Determination of Bromate and Bromide in Seawater by Ion Chromatography, with an Ammonium Salt Solution as Mobile Phase, and Inductively Coupled Plasma Mass Spectrometry

A method has been developed for determination of bromate and bromide in water containing high concentrations of chloride (e.g. seawater). Separation of bromate and bromide on an anion-exchange column was followed by ICP–MS detection. To reduce interference of chloride with determination of bromate and bromide, and to avoid clogging, ammonium salts, for example NH₄H₂PO₄, (NH₄)₂HPO₄, (NH₄)₂CO₃, and NH₄NO₃ were examined as mobile-phase components. It was found that mobile phase containing 20 mM NH₄NO₃ at pH 5.80 was compatible with the anion-exchange column and enabled reasonable resolution and separation of bromate and bromide within 7 min. Detection limits for bromate and bromide ranged from 2.0 to 3.0 μg L⁻¹ for direct injection of 50 μL sample without matrix elimination. The proposed method was used for analysis of bromate and bromide in seawater.     

A novel kinetic-spectrophotometric method for determination of nitrites in water

A simple, selective and sensitive kinetic method for the determination of nitrite in water was developed. The method is based on the catalytic effect of nitrite on the oxidation of methylene blue (MB) with bromate in a sulfuric acid medium. During the oxidation process, absorbance of the reaction mixture decreases with the increasing time, inversely proportional to the nitrite concentration. The reaction rate was monitored spectrophotometrically at λ = 666 nm within 30 s of mixing. Linear calibration graph was obtained in the range of 0.005–0.5 μg mL⁻¹ with a relative standard deviation of 2.09 % for six measurements at 0.5 μg mL⁻¹. The detection limit was found to be 0.0015 μg mL⁻¹. The effect of different factors such as acidity, time, bromate concentration, MB concentration, ionic strength, and order of reactants additions is reported. Interference of the most common foreign ions was also investigated. The optimum experimental conditions were: 0.38 mol L⁻¹ H₂SO₄, 5 × 10.4 mol L⁻¹ KBrO₃, 1.25 × 10.5 mol L⁻¹ MB, 0.3 mol L⁻¹ sodium nitrate, and 25°C. The proposed method was conveniently applied for the determination of nitrite in spiked drinking water samples.     

Multisyringe flow injection analysis hyphenated with liquid core waveguides for the development of cleaner spectroscopic analytical methods: improved determination of chloride in waters

In this work, the hyphenation of the multisyringe flow injection analysis technique with a 100-cm-long pathlength liquid core waveguide has been accomplished. The Cl⁻/Hg(SCN)₂/Fe³⁺ reaction system for the spectrophotometric determination of chloride (Cl⁻) in waters was used as chemical model. As a result, this classic analytical methodology has been improved, minimizing dramatically the consumption of reagents, in particular, that of the highly biotoxic chemical Hg(SCN)₂. The proposed method features a linear dynamic range composed of two steps between (1) 0.2–2 and (2) 2–8 mg Cl⁻ L⁻¹, thus extended applicability due to on-line sample dilution (up to 400 mg Cl⁻ L⁻¹). It also presents improved limits of detection and quantification of 0.06 and 0.20 mg Cl⁻ L⁻¹, respectively. The coefficient of variation and the injection throughput were 1.3% (n = 10, 2 mg Cl⁻ L⁻¹) and 21 h⁻¹. Furthermore, a very low consumption of reagents per Cl⁻ determination of 0.2 μg Hg(II) and 28 μg Fe³⁺ has been achieved. The method was successfully applied to the determination of Cl⁻ in different types of water samples. Finally, the proposed system is critically compared from a green analytical chemistry point of view against other flow systems for the same purpose.     

Voltammetric determination of the trace amounts of bromate in drinking water after pre-concentration on hydrous γ-Al<Subscript>2</Subscript>O<Subscript>3</Subscript>

A differential pulse voltammetric (DPV) method for the determination of bromate in drinking water, after pre-concentration on γ-Al₂O₃, is proposed. The reduction peak of bromate has been observed at the potential E _p -−1.6 V in an ammonia buffer as a supporting electrolyte. The method has been successfully applied to determine a bromate concentration of 2.5 μg·l⁻¹ in drinking water (RSD=6.1%, n=7). A sample pre-treatment with a column filled with mixed cation-exchange resin in Ag, Ba and H forms was needed before pre-concentration of bromate on alumina.     

Chemical origin of the sustained-like pattern formation observed in the bromate — Dual substrate — Dual catalyst oscillatory batch system

The BrO ₃ ⁻ — BrAc — Ru(bpy) ₃ ²⁺ subsystem is shown to represent the core oscillator that serves as source of the long lasting temporal and spatial periodic behaviors observed in the BrO ₃ ⁻ — H₂PO ₂ ⁻ — acetone — Mn²⁺ — Ru(bpy) ₃ ²⁺ — acid “double substrate-double catalyst” oscillatory batch system. The BrAc — the substrate of the core oscillator — is formed and accumulated in the reactions taking place in the six-component system. BrAc was produced in a separate experiment with bromide, acetone, acid and excess bromate and the mixture was used for bringing about patterns in the thin solution layer after adding the Ru(bpy) ₃ ²⁺ catalyst. The two-dimensional reaction-diffusion patterns that appear in the subsystem and its parent system are very similar in wave speed, wavelength, color and in the duration of the pattern evolution, therefore a common chemical origin is supposed to exist in their formation. The role that the BrAc may play in the mechanism of the BrO ₃ ⁻ — reductant — acetone — catalyst type oscillators (∼ 30 variants) is also pointed out.     

Interference of Humic Substances in the Spectrophotometric Determination of Bromate by Phenothiazines in Natural Waters

Abstract

The spectrophotometric method of bromate (BrO₃ ^?) determination by phenothiazines was applied to natural water samples and the interferences due to the presence of inorganic and humic substances were investigated. Common ions present in natural waters did not interfere and only the less abundant NO₂ ^? and Fe²⁺ exhibited strong interferences. Interferences of the two latter ions, if they existed, could be controlled and the method proved to be accurate and with a low detection limit. However, it was found that the presence of soluble humic substances resulted in positive interference, rendering the method unsuitable for bromate determination in natural waters and restricted its use in pure bromate solutions. This interference can be attributed to the electron acceptor groups invariably existing in the humic molecules. Since humic substances can remain in the water even after its ozonation, they will also contribute to a positive interference in bromate determination in potable waters.     

Simultaneous Determination of Lidocaine, Proline and Lomefloxacin in Human Urine by CE with Electrochemiluminescence Detection

A new method was developed for the simultaneous determination of lidocaine, proline and lomefloxacin in human urine by capillary electrophoresis-electrochemiluminescence detection with Ru(bpy)₃ ²⁺. Conditions of the separation and detection were investigated and optimized. It was proved that 20 mM phosphate buffer at pH 6.7 could achieve the most favorable resolution, and the high sensitivity of detection was obtained by using the detection potential at 1.15 V and 5 mM Ru(bpy)₃ ²⁺–60 mM phosphate buffer at pH 7.6 in the detection reservoir. The detection limits were 0.02 μg mL⁻¹ for lidocaine, 0.03 μg mL⁻¹ for proline and 0.06 μg mL⁻¹ for lomefloxacin. Relative standard deviations of the ECL intensity and the migration time were 3.5 and 1.1% for 6 μg mL⁻¹ lidocaine, 3.2 and 1.0% for 6 μg mL⁻¹ proline and 3.7 and 1.2% for 6 μg mL⁻¹ lomefloxacin, respectively. A baseline separation for lidocaine, proline and lomefloxacin was achieved within 360 s. The developed method was successfully applied to determine the amounts of lidocaine, proline and lomefloxacin in human urine. The recovery and RSD were in the range of 93.3–97.2 and 3.8–4.9%, respectively.     

Flow injection spectrophotometric determination of iron(III) using diphenylamine-4-sulfonic acid sodium salt

A highly sensitive and very simple spectrophotometric flow-injection analysis (FIA) method for the determination of iron(III) at low concentration levels is presented. The method is based on the measurement of absorbance intensity of the red complex at 410 nm formed by iron(III) and diphenylamine-4-sulfonic acid sodium salt (DPA-4-SA). It is a simple, highly sensitive, fast, and low cost alternative method using the color developing reagent DPA-4-SA in acetate buffer at pH 5.50 and the flow-rate of 1 mL min⁻¹ with the sample throughput of 60 h⁻¹. The method provided a linear determination range between 5 μg L⁻¹ and 200 μg L⁻¹ with the detection limit (3S) of 1 μg L⁻¹ of iron(III) using the injection volume of 20 μL. FIA variables influencing the system performance were optimized. The amount of iron(III) and total iron in river and seawater samples was successfully determined. Repeatability of the measurements was satisfactory at the relative standard deviation of 3.5 % for 5 determinations of 10 μg L⁻¹ iron(III). The accuracy of the method was evaluated using the standard addition method and checked by the analysis of the certified material Std Zn/Al/Cu 43 XZ3F.     

Resonance Rayleigh scattering spectra of tetracycline antibiotic–Cu(II)–titan yellow systems and their applications in analytical chemistry

Tetracycline antibiotics (TCs) such as doxycycline (DOTC), chlortetracycline (CTC), oxytetracycline (OTC), and tetracycline (TC) react with Cu(II) in pH 3.5 BR buffer medium to form 1:1 cationic chelates, which further react with titan yellow to form 2:1 ion association complexes. These result in great enhancement of resonance Rayleigh scattering (RRS) and the appearance of new RRS spectra. The ion association complexes of DOTC, CTC, OTC, and TC have similar spectral characteristics and their maximum RRS wavelengths are all located at 464 nm. The quantitative determination ranges and the detection limits (3σ) of the four TCs are 0.037–4.8 μg mL⁻¹ and 11.2 ng mL⁻¹ for DOTC, 0.041–5.2 μg mL⁻¹ and 12.4 ng mL⁻¹ for CTC, 0.050–4.8 μg mL⁻¹ and 15.1 ng mL⁻¹ for TC, and 0.088–5.0 μg mL⁻¹ and 26.3 ng mL⁻¹ for OTC, respectively. The optimum reaction conditions, the effects of foreign substances, the structure of ternary complexes, and the reaction mechanism are discussed. A sensitive, rapid, and simple RRS method for the determination of DOTC has been developed.     

Improvement in the determination of traces of uranium in aqueous medium having high dissolved organic carbon and chloride ion by alpha-spectrometry

During this work the determination of uranium in the range of μg·L⁻¹ to tens of μg·L⁻¹ was done by alpha-spectrometry after electroplating the aliquots of water sample using (NH₄)₂SO₄ as an electrolyte. In general, the determination of uranium by alpha-spectrometry needs its separation from other transuranics specially thorium. The process described here does not involve any sample digestion and radiochemical separation of uranium from other transuranics. In this method an aliquot (1 to 3 mL) of the sample was dried and dissolve in (NH₄)₂SO₄ and thereafter the sample was electroplated on a stainless steel (SS) planchet by using an electrochemical cell of special design. The proposed techniques have a distinct advantage over the determination of uranium by adsorptive stripping voltammetry (AdSV) in which uranium-chloranilic (2,5-dichloro-3,6-dihydroxy-1,4-benzoquinone) acid complex was used for concentrating the uranium from the solution. Since in the case of AdSv, the determination of uranium was not possible for samples having dissolved organic carbon (DOC) more than 15 mg·L⁻¹ and Cl⁻ concentration is in the range of 40,000 μ·g⁻¹. In the case of spike experiments with ²³²U the recovery was observed in the range of 90–95% in aqueous medium having higher concentration of Cl⁻ and DOC as indicated above.     

A new zinc complex of 1-propyl-1H-benzo[d] imidazole: synthesis, characterization and electrocatalysis

The present work reports the synthesis, characterization and performance of a new zinc(II) complex of [Zn(C₃H₇-bim)₂Br₂] (bim = benzimidazole) as electrocatalyst for trichloroacetic acid and bromate reduction. Its structure was characterized by X-ray crystallography, IR spectroscopy and elemental analysis. The zinc atom adopts a distorted tetrahedral geometry by coordinating to two bromine atoms and two nitrogen atoms from two 1-propyl-1H-benzo[d]imidazole ligands. The electrochemical behavior and electrocatalysis of the zinc complex bulk-modified carbon paste electrode (Zn-CPE) have been studied by cyclic voltammetry. The Zn-CPE shows good electrocatalytic activities toward the reduction of trichloroacetic acid and bromate. The detection limit and the sensitivity are 0.05 μM, 67.43 μA μM⁻¹ for trichloroacetic acid detection, and 0.02 μM, 69.94 μA μM⁻¹ for bromate detection, respectively. This modified electrode shows good reproducibility, high stability, low detection limit, technical simplicity and possibility of rapid preparation, which is important for practical applications.      

Flow injection spectrofluorimetric determination of iron(III) in water using salicylic acid

A simple and fast flow injection fluorescence quenching method for the determination of iron in water has been developed. Fluorimetric determination is based on the measurement of the quenching effect of iron on salicylic acid fluorescence. An emission peak of salicylic acid in aqueous solution occurs at 409 nm with excitation at 299 nm. The carrier solution used was 2 × 10⁻⁶ mol L⁻¹ salicylic acid in 0.1 mol L⁻¹ NH₄⁺/NH₃ buffer solution at pH 8.5. Linear calibration was obtained for 5–100 μg L⁻¹ iron(III) and the relative standard deviation was 1.25 % (n = 5) for a 20 μL injection volume iron(III). The limit of detection was 0.3 μg L⁻¹ and the sampling rate was 60 h⁻¹. The effect of interferences from various metals and anions commonly present in water was also studied. The method was successfully applied to the determination of low levels of iron in real samples (river, sea, and spring waters).     

Simultaneous ion chromatographic determination of selenium and metal ions in waters at trace level

Summary An ion-chromatographic procedure is described for the determination of selenium (VI) at μg L⁻¹ level in the presence of anions and heavy metal ions. Maximum permissible concentrations and effects from each interfering substance were investigated for the Se concentration range 12.5–1,000 μg L⁻¹. The method, optimized for the detection of SeO ₄ ²⁻ , gives results suitable for speciation analysis. Total selenium can be determined after complete conversion to selenate ion by oxidation with KMnO₄. The detection limit of selenium is 4.8 μg L⁻¹ (0.96 ng for 200 μL sample). Paper presented at the 41st Pittsburgh Conference, New York, March 5–9, 1990.     

Interaction of [Mo6Cl14]2− with H2Se: Selective Preparation of [Mo6SeCl13]3−

Reaction of [Mo₆(μ₃-Cl)₈Cl₆]²⁻ with H₂Se, generated in situ from ZnSe and 4 M HCl under hydrothermal conditions lead to the substitution of one or two bridging chlorides, depending on the reagents ratio. With the Mo₆/ZnSe 1:3 molar ratio [Mo₆(μ₃-SeCl₇)Cl₆]³⁻ forms selectively in high yield. Further substitution is more hindered, and even at 1:20 cluster-to-selenide molar ratio a mixture of [Mo₆(μ₃-SeCl₇)Cl₆]³⁻ and [Mo₆(μ₃-Se₂Cl₆)Cl₆]⁴⁻ is formed. The products were characterized by X-ray, Raman spectra and electrospray ionization mass spectrometry.     

An iron(III)-containing ionic liquid: characterization,magnetic property and electrocatalysis

The present work reports on the synthesis, characterization and performance of a new iron(III)-containing ionic liquid [(C₄H₉)₂-bim][FeCl₄] (Fe-IL, bim = benzimidazolium) as an electrocatalyst for nitrite and bromate reduction. The melting point of Fe-IL is 70 °C. Thermal behavior of the Fe-IL was studied by differential scanning calorimetry and thermalgravimetry. The value of magnetic moment and its temperature dependence were measured. A conductive carbon paste electrode (Fe-IL/CPE) comprised of Fe-IL and carbon powder was fabricated by the direct mixing method. The Fe-IL has double functions—a binder and an electrocatalyst. The electrochemical behavior and electrocatalysis of Fe-IL/CPE have been studied by cyclic voltammetry. The Fe-IL/CPE shows excellent electrocatalytic activities toward nitrite and bromate reduction. The detection limit and the sensitivity are 0.01 μM and 100.58 μA μM⁻¹ for nitrite, and 0.01 μM and 83.11 μA μM⁻¹ for bromate detection, respectively. This work demonstrates that the Fe-IL may become a new kind of functional material in constructing chemicals and biosensors.     

Determination of lead in wine by hydride generation atomic fluorescence spectrometry in the presence of hexacyanoferrate(III)

A rapid, accurate, and precise method is described for the determination of Pb in wine using continuous-flow hydride generation atomic fluorescence spectrometry (CF-HGAFS). Sample pretreatment consists of ten-fold dilution of wine followed by direct plumbane generation in the presence of 0.1 mol L⁻¹ HCl and 1% m/v K₃[Fe(CN)₆] with 1% m/v NaBH₄ as reducing agent. An aqueous standard calibration curve is recommended for Pb quantification in wine sample. The method provides a limit of detection and a limit of quantification of 0.3 μg L⁻¹ and 1 μg L⁻¹, respectively. The relative standard deviation varies between 2–6% (within-run) and 4–11% (between-run) at 3–30 μg L⁻¹ Pb levels in wine. Good agreement has been demonstrated between results obtained by CF-HGAFS and direct electrothermal atomic absorption spectrometry in analyses of red and white wines within the concentration range of 9.2–25.8 μg L⁻¹ Pb.     

W3Cl10(Hg2Cl2)2, A Reactive One-Dimensional Polymer of Triangular Tritungsten Clusters with Terminal and Intercluster-Bridging Mercurous Chloride Ligands: Main Group Metal Halide By-Products as Versatile Ligands in Reductive Synthesis of Early Transition Metal Halide Clusters

Solid-state reduction of WCl₆ with Hg followed by incomplete sublimation of mercury chlorides generated the tritungsten decachloride—mercury chloride adducts W₃Cl₁₀(Hg₂Cl₂)_2−x(HgCl₂)_x. Thermal equilibration of the solid-state products followed by sublimation of HgCl₂ afforded single crystals that include the mercurous chloride adduct W₃Cl₁₀(Hg₂Cl₂)₂. Single-crystal diffractometry revealed a one-dimensional polymer of tritungsten decachloride triangular clusters with novel terminal and inter-cluster-bridging ClHgHgCl ligands. The W₃ cluster core has similar metrics to that of the benzyltriethylammonium salt of W₃(μ₃-Cl)(μ-Cl)₃Cl₉ ³⁻. W₃Cl₁₀(Hg₂Cl₂)₂ is the first reported adduct of the binary tungsten chloride W₃Cl₁₀. The ClHgHgCl ligands are more labile that the terminal chlorine atoms of W₃(μ₃-Cl)(μ-Cl)₃Cl₉ ³⁻. These results demonstrate diverse roles and potential utility of main group element halide by-product ligands in solid-state reductions of transition metal halides.     

Flow-injection analysis for the determination of total inorganic carbon and total organic carbon in water using the H2O2–luminol–uranine chemiluminescent reaction

In the presence of carbonate and uranine, the chemiluminescent intensity from the reaction of luminol with hydrogen peroxide was dramatically enhanced in a basic medium. Based on this fact and coupled with the technique of flow-injection analysis, a highly sensitive method was developed for the determination of carbonate with a wide linear range. The method provided the determination of carbonate with a wide linear range of 1.0 × 10⁻¹⁰–5.0 × 10⁻⁶ mol L⁻¹ and a low detection limit (S/N = 3) of carbonate of 1.2 × 10⁻¹¹ mol L⁻¹. The average relative standard deviation for 1.0 × 10⁻⁹–9.0 × 10⁻⁷ mol L⁻¹ of carbonate was 3.7% (n = 11). Combined with the wet oxidation of potassium persulfate, the method was applied to the simultaneous determination of total inorganic carbon (TIC) and total organic carbon (TOC) in water. The linear ranges for TIC and TOC were 1.2 × 10⁻⁶–6.0 × 10⁻² mg L⁻¹ and 0.08–30 mg L⁻¹ carbon, respectively. Recoveries of 97.4–106.4% for TIC and 96.0–98.5% for TOC were obtained by adding 5 or 50 mg L⁻¹ of carbon to the water samples. The relative standard deviations (RSDs) were 2.6–4.8% for TIC and 4.6–6.6% for TOC (n = 5). The mechanism of the chemiluminescent reaction was also explored and a reasonable explanation about chemical energy transfer from luminol to uranine was proposed. Figure Chemiluminescence profiles in batch system. 1, Injection of 100 μL of K₂CO₃ into 1.0 mL luminol-1.0 mL H₂O₂ solution; 2-3 and 4-5, Injection in sequence of 100 μL of K₂CO₃ and 100 μL of uranine into 1.0 ml luminol-1.0 mL H₂O₂ solution; C_luminol = 1.0 × 10⁻⁷ mol/L, C_H2O2 = 1.0 × 10⁻⁵ mol/L, C_uranine = 1.0 × 10⁻⁵ mol/L, C_K2CO3 = 1.0 × 10⁻⁷ mol/L except for 4-5 where C_K2CO3 = 1.0 × 10⁻⁴ mol/L     

Separation of polychlorinated biphenyls from chlorinated pesticides using aminopropyl bonded-phase cartridge and determination by GC-ECD

Summary Gas chromatography of polychlorinated biphenyls and chlorinated pesticides in water samples is carried out after adsorption from a 25–500 mL sample, on a cartridge containing 100 mg aminopropyl-bonded porous silica. The clean-up step in which the PCBs and chlorinated pesticides are separated in different eluates is achieved by passing 25 mL of 40% aqueous methanol through the NH₂ Sep-Pak cartridge. The PCBs are desorbed with 500 μL ethylacetate, which is concentrated and analysis by GC-ECD. The average recovery, at 1 ppb is >97% with a standard deviation <2. The limits of detection are 0.1 ng μL⁻¹ and 5 pg μL⁻¹ respectively for Cl₃-PCB and Cl₈-PCB congeners. In the separation of PCBs from the chlorinated pesticides tested in this work, only the Aldrin is adsorbed for 60% with the PCBs by the NH₂ Sep-Pak cartridge. The method described is rapid, simple and reproducible.     

Time-resolved chemiluminescent analysis of hydralazine in pharmaceuticals

A new analytical method is proposed for determination of hydralazine (HZ) in pharmaceuticals—measurement of the chemiluminescence (CL) emitted after reaction with phosphoric-acidified KMnO₄. The novelty of this method is the recording of the whole CL–time profile. Such a recording is possible by use of a CL-detector operating in tandem which enables the reactants to be mixed in the measurement cell only and, therefore, the CL is reaction monitored from beginning. At the precise time the pump is stopped signal recording is triggered and so CL evolution is recorded completely. The optimum chemical conditions for the determination were 0.8 mol L⁻¹ formaldehyde, 0.3 mmol L⁻¹ KMnO₄, 4.0 mol L⁻¹ H₃PO₄, and a total flow of 0.37 mL s⁻¹. Two calibration graphs were plotted, CL intensity and area under the profile curve against HZ concentration. Exhaustive statistical analysis provided very interesting results, for example, accordance with Clayton’s theory, detection limit below 0.2 μg mL⁻¹, and linear calibration ranges from 0.2 to 5.0 μg mL⁻¹. This method was successfully applied to the determination of HZ in pharmaceuticals. Because they are usually formulated in association with diuretics and β-blockers, the method was used for analysis of HZ in pharmaceuticals that contained either HZ only or HZ with other hypotensive substances. Obtained and nominal content were approximately the same and experimental Student t values indicated there were no significant differences between the values.