Effect of Lipid Oxidation on Dough Bleaching

The effect of lipid composition and oxidation on dough bleaching has been determined. At >2.25% (flour basis), pure linoleic acid was very efficient in degrading β‐carotene in dough, unlike colza, corn, peanut, soy, or sunflower oil, which were mainly characterized by different polyunsaturated fatty acids content. In a very oxidized state, as determined by a peroxide index of >15 meq/kg of oil, sunflower oil (rich in polyunsaturated fatty acids) had a major bleaching activity on β‐carotene when compared with colza oil (less polyunsaturated), especially in combination with long mixing times. A combination of lipase (815 U), slightly oxidized oil (peroxide index of 2–5 meq/kg of oil), and linoleic acid (90 mg/100 g of flour) significantly degraded flour pigments (P < 0.05).     

Liquid chromatographic determination of paralytic shellfish poisons in shellfish after prechromatographic oxidation.

A liquid chromatographic method for quantitating paralytic shellfish poison toxins in shellfish has been developed in which the toxins are converted to fluorescent purines by prechromatographic oxidation under mildly basic conditions with hydrogen peroxide or periodate. The addition of ammonium formate to the periodate oxidation reaction greatly improved the yield of fluorescent derivatives for neosaxitoxin, gonyautoxin-1, B-2, and C-3 compared to the same reaction without ammonium formate. As little as 3-6 ng of each of the nonhydroxylated toxins and 7-12 ng of the hydroxylated compounds per gram of shellfish could be detected. Reversed-phase chromatography using ammonium formate in the mobile phase improved the chromatography of neosaxitoxin and B-2 compared to results obtained earlier. Because the oxidation products of neosaxitoxin and B-2 could not be separated, parent compounds were separated before oxidation by using an SPE-COOH ion exchange cartridge. The repeatability coefficient of variation for the oxidation reactions ranged from 3 to 8% for the peroxide reaction, and from 4 to 11% for the periodate reaction, depending upon the individual toxin determined and its concentration in the extract (0.04-0.55 micrograms/g). The method was compared to the mouse bioassay and the postcolumn oxidation method. In most cases, results were comparable.     

Transformation of the fungicide chlorothalonil by Fenton reagent

A modified Fenton reagent (Fe(3+)/H(2)O(2)) transformed the fungicide chlorothalonil within 60 min in aqueous solution at unadjusted pH. Transformation varied with ferric salt. Transformation was greatest with ferric nitrate and least when ferric sulfate was used. UV irradiation enhanced the transformation of chlorothalonil. The transformation of chlorothalonil was enhanced, which increased with ferric ion or hydrogen peroxide concentration. Maximum transformation was achieved at 2 mM ferric ion and 100 mM hydrogen peroxide. Additionally, chlorothalonil was more dechlorinated in the UV irradiation condition. The proposed reaction pathway includes reduction of chlorothalonil to trichloroisophthalonitrile, dichloroisophthalonitrile, and monochloroisophthalonitrile; oxidation of trichloroisophthalonitrile to trichloro-3-cyanobenzoic acid and 3-carbamyltrichlorobenzoic acid; and oxidation of hydroxychlorothalonil to trichloro-3-cyanohydroxybenzoic acid and trichlorocyanophenol.     

Microwave-Enhanced Advanced Oxidation Treatment of Lipids and Food Wastes

Fats, oils, and grease (FOG) and source separated organics (SSO) were treated with the microwave-enhanced advanced oxidation process (MW-AOP) at 90 and 110 °C, with varying amounts of hydrogen peroxide dosages. The treatment efficiency, in terms of soluble substrates and volatile fatty acids (VFA), increased with an increase in both temperature hydrogen peroxide dosages. Fatty acids and compounds with carbonyl group and/or hydroxyl group in both initial and treated FOG samples were identified by gas chromatography-mass spectrometry. MW-AOP treatment temperatures and hydrogen peroxide dosages dictated the formation of degradation products. The degradation followed peroxidation mechanism to produce lower molecular weight substrates such as short chain fatty acids which would be less inhibitory to microbes. After the MW-AOP treatment, both SSO and FOG comprised of more soluble and low molecular weight compounds. These compounds included VFA and nutrients that would be readily available for bacterial or plant uptake.     

Mineralisation of Surfactants Using Ultrasound and the Advanced Fenton Process

The destruction of the surfactants, sodium dodecylbenzene sulfonate (DBS) and dodecyl pyridinium chloride (DPC), using an advanced oxidation process is described. The use of zero valent iron (ZVI) and hydrogen peroxide at pH = 2.5 (the advanced Fenton process), with and without, the application of 20 kHz ultrasound leads to extensive mineralisation of both materials as determined by total organic carbon (TOC) measurements. For DBS, merely stirring with ZVI and H₂O₂ at 20°C leads to a 51% decrease in TOC, but using 20 kHz ultrasound at 40°C, maintaining the pH at 2.5 throughout and adding extra amounts of ZVI and H₂O₂ during the degradation, then the extent of mineralisation of DBS is substantially increased to 93%. A similar result is seen for DPC where virtually no degradation occurs at 20°C, but if extra amounts of both ZVI and hydrogen peroxide are introduced during the reaction at 40°C and the pH is maintained at 2.5, then an 87% mineralisation of DPC is obtained. The slow latent remediation of both surfactants and the mechanism of degradation are also discussed.     

Remediation of Diesel-Contaminated Soils Using Persulfate Under Alkaline Condition

A laboratory study was conducted to assess the feasibility of remediating diesel-contaminated soils using sodium persulfate (SPS) oxidation under an alkaline pH. Lime (CaO) and sodium hydroxide (NaOH) were used as the alkaline sources, and various factors, including temperature, reaction time and concentration level, were investigated. Moreover, the combined usage of hydrogen peroxide (HP) and SPS in the presence or absence of NaOH was also studied. It was found that lime hydration resulted in rapid increases in pH (>12) and temperature (75?°C maximum) at a CaO/H₂O mass ratio of 3/20. In the NaOH or CaO/SPS system, the maximum diesel degradation achieved was approximately 30?%. It was observed that using a larger amount of alkaline increased SPS decomposition and had almost no effect on diesel degradation. Limited solubilization of contaminants may have inhibited the effectiveness of alkaline-activated persulfate oxidation during the aqueous phase and hence resulted in incomplete diesel degradation. The highest rate of diesel degradation (i.e., 56?% in 7 days) was achieved using the dual oxidation system, in which a HP/SPS molar ratio of 3.3/0.5 was used. An aggressive oxidation process, coupled with HP, may enhance desorption of diesel from soils and allow oxidation to occur during the aqueous phase.     

The oxidation products formed from: Soil organic matter by hydrogen peroxide treatment

The oxidation products formed from soil organic matter during hydrogen peroxide digestion were studied by means of analyses of carbon and nitrogen, thin layer chromatography, infrared Spectroscopy, and redox titration.

The carbon remaining after hydrogen peroxide digestion, as expressed in percentage by WeIght of the original soil was 0.57 to 4.09, corresponding to 17.81 to 29.00 per cent of the carbon fOUnd in the original soil. The nitrogen remaining after the same treatment was 75 to 100 per cent of total nitrogen in the original soil. The greater part of the remaining water soluble nItrogen was NH₃-N. The thin layer chromatography showed the presence of oxalic acid and V.V. light-ahsorbing substances in the oxidation products. No organic matter other than oxalate Was indicated on the infrared spectra. The amount of water soluble oxalate formed from 100 g of soil determined by means of redox titration was 5.7 to 117.0 mmole. Assuming that the ratio of solution: soil is 5:1 at the final stage of per oxidation, the concentration of oxalate in the SUpernatant solution was in the range from 0.011 to 0.234 M.     

四氯乙烯和萘在氧化前后的含水层土壤上的吸附 与加标解吸研究

采用批量平衡实验法研究了四氯乙烯和萘在过氧化氢氧化前后含水层土壤上的吸附。原土经过氧化氢处理后有机质含量明显降低,但是处理前后的土样对四氯乙烯和萘的吸附差别极小。过氧化氢对原土中极性官能团的破坏使原土中的大分子有机质变为小分子的可溶性有机质离开体系,造成土壤有机质含量降低。这些具有极性官能团的大分子有机质对研究的两种化合物的吸附贡献很小。在调节液固比使各种单一体系中的液相浓度差异达到一至两个数量级的情况下,加标解吸体系下的等温线仍表现为非常规的近似水平线,说明液相浓度的降低不足以使土壤中吸附的化合物发生解吸。这一结果从另一侧面说明两种目标物在研究土壤上的吸附是以在致密有机相上的吸附为主,而这部分有机质不会被过氧化氢所氧化。因此,在评估污染土壤对地下水的危害时,需慎重使用通过吸附实验得到并基于有机质总量的分配系数。     

Comparative analysis of different hemoglobins: autoxidation,reaction with peroxide,and lipid oxidation

Beef hemoglobin (Hb) had lower levels of deoxyHb and autoxidized much slower as compared to trout Hb at pH 6.3. Chicken Hb autoxidized at a rate intermediate between beef and trout Hb. In the presence of hydrogen peroxide, metHb formed rapidly from trout Hb whereas beef Hb was essentially nonreactive with hydrogen peroxide. The autoxidation rate of perch Hb was more rapid than trout Hb despite the low deoxyHb content of perch Hb. Perch Hb was a better catalyst of lipid oxidation than trout Hb when added to washed cod muscle based on formation of lipid hydroperoxides and thiobarbituric acid reactive substances. These studies indicate that autoxidation rate does not always increase with increasing deoxyHb content. The role of heme crevice volume in heme protein autoxidation is discussed. Among other factors, these studies suggest that rates of lipid oxidation in various muscle foods may depend on the relative ability of hemoglobins from different animal species to promote lipid oxidation.     

Loading of VO2+ and Cu2+ to partially oxidized charcoal fines rejected from Brazilian metallurgical industry

Purpose

Charcoal is utilized in Brazil for the metallurgical industry. Small size pieces, called charcoal fines, are rejected and sometimes are used to produce energy by burning. This charcoal can be used as soil conditioner to improve retention of metal ions in soil. However, changing the charcoal's surface chemistry via oxidation may increase retention of metal ions.

Materials and methods

Two kinds of oxidants were employed, nitric acid and selenium dioxide/hydrogen peroxide. Vanadyl ion (VO²⁺) and copper ion (Cu²⁺) were utilized as probe to study the metal ion complexation by the partially oxidized charcoal obtained. FTIR and EPR spectroscopy were used to characterize the materials.

Results and discussion

Oxidation with nitric acid increased nitrogen content, while oxidation with SeO₂/H₂O₂ elevated carbon content of treated charcoals. Organic free radicals (OFRs) with the unpaired electron in p orbitals of aromatic structures were confirmed by the EPR g-factors that ranged from 2.0038 to 2.0031. The oxidation with selenium dioxide/hydrogen peroxide formed charcoal with largest quantity of OFR. Loading charcoal with VO²⁺ and Cu²⁺ resulted in formation of complexes were oxygen acted as coordination atom. The formed complexes were of axial symmetry. The configurations around the Cu²⁺ ions were: CUNCu²⁺ complex (more stable square planar symmetry) and CFNCu²⁺ complex (less stable distorted tetrahedral configuration). Both complexes had oxygen as coordinating atoms. CFNVO²⁺ and CFSeVO²⁺ complexes presented complexation sites of axial symmetry, C_4v, with oxygen as coordinating atoms.

Conclusions

The oxidative treatment of charcoal with SeO₂/H₂O₂ is more appropriate to produce soil organic conditioner for complexation of metal ions.     

Photodegradation of metolachlor applying UV and UV/H2O2

Metolachlor is one of the most widely used herbicides in the world for controlling weeds. It has been detected in both ground and surface waters in the United States, and there are rising concerns in regard to its health risks and in developing effective treatment processes for its removal from water. Degradation of metolachlor via ultraviolet (UV) photolysis and an UV/hydrogen peroxide advanced oxidation process (AOP) was studied. The quantum yield of metolachlor at 254 nm was found to be 0.302 +/- 0.001 mol E-1 through direct UV photolysis in the range of pH 6-8. The second-order rate constant of the reaction between metolachlor and hydroxyl radical was determined to be 9.07 (+/-0.21) x 10(9) M-1 s-1 by using a competition kinetics model that utilized nitrobenzene as a reference compound. In addition, these parameters were successfully applied in modeling the kinetics of elimination of metolachlor using an UV/H2O2 process in both laboratory and natural waters. The formation of several photolysis byproducts was identified using gas chromatography/mass spectrometry, and a scheme for the metolachlor photodegradation pathway is proposed.     

磷酸铁盐涂层: 控制黄铁矿氧化的新手段

A novel coating technique was develped for controlling pyrite oxidation .The technique involved leaching pyrite particles with a solution containing low concentrations of phosphate and hydrogen peroxide.During the leaching rpocess,the iron released from pyrite by hydrogen proxide was precipitated by phosphate as a ferric phosphate coating .This coating was shown to be able to effectively prevent pyirte from oxidation and it could be established at the expense of only surface portions of pyrite.The emergence of this technique could provide a unique potential route for abating acid mine draingage and reclaiming sulfide-containing degraded mining land.     

Evaluation of chemical and photochemical oxidation processes for degradation of phosmet on lowbush blueberries (Vaccinium angustifolium)

Chemical and photochemical oxidation processes were evaluated for their ability to degrade residual phosmet on lowbush blueberries and for their role in the conversion of phosmet to phosmet oxon--a toxic metabolite of phosmet. Chemical processes included 1 ppm of aqueous ozone, 1% hydrogen peroxide, 100 ppm of chlorine, and UV, whereas photochemical processes included hydrogen peroxide/UV, chlorine/UV, and ozone/hydrogen peroxide/UV. Phosmet applied as Imidan 2.5EC under laboratory conditions resulted in a mean residual concentration of 44.4 ppm, which was significantly degraded (p < 0.05) by ozone and chlorine, yielding reductions of 57.7 and 46%, respectively. Interaction between phosmet (Imidan 2.5EC) and any chemical or photochemical treatment did not result in conversion to phosmet oxon. Residual analysis of commercially grown blueberries revealed mean phosmet (Imidan 70W) levels of 10.65 ppm and phosmet oxon levels of 12.49 ppm. Treatment of commercial blueberries resulted in significant reductions in phosmet regardless of treatment type; however, only UV, hydrogen peroxide/UV, and ozone treatments degraded phosmet (Imidan 70W) to less toxic metabolites and reduced phosmet oxon levels. Treatment-induced conversion of phosmet to phosmet oxon was noticeably influenced by variations between phosmet formulations. Acceleration of photochemical degradation by UV was not observed. Selective oxidation by ozone represents a significant postharvest process for degrading residual phosmet on lowbush blueberries.     

Effect of peroxidation on soil electrochemical properties

Treatment with hydrogen peroxide to destroy the organic matter shifts the surface charge towards positive values. This is in agreement with the suggestion that per oxidation produces artefacts in the soil residues, since metals released from organic matter precipitate as hydroxide coating and produce positively charged surfaces. In the presence of 0.1 M sodium pyrophosphate, treatment with hydrogen peroxide always shifts the surface charge towards negative values, notwithstanding the removal of the electronegative organic components. It is suggested that the bulk of electropositive iron and aluminium oxides in soil are associated with the organic matter and removed by the treatment, so that permanent negative charges of clay minerals dominate in soil residue.     

Oxidation of resveratrol catalyzed by soybean lipoxygenase

In this work the oxidative degradation of resveratrol catalyzed by lipoxygenase-1 (LOX-1) has been studied. The process has been characterized by spectroscopic and polarographic measurements. The oxidation of resveratrol was dependent on the concentration of resveratrol and the enzyme. When resveratrol was incubated in the presence of lipoxygenase at pH 9.0, the reaction displayed a k(M) value of 18.6 x 10(-)(6) M and a catalytic efficiency (k(cat)/k(M)) of 4.3 x 10(4) s(-)(1) M(-)(1). These values are close to those shown by the enzyme when linoleic acid is used as the substrate. The effect of lipoxygenase inhibitors on the lipoxygenase-catalyzed resveratrol oxidation was also evaluated. The rate of resveratrol oxidation was markedly decreased by the presence of NDGA in the incubation mixture. From HPLC measurements, it can be deduced that resveratrol is oxidatively decomposed to a complex mixture of products similar to those obtained when the molecule is oxidized by hydrogen peroxide.     

Antifungal and peroxidative activities of nonheme chloroperoxidase in relation to transgenic plant protection

Nonheme chloroperoxidase (CPO-P) of Pseudomonas pyrrocinia catalyzes the oxidation of alkyl acids to peracids by hydrogen peroxide. Alkyl peracids possess potent antifungal activity as found with peracetate: 50% killing (LD(50)) of Aspergillus flavus occurred at 25 microM compared to 3.0 mM for the hydrogen peroxide substrate. To evaluate whether CPO-P could protect plants from fungal infection, tobacco was transformed with a gene for CPO-P from P. pyrrocinia and assayed for antifungal activity. Leaf extracts from transformed plants inhibited growth of A. flavus by up to 100%, and levels of inhibition were quantitatively correlated to the amounts of CPO-P activity expressed in leaves. To clarify if the peroxidative activity of CPO-P could be the basis for the increased resistance, the antifungal activity of the purified enzyme was investigated. The LD(50) of hydrogen peroxide combined with CPO-P occurred at 2.0 mM against A. flavus. Because this value was too small to account for the enhanced antifungal activity of transgenic plants, the kinetics of the enzyme reaction was examined and it was found that the concentration of hydrogen peroxide needed for enzyme saturation (K(m) = 5.9 mM) was already lethal. Thus, the peroxidative activity of CPO-P is not the basis for antifungal activity or enhanced resistance in transgenic plants expressing the gene.     

Cyanidadsorption an Sesquioxiden,Tonmineralen und Huminstoffen

Cyanide adsorption on sesquioxides, clay-minerals and humic substances The adsorption of cyanide (KCN) on sesquioxides, clay minerals, and humic substances at different pH-values was studied. Moreover we looked for the CN-adsorption on L-layers of the humus forms mull, moder and mor. Cyanide was only adsorbed by humic acid. The amount of CN adsorbed increased with increasing pH of the reaction solution. IR-spectroscopic investigations of CN treated humic acids revealed that the cyanide was adsorbed at low pH (<7) as HCN-molecules by formation of hydrogen bonds with COOH-, COH-, OH- and NH₂-groups of the humic acid. At pH > 7 the cyanide was mainly adsorbed as CN^? by charge transfer with acceptor-molecules such as chinones. The cyanide adsorption of L-layers of humus forms decreased in the order mor > mull > moder. It is surmised that the HCN-molecules were not only adsorbed by humic acids in these layers but also by oxidation products of lignin, pectin, protein, cellulose, and carbon-hydrates of fulvic acids. Solutions of K₂HPO₄ did not desorb cyanides from humic acids to any great extent.     

A critical examination of some common field tests to assess the acid-sulphate condition in soils

Acid‐sulphate soils are of major environmental concern in many wetlands. Severe acidification episodes have occurred worldwide because of the oxidation of iron sulphides to sulphuric acid by human activities, and diverse techniques have been set up to determine the presence of acid‐sulphate soils. This paper evaluates the usefulness of four common easy‐to‐apply field survey tests for potential acid‐sulphate diagnosis in some Histosols and Entisols in wetlands: incomplete oxidation by fast air‐drying, incubation, fast oxidation with hydrogen peroxide, and the indirect determination of sulphide with lead acetate. Samples of 227 surface‐organic and underlying mineral soils of poorly drained Histosols and Entisols of the Orinoco river delta plain were tested. Results showed that for highly organic samples the interpretation of results obtained from the acid‐sulphate soil tests may be misleading, because they cannot be unambiguously related to the production of sulphuric acid derived from pyrite oxidation. Mineral samples yielded more reliable results. The incomplete oxidation by fast air‐drying test did not induce significant acidification either in organic or in mineral samples; the final pH values were dependent on the original pH values. The fast oxidation with hydrogen peroxide test was effective with mineral samples. During the incubation test, the slower rate of pH decrease and the final values obtained with the organic samples suggested retardation in the rate and amount of acid generation by pyrite oxidation because of the concurrent oxygen consumption by organic matter and bacterial activity. The indirect determination of sulphide with lead acetate yielded only qualitative results in organic samples, but worked well in mineral samples, indicating a higher content of pyrite intermediates. Effective estimation of the actual presence and potential for acidification of soil is important, in order to avoid excessive or inappropriate amelioration techniques to prevent acid production.     

Mild photochemical synthesis of the antioxidant hydroxytyrosol via conversion of tyrosol

Hydroxytyrosol, a naturally occurred orthodiphenolic antioxidant molecule found in olive oil and olive mill wastewaters, was obtained from the wet hydrogen peroxide photocatalytic oxidation of its monophenolic precursor tyrosol. The liquid-phase oxidation of tyrosol to hydroxytyrosol was performed by use of an iron-containing heterogeneous catalyst (Al-Fe)PILC with the assistance of UV irradiation at 254 nm and at room temperature. The spectroscopic and HPLC data of the synthesized compound proved to coincide fully with those of a pure sample obtained by continuous countercurrent extraction. This reaction was found to be light-induced. The hydroxytyrosol synthesis reaction reached its maximum yield of 64.36% under the optimized operating conditions of 3.6 mM tyrosol, 0.5 g L(-1) catalyst, and 10(-2) M H2O2 with the assistance of UV light. Increasing the initial hydrogen peroxide concentration more than 10(-2) M has a diminishing return on the reaction efficiency. Catalyst can be recuperated by means of filtration and then reused in a next run after regeneration since its activity did not significantly decrease (<10%). The reaction synthesis is operationally simple and could find application for industrial purposes.     

Novel antioxidant reactions of cinnamates in wine

Plant-derived polyphenolic compounds have received much attention for their ability to sequester high-energy free radicals in a great variety of food-related and biological systems, protecting those systems from oxidative change. The ability of these compounds to scavenge free radicals has always been attributed to their phenolic functionality, from which a hydrogen atom can be easily abstracted. In this study, the cinnamates and the ubiquitous hydroxycinnamates were found to equally suppress the formation of oxidation products in wine exposed to the Fenton reaction (catalytic Fe(II) with hydrogen peroxide). Mechanistic investigations led to the unexpected discovery that the α,β-unsaturated side chain of cinnamic acids could efficiently trap 1-hydroxyethyl radicals, representing a newly discovered mode of antioxidant radical scavenging activity for these broadly occurring compounds in a food system. The proposed pathway is supported by prior fundamental studies with radiolytically generated radicals.