Discoloration and mineralization of Orange II using different heterogeneous catalysts containing Fe: a comparative study

Four heterogeneous catalysts containing Fe including a bentonite-clay-based Fe nanocomposite (Fe-B), hematite (alpha-Fe2O3), amorphous FeOOH, and calcined FeOOH (denoted as FeOOH-M) were employed for the photo-Fenton discoloration and mineralization of 0.2 mM Orange II in the presence of 10 mM H2O2 and 8 W UVC at two different initial solution pH values (3.0 and 6.6). It was found that, at an initial solution pH of 3.0, their photocatalytic activities follow the order Fe-B > FeOOH, FeOOH-M > alpha-Fe2O3. When the Fe-B nanocomposite, FeOOH, and FeOOH-M were used as heterogeneous catalysts, both heterogeneous and homogeneous photo-Fenton reactions were responsible for the discoloration and mineralization of 0.2 mM Orange II because homogeneous photo-Fenton reaction occurred due to the presence of Fe ions leached from the catalysts. At an initial solution pH of 6.6, their photocatalytic activities still follow the order Fe-B > FeOOH, FeOOH-M > alpha-Fe2O3. However, only heterogeneous photo-Fenton reaction accounted for the discoloration and mineralization of 0.2 mM Orange II because Fe leaching from the catalysts was significantly depressed. In the case of alpha-Fe2O3 as a catalyst, whether at an initial solution pH of 3.0 or 6.6, only heterogeneous photo-Fenton reaction happened for the discoloration and mineralization of 0.2 mM Orange II because Fe leaching from the catalyst is negligible. The apparent discoloration kinetics of Orange II with the four catalysts at two different initial solution pH values was also investigated.     

Diuron degradation in irradiated, heterogeneous iron/oxalate systems: the rate-determining step

The purpose of this study was to examine the various factors that control the kinetics of diuron degradation in irradiated, aerated suspensions containing goethite (alpha-FeOOH) and oxalate, in the following denoted as heterogeneous photo-Fenton systems. In these systems, attack by hydroxyl radicals (HO.) was the only pathway of diuron degradation. Studies were conducted in systems containing initially 80 or 200 mg L(-1) goethite (corresponding to 0.9 or 2.25 mM total iron) and 20, 50, 75, 100, 200, and 400 microM oxalate at 3 < or = pH < or = 6. Both oxalate concentration and pH greatly affected the rate of light-induced diuron transformation. In the presence of initial 200 microM oxalate, the rate of diuron degradation was maximal at pH 4, coinciding with the maximal extent of oxalate adsorption on the surface of goethite. At pH 4,the rate of light-induced diuron degradation increased with increasing oxalate concentration, reaching a plateau at initial 200 microM oxalate, i.e., at the oxalate solution concentration at which the extent of oxalate adsorption on the surface of goethite reached a maximum. These experimental results suggest that the rate of Fe(II)(aq) formation through photochemical reductive dissolution of goethite, with oxalate acting as electron donor, determines the kinetics of diuron degradation in these heterogeneous photo-Fenton systems.     

APPLICATION OF SURFACE FRICTION MEASUREMENTS FOR SURFACE CHARACTERIZATION OF HEAT-SET WHEY PROTEIN GELS

The surface properties of heat‐set whey protein gels (14 wt %) was studied by measuring the friction at the gel's surface. A simple device was constructed that can be conveniently attached to a Texture Analyzer. Surface friction forces of gels with and without addition of salt were measured as a function of sliding speed and surface load. Surface friction strongly depended on the sliding speed for all three gel systems over the speed range 0.01 mm/s to 10 mm/s. The gel without salt addition showed the highest speed dependency, while the gel containing 200 mM NaCl had the lowest speed dependency. Surface load tests showed nearly linear relationships for both protein gels (with and without salt addition). Unlike solid materials, both protein gels exhibited a surface friction even as the surface load approached zero. Possible contributions of surface attraction and viscous flow to the measured forces are discussed. Results from surface friction tests were further confirmed by optical observation of the surface using a confocal laser scanning microscope (CLSM), where a very smooth surface was observed for the whey protein gel without salt addition, but a much rougher surface was observed for the gel containing 200 mM NaCl.     

EFFECTS OF ANTIOXIDANTS ON COPPER INDUCED LIPID OXIDATION DURING SALTING OF COD (GADUS MORHUA L.)

A model system for studying lipid oxidation of salted cod muscle was used for investigating the interaction effects of antioxidants and copper in the brine. The results showed that ascorbate might have pro-oxidative or antioxidative effects depending on the ascorbate and metal concentrations. Without added copper in the brine, concentrations of <500 ppm ascorbate had a pro-oxidative effect. With 5 ppm copper added in the brine, low concentrations of ascorbate (<50 ppm) inhibited the formation of TBARS (thiobarbituric acid - reactive substances) in the cured product. At slightly higher concentrations (100–200 ppm), the antioxidative properties were lost. Above 200 ppm the added ascorbate reduced the oxidation level in the salt-ripened product. The application of ascorbate as an antioxidant in salt curing of cod requires the use of high concentrations (> 1, 000 ppm) in the brine. When similar concentrations (0.5 mM) of EDTA (ethylenediaminetetraacetic acid), citrate or ascorbate were included with 3 ppm copper in the brine, EDTA was the only compound that efficiently inhibited copper-induced lipid oxidation.     

Abatement of the inhibitory effect of chloride anions on the photo-Fenton process

The inhibition of the photo-Fenton (Fe2+/Fe3+, H2O2, UV light) degradation of synthetic phenol wastewater solutions by chloride ions is shown to affect primarily the photochemical step of the process, having only a slight effect on the thermal or Fenton step. Kinetic studies of the reactions of oxoiron (IV) (FeO2+) with phenol indicate that, if FeO2+ is formed in the photo-Fenton degradation, its role is probably minor. Finally, it is shown that, for both a synthetic phenol wastewater and an aqueous extract of Brazilian gasoline, the inhibition of the photo-Fenton degradation of the organic material in the presence of chloride ion can be circumvented by maintaining the pH of the medium at or slightly above 3 throughout the process, even in the presence of significant amounts of added chloride ion (0.5 M).     

Treatment of municipal wastewater treatment plant effluents with modified photo-Fenton as a tertiary treatment for the degradation of micro pollutants and disinfection

The goal of this paper was to develop a modified photo-Fenton treatment able to degrade micro pollutants in municipal wastewater treatment plant (MWTP) effluents at a neutral pH with minimal iron and H(2)O(2) concentrations. Complexation of Fe by ethylenediamine-N,N'-disuccinic acid (EDDS) leads to stabilization and solubilization of Fe at natural pH. Photo-Fenton experiments were performed in a pilot compound parabolic collector (CPC) solar plant. Samples were treated with solid phase extraction (SPE) and analyzed by HPLC-Qtrap-MS. The rapid degradation of contaminants within the first minutes of illumination and the low detrimental impact on degradation of bicarbonates present in the water suggested that radical species other than HO(?) are responsible for the efficiency of such photo-Fenton process. Disinfection of MWTP effluents by the same process showed promising results, although disinfection was not complete.     

Physical properties of egg whites and whole eggs relevant to microwave pasteurization

Microwave pasteurization is a novel thermal processing technology in which non-uniform heating may be a major challenge. In this study, the suitability of using egg whites (EWs) and whole eggs (WEs) as model foods to evaluate the heating uniformity and to determine the cold and hot spots during microwave pasteurization was investigated. The samples were prepared from mixtures of water with commercial EW or WE powders at different solid concentrations (20%, 25%, 27.5%, and 30%) and salt contents (0, 50, 100, and 200 mM). Critical physical properties for desirable model food systems include appropriate dielectric properties, gelation temperatures, gel strengths, and water holding capacities (WHCs). The gelation temperature of liquid EW and WE were 70 and 80 °C; both fell in the pasteurization temperature range. At 915 MHz, the dielectric constants of liquid EW and WE samples and their heat induced gels decreased with solid concentration while the loss factor was not affected. Loss factors of liquid EW and WE samples increased linearly with salt addition, which could be explained by the linear increase of electrical conductivities by adding salt. The strength and WHC of heat induced EW and WE gels increased linearly with solid concentration, while salt addition had no significant effect. The results demonstrated the suitability of using EW and WE as model foods to determine the heating uniformity during microwave pasteurization process.     

Effects of long chain fatty acids on lipid and glucose metabolism in monolayer cultures of bovine hepatocytes

The objectives were to determine the long-term (48 h) effects of specific long chain fatty acids on hepatic lipid and glucose metabolism in monolayer cultures of bovine hepatocytes. From 16 to 64 h after plating, hepatocytes from three 7- to 10-d-old calves were exposed to one of the following treatments: 1 mM palmitic acid (1 mM C16:0), 2 mM palmitic acid (2 mM C16:0), or 1 mM palmitic acid plus 1 mM of either stearic (C18:0), oleic (C18:1), linoleic (C18:2), linolenic (C18:3), eicosapentaenoic (C20:5), or docosahexaenoic (C22:6) acid, or 0.5 mM each of eicosapentaenoic and docosahexaenoic acid (C20:5 + C22:6). The two treatments containing 2 mM of saturated fatty acids, 2 mM C16:0 and 1 mM C16:0 plus 1 mM C18:0, increased beta-hydroxybutyrate concentrations in the medium and [1-(14)C]palmitic acid oxidation to acid-soluble products compared with all other treatments. The treatment containing C22:6 increased total cellular triglyceride content and incorporation of [1-(14)C]palmitic acid into cellular triglycerides. The treatments containing C22:6 or C20:5 + C22:6 increased [1-(14)C]palmitic acid metabolism to phospholipids and cholesterol. The presence of C22:6 in the medium decreased metabolism of [2-(14)C]propionic acid either to glucose in the medium or to cellular glycogen. Overall, fatty acids differed in their effects on lipid and glucose metabolism in monolayer cultures of bovine hepatocytes with C22:6 eliciting the most profound changes.     

基于离子电流盐渍蘑菇的工艺条件优化

为了缩短盐渍时间,利用交变磁通在强电解质盐渍液回路体系生产由感应电动势驱动Na+、Cl－形成离子电流对蘑菇进行浸渍处理。结果表明,对孔隙率为41.4%的蘑菇进行离子电流处理后可使盐分质量分数快速增加,且明显高于常规湿法腌渍的蘑菇,渗盐量和结实度随质量分数和时间单调递增,通过电子显微镜观察微观结构发现蘑菇具有多孔结构且盐分聚集在样品内部组织。以盐渍液质量分数和处理时间为影响渗盐量的因素,通过单因素选择水平,根据Central-Composite星点试验设计原理,采用两因素四水平响应面进行分析得到渗盐量数学模型（R2=0.966 9）。使用回归模型的工艺参数进行预测和验证,得到经过盐渍液质量分数9.0%和35 min处理后的蘑菇平均含盐量为3.8%,表明回归模型拟合度较好。优化后的工艺可以完成对多孔状农产品和食品材料的快速盐渍处理。     

Novel bentonite clay-based Fe-nanocomposite as a heterogeneous catalyst for photo-Fenton discoloration and mineralization of Orange II

A novel bentonite clay-based Fe-nanocomposite (Fe-B) was successfully developed as a heterogeneous catalyst for photo-Fenton discoloration and mineralization of an azo-dye Orange II. X-ray diffraction (XRD) analysis clearly reveals that the Fe-B nanocomposite catalyst mainly consists of Fe2O3 (hematite) and SiO2 (quartz) crystallites, and the Fe concentration of the Fe-B catalyst determined by X-reflective fluorescence (XRF) is 31.8 wt %. The catalytic activity of the Fe-B was evaluated in the discoloration and mineralization of Orange II in the presence of H2O2 and UVC light (254 nm). It was found that the optimal Fe-B catalyst dosage is around 1.0 g/L, and the efficiency of discoloration and mineralization of Orange II increases as initial Orange II concentration decreases or reaction temperature increases. In addition, at optimal conditions (10 mM H2O2, 1.0 g of Fe-B/L, 1 x 8W UVC, and pH = 3.0), complete discoloration and mineralization of 0.2 mM Orange II can be achieved in less than 60 and 120 min, respectively. The result strongly indicates that the Fe-B nanocomposite catalyst exhibits a high catalytic activity not only in the photo-Fenton discoloration of Orange II but also in the mineralization of Orange II. The reaction kinetics analysis illustrates that the photo-Fenton discoloration of Orange II in the first 15 min obeys the pseudo-first-order kinetics. The reaction activation energy calculated was 9.94 kJ/mol, indicating that the photo-Fenton discoloration of Orange II is not very sensitive to reaction temperature.     

Influence of biopolymer emulsifier type on formation and stability of rice bran oil-in-water emulsions: whey protein, gum arabic, and modified starch

Rice bran oil (RBO) is used in foods, cosmetics, and pharmaceuticals due to its desirable health, flavor, and functional attributes. We investigated the effects of biopolymer emulsifier type and environmental stresses on the stability of RBO emulsions. Oil-in-water emulsions (5% RBO, 10 mM citrate buffer) stabilized by whey protein isolate (WPI), gum arabic (GA), or modified starch (MS) were prepared using high-pressure homogenization. The new MS used had a higher number of octenyl succinic anhydride (OSA) groups per starch molecule than conventional MS. The droplet diameters produced by WPI and MS were considerably smaller (d < 300 nm) than those produced by GA (d > 1000 nm). The influence of pH (3 to 8), ionic strength (0 to 500 mM NaCl), and thermal treatment (30 to 90 °C) on the physical stability of the emulsions was examined. Extensive droplet aggregation occurred in WPI-stabilized emulsions around their isoelectric point (4 < pH < 6), at high salt (> 200 mM, pH 7), and at high temperatures (>70 °C, pH 7, 150 mM NaCl), which was attributed to changes in electrostatic and hydrophobic interactions between droplets. There was little effect of pH, ionic strength, and temperature on emulsions stabilized by GA or MS, which was attributed to strong steric stabilization. In summary: WPI produced small droplets at low concentrations, but they had poor stability to environmental stress; GA produced large droplets and needed high concentrations, but they had good stability to stress; new MS produced small droplets at low concentrations, with good stability to stress. Practical Application: This study showed that stable rice bran oil-in-water emulsions can be formed using biopolymer emulsifiers. These emulsions could be used to incorporate RBO into a wide range of food products. We compared the relative performance of whey protein, GA, and a new MS at forming and stabilizing the emulsions. The new OSA MS was capable of forming small stable droplets at relatively low concentrations.     

Mangosteen Oil-In-Water Emulsions: Rheology, Creaming, and Microstructural Characteristics during Storage

The rheological properties and physical stability of mangosteen (Garcinia mangostana L.) extract in oil-in-water (MIO/W) emulsions were investigated. Rheological study on the emulsions exhibited Newtonian flow behavior. The 20?wt.% emulsion showed higher apparent viscosity than 10?wt.% MIO/W sample. The effects of salt (NaCl) concentration (0, 50, 100, and 200?mM) and heat treatment (70?°C) on the stability of the emulsions were also examined. Heat (70?°C)- and NaCl (100 and 200?mM)-treated emulsions showed creaming and droplet aggregation on storage for a period of 60?days. The 10?wt.% MIO/W emulsions stored at 4?°C showed a homogeneous distribution of oil droplets with good stability to creaming and viscosity independent of shear stress (i.e., a Newtonian liquid).     

Fermentation of Cucumbers Brined with Calcium Chloride Instead of Sodium Chloride

ABSTRACT: Waste water containing high levels of NaCl from cucumber fermentation tank yards is a continuing problem for the pickled vegetable industry. A major reduction in waste salt could be achieved if NaCl were eliminated from the cucumber fermentation process. The objectives of this project were to ferment cucumbers in brine containing CaCl₂ as the only salt, to determine the course of fermentation metabolism in the absence of NaCl, and to compare firmness retention of cucumbers fermented in CaCl₂ brine during subsequent storage compared to cucumbers fermented in brines containing both NaCl and CaCl₂ at concentrations typically used in commercial fermentations. The major metabolite changes during fermentation without NaCl were conversion of sugars in the fresh cucumbers primarily to lactic acid which caused pH to decrease to less than 3.5. This is the same pattern that occurs when cucumbers are fermented with NaCl as the major brining salt. Lactic acid concentration and pH were stable during storage and there was no detectable production of propionic acid or butyric acid that would indicate growth of spoilage bacteria. Firmness retention in cucumbers fermented with 100 to 300 mM CaCl₂ during storage at a high temperature (45 °C) was not significantly different from that obtained in fermented cucumbers with 1.03 M NaCl and 40 mM CaCl₂. In closed jars, cucumber fermentations with and without NaCl in the fermentation brine were similar both in the chemical changes caused by the fermentative microorganisms and in the retention of firmness in the fermented cucumbers.     

Oxidation of 4-chloro-3-methylphenol in pressurized hot water/supercritical water with potassium persulfate as oxidant

4-Chloro-3-methylphenol (c = 2.0 mM), representing a model pollutant, was oxidized in pressurized hot water and in supercritical water in a continuous flow system. Potassium persulfate was used as oxidant in concentrations of 8.0 and 40.0 mM. Contact times (reaction times) were 3-59 s, temperatures 110-390 degrees C, and pressures 235-310 bar. A wide temperature range was tested to determine the range over which potassium persulfate can be used effectively. Good oxidation efficiencies for 4-chloro-3-methylphenol were obtained at both oxidant concentrations and with short contact times at temperatures clearly underthe critical temperature of water; total organic carbon content of the effluent was low under optimized conditions. Corrosion, measured as nickel and chromium concentrations of the effluent, was more severe at oxidant concentration of 40.0 mM. Sulfate was present in the effluent in high concentrations. Sulfate is the limiting factor in the use of potassium persulfate in wastewater treatment and requires further water treatment.     

Effect of oral sodium chlorate administration on Escherichia coli O157:H7 in the gut of experimentally infected pigs.

Strategies are sought to reduce pathogenic Escherichia coli concentrations in food animals. Because E. coli possess respiratory nitrate reductase activity, which also reduces chlorate to cytotoxic chlorite, we tested and found that oral sodium chlorate administration reduced gut concentrations of E. coli O157:H7 in experimentally infected pigs and wildtype E. coli concentrations in nonchallenged pigs. Mean +/- S.E. concentrations (log10 CFU/g) of E. coli O157:H7 in ileal, cecal, colonic and rectal contents from placebo-treated pigs were 4.03 +/- 0.66, 3.82 +/- 0.24, 4.42 +/- 0.25 and 4.03 +/- 0.16, respectively. In contrast, E. coli O157:H7 concentrations were reduced (P < 0.05) in ileal (1.56 +/- 0.22) cecal (2.65 +/- 0.38), colonic (3.05 +/- 0.38) and rectal (3.00 +/- 0.29) contents from pigs orally administered three successive (8 h apart) 10-ml doses of 100 mM chlorate. Wildtype E. coli concentrations in gut contents of non-E. coli O157:H7-challenged pigs likewise treated with chlorate were reduced by 1.1 to 4.5 log10 units compared to concentrations in placebo-treated pigs, which exceeded 6.0 log10 CFU/g. As before, the reductions were greater in anterior regions of the gut than regions more caudal. Similar treatment of E. coli O157:H7-challenged pigs with 200 mM chlorate caused reductions in gut concentrations of E. coli O157:H7; however, the reductions were not necessarily greater than those achieved with the 100 mM chlorate treatment.     

Effects of pH, chloride, and bicarbonate on Cu(I) oxidation kinetics at circumneutral pH

The oxidation kinetics of nanomolar concentrations of Cu(I) in NaCl solutions have been investigated over the pH range 6.5-8.0. The overall apparent oxidation rate constant was strongly affected by chloride, moderately by bicarbonate, and to a lesser extent by pH. In the absence of bicarbonate, an equilibrium-based speciation model indicated that Cu(+) and CuClOH(-) were the most kinetically reactive species, while the contribution of other Cu(I) species to the overall oxidation rate was minor. A kinetic model based on recognized key redox reactions for these two species further indicated that oxidation of Cu(I) by oxygen and superoxide were important reactions at all pH values and chloride concentrations considered, but back reduction of Cu(II) by superoxide only became important at relatively low chloride concentrations. Bicarbonate concentrations from 2 to 5 mM substantially accelerated Cu(I) oxidation. Kinetic analysis over a range of bicarbonate concentrations revealed that this was due to formation of CuCO(3)(-), which reacts relatively rapidly with oxygen, and not due to inhibition of the back reduction of Cu(II) by formation of Cu(II)-carbonate complexes. We conclude that the simultaneous oxygenation of Cu(+), CuClOH(-), and CuCO(3)(-) is the rate-limiting step in the overall oxidation of Cu(I) under these conditions.     

Effect of salt stress on phenolic compounds,glucosinolates, myrosinase and antioxidant activity in radish sprouts

The germination, growth, total phenolics, glucosinolate, myrosinase and antioxidant activity of radish sprouts germinated under 0 (control), 10, 50 and 100 mM of NaCl were investigated. The glucoraphasatin (4-methylthio-3-butenyl-glucosinolate), total glucosinolate and total phenolic contents of 5- and 7-day-old sprouts treated with 10 and 50 mM of NaCl were significantly decreased. However, the antioxidant activity of sprouts treated with 10 and 50 mM of NaCl was not affected. The glucoraphasatin and total glucosinolate contents of 5- and 7-day-old sprouts, total phenolic contents of 3- and 5-day-old sprouts were significantly increased and myrosinase activities of 3- and 5-day-old sprouts were inhibited, although the germination was dramatically inhibited by 100 mM of NaCl treatment. These results indicated that salt stress (100 mM of NaCl treatment) could improve the nutritional value of radish sprouts, and germination of sprouts under adequate salt stress could be one useful way to enhance health-promoting compounds of plant food.     

Heated scallop-shell powder slurry treatment of shredded cabbage

The main component of scallop-shell powder is calcium carbonate (CaCO3). Through heat treatment, CaCO3 in the shell is converted to CaO, which exhibits antibacterial activity. The disinfecting effect of heated scallop-shell powder on shredded cabbage was investigated for various powder concentrations (0.1 to 1.0 g dm(-3)) and treatment temperatures (10 to 40 degrees C). Scallop-shell powder treatment was found to reduce the aerobic bacteria count in cabbage, with increasing effectiveness at higher powder concentrations and treatment temperatures. Coliforms were completely eliminated within 5 min with as little as 0.1 g dm(-3) powder treatment. During storage at 4 degrees C, aerobic bacterial counts did not increase after powder treatment, whereas counts increased with water-washing or sodium hypochlorite treatment at 200 microg dm(-3). The inactivation pattern of bacterial cells in shredded cabbage involved an accelerated decline followed by an extended tail at powder concentrations of 0.1 and 0.5 g dm(-3). We postulate that a fraction of bacterial cells in the initial population becomes tolerant to the shell powder. A proposed model accurately predicts the reducing bacterial counts on shredded cabbage by scallop-shell powder treatment. The decrease in the L-ascorbic acid content of shredded cabbage was approximately 20 to 30% for scallop-shell powder treatment at 0.1 and 0.5 g dm(-3) (20 degrees C), which is almost identical to that by sodium hypochlorite treatment at 200 micorg dm(-3).     

The analysis of saturated and aromatic mineral oil hydrocarbons in dry foods and from recycled paperboard packages by online HPLC–GC–FID

ABSTRACT

The purpose of this study was to determine the concentrations of mineral oil hydrocarbons in dry foodstuffs packed in recycled paperboard, which were imported from different foreign countries to Germany. After collection, mineral oil saturated hydrocarbons (MOSH) and mineral oil aromatic hydrocarbons (MOAH) in dry foodstuffs and recycled paperboard were analysed using online coupled high-performance liquid chromatography–gas chromatography–flame ionisation detection (online HPLC–GC–FID) far before the end of the shelf life of the samples. Our results showed that recycled paperboard has MOAH content higher than that of dry foodstuffs. The proportion of MOAH within total mineral oil hydrocarbons was determined to be 7–45% in dry foodstuffs and 4–48% in paperboard. In addition, 29% of the products were found to contain over 1.00 mg/kg MOAH, with a maximum of 2.72 mg/kg in oatmeal. White colour recycled paperboard contained lower amounts of MOSH and MOAH than that of brown and grey colour recycled paperboard. The MOSH concentration in dry foodstuffs ranged from 0.11 to 21.92 mg/kg (?C25 hydrocarbons), which may be an indication of rapid migration. The lowest determined MOSH concentrations (?C25 hydrocarbons) were found in sea salt and soda samples, even when their paperboard contained high mineral oil hydrocarbons. Our three samples in packages containing internal bags (for complete barriers) were found to have low mineral oil concentration due to reduced migration through plastic (acrylate-coated polypropylene). However, one sample, a ‘crispy’ product with an internal bag, contained the extreme amount of 21.92 mg/kg. Differences in contaminants observed in both dry foodstuffs and recycled paperboard may have been due to the different packaging and production techniques of the different countries. In addition, 8 of 24 dry foodstuff samples contained MOSH concentrations frequently exceeding the 2.0 mg/kg limit for MOSH C₂₀–C₃₅.     

Mechanisms of dioxin formation from the high-temperature pyrolysis of 2-bromophenol

Brominated hydrocarbons are the most commonly used flame retardants. Materials containing brominated hydrocarbons are frequently disposed in municipal and hazardous waste incinerators as well as being subjected to thermal reaction in accidental fires. This results in the potential for formation of brominated dioxins and other hazardous combustion byproducts. In contrast to chlorinated hydrocarbons, the reactions of brominated hydrocarbons have been studied only minimally. As a model brominated hydrocarbon that may form brominated dioxins, we studied the homogeneous, gas-phase pyrolytic thermal degradation of 2-bromophenol in a 1-cm i.d., fused-silica flow reactor at a concentration of 90 ppm, with a reaction time of 2.0 s, and over a temperature range of 300 to 1000 degrees C. Observed products included dibenzo-p-dioxin (DD), 1-monobromodibenzo-p-dioxin (1-MBDD), 4-monobromodibenzofuran (4-MBDF), dibenzofuran (DF), naphthalene, bromonaphthalene, 2,4- and 2,6-dibromophenol, phenol, bromobenzene, and benzene. These results are compared and contrasted with previous results reported for 2-chlorophenol. At temperatures lower than 700 degrees C, formation of 2-bromophenoxyl radical, which decomposes through CO elimination to form a bromocyclopentadienyl radical, forms naphthalene and 2-bromonaphthalene through radical recombination/rearrangement reactions. However, unlike the results for 2-chlorophenol, where naphthalene is the major product, DD becomes the major product for the pyrolysis of 2-bromophenol. The formation of DD and 1-MBDD are attributed to radical-radical reactions involving 2-bromophenoxyl radical with the carbon- (bromine) centered radical and the carbon- (hydrogen) centered radical mesomers of 2-bromophenoxyl radical, respectively. The potential product, 4,6-dibromodibenzofuran (4,6-DBDF) for which the analogous product, 4,6-dichlorodibenzofuran (4,6 DCDF), was observed in the oxidation of 2-chlorophenol, was not detected. This is attributed to the pyrolytic conditions of our experiments (e.g., shorter reaction times and higher temperatures) that favor reaction intermediates that form DD and 1-MBDD.