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PubMed1995

Bromate reduction by denitrifying bacteria.

In the presence of bromide, ozonation as applied in water treatment results in the formation of bromate, an ion with carcinogenic properties. The reduction of bromate by mixed bacterial populations as well as pure cultures was studied under laboratory conditions. Bromate was reduced to bromide by a mixed bacterial population with and without a preceding nitrate reduction step in an anaerobically incubated medium with ethanol as the energy and carbon source at 20 and 25 deg C. The predominating bacteria isolated from the batches showing bromate reduction were identified as Pseudomonas spp. Strains of Pseudomonas fluorescens reduced BrO(inf3)(sup-) to Br(sup-) but at a much lower rate than the mixed bacterial population did. Nitrate is a preferred electron acceptor for the bromate-reducing bacteria. Bromate reduction did not occur in the presence of NO(inf3)(sup-), and the rate of bromate reduction was at least 100 times lower than the rate of nitrate reduction. Bromate was completely converted to Br(sup-), indicating that intermediates, e.g., BrO(inf2)(sup-), did not accumulate during bromate reduction.

Journal Article↗
PubMed2006

Effects of copper and palladium on the reduction of bromate by Fe(0).

Bromate reduction by Fe(0) with incorporation of copper or palladium was investigated in batch tests. The incorporation of copper led to an increase in the rate of bromate reduction, while incorporation of palladium did not show any effect on bromate reduction by Fe(0), regardless of the bimetal application techniques (either simultaneous addition of Cu(II) or Pd(IV) into the Fe-BrO3- reaction system or using copper or palladium amended iron for bromate removal). Surface analyses by X-ray photoelectron spectroscopy (XPS) and X-ray powder diffraction (XRD) techniques indicated that aqueous Cu(II) was reduced and incorporated into the iron surface to form Cu2O and Cu(0). Among these two species, pure Cu(0) is not an active electron donor to the bromate reduction reaction, as shown by there being no reduction from using Cu(0) powders alone and no enhancement by Fe(0) when physically mixed with Cu(0). Although it has been proposed in the literature that the enhancement of adsorption also contributes to the enhancement of chemical reduction, this is not the case here because adsorption decreased when Cu increased. The enhanced bromate reduction rate in the presence of copper observed here is most likely the result of the newly formed active Cu(I). The presence of PdO was evidenced by XPS but yielded no enhancement in bromate reduction. Finally, the Cu2O present on the iron surface because of copper impurities in commercially available iron was found to be involved in the bromate reduction and to accelerate the reduction rate.

Bromates↗
PubMedDate not supplied

Determination of bromate in bread by capillary gas chromatography with a mass detector (GC/MS).

A sensitive method was developed for the determination of bromate in bread by capillary gas chromatography with a mass detector (GC/MS). Bromate was extracted with water from bread samples. After centrifugation, the supernatant was filtered and Cl- was removed by an OnGuard-Ag cartridge column. The mixture was absorbed on a DEA solid phase extraction column and washed with water. Bromate was then eluted with 3 M potassium chloride solution. Two ml of 4 x 10(-3) M styrene monomer solution (washed with 1% sodium hydroxide solution before use), 1 ml 0.01 M potassium bromide solution and 1 ml sulphuric acid were added to the eluent and shaken vigorously. The styrene bromo derivative (alpha-bromomethyl-benzenemethanol[2-bromo-1-phenylethanol]) was extracted with 2 ml n-hexane, and determined by GC/MS. Recoveries of bromate from breads were in the range 91.3-98.1% (0.03-0.50 micrograms/g), and the limit of detection was 0.03 microgram/g. Pullman and open top types of white bread, produced by a sponge and dough method and a short process method respectively, were prepared in our laboratory for measurement of residual bromate. When 30 micrograms/g or less bromate as HBrO3 (pullman type), and 75 micrograms/g bromate or less as KBrO3 (open top type), was added to flour, no residual bromate was detected in either type of bread.

Bread↗
PubMedDate not supplied

The determination of the flour improver potassium bromate in bread by gas chromatographic and ICP-MS methods.

The development and application of two methods for determining bromate in bread are described. A gas chromatographic (GC) method which relied on the formation of a volatile derivative of bromate gave a detection limit of 12 micrograms/kg. Duplicate analyses agreed well but recovery from breads spiked with bromate were low and averaged 30% for brown bread and 42% for white bread. Further studies indicated that this was caused by the derivatization reaction being suppressed by components of the sample and reagents used in their preparation. After taking both these factors into account, a recovery of 80% could be achieved. The GC method was used to carry out a survey of retail bread samples in 1989. Bromate was found in all six unwrapped breads analysed (median 35 micrograms/kg, range 17-317 micrograms/kg), whilst for 22 wrapped breads, seven were found to contain bromate (median < 12 micrograms/kg, range < 12-238 micrograms/kg). A second method of analysis employing inductively coupled plasma-mass spectrometry (ICP-MS) was developed which provided independent confirmation of the presence of bromate in these retail samples. The method gave a mean recovery of 71% from five spiked samples and a detection limit of 20 micrograms/kg. The GC and ICP-MS methods were compared by performing replicate analyses of a bread sample prepared with bromate-treated flour. Quantitative agreement between the two techniques was good. The precision of the ICP-MS technique (CV 12%) proved better than that found for the GC method (CV 18%). The Potassium Bromate (Prohibition as a Flour Improver) Regulation 1990 came into force on 1 April 1990 (Statutory Instrument 1990 Number 399).(ABSTRACT TRUNCATED AT 250 WORDS)

Bread↗
PubMed2005

Bromate formation on the non-porous TiO2 photoanode in the photoelectrocatalytic system.

The increasing use of ozone in water disinfection processes has been the focus of considerable concern in regards to inorganic disinfection by product formation of bromate in waters containing bromide. Due to the public health risk caused by the presence of bromate as a suspected carcinogen, attention had been addressed to the conditions under which bromate is formed. In this study, photoanodic bromine generation and bromate (BrO(3)(-)) formation were investigated using a TiO(2) electrode in a photoelectrocatalytic (PEC) treatment process. The separation of anodic and cathodic reactions in the PEC system resulted in a pH decrease from 9.3 to 3.0 in the photoanode compartment and an increase to 11.0 in the cathode compartment. Under a photo-illumination intensity of 5.7 m W cm(-2) UV, a biasing potential of +1.0V vs SCE, a pH of 6.0 and at a NaBr concentration of 1.0 x 10(-2) M, active bromine formation increased over time with 2.4 x 10(-6) M min(-6) rate and reached a steady-state concentration of 1.44 x 10(-4) M in 60 min. Bromate formation was detected after a lag-period of 15 min and exhibited a continuous increasing trend with respect to irradiation time. No bromate formation was observed below pH 6.5 whereas an increasing bromate concentrations and pH up to pH=8.5 were noted.

Bromates↗
PubMed2006

Genotoxic effects of potassium bromate on human peripheral lymphocytes in vitro.

The aim of this study was to investigate the genotoxic effects of potassium bromate, which is used as a bleaching agent in flour, on human peripheral blood lymphocytes in vitro by sister chromatid exchange (SCE), chromosomal aberrations (CA) and micronucleus (MN) tests, and also to determine whether it has any genotoxic potential for humans. Cells were treated with 400, 450, 500, 550 microg/ml concentrations of potassium bromate for 24 and 48 h. The SCE frequencies showed an increase after both treatment periods, however, the differences between the treated cells and the control groups were found to be statistically significant only for the 48-h treatment. In addition, potassium bromate statistically significantly induced CA after the 24-h and 48-h treatment periods. Strikingly, potassium bromate induced CA as much as the positive control, mitomycin-C (MMC). Furthermore, potassium bromate decreased both the cell proliferation index (PI) and the mitotic index (MI). Although micronucleus formation was induced by potassium bromate during the 24-h treatment period in a dose-dependent manner, only the doses 500 and 550 microg/ml yielded statistically significant results. In contrast, MN formation was significantly induced at all doses during the 48-h treatment period. These in vitro results provide important evidence about genotoxicity of potassium bromate on a human cell culture system.

Adult↗
PubMed2006

Remediation of bromate-contaminated groundwater in an ex situ fixed-film bioreactor.

Use of a pilot-scale fixed-film bioreactor was investigated for remediation of bromate contamination within groundwater. Bromate reduction with stoichiometric production of bromide was observed, providing supporting evidence for complete reduction of bromate with no production of stable intermediates. Reduction of 87-90% bromate from an influent concentration of 1.1 mg L(-1) was observed with retention times of 40-80 h. Lower retention times led to decreases in bromate reduction capability, with 11.5% removal at a 10 h retention time. Nitrate reduction of 76-99% from a 30.7 mg L(-1) as NO(3)(-) influent was observed at retention times of 10-80 h, although an increase in nitrite production to 2.7 mg L(-1) occurred with a 10 h retention time. Backwashing was not required, with the large plastic packing media able to accommodate biomass accumulation without decreases in operational efficiency. This study has provided proof of concept and demonstrated the potential of biological bromate reduction by fixed-film processes for remediation of a bromate contaminated groundwater source.

Biomass↗
PubMed2005

Feasibility of conducting human studies to address bromate risks.

Findings from epidemiologic studies have been important in evaluating risk of exposure to many contaminants in drinking water. In the case of bromate, a byproduct of ozone disinfection of water, it is unlikely that observational studies of populations exposed to bromate in drinking water will be as revealing as studies of other contaminants, unless risks are much higher than predicted from laboratory studies of rodents. Occupational exposure to bromate has occurred in the flour milling and baking industries, as well as in chemical production of potassium bromate, used as a flour additive. The feasibility of a cohort study of bromate-exposed workers should be evaluated by studying the conditions and levels of exposure in these occupational settings. Bromate exposure causes oxidative damage to guanine bases of DNA, producing 8-hydroxy-guanine (8-OH-Gua), which is excised by 8-oxoguanosine glycosylase (OGG1) and excreted in the urine. Polymorphic variants of OGG1 in human populations have been associated with elevated cancer risk. 8-OH-Gua and 8-hydroxy-deoxyguanosine (8-OHdG) have been used as biomarkers of oxidative damage in many human studies, and it would be feasible to employ these indicators in controlled clinical experimental settings to see if exposure to bromate in water at levels close to the maximum contaminant level influences urinary levels of excretion, and if so, to help quantify the level of oxidative damage. Such a study could fill an important data gap by providing human data to help estimate the carcinogenic risk from this exposure.

Animals↗
PubMed2006

Molecular biomarkers of oxidative stress associated with bromate carcinogenicity.

Potassium bromate (KBrO3) is a chemical oxidizing agent found in drinking water as a disinfection byproduct of surface water ozonation. Chronic exposures to KBrO3 cause renal cell tumors in rats, hamsters and mice and thyroid and testicular mesothelial tumors in rats. Experimental evidence indicates that bromate mediates toxicological effects via the induction of oxidative stress. To investigate the contribution of oxidative stress in KBrO3-induced cancer, male F344 rats were administered KBrO3 in their drinking water at multiple concentrations for 2-100 weeks. Gene expression analyses were performed on kidney, thyroid and mesothelial cell RNA. Families of mRNA transcripts differentially expressed with respect to bromate treatment included multiple cancer, cell death, ion transport and oxidative stress genes. Multiple glutathione metabolism genes were up-regulated in kidney following carcinogenic (400 mg/L) but not non-carcinogenic (20 mg/L) bromate exposures. 8-Oxodeoxyguanosine glycosylase (Ogg1) mRNA was up-regulated in response to bromate treatment in kidney but not thyroid. A dramatic decrease in global gene expression changes was observed following 1mg/L compared to 20 mg/L bromate exposures. In a separate study oxygen-18 (18O) labeled KBrO3 was administered to male rats by oral gavage and tissues were analyzed for 18O deposition. Tissue enrichment of 18O was observed at 5 and 24 h post-KBr18O3 exposure with the highest enrichment occurring in the liver followed by the kidney, thyroid and testes. The kidney dose response observed was biphasic showing similar statistical increases in 18O deposition between 0.25 and 50 mg/L (equivalent dose) KBr18O3 followed by a much greater increase above 50 mg/L. These results suggest that carcinogenic doses of potassium bromate require attainment of a threshold at which oxidation of tissues occurs and that gene expression profiles may be predictive of these physiological changes in renal homeostasis.

Animals↗
PubMed2006

Approaches to determining regulatory values for carcinogens with particular reference to bromate.

There are challenges in developing standards for substances that are carcinogenic in laboratory animals. In general, acceptable levels of substances that are shown to act through a mechanism that involves direct genotoxicity are determined by applying a mathematical model to extrapolate the risk at high doses to the risk at low environmental exposures. Most such models assume linearity at the low doses, which is not experimentally verifiable. Levels for substances that act through an indirect mechanism for which there is an experimentally verifiable threshold, such as cytotoxicity and regenerative hyperplasia, are generally determined by applying an uncertainty factor to a no effect level or a benchmark dose. Bromate is a potentially important contaminant in hypochlorite, and also as a consequence of the use of ozone in drinking water treatment. Although it has been used for many years as a flour improver it is known to cause cancers of the kidney, tunica vaginalis testis and thyroid in laboratory rodents. There are species differences in the sensitivity to bromate and differences in the tumours observed. The mechanism by which bromate causes cancer in laboratory animals is uncertain. There is evidence that bromate is a genotoxin but there is also indication that the dose response is not linear at low doses and that bromate may act through an intermediate mechanism. There is also evidence to suggest that bromate may be inactivated by antioxidants in the gastrointestinal tract and blood and so may not reach the sensitive tissues at low doses. Bromate has been considered by WHO, USEPA and Canada with slightly differing outcomes depending on the assumptions made. Because the acceptable levels determined are close to or below the concentrations that can be practically achieved in drinking water, even small differences have become very important. Determining whether it is appropriate to use a linear assumption and which is the most relevant tumour site are important steps in refining the risk assessment to for drinking water disinfection with hypochlorite and ozone.

Bromates↗
PubMed2001

Bromate minimization during ozonation: mechanistic considerations.

Bromate formation during ozonation of bromide-containing natural waters is somewhat inversely connected to the ozone characteristics: an initial fast increase followed by a slower formation rate. During the initial phase mostly OH radical reactions contribute to bromate formation,whereas in the secondary phase both ozone and OH radicals are important. To minimize bromate formation several control options are presented: ammonia addition, pH depression, OH radical scavenging, and scavenging or reduction of hypobromous acid (HOBr) by organic compounds. Only the two first options are applicable in drinking watertreatment. By both methods a similar effect of a bromate reduction of approximately 50% can be achieved. However, bromate formation during the initial phase of the ozonation cannot be influenced by either method. Ammonia (NH3) efficiently scavenges HOBrto NH2Br. However, this reaction is reversible which leads to higher required NH3 concentrations than expected. The rate constant kNH2Br for the hydrolysis of NH2Br by OH- to NH3 and OBr- was found to be 7.5-10(6) M(-1) s(-1). pH depression shifts the HOBr/ OBr- equilibrium to HOBr and also affects the ozone chemistry. The effect on ozone chemistry was found to be more importantfor bromate formation. For a given ozone exposure, the OH radical exposure decreases with decreasing pH. Therefore, for pH depression the overall oxidation capacity for a certain ozone exposure decreases which in turn leads to a smaller bromate formation.

Ammonia↗
PubMed2005

Trace analysis of bromate, chlorate, iodate, and perchlorate in natural and bottled waters.

A simple and rapid method has been developed to simultaneously measure sub-microg/L quantities of the oxyhalide anions bromate, chlorate, iodate, and perchlorate in water samples. Water samples (10 mL) are passed through barium and hydronium cartridges to remove sulfate and carbonate, respectively. The method utilizes the direct injection of 10 microL volumes of water samples into a liquid chromatography-tandem triple-quadrupole mass spectrometry (LC-MS/MS) system. Ionization is accomplished using electrospray ionization in negative mode. The method detection limits were 0.021 microg/L for perchlorate, 0.045 microg/L for bromate, 0.070 microg/L for iodate, and 0.045 microg/L for chlorate anions in water. The LC-MS/MS method described here was compared to established EPA methods 300.1 and 317.1 for bromate analysis and EPA method 314.0 for perchlorate analysis. Samples collected from sites with known contamination were split and sent to certified laboratories utilizing EPA methods for bromate and perchlorate analysis. At concentrations above the reporting limits for EPA methods, the method described here was always within 20% of the established methods, and generally within 10%. Twenty-one commercially available bottled waters were analyzed for oxyhalides. The majority of bottled waters contained detectable levels of oxyhalides, with perchlorate < or = 0.74 microg/L, bromate < or = 76 microg/L, iodate < or = 25 microg/ L, and chlorate < or = 5.8 microg/L. Perchlorate, iodate, and chlorate were detectable in nearly all natural waters tested, while bromate was only detected in treated waters. Perchlorate was found in several rivers and reservoirs where itwas not found previously using EPA 314.0 (reporting limit of 4 microg/L). This method was also applied to common detergents used for cleaning laboratory glassware and equipmentto evaluate the potential for sample contamination. Only chlorate appeared as a major oxyhalide in the detergents evaluated, with concentrations up to 517 microg/g. Drinking water treatment plants were also evaluated using this method. Significant formations of chlorate and bromate are demonstrated from hypochlorite generation and ozonation. From the limited data set provided here, it appears that perchlorate is a ubiquitous contaminant of natural waters at trace levels.

Bromates↗
PubMedDate not supplied

Measurement of bromate in bread by high performance liquid chromatography with post-column flow reactor detection.

An analytical procedure was developed to measure bromate residues in baked goods using a sequence of clean-up procedures followed by high performance liquid chromatography (HPLC) with a post-column reaction for oxidants. Deionized water was used to extract bromate from bread samples. The extract was treated with a C-18 solid phase extraction column to remove lipids, a cation exchange column with the silver cation to remove chloride, and an ultrafiltration membrane to remove proteins. Further treatment of the extract with the sodium form of a propylsulphonic acid ion exchange column was necessary to remove the silver that leached from the silver column. The method had a detection limit of 3 ng/g in baked goods. Recoveries of bromate from breads ranged from 73 to 86% at a fortified bromate level of 5-100 ng/g. Pullman-type white bread, produced by a sponge and dough method, was prepared in our laboratory for measurement of residual bromate. The dough was scaled in three different weights at different specific volumes (3.8, 4.1, 4.3), and samples of each of the three weights were baked for six different baking times ranging from 24 to 34 min. When bromate at a level of 25 mg/kg was added to flour, no residual bromate was detected in any of the samples, regardless of weight and baking time.

Bread↗
PubMed2002

Removal of bromate ion from water using TiO2 and alumina-loaded TiO2 photocatalysts.

The effects of pH and the surface charge of photocatalyst on photocatalytic reduction of bromate ions in water were examined by using TiO2 and alumina-loaded TiO2 photocatalysts. The amount of adsorbed bromate ion on TiO2 and the reduction rate of bromate ion by the TiO2 photocatalyst increased with lowering pH. It was suggested that the bromate ion adsorbed predominantly on the positively charged surface sites of TiO2 at lower pH, which thus promotes the rate of reduction. The iso-electric point of the TiO2 photocatalyst was shifted to the higher pH region by loading alumina on the TiO2 surface, which resulted in the increase of the adsorbed amount of bromate on the photocatalyst and the reduction rate of bromate ion by the photocatalyst at neutral pH. It was concluded from these results that the photocatalytic reduction of bromate ion can be promoted by pH control of water or by controlling the surface charge of the photocatalyst by loading alumina without pH control of water.

Adsorption↗
PubMed2005

Reduction of bromate in groundwater with an ex situ suspended growth bioreactor.

A potential remediation technique for groundwater contaminated by bromate has been investigated, utilising biological bromate reduction to bromide by augmentation of indigenous microbial populations. This technique, involving addition of a carbon source to contaminated groundwater, is being developed as an ex-situ methodology analogous to commercial denitrification systems, but may also have in-situ applications. Trials have focussed on a laboratory-scale anaerobic suspended growth chemostat system, investigating glucose addition to real groundwater supplies. Steady states for a range of glucose and bromate concentrations demonstrated bromate reduction up to 700 microgl(-1) (50% of 1400 microgl(-1) influent) with glucose excess (above 52 mgl(-1)), but specific reduction rates (up to 2.83 micromol Br.g dry wt(-1) hr(-1) for 1400 microgl(-1) bromate influent) were low compared to denitrification (up to 305 micromol N g dry wt(-1) hr(-1)). More recent enrichment trials have demonstrated reduction of 32 mgl(-1) bromate within a 40 hour residence time with specific reduction rates of up to 160.48 micromol Br.g dry wt(-1) hr(-1), suggesting the presence of high rate bromate reducing bacterial strains.

Bacteria, Anaerobic↗
PubMed2006

[Determination of trace bromate in drinking water by ion chromatography with suppressed conductivity detection].

Bromate is a common disinfection by-product produced from the ozonation of source water containing bromide. An ion exchange chromatographic method with suppressed conductivity detection for the determination of trace bromate in drinking water was developed. The separation of the bromate in drinking water was achieved on a Metrosep A Supp 5 anion exchange column and a Metrosep A Supp 4/5 Guard column with a carbonate eluent. A new dual suppressed system, an MSM II chemical suppressor combined with a CO2 suppressor, was used to suppress the background conductivity, and to improve the detection limit of bromate. Ion chromatographic experiments were carried out by using a Metrosep A Supp 5 anion exchange column with a suppressed conductivity detector and an eluent of 3.2 mmoL/L Na2CO3-1.0 mmol/L NaHCO3 at a flow rate of 0.65 mL/min. This method had good linearity (r = 0.9999) in the range of 5-100 microg/L and high precision (relative standard deviation (RSD) < 4% ) for three concentration levels of bromate. The average recoveries of the spiked samples including tap water, pure water and mineral water were 96.1%-107%, and the detection limit for bromate was 0.50 microg/L. This method has a simple operation procedure, good separation results, high sensitivity and good repeatability. It can be used as a standard method for the determination of bromate in drinking water.

Bromates↗
PubMed2005

Determination of trace concentrations of bromate in municipal and bottled drinking waters using a hydroxide-selective column with ion chromatography.

The International Agency for Research on Cancer determined that bromate is a potential human carcinogen, even at low micro/l levels in drinking water. Bromate is commonly produced from the ozonation of source water containing naturally occurring bromide. Traditionally, trace concentrations of bromate and other oxyhalides in environmental waters have been determined by anion exchange chromatography with an IonPac AS9-HC column using a carbonate eluent and suppressed conductivity detection, as described in EPA Method 300.1 B. However, a hydroxide eluent has lower suppressed background conductivity and lower noise compared to a carbonate eluent and this can reduce the detection limit and practical quantitation limit for bromate. In this paper, we examine the effect of using an electrolytically generated hydroxide eluent combined with a novel hydroxide-selective anion exchange column for the determination of disinfection byproduct anions and bromide in municipal and bottled drinking water samples. EPA Methods 300.1 B and 317.0 were used as test criteria to evaluate the new anion exchange column. The combination of a hydroxide eluent with a high capacity hydroxide-selective column allowed sub-microg/l detection limits for chlorite, bromate, chlorate, and bromide with a practical quantitation limit of 1 microg/l bromate using suppressed conductivity detection and 0.5 microg/l using postcolumn addition of o-dianisidine followed by visible detection. The linearity, method detection limits, robustness, and accuracy of the methods for spiked municipal and bottled water samples will be discussed.

Bromates↗
PubMed2006

Determination of bromate ion in drinking water by capillary zone electrophoresis with direct photometric detection.

Bromate ion in drinking water was determined by capillary zone electrophoresis (CZE) with direct photometric detection. Bromate ion in the sample solution was introduced and concentrated into the capillary by electrokinetic injection for 50s at -10 kV. Electrophoretic separation was made at an applied voltage of -25 kV and bromate ion was detected at wavelength 193 nm, at which the baseline was stabilized with less UV-absorbing acidic phosphate buffer. Bromate ion was detected within 5 min in the electropherogram. By increasing the electric conductivity in the migrating solution with 10 mM Na2SO4, a limit of detection (LOD) of 9 x 10(-10)M (0.1 microg/L BrO3-) was achieved. The proposed method was applied to the analysis of tap water and river water samples, but bromate ion was not detected. Because the practical samples contain relatively large amount of foreign ionic substances, the tap water sample was diluted to avoid the matrix ions. Bromate ion added in a tap water at the concentration of 8 x 10(-8)M was quantitatively recovered by diluting it 1/10.

Bromates↗