Catalytic-kinetic spectrophotometric determination of vanadium (V) based on the Celestine blue-bromate-vanadium (V)-citric acid reaction

A novel sensitive and relatively selective kinetic method is presented for the determination of V（V） based on its catalytic effect on the oxidation reaction of Celestine blue by potassium bromate in the presence of citric acid as an activator. The reaction was monitored spectropho- tometrically by measuring the decrease in absorbance of Celestine blue at a maximum absorption wavelength of 540 nm between 0.5 and 9 min （the fixed-time method） in an H3PO4 medium at 45℃. The effect of various parameters such as concentrations of H3PO4, citric acid, potassium bromate and Celestine blue, ionic strength, reaction temperature and time on the rate of V（V） catalyzed reaction was studied. The method is free from the most interferences, especially from large amounts of V（IV）. The decrease in absorbance is proportional to the concentration of V（V） over the entire concentration range tested （0.025-1.25 lag.mL^-1） with a detection limit of 6.80 tag.L^-1 （according to statistical 3Sblank/k criterion） and a coefficient of variation （CV） of 1.78% （for ten replicate measurements at 95% confidence level）. The proposed method suffers from a few interferences such as Cr（VI） and Hg（Ⅱ） ions. The method was successfully applied to the determination of V（V） in river water, lake water, tap water, natural drinking water samples and a certified standard reference material such as SRM-1640 with satis- factory results. The vanadium contents of natural water samples were detected by using both linear calibration curve and standard addition curve methods. The recoveries of spiked vanadium （V） into the certified standard water sample were found to be quantitative, and the reproducibility was satisfactory. It was observed that the results of the SRM 1640 were in good agreement with the certified value.

Bromate ion formation in dark chlorination and ultraviolet/chlorination processes for bromide-containing water

Bormate （BrO3^-） is a carcinogenic chemical produced in ozonation or chlorination of bromide-containing water. Although its formation in seawater with or without sunlight has been previously investigated, the formation of bromate in dilute solutions, particularly raw water for water treatment plant, is unknown. In this article, the results of bench scale tests to measure the formation rates of bromate formation in dilute solutions, including de-ionized water and raw water from Yangtze River, were presented in dark chlorination and ultraviolet （UV）/chlorination processes. And the effects of initial pH, initial concentration of NaOCl, and UV light intensity on bromate formation in UV/chlorination of the diluted solutions were investigated. Detectable bromate was formed in dark chlorination of the two water samples with a relatively slow production rate. Under routine disinfecting conditions, the amount of formed bromate is not likely to exceed the national standards （10 μg/L）. UV irradiation enhanced the decay of free chlorine, and, simultaneously, 6.6%-32% of Br^- was oxidized to BrO3^-. And the formation of bromate exhibited three stages： rapid stage, slow stage and plateau. Under the experimental conditions （pH = 4.41-11.07, CCl2= 1.23-4.50 mg/L）, low pH and high chlorine concentration favored the generation of bromate. High light intensity promoted the production rate of bromate, but decreased its total generation amount due to acceleration of chlorine decomposition.

Effect of Fe(Ⅲ) on the bromate reduction by humic substances in aqueous solution

Humic substances are ubiquitous redox-active organic compounds of environment. In this study, experiments were conducted to determine the reduction capacity of humic acid in the man-ix of bromate and Fe（Ⅲ） solutions and the role of Fe（Ⅲ） in this redox process. The results showed that the humic acid regenerated Fe（Ⅱ） and reduced bromate abiotically. The addition of Fe（Ⅲ） could accelerate the bromate reduction rate by forming humic acid-Fe（Ⅲ） complexes. Iron species acts as electron mediator and catalyst for the bromate reduction by humic acid, in which humic acid transfers electrons to the complexed Fe（Ⅲ） to form Fe（Ⅱ）, and the regenerated Fe（Ⅱ） donate the electrons to bromate. The kinetics study on bromate reduction further indicated that bromate reduction by humic acid-Fe（Ⅲ） complexes is pH dependent. The rate decreased by 2-fold with the increase in solution pH by one unit. The reduction capacity of Aldrich humic acid was observed to be lower than that of humic acid or natural organic matter of Suwanne River, indicating that such redox process is expected to occur in the environment.

Preozonation of bromide-bearing source water in south China

The effectiveness of preozonation was evaluated on treating a bromide-bearing dam source water in south China through batch-scale experiments. Preozonation at ozone doses of 0.5-1.0 mg/L （at ozone consumption base） enhanced total organic carbon （TOC） removal through coagulation, and resulted in an almost linear reduction of ultraviolet absorbance at 254 nm （LW2s4）. The removals of TOC （after coagulation） and UV254 at the ozone dose of 1.0 mg/L were 36% and 70%, respectively. Preozonation at an ozone dose between 0.5 and 1.0 mg/L resulted in the removal of disinfection byproducts formation potential （DBFP） including trihalomethane formation potential （THMFP） and haloacetic acid formation potential （HAAFP） for about 50%. The removals of THMFP and HAAFP decreased with the further increase of ozone dose. Ozonation of bromide-bearing water （bromide concentration, 34 μg/L） produced a bromate concentration under the detection limit（2μg/L） at ozone doses 〈1.5 mg/L. However, bromate 〉10μg/L could be produced when the bromide concentration was increased to 96 μg/L.

Catalytic effects of trace ruthenium on oxidation of dimethyl yellow with bromate and its application

A spectrophotometric method for the determination of ruthenium(III) is described, based on its catalytic effect on the oxidation reaction of dimethyl yellow (DMY) with potassium bromate in an acid solution medium and in the presence of an OP emulsifier (p-iso-octyl phenoxy polyethoxy ethanol) at 100 °C. This reaction was followed spectrophotometrically by measuring the decrease in the absorbance at 530 nm of the catalytic reaction of DMY. The calibration curve for the recommended method was linear in the concentration range over 0.0–1.0 μg/L and the detection limit of the method for Ru(III) was 0.01 μg/L. The method is highly sensitive, selective and very stable and has been successfully applied for the determination of trace amounts of ruthenium in some ores and metallurgy products with the relative standard deviations (RSD) over 1.6%–2.8% and a recovery over 98.7%–104.0%.

Spectrophotometric Determination of Trace Amounts of Vanadium(Ⅴ) by Means of Its Catalytic Effect on Oxidation of Azomethine-H by Bromate

A new selective and sensitive kinetic method for determination of trace amounts of vanadium(Ⅴ) (0.5～40ng/ml) based on its catalytic effect on the oxidation of azomethine H by bromate at pH 4.2 and 25 ℃ was reported and its reaction mechanism was studied.The reaction was monitored spectrophotometrically by measuring the increase in absorbance of oxidation product of azomethine H at 436 nm after a fixed time ( 5 min ).The detection limit of the method is down to 2.0×10 -10 g/ml and the relative standard deviation (RSD) for 30 ng/ml of V(Ⅴ) is 0.26 % ( n =6). The effect of foreign ions on V(Ⅴ) determination was also discussed,and the method is mostly free from interferences of other ions.The proposed method was successfully applied to the determination of trace amounts of vanadium in water samples.

Bromate removal by activated carbon adsorption:material selection and impact factors study

Studies are conducted by using activated carbon process aimed at bromate removal from the raw water.Screening of activated carbon for bromate removal was performed in different activated carbons.GAC Merck possesses the highest iodine number and surface area,the highest number of basic groups and Vmeso,thereby contains the highest adsorption velocity and adsorption capacity.Impact factors of bromate removal on activated carbon were studied.Through static absorption experiments we studied the effect of adsorption time,pH,temperature,anions and organic matter on bromate removal.With the decrease of pH,removal of bromate enhanced,suggests that it may be possible to increase bromate reduction through pH control.The increase of temperature will be favorable to adsorption of bromate on activated carbon.Anions and organic matter can inhibit the adsorption of bromate on activated carbon through competing active sites.Bromate removal can be improved by controlling key water quality parameters.

Control of Bromate and THM Precursors Using Ozonation Combined System

Objective To investigate the feasibility of reducing THM precursors and controlling bromate taste and odor in drinking water taken from the Yellow River by an ozonation combined system. Methods The appropriate ozone dosage was determined, and then the changes of TOC, UV254 and THM formation potential （THMFP） in the combined system were evaluated. Results One mg/L ozone could effectively remove taste and odor and meet the maximum allowable bromate level in drinking water. The pre-ozonation increased THMFP, but the conventional treatment system could effectively reduce the odor. The bio-ceramic filter could partly reduce CHC13FP, but sometimes might increase CHCl2BrFP and CHClBr2FP. The biological activated carbon （BAC） filter could effectively reduce CHC13FP and CHCl2BrFP, but increase CHClBr2FP. Compared with other filters, the fresh activated carbon （FAC） filter performed better in reducing THMFP and even reduced CHClBr2FP. Conclusion The combined system can effectively reduce taste, odor, CHC13FP, and CHCl2BrFP and also bring bromate under control.

Selected Mineral Contents in Wheat from Paraguay by X-ray Fluorescence

The two fold purpose of this paper is to determine the composition of selected elements in Paraguayan wheat and flour as well as to analyse the implications of the bromine/bromate content on bakery products： the use （malpractice） of KBrO3 as an additive in the bakery dough to improve the whiteness and other characteristics of bread is well known. Accordingly, selected minor and trace elements in eight varieties of wheat from the center and south areas of Eastern Paraguay as well as commercial flour samples and bakery products were analyzed by XRF （X-ray fluorescence） techniques. The examined elements were K, Ca, Ti, Mn, Fe, Cu, Zn, Br, Rb, Sr. The results on wheat and commercial flour were consistent with those found elsewhere. With regard to the bakery products, in about 35% of the samples, the bromine/bromate content exceeded the normal Br values of Paraguayan flour showing bromate malpractice. From dietary point of view, it should be emphasized that KBrO3 is a complete carcinogen and its use as food additive has been banned. The employment of XRF to analyze bromine is easy, simple and reliable.

Synthesis of α-Bromine-Terminated Polystyrene Macroinitiator and Its Initiation of MMA Polymerization by ATRP

In the present paper the synthesis of block copolymers via the transformation from living anionic polymerization (LAP) to atom transfer radical polymerization (ATRP) was described. α-Bromine-terminated polystyrenes(PStBr) in the LAP step was prepared by using n-BuLi as initiator, tetrahydrofuran (THF) as the activator, α-methylstyrene (α-MeSt) as the capping group and liquid bromine (Br_2) as the bromating agent. The effects of reaction conditions such as the amounts of α-MeSt, THF, and Br_2 as well as molecular weight of polystyrene on the bromating efficiency (BE) and coupling extent (CE) were examined. The present results show that the yield of PStBr obtained was more than 93. 8% and the coupling reaction was substantially absent. PStBr was further used as the macroinitiator in the polymerization of methyl-methacrylate (MMA) in the presence of copper (I ) halogen and 2, 2' -bipyridine (bpy) complexes. It was found that the molecular weight of the resulted PSt-b-PMMA increased linearly with the increase of the conversion of MMA and the polydispersity was 1. 2-1.6. The structures of PStBr and P(St-b-MMA) were characterized by ~1H NMR spectra.

NEW OSCILLATING REACTIONS CATALYZED BY TETRAMETHYLTETRAAZACYCLOTETRAENE （TIM）NICKEL（Ⅱ）COMPLEX IN BROMATE－PYRUVIC ACID ──SULFURIC ACID SYSTEM

New oscillating reaction with the participation of a macrocyclic nickel(Ⅱ) complex ion [Ni(TIM )]2+ as catalyst and pyruvic acid as organic substrate in acidic bromate medium are described' This complex ion contains the ligand: 2, 3,9, 10-tetramethyl - 1, 4, 8, 11 - tetraazacyclotetradeca - 1, 3, 8, 10 - tetraene. The [Ni (TIM ) ]2+ion can undergo oxidation reaction of Ni (Ⅱ ) Ni (Ⅲ ). Detailed research on the system's oscillation characters and influential factors is made and the mechanism is briefly discussed.

Orthogonal Experiments for Controlling the Formation of DBPs During Preozonation of Bromide-Containing Raw Water

Orthogonal method was adopted to optimize the preozonation process and to minimize the bromate formation. Factors such as contact time, pH and ammonia concentration were investigated by orthogonal experiments to understand the interaction of various operation conditions on the formation of bromate and other disinfection byproducts(DBPs). Results showed that pH had the most significant influence on the minimization of bromate formation. The factors influencing the formation of bromate were in order of pH > contact time > ammonia concentration. For the formation of trihalomethanes(THMs) and haloacetic acids(HAAs), however, contact time significantly influenced their formation potential. In the practical preozonation process of waterworks, it is appropriate to set preozonation contact time to be 20 min. In order to minimize the formation of bromate, pH value of the raw water should be adjusted to 6. 0, and a certain concentration of ammonia could be added into the water to strengthen the minimization effect when the concentration of bromide in the raw water is higher than that in the experimental water.

Potassium Bromate-induced Changes in the Adult Mouse Cerebellum Are Ameliorated by Vanillin

Objective The current study aimed to elucidate the effect of vanillin on behavioral changes, oxidative stress, and histopathological changes induced by potassium bromate （KBrO3）, an environmental pollutant, in the cerebellum of adult mice.Methods The animals were divided into four groups： group 1 served as a control, group 2 received KBrO3, group 3 received KBrO3 and vanillin, and group 4 received only vanillin. We then measured behavioral changes, oxidative stress, and molecular and histological changes in the cerebellum.Results We observed significant behavioral changes in KBrO3-exposed mice. When investigating redox homeostasis in the cerebellum, we found that mice treated with KBrO3 had increased lipid peroxidation and protein oxidation in the cerebellum. These effects were accompanied by decreased Na＋-K＋ and Mg2＋ ATPase activity and antioxidant enzyme gene expression when compared to the control group. Additionally, there was a significant increase in cytokine gene expression in KBrO3-treated mice. Microscopy revealed that KBrO3 intoxication resulted in numerous degenerative changes in the cerebellum that were substantially ameliorated by vanillin supplementation. Co-administration of vanillin blocked the biochemical and molecular anomalies induced by KBrO3.Conclusion Our results demonstrate that vanillin is a potential therapeutic agent for oxidative stress associated with neurodegenerative diseases.

Efficient oxidative deprotection of trimethylsilyl,tetrahydropyranyl and methoxymethyl ethers under solvent-free conditions

A mild, efficient and fast method for direct oxidation of trimethylsilyl, tetrahydropyranyl and methoxymethyl ethers to their corresponding carbonyl compounds using trinitratocerium（Ⅳ） bromate （TNCB） supported on NaHSO4.H2O under solvent-free conditions is reported.

Fluorescence Spectral Study on the Rhodamine B-I_3^- Association Nanoparticle System and Its Analytical Applications

In acid medium, rhodamine B（RhB）, rhodamine S（RhS）, rhodamine 6G（RhG） and butyl rhodamine B（b-RhB） have a fluorescence peak at 580, 549, 553 and 580nm, respectively. BrO^-3 oxidizes excess I^- into I^-3 Rhodamine dyes combine I^-3 to form ion association nanoparticles, resulting in fluorescence quenching at 580, 549, 553 and 580 rim, respectively. The fluorescence quenching intensity is proportional to the concentration of BrO^-3 in the range of 0.020 4 - 0.710 μg/mL for RhB, 0.025 - 0. 512μg/mL for RhS, 0.025 - 0.260 μg/mL for RhG, 0.025 - 1.28μg/mL for b-RhB, respectively. In the four systems, RhB system has good stability and high sensitivity. Thus, a simple, sensitive fluorescence method was proposed for the determination of BrO^-3 in commercial bread additives and flours, with satisfactory results. The results of the fluorescence spectra and scan electron microscopy show that the formation of about 60 ran （RhB - I^-3） n association nanoparticles and the interface between the nanoparticles and solution are main factors that cause the fluorescence quenching.

The Impacts of Different Bromide Concentrations and Advanced Oxidation Ways on the Bromate Generation

Taking reservoir water diverting from Yellow River as raw water, and using 5 m^3/h of pilot device, the impacts of different bromide concentrations and advanced oxidation ways on bmmate generation in effluent of ozone -upward flow BAC -sand filtration technology. Results showed that when bromine ion of raw water was about 100 μg/L, and ozone dosage was 2 mg/L, bromate exceeding risk existed in the effluent of ozone - upward flow BAC technology, and bromate content in the effluent reached 10 μg/L. Moreover, generation amount of bromate had certain linear rela- tionship with bromine ion of influent. Both dosing hydrogen peroxide and potassium permanganate could effectively inhibit bromate production, and there was no bromate generation in final effluent of the technology. Moreover, it also could improve the removal of major pollutants in the water by the combined process. Compared with advanced oxidation of hydrogen peroxide, potassium permanganate pre-oxidation could better control production costs.

A New Reaction for Kinetic Spetrophotometric Determination of Trace Ruthenium——Catalytic Oxidation of Methyl Green by Bromate

A sensitive catalytic spectrophotometric method for the determination of ruthenium （Ⅲ） has been developed, based on its catalytic effect on the oxidation reaction of methyl green with potassium bromate in acid solution medium at 100℃. The above reaction is followed spectrophotometrically by measuring the decrease in the absorbance at 625 nm for the catalytic reaction of methyl green. The calibration curve for the recommended reaction-rate method was linear in the concentration range over 0.00-0.80 μg/L and the detection limit of the method for Ru （III） is 0.006 μg/L. Almost no foreign ions interfered in the determination at less than 25-fold concentration of Ru （Ⅲ）. The method is highly sensitive, more selective and very stable, and has been successfully applied for the determination of trace ruthenium in some ores and metallurgy products.

Mechanistic Study of Ruthenium(III) Catalyzed Oxidation of Cyclohexanone by Acidic Bromate

In this work, kinetics and mechanism of Ru(III) catalyzed oxidation of cyclohexanone by acidified solution of potassium bromate has been studied. Present study employ mercuric acetate Hg (OAc)2 as a scavenger for Br¯?ion to prevent parallel oxidation by bromine. The kinetics and mechanism have also been studied in the temperature range of 30°C - 45°C. The reaction exhibits first order kinetics with respect to Ru (III), while zero order kinetics with respect to KBrO3 and HClO4. The influence of Hg(OAc)2 and ionic strength on the rate of reaction was found to be insignificant. Positive effect in the reaction mixture was also observed upon addition of chloride ion;while as the negative effect was revealed with acetic acid. A suitable mechanism in conformity with the kinetic observations has been proposed and the rate law is derived on the basis of obtained data. The various activation parameters such as energy of activation (ΔE*), Arrhenius factor (A), entropy of activation (ΔS*) were calculated from the rate measurements at 30°C, 35°C - 40°C and 45°C.

Health Risk Assessment for Bromate (BrO₃^–) Traces in Ozonated Indian Bottled Water

For this study, bromide and bromate ions in various commercial brands of Indian bottled water samples were estimated using ion chromatography. The measured mean concentration of bromide and bromate ions in water samples was found to be 28.13 μg/L and 11.17 μg/L respectively. The average level of bromate in Indian bottled water was found to be slightly higher (~ 12%) than the acceptable limits (10 μg/L) recommended by USEPA (US Environmental Protection Agency). Though, kinetically, it is predicted that 62.5% (6.25 μg/L) of bromide in bottled water is needed to convert into bromate upon ozonation to exceed the minimum acceptable limits, but the average formation of bromate determined to be only 26.77% of the predicted concentration. Bromate concentration in bottled water showed a strong correlation with bromide suggesting that its formation in water is very much influenced and controlled by bromide content. The objective of the present study was to determine the BrO3–) content of commercially available different brands of bottled drinking water in India and to estimate the health risks to population due to ingestion. Results of estimated excess cancer risk and chemical toxicity risk to Indian population due to ingestion of bottled water were presented and discussed.

X-Ray Crysatllographic and Vibrational Spectroscopic Studies of Thorium Bromate Hydrate

Th(BrO3)3·H2O single crystals were grown from its aqueous solution at room temperature. Single crystal XRD, Raman and FTIR techniques were used to investigate the crystal structure. The crystal structure was solved by Patterson method. The as grown crystals are in monoclinic system with space group P21/c. The unit cell parameters are a = 12.8555(18) ?, b = 7.8970(11) ?, c = 9.0716(10)?, α = 90°, β = 131.568° and γ = 90° and unit cell volume is 689.1(2)?3. Z = 8, R factor is 5.9. The Raman and FTIR studies indicate the lowering of symetry of bromate anion from C3V to C1. Hydrogen bonds with varying strengths are present in the crystal. The centrosymmetric space group P21/c of the crystal is confirmed by the non-coincidence of majority of Raman and IR bands.