Anaerobic, nitrate-dependent oxidation of pyrite nanoparticles by Thiobacillus denitrificans

Pyrite is a key mineral in the global biogeochemical cycles of sulfur and iron, yet its anaerobic microbial oxidation has eluded geochemists and microbiologists for decades. Recent reports indicated that anaerobic oxidation of pyrite is occurring, but the mechanism remains unclear. Here, we provide evidence for the capability of Thiobacillus denitrificans to anaerobically oxidize a putatively nanosized pyrite particle fraction with nitrate as electron acceptor. Nanosized pyrite was readily oxidized to ferric iron and sulfate with a rate of 10.1 μM h(-1). The mass balance of pyrite oxidation and nitrate reduction revealed a closed recovery of the electrons. This substantiates a further "missing lithotrophy" in the global cycles of sulfur and iron and emphasizes the high reactivity of nanominerals in the environment.     

PCE oxidation by sodium persulfate in the presence of solids

Batch reactor experiments were performed to determine the effects of solids on the oxidation of tetracholoroethylene (PCE) by sodium persulfate in aqueous solution. Based on the rates of PCE degradation and chloride formation, PCE oxidation by heat-activated sodium persulfate at 50 °C in the presence of solids ranged from no detectable oxidation of PCE to the levels observed in water-only reactors. Repeated doses of sodium persulfate, undertaken to overcome the inherent solids oxidant demand, improved the rate and extent of PCE oxidation in reactors containing reference solids; however, no improvement was observed in reactors containing field soils. Additionally, no improvements in PCE oxidation were observed after pretreating Great Lakes and Appling soils with ca. 15 g/kg of sodium persulfate or 30% hydrogen peroxide to remove oxidizable fractions, or acetic acid to remove the carbonate fraction. Based on these results, in situ treatment of Great Lakes and Appling soils with heat-activated sodium persulfate is not anticipated to result in substantial PCE oxidation, while in situ treatment of Fort Lewis soils is anticipated to result in PCE oxidation. This work demonstrates the need to perform soil-specific contaminant treatability tests rather than soil oxidant demand tests when determining oxidant dosage requirements.     

Influence of heterotrophic microbial growth on biological oxidation of pyrite

The rate and extent of pyrite oxidation by the iron-oxidizing bacteria Acidithiobacillus ferrooxidans was limited by the growth of the heterotrophic microbe Acidiphilium acidophilum. In batch systems containing a mixture of both organisms, the maximum zero-order rate of ferric iron accumulation was about 1.4 mg of Fe3+ L(-1) d(-1) as compared to 9.4 mg of Fe3+ L(-1) d(-1) for pure cultures of A. ferrooxidans under the same conditions. Pyrite oxidation was limited in cases where both cultures of organisms were initially present as well as situations where the heterotrophic organisms were added to established, pyrite-oxidizing systems containing A. ferrooxidans. Results also indicated that organic carbon remaining in solution following heterotrophic bacterial growth reduced the rate of abiotic pyrite oxidation by the ferric ion. Furthermore, a cell-free solution of the residual organic carbon resulted in a lag of A. ferrooxidans growth in soluble ferrous medium. The residual organic carbon solution that accumulated during the growth of Aph. acidophilum had a diverse molecular weight distribution, indicating that different compounds could be responsible for the inhibition of chemical pyrite oxidation and the A. ferrooxidans growth lag observed. Titration of dissolved copper ions with residual dissolved organic carbon originating from Aph. acidophilum cultures indicated that a metal complexation mechanism could be responsible for the lower rates of pyrite oxidation observed. These data suggest that encouraging the growth of heterotrophic microorganisms under acid mine drainage conditions may be a feasible strategy for decreasing both the rate and the extent of sulfide mineral oxidation.     

Fenton-mediated oxidation in the presence and absence of oxygen

The increased use of Fenton systems for the treatment of contaminated waters and wastewaters necessitates the development of kinetic models capable of accurately simulating key species concentrations in order to optimize system performance and efficiency. In this work a reaction mechanism in which the hydroxyl radical is nominated to be the active oxidant in Fenton systems is used to describe the oxidation of formic acid (HCOOH) under a variety of experimental conditions. A kinetic model based on this reaction mechanism is shown to adequately describe results of experiments in which starting concentrations of H202 and HCOOH varied over 1 and 4 orders of magnitude, respectively, under both air-saturated and deaerated conditions. The intermediate generated during HCOOH oxidation was observed to increase oxidation efficiency, especially at high initial organic concentrations [relative to Fe(II)], by assisting in the redox cycling of iron. In the presence of oxygen, however, such improvement was attenuated through competition for the organic intermediates. While mechanistic analysis and associated kinetic modeling is invaluable in optimization of Fenton systems, a clear understanding of reaction byproducts and their reactivity toward other species in the system is critical for accurate simulations.     

海洋磷脂氧化及其对食品风味的影响

海洋磷脂因其独特的结构和生物活性引起人们的关注。海洋磷脂广泛存在于水产品中,由于多不饱和脂肪酸含量高,在加工和储运过程中易发生脂质氧化反应、非酶促褐变反应等,这一系列反应生成的产物一方面引起水产品的酸败,降低食品的品质;另一方面适当的磷脂氧化,提供了脂质来源的风味前体物质,是水产品特征香气物质产生的关键。在水产品的挥发性风味物质中已鉴定出醇、醛、2-戊基呋喃、苯甲醛等特征香气成分,此类风味物质的形成来源于脂质氧化以及非酶褐变等反应,受这些反应共同作用的影响,形成了食品独特诱人的品质和风味。该文综述了海洋磷脂氧化及其在食品风味中的作用,为深入理解食品特征风味物质形成提供参考。     

Inhibition of lipid oxidation in fried chips and cookies by Majorana syriaca

This study evaluates the antioxidant effectiveness of a natural extract obtained from Majorana syriaca in fried and baked foods. Majorana syriaca was extracted with ethyl acetate (yield 129 g kg^?1, dry basis) and the extract was added to refined corn oil at a concentration of 500 ppm. The oil was used in deep frying of potato chips at 185 °C and in making baked cookies. Potato chips and cookies were further subjected to accelerated oxidation at 70 °C. The protection of the frying oil was moderate as indicated by the polar content and conjugated dienes (CD) measurements, however, a remarkable improvement of the oxidative stability of the fried chips was observed through the decrease of peroxide value (PV) and CD by 59–72% and 51–79%, respectively, compared to samples with no additive. Also, the PV and CD of cookies decreased by 79% and 72%, respectively.     

Inhibition of hemoglobin-mediated lipid oxidation in washed fish muscle by cranberry components

Fractions enriched in phenolic acids (Fraction 1), anthocyanins (Fraction 2), flavonols (Fractions 3 and 4) and proanthocyanidins (Fractions 5 and 6) were prepared from cranberry powder using Sephadex LH-20 chromatography. Fractions 2, 3, 4, and 5 had nearly equivalent reactivity in the total phenolate assay employed per mg dry weight of each fraction while Fractions 1 and 6 were less reactive. The ability of cranberry fractions to scavenge 1,1-diphenyl-2-picrylhydrazyl (DPPH) radicals as well as their inhibitory effects on hemoglobin (Hb)-mediated lipid oxidation in washed cod muscle were assessed. Addition of cranberry fractions at a level of 74 μmol quercetin equivalents per kg of washed cod muscle extended the induction time of thiobarbituric acid reactive substances (TBARS) formation in the order: Fraction 1, Fraction 3, Fraction 4 > Fraction 2 > Fraction 5 > Fraction 6. This suggests that oligomeric polyphenols (e.g., proanthocyanidins) were least effective at inhibiting Hb-mediated lipid oxidation in washed cod muscle compared to the other classes of polyphenolics in cranberry. The ability of the different cranberry fractions to scavenge DPPH radicals did not reflect their relative ability to inhibit lipid oxidation in the washed cod muscle system. Quercetin was tentatively identified as a component in cranberry that was especially effective at inhibiting Hb-mediated lipid oxidation. The ability of flavonol and proanthocyanidin-enriched fractions to inhibit Hb-mediated lipid oxidation in spite of efforts to wash away the added polyphenolics prior to Hb addition indicated these classes of polyphenolics had binding affinities for insoluble components of washed cod muscle.     

Sedimentary pyrite in a buried gymnosperm

Ohne Zusammenfassung     

Inhibition of pork and fish oxidation by a novel plastic film coated with horseradish extract

An anti-oxidative plastic film coated with microcapsules containing volatile horseradish extract was developed. The oil-in-water-type microcapsule was produced by a modified orifice method to encapsulate the methanol extract of horseradish. The presence of naturally occurring antioxidants in the extract was confirmed by high performance liquid chromatography. Increasing the amount of chitosan during microcapsule formation increased the size of the microcapsules and decreased the rate of release of the horseradish extract, suggesting that the amount of extract released from the film can be modulated by the chitosan content of the microspheres. Covering pork and fish fillets with the anti-oxidative film delayed oxidative discoloration and rancidization. Collectively, these results showed that a horseradish-coated film containing natural antioxidants efficiently enhanced the stability of both pork and fish. This novel film may be a promising tool to prolong the shelf-life of meats.     

Photoinduced oxidation of arsenite to arsenate in the presence of goethite

The photochemistry of an aqueous suspension of goethite in the presence of arsenite (As(III)) was investigated with X-ray absorption near edge structure (XANES) spectroscopy and solution-phase analysis. Irradiation of the arsenite/goethite under conditions where dissolved oxygen was present in solution led to the presence of arsenate (As(V)) product adsorbed on goethite and in solution. Under anoxic conditions (absence of dissolved oxygen), As(III) oxidation occurred, but the As(V) product was largely restricted to the goethite surface. In this circumstance, however, there was a significant amount of ferrous iron release, in stark contrast to the As(III) oxidation reaction in the presence of dissolved oxygen. Results suggested that in the oxic environment ferrous iron, which formed via the photoinduced oxidation of As(III) in the presence of goethite, was heterogeneously oxidized to ferric iron by dissolved oxygen. It is likely that aqueous reactive oxygen species formed during this process led to the further oxidation of As(III) in solution. Results from the current study for As(III)/goethite also were compared to results from a prior study of the photochemistry of As(III) in the presence of another iron oxyhydroxide, ferrihydrite. The comparison showed that at pH 5 and 2 h of light exposure the instantaneous rate of aqueous-phase As(V) formation in the presence of goethite (12.4 × 10(-5) M s(-1) m(-2)) was significantly faster than in the presence of ferrihydrite (6.73 × 10(-6) M s(-1) m(-2)). It was proposed that this increased rate of ferrous iron oxidation in the presence of goethite and dissolved oxygen was the primary reason for the higher As(III) oxidation rate when compared to the As(III)/ferrihydrite system. The surface area-normalized pseudo-first-order rate constant, for example, associated with the heterogeneous oxidation of Fe(II) by dissolved oxygen in the presence of goethite (1.9 × 10(-6) L s(-1) m(-2)) was experimentally determined to be considerably higher than if ferrihydrite was present (2.0 × 10(-7) L s(-1) m(-2)) at a solution pH of 5.     

Inhibition of corn oil oxidation by N-acetyl-cysteine and glutathione

The ability of N-acetyl-cysteine and glutathione to inhibit the oxidation of corn oil was evaluated.     

Inhibition of cholesterol oxidation in marinated foods as affected by antioxidants during heating

Chinese marinated foods rich in cholesterol, such as eggs and pork, can be susceptible to formation of carcinogenic cholesterol oxidation products (COPs) during prolonged heating. The objectives of this study were to compare the effects of various antioxidants on the inhibition of COPs in marinated eggs, pork and juice. The various COPs in marinated food samples were analyzed by a GC–MS technique. The incorporation of antioxidants, vitamin C, vitamin E, BHA and trolox were all effective in inhibiting COPs formation, with vitamin C being the most pronounced in marinated eggs, and BHA in marinated pork and juice. The inhibition effect increased with increasing levels of BHA and trolox. However, vitamin E was more effective at a low level (0.02%) than at a high level (0.1%), probably because of prooxidant activity of the latter. The same phenomenon also occurred for 0.1% vitamin C in marinated eggs, but a reversed trend was observed in marinated pork and juice. The residual amounts of each antioxidant in marinated eggs, pork and juice were also determined by HPLC.     

Catalytic mechanisms of metmyoglobin on the oxidation of lipids in phospholipid liposome model system

The catalytic mechanism of metmyoglobin (metMb) on the development of lipid oxidation in a phospholipid liposome model system was studied. Liposome model system was prepared with metMb solutions (2.0, 1.0, 0.5, and 0.25 mg metMb/mL) containing none, diethylenetriamine pentaacetic acid (DTPA), desferrioxamine (DFO), or ferric chloride and lipid oxidation was determined at 0, 15, 30, 60, and 90 min of incubation at 37 °C. Metmyoglobin catalysed lipid oxidation in the liposome system, but the rate of lipid oxidation decreased as the concentration of metMb increased. The amount of free ionic iron in the liposome solution increased as the concentration of metMb increased, but the rate of metMb degradation was increased as the concentration of metMb decreased. The released free ionic iron was not involved in the lipid oxidation of model system because ferric iron has no catalytic effect without reducing agents. Both DFO and DTPA showed antioxidant effects, but DFO was more efficient than DTPA because of its multifunctional antioxidant ability as an iron and haematin chelator and an electron donor. The antioxidant activity of DTPA in liposome solution containing 0.25 mg metMb/mL was two times greater than that with 2 mg metMb/mL due to the increased prooxidant activity of DTPA-chelatable compounds. It was concluded that ferrylmyoglobin and DTPA-chelatable haematin generated from the interaction of metMb and LOOH, rather than free ionic iron, were the major catalysts in metMb-induced lipid oxidation in phospholipid liposome model system.     

Polyoxometalate-enhanced oxidation of organic compounds by nanoparticulate zero-valent iron and ferrous ion in the presence of oxygen

In the presence of oxygen, organic compounds can be oxidized by zerovalent iron or dissolved Fe(II). However, this process is not a very effective means of degrading contaminants because the yields of oxidants are usually low (i.e., typically less than 5% of the iron added is converted into oxidants capable of transforming organic compounds). The addition of polyoxometalate (POM) greatly increases the yield of oxidants in both systems. The mechanism of POM enhancement depends on the solution pH. Under acidic conditions, POM mediates the electron transfer from nanoparticulate zerovalent iron (nZVI) or Fe(II) to oxygen, increasing the production of hydrogen peroxide, which is subsequently converted to hydroxyl radical through the Fenton reaction. At neutral pH values, iron forms a complex with POM, preventing iron precipitation on the nZVI surface and in bulk solution. At pH 7, the yield of oxidant approaches the theoretical maximum in the nZVI/O2 and the Fe(II)/O2 systems when POM is present, suggesting that coordination of iron by POM alters the mechanism of the Fenton reaction by converting the active oxidant from ferryl ion to hydroxyl radical. Comparable enhancements in oxidant yields are also observed when nZVI or Fe(II) is exposed to oxygen in the presence of silica-immobilized POM.     

Mechanistic aspects of pyrite oxidation in an oxidizing gaseous environment: an in situ HATR-IR isotope study

The reaction of FeS2 (pyrite) with gaseous H2O, O2, and H2O/O2 was investigated using horizontal attenuated total reflection Fourier transform infrared spectroscopy (HATR-FTIR). Spectra were interpreted with the aid of hybrid molecular orbital/density functional theory calculations of sulfate-iron hydroxide clusters. Reaction of pyrite in gaseous H2O led primarily to the formation of iron hydroxide on pyrite. Exposure of the pyrite to gaseous O2 after exposure to H2O vapor led to the formation of sulfur oxyanions that included SO42-. Isotopic labeling experiments showed that after this exposure sequence the oxygen in the sulfate product was primarily derived from the H2O reactant. If, however, pyrite was exposed to gaseous O2 prior to pure H2O vapor, both SO42- and iron oxyhydroxide became significant products. Isotopic rabeling experiments using the O2-then-H2O sequence showed that the oxygen in the SO42- product was derived from both H2O and O2. The results indicate that H2O and O2 exhibit a competitive adsorption on pyrite, with H2O blocking surface sites for O2 adsorption. The extent of oxygen incorporation from either the H2O or the O2 component into the surface-bound sulfur oxyanion product appears to be a strong function of the relative concentration ratio of the reactant H2O and O2.     

Photoinduced oxidation of antimony(III) in the presence of humic acid

Interactions of antimony with natural organic matter (NOM) are important for the fate of Sb in aquatic systems. The kinetics of the photosensitized oxidation of Sb(III) to Sb(V) in the presence of Suwannee River Humic Acid (SRHA) was investigated using UV-A and visible light (medium-pressure mercury lamp). At a concentration of 5 mg L(-1) dissolved organic carbon (DOC) the light-induced reaction was 9000 times faster (rate coefficient k(exp) = 7.0 +/- 0.05 x 10(-4) s(-1)) than the dark reaction and followed pseudo-first-order kinetics. Rates increased linearly with the concentration of DOC. Between pH 4 and 8 rates increased by a factor of 5. Further results and kinetic considerations indicate that singlet oxygen, hydroxyl radicals, hydrogen peroxide, and hydroperoxyl radicals/superoxide are not important photooxidants in this system, while other NOM-derived reactive species, in particular excited triplet states and/or phenoxyl radicals, seem to be relevant. The dependence of rate coefficients on Sb(III)/DOC ratio was consistent with a two binding site model including (i) a strong binding site at low concentration inducing fast oxidation, (ii) a weak binding site at high concentration inducing slower oxidation, and (iii) the even slower oxidation of Sb(OH)3. Photoirradiation of natural water samples spiked with Sb(III) showed that the oxidation rates could be well predicted based on DOC.     

Inhibition of oxidation of omega-3 polyunsaturated fatty acids and fish oil by quercetin glycosides

The antioxidant properties of naturally occurring flavonols, quercetin glycosides, were examined and compared with common food antioxidants butylated hydroxytoluene (BHT) and α-tocopherol. Antioxidants were incorporated into selected polyunsaturated fatty acids (PUFA) or fish oil in aqueous emulsions and bulk oil systems. The effectiveness of quercetin was similar to or greater than quercetin glycosides in inhibiting lipid oxidation in the oil-in-water emulsion systems when oxidation was induced by heat, light, peroxyl radical or ferrous ion. In bulk fish oil, C-3 glycosylation enhanced the antioxidant activity of quercetin. The effectiveness of quercetin and its glycosides was greater than that of α-tocopherol in the emulsions. Quercetin and quercetin-3-O-glucoside exhibited a better antioxidant activity than BHT in bulk fish oil; however, the reverse was observed in the emulsions of omega-3 PUFA and fish oil systems in agreement with the polar paradox theory. Quercetin and its glycosides were more effective than α-tocopherol in emulsion systems.