganic arsenic species in freshwater samples.

On-line preconcentration using dual mini-columns for the speciation of chromium(III) and chromium(VI) and its application to water samples as studied by inductively coupled plasma-atomic emission spectrometry

On-line preconcentration system for the selective, sensitive and simultaneous determination of chromium species was investigated. Dual mini-columns containing chelating resin were utilized for the speciation and preconcentration of Cr(III) and Cr(VI) in water samples. In this system, Cr(III) was collected on first column packed with iminodiacetate resin. Cr(VI) in the effluent from the first column was reduced to Cr(III), which was collected on the second column packed with iminodiacetate resin. Hydroxyammonium chloride was examined as a potential reducing agent for Cr(VI) to Cr(III). The effects of pH, sample flow rate, column length, and interfering ions on the recoveries of Cr(III) were carefully studied. Five millilitres of a sample solution was introduced into the system. The collected species were then sequentially washed by 1M ammonium acetate, eluted by 2M nitric acid and measured by ICP-AES. The detection limit for Cr(III) and Cr(VI) was 0.08 and 0.15mugl(-1), respectively. The total analysis time was about 9.4min. The developed method was successfully applied to the speciation of chromium in river, tap water and wastewater samples with satisfied results.

Synthesis of cross-linked chitosan possessing N-methyl-d-glucamine moiety (CCTS-NMDG) for adsorption/concentration of boron in water samples and its accurate measurement by ICP-MS and ICP-AES

A chitosan resin derivatized with N-methyl-d-glucamine (CCTS-NMDG) was synthesized by using a cross-linked chitosan (CCTS) as base material. The N-methyl-d-glucamine (NMDG) moiety was attached to the amino group of CCTS through the arm of chloromethyloxirane. The adsorption behavior of 59 elements on the synthesized resin was systematically examined by using the resin packed in a mini-column, passing water samples through it and measuring the adsorbed elements in eluates by ICP-MS. The CCTS-NMDG resin shows high ability in boron sorption with the capacity of 0.61mmolml(-1) (=2.1mmol g(-1)). The sorption kinetics of this resin was faster than that of the commercially available resins. Other advantages of the synthesized resin are: (1) quantitative collection of boron at neutral pH regions; (2) complete removal of large amounts of matrices; (3) no loss of efficiency over prolonged usage; (4) effective collection of boron in wide range concentration using a mini column containing 1ml resin; (5) complete elution of boron with 1moll(-1) nitric acid. The resin was applied to the collection/concentration of boron in water samples. Boron in tap water and river water was found to be in the range of 6-8microgl(-1). The limit of detection (LOD) of boron after pretreatment with CCTS-NMDG resin and measurement by ICP-MS was 0.07microgl(-1) and the limit of quantification (LOQ) was 0.14microgl(-1) when the volume of each sample and eluent was 10ml.

Synthesis of novel chitosan resin possessing histidine moiety and its application to the determination of trace silver by ICP-AES coupled with triplet automated-pretreatment system.

A novel chitosan resin, cross-linked chitosan functionalized with histidine moiety (histidine-type chitosan resin), was synthesized for the collection and concentration of trace silver in aquatic samples. A triplet automated-pretreatment system (Triplet Auto-Pret System) installed mini-columns packed with the synthesized histidine-type chitosan resin was coupled with an inductively coupled plasma-atomic emission spectrometry (ICP-AES) for a rapid and sensitive analysis. Adsorption behavior of 50 elements on the histidine-type chitosan resin was examined. A trace amount of Ag(I) was shown a good adsorption in wide pH regions (pH 5-9), and Ag(I) adsorbed was readily recovered with 1 M nitric acid solution. The limit of detection (3sigma) for silver was 0.03 microg L(-1). The system was successfully applied to river water and dipped water in silver coated container.

Electroanalysis of sulfonamides by flow injection system/high-performance liquid chromatography coupled with amperometric detection using boron-doped diamond electrode☆

Sulfonamides (SAs) were electrochemically investigated using cyclic voltammetry at a boron-doped diamond (BDD) electrode. Comparison experiments were carried out using a glassy carbon electrode. The BDD electrode provided well-resolved oxidation, irreversible cyclic voltammograms and higher current signals when compared to the glassy carbon electrode. Results obtained from using the BDD electrode in a flow injection system coupled with amperometric detection were illustrated. The optimum potential from a hydrodynamic voltammogram was found to be 1100mV versus Ag/AgCl, which was chosen for the HPLC-amperometric system. Excellent results of linear range and detection limit were obtained. This method was also used for determination of sulfonamides in egg samples. The standard solutions of 5, 10, and 15ppm were spiked in a real sample, and percentage of recoveries was found to be between 90.0 and 107.7.

Determination of trace amounts of phosphate in river water by flow-injection analysis

A flow-injection analysis system for the determination of trace amounts of phosphate in river water has been developed. The phosphate is reacted with molybdate and Malachite Green in acidic medium to form a green species, the absorbance of which is measured at 650 nm. Phosphorus (as inorganic phosphate) can be determined at the level of several ng ml in water. Analyses can be done at a rate of up to 40 per hour.