Degradation and Mineralization of Simazine in Aqueous Solution by Ozone/Hydrogen Peroxide Advanced Oxidation

Advanced oxidation of simazine in aqueous solution by the peroxone (hydrogen peroxide/ozone) treatment was investigated using Box-Behnken statistical experiment design and response surface methodology. Effects of pH, simazine and H2O2 concentrations on percent simazine and total organic carbon (TOC) removals were investigated. Ozone concentration was kept constant at 45?mg?L?1. The optimum conditions yielding the highest simazine and TOC removals were also determined. Both simazine and peroxide doses affected simazine removal while pH and pesticide dose had more pronounced effect on mineralization (TOC removal) of simazine. Nearly 95% removal of simazine was achieved within 5 min for simazine and peroxide concentrations of 2.0 and 75?mg?L?1, respectively at pH = 7. However, mineralization of simazine was not completed even after 60 min at simazine doses above 2?mg?L?1 indicating formation of some intermediate compounds. The optimum H2O2/pH/Simazine ratio resulting in maximum pesticide (94%) and TOC removal (82%) was found to be 75/11/0.5(mg?L?1).     

Modeling the Transformation of Chromophoric Natural Organic Matter during UV/H2O2 Advanced Oxidation

This research developed a differential kinetic model to predict the partial degradation of natural organic matter (NOM) during ultraviolet plus hydrogen peroxide (UV/H2O2) advanced oxidation treatment. The absorbance of 254?nm UV, representing chromophoric NOM (CNOM) was used as a surrogate to track the degradation of NOM. To obtain reaction rate constants not available in the literature, i.e., reactions between the hydroxyl radical (?OH) and NOM, experiments were conducted with “synthetic” water, using isolated Suwannee River NOM, and parameter estimation was applied to obtain the unknown model parameters. The reaction rate constant for the reaction between ?OH and total organic carbon (TOC), k?OH,TOC, was estimated at 1.14(±0.10)×104??L?mg-1?s-1, and the reaction rate constant between ?OH and CNOM, k?OH,CNOM, was estimated at 3.04(±0.33)×104??L?mol-1?s-1. The model was evaluated on two natural waters to predict the degradation of CNOM and H2O2 during UV/H2O2 treatment. Model predictions of CNOM degradation agreed well with the experimental results for UV/H2O2 treatment of the natural waters, with errors up to 6%. For the natural water with additional alkalinity, the model also predicted well the slower degradation of CNOM during UV/H2O2 treatment, owing to scavenging of ?OH by carbonate species. The model, however, underpredicted the degradation of H2O2, suggesting that, when NOM is present, mechanisms besides the photolysis of H2O2 contribute appreciably to H2O2 degradation.     

Advanced Oxidation of Diuron by Photo-Fenton Treatment as a Function of Operating Parameters

Advanced oxidation of diuron in aqueous solution by photo-Fenton treatment was investigated by batch experiments. Effects of operating parameters, namely, the concentrations of pesticide (diuron), hydrogen peroxide (H2O2), and ferrous ion [Fe (II)] on oxidation of diuron were investigated by using Box-Behnken statistical experiment design and the response surface methodology. Diuron oxidation by photo-Fenton treatment was evaluated by determining the total organic carbon (TOC), diuron, and adsorbable organic halogen (AOX) removals. Concentration ranges of the reagents resulting in the highest level of diuron oxidation were determined. Diuron removal increased with increasing H2O2 and Fe (II) concentrations, up to a certain level. H2O2 concentration had a more profound effect than diuron and Fe (II) on removal of diuron, TOC, and AOX from the aqueous solution. Complete (100%) disappearance of diuron was achieved after a 15?min reaction period. However, 85% of diuron was mineralized after 240?min, indicating a low level of intermediate formation. Optimal H2O2/Fe (II)/diuron ratio resulting in maximum diuron (100%), TOC (85%), and AOX (100%) removals was found to be 267/36/25?(mg?L?1).     

Comparison of Aniline Oxidation by Electro-Fenton and Fluidized-Bed Fenton Processes

This study investigated the aniline oxidation at various conditions, namely, pH, H2O2 dose, Fe2+ dose, and aniline concentration, as well as the effects of inorganic ion concentrations on the electro-Fenton and fluidized-bed Fenton processes. Aniline degradation depended on the H2O2 and Fe2+ dose for both processes. The results showed that both processes had the best aniline oxidation efficiency at pH 2.8–3.2. In the electro-Fenton process, approximately 95% of the aniline was removed after 60?min. While the SiO2 carrier contents of fluidized-bed Fenton process was adjusted to 74??g/L, the aniline was gradually removed, and the degradation rate finally reached 83%. The inhibition effect of phosphate ions on aniline oxidation on both processes was more significant than that of chloride ions. Chloride ions have higher inhibition ability on aniline oxidation in the fluidized-bed Fenton process than in the electro-Fenton process. However, the inhibition of phosphate ions on aniline oxidation in the electro-Fenton process was more obvious than in the fluidized-bed Fenton process.     

贵州鲕状赤铁矿的氢气还原行为

在800～1100℃范围内、H2体积分数为99.99％的气氛条件下,采用气基直接还原工艺对贵州鲕状赤铁矿进行了恒温还原研究,使用X射线衍射仪和光学显微镜对还原产物进行了表征,通过阿伦尼乌斯公式计算了还原反应的表观活化能,并采用未反应核模型判断了还原反应的限制性环节.结果表明:当还原温度为1100℃,还原时间为150 min,二元碱度为1.0时,可以获得金属化率为91.15％的直接还原产物,原矿中加入CaO促进了FeAl2O4和Fe2SiO4的还原,是还原产物金属化率提高的主要原因.动力学结果表明:原矿在900～1 100℃的还原过程中受气体内扩散控制,其表观活化能为18.95 kJ/mol,并且在典型气体内扩散范围内.     

Predicting Fenton-Driven Degradation Using Contaminant Analog

The reaction of hydrogen peroxide (H2O2) and Fe(II) (Fenton's reaction) generates hydroxyl radicals (?OH) that can be used to oxidize contaminants in soils and aquifers. In such environments, several factors can limit the effectiveness of chemical oxidation, including reactions involving H2O2 that do not yield ?OH, ?OH reactions with nontargeted chemicals, and insufficient iron in the soil or aquifer. Consequently, site-specific studies may be necessary to evaluate the feasibility of chemical oxidation using H2O2. Here, the degradation of a contaminant analog, α-(4-pyridyl-1-oxide) N-tert-butylnitrone (4POBN), was used to estimate ?OH concentration and simplify testing procedures. A kinetic model was developed, calibrated using 4POBN degradation kinetics, and used to predict the disappearance of 2-chlorophenol (2CP), a representative target. Good agreement between predicted (Y) and measured (X) values for 2CP (Y = 0.95X) suggests that the kinetics of analog degradation can be used to predict the degradation rate of compounds for which the rate constant for reaction with ?OH is known.     

Treatment of TCE-Contaminated Groundwater Using Fenton-Like Oxidation Activated with Basic Oxygen Furnace Slag

The industrial solvent trichloroethylene (TCE) is among the ubiquitous chlorinated organic compounds found in groundwater contamination. The objective of this study was to evaluate the potential of applying basic oxygen furnace (BOF) slag as the catalyst to enhance the Fenton-like oxidation to remediate TCE-contaminated groundwater. Results indicate that TCE oxidation via the Fenton-like process can be enhanced with the addition of BOF slag. Results from the X-ray powder diffraction analysis reveal that the major iron type of BOF slag/quartz sand media was iron oxyhydroxide (α-Fe2O3). Approximately 81% of TCE removal was observed (with initial TCE concentration of approximately 5?mg?L?1), with the addition of 1,000?mg?L?1 of H2O2 and 10?g?L?1 of BOF slag. Results also show that TCE concentrations dropped from 5 to 1.1?mg?L?1, and chloride concentrations increased from 0 to 2.7?mg?L?1 after 60 min of reaction with the presence of H2O2 and BOF slag. This indicates that the depletion of TCE corresponded with the oxidation reactions and release of chloride ions very well in this study. Results demonstrate that the BOF slag can be used to supply catalysts continuously, and it can be installed in a permeable barrier system to enhance the Fenton-like process in situ.     

Iron-Activated Persulfate Oxidation of an Azo Dye in Model Wastewater: Influence of Iron Activator Type on Process Optimization

The study explores the potential of iron-activated persulfate oxidation of an azo dye in model wastewater. The influence of the type of iron activator on process efficiency was investigated by using ferrous and zero valent iron. The Box-Behnken experimental design and response surface methodology were applied for the modeling of the Fe2+/S2O82- and Fe0/S2O82- processes. The combined effect of three important process parameters was investigated and presented by the means of the quadratic polynomial model. The statistical analysis of model performance was evaluated by ANOVA. The optimal process conditions giving the maximal mineralization for both processes were determined: pH 4.81, [Fe2+] = 1.64??mM, and [S2O82-] = 84.87??mM predicting 35.14% mineralization and pH 5.52; [Fe0] = 4.27??mM and [S2O82-] = 138.43mM predicting 54.38% mineralization by the Fe2+/S2O82- and Fe0/S2O82- processes, respectively. The predicted values of dye mineralization obtained by model equations were in good agreement with the experimental values. The type of iron activator was demonstrated to significantly influence both process efficiency and optimal conditions.     

渣系碱度对含碳球团渣相组成和渣铁分离的影响

采用煤基直接还原熔分技术和FactSage热力学分析软件以及XRD分析手段,研究了渣系碱度wCaO/wSiO2对高铁铝土矿含碳球团渣相组成和渣铁分离效果的影响。实验结果表明,渣系碱度对含碳球团的渣系组成和渣铁分离效果有重要影响。当碱度为1.0和1.5时,粒铁尺寸最大,渣铁的分离效果最好,粒铁收得率分别为91.55%和91.86%;当碱度为0.5时,粒铁尺寸较小,渣铁分离效果较差,粒铁收得率为65.43%。当碱度为2.0时;粒铁尺寸最小,渣铁分离效果最差,粒铁收得率只有44.53%。XRD分析结果表明,当渣系碱度分别为0.5、1.0、1.5和2.0时,熔分渣的主要组成分别为α-Al2O3-CaAl2Si2O8、α-Al2O3-CaO·6Al2O3-Ca2Al2SiO7、CaO·6Al2O3-Ca2SiO4-Ca2Al2SiO7、Ca2Al2SiO7-Fe2SiO4。FeAl4O7、CaAl4O7以及金属铁在熔分渣中的含量较少。     

Photocatalytic Degradation of Orange II in Aqueous Iron-Rich Montmorillonite Solutions

In this work the photodegradation of orange II was carried out in the presence of iron-rich montmorillonite (MMt) (2.24% Fe2O3) using a 15-W low-pressure ultraviolet lamp (λ = 254?nm,?I = 48.4?μW/cm2). The effects of pH, MMt dose, and dye concentration were studied. A low pH value is favorable for the decolorization of orange II. The hydroxyl radical (?OH) concentration increased with increasing concentration of MMt in aqueous solutions in the range of 0–1.5 g/L. Concentrations higher than 5.0 g/L MMt inhibited the ?OH production. There was no significant decrease in photocatalytic activity when the catalyst was reused. Hydroxyl radicals were detected by tert-butyl alcohol in aqueous MMt suspensions under ultraviolet irradiation and were responsible for the degradation of orange II. Free iron ions dissolved in MMt suspensions, structural iron in the MMt structural and the charged surface of nanoclay are responsible for the hydroxyl radical (?OH) production. Free iron ions dissolved in solution plays a predominant role in the degradation of orange II. This study shows that iron-rich MMt is a potential photocatalyst for dye wastewater treatment.     

Reaction paths of iron oxidation and hydrolysis in horse spleen and recombinant human ferritins

UV-visible spectroscopy, electrode oximetry, and pH stat were used to study Fe(II) oxidation and hydrolysis in horse spleen ferritin (HoSF) and recombinant human H-chain and L-chain ferritins (HuHF and HuLF). Appropriate test reactions and electrode responses were measured, establishing the reliability of oxygen electrode/pH stat for kinetics studies of iron uptake by ferritin. Stoichiometric ratios, Fe(II)/O2 and H+/Fe(II), and rates of oxygen uptake and proton production were simultaneously measured as a function of iron loading of the protein. The data show a clear distinction between the diiron ferroxidase site and mineral surface catalyzed oxidation of Fe(II). The oxidation/hydrolysis reaction attributed to the ferroxidase site has been determined for the first time and is given by 2Fe2+ + O2 + 3H2O --> [Fe2O(OH)2]2+ + H2O2 + 2H+ where [Fe2O(OH)2]2+ represents the hydrolyzed dinuclear iron(III) center postulated to be a mu-oxo-bridged species from UV spectrometric titration data and absorption band maxima. The transfer of iron from the ferroxidase site to the mineral core has been now established to be [Fe2O(OH)2]2+ + H2O --> 2FeOOH(core) + 2H+. Regeneration of protein ferroxidase activity with time is observed for both HoSF and HuHF, consistent with their having enzymatic properties, and is facilitated by higher pH (7.0) and temperature (37 degreesC) and by the presence of L-subunit and is complete within 10 min. In accord with previous studies, the mineral surface reaction is given by 4Fe2+ + O2 + 6H2O --> 4FeOOH(core) + 8H+. As the protein progressively acquires iron, oxidation/hydrolysis increasingly shifts from a ferroxidase site to a mineral surface based mechanism, decreasing the production of H2O2.     

Ozone Degradation of Iodinated Pharmaceutical Compounds

This study investigates the aqueous degradation of four iodinated x-ray contrast media (ICM) compounds (diatrizoate, iomeprol, iopromide, and iopamidol) by ozone and combined ozone and hydrogen peroxide. In laboratory scale experiments, second-order kinetic rate constants for the reactions of the ICM compounds with molecular ozone and hydroxyl radicals, and overall at pH 7.5, were determined. For the four ICM compounds the degradation rate constants with molecular ozone were low and in the range of 1–20?M?1?s?1, whereas the rate constants with hydroxyl radicals were in the range of 1×109–3×109?M?1?s?1. Diatrizoate had the lowest rate constant of the four compounds with respect to molecular ozone reactions. At pH 7.5, the extent of compound degradation was proportional to the applied ozone dose and inversely related to the initial compound concentration at a given ozone dose. At this pH approximately 90% of the degradation could be attributed to hydroxyl radical reactions. Enhancement of the radical mechanism by the addition of hydrogen peroxide during ozonation led to complete removal of the nonionic compounds, and >80% removal of diatrizoate, at relatively low oxidant mass ratios (H2O2/O3<0.25). A similar enhancement in compound degradation was evident with the presence of small concentrations of humic substances ( ～ 4–5?mg?L?1). Ozone oxidation led to major cleavage of the ICM compounds and the release of inorganic iodine; the proportion of iodine release was similar among the nonionic ICM compounds but much greater for diatrizoate.     

Fenton and Electro-Fenton Methods for Oxidation of H-Acid and Reactive Black 5

Oxidative treatment of H-acid (HA) and Reactive Black 5 (RB5) using Fenton reagent (Fe2+/H2O2) and the electro-Fenton (EF) method is reported. Optimization of doses of ferrous iron and hydrogen peroxide was carried out in each case using HA; and the oxidation of RB5 was also carried out under the optimized conditions. Approximately 71% chemical oxygen demand (COD) was removed in 2 h using the conventional Fenton method at optimized doses: Fe2+ = 0.3?g/L (5.37 mM), H2O2 = 6?mL/L (53.0 mM), H2O2/Fe2+ = 10. In contrast, more than 92% COD was removed in 15 min using the EF method with an optimized Fe2+ dose of 0.130?g/L (2.34 mM) and 8?ml/L (70.6 mM) of H2O2. The pseudo-first-order rate constants (k) for the Fenton reagent and EF method were 0.054 and 0.38?min?1. The COD removal through the EF method was seven times faster. The calculated energy requirement of the EF method was 0.82?kg?COD/kW?h at the minimum applied current (0.25 A) when approximately 92.5% COD was removed. In the case of RB5, about 67 and 87% COD was removed under optimized Fenton and electro-Fenton conditions, respectively. The higher efficiency of the EF method was attributed to incremental addition of Fe2+ and accompanying higher H2O2/Fe2+ molar ratio. The results are discussed in the light of the mechanism for Fenton’s oxidation.     

Environmental Factors and the Application of Hydrogen Peroxide for the Removal of Toxic Cyanobacteria from Waste Stabilization Ponds

Toxin-producing cyanobacteria constitute a serious threat to human and environmental health. It is thus essential that an effective treatment guarantees the removal of cyanobacteria from wastewater before its inclusion in water recycling or environmental flow. Hydrogen peroxide (H2O2) has been shown to induce cyanobacterial decay in laboratory cultures. However, its application for the removal of cyanobacteria from wastewater treatment ponds under environmental conditions has not been investigated. To examine the effects of environmental factors, field trials were performed at both the mesocosm and full-scale levels. The mesocosm trial was completed under field conditions of incident radiation, with various H2O2 concentrations. A concentration of 1.1×10-4??gH2O2/μg chl-a resulted in a 32% decrease in cyanobacterial concentration after 24?h, and this approximate concentration was then applied to a wastewater treatment pond in the full-scale trial. In the full-scale experiment, intense spatial and temporal monitoring of phytoplankton concentrations and temperature throughout the pond was performed. Cyanobacterial biomass was reduced by 57% and total phytoplankton biomass by 70% within 48?h of H2O2 addition. Mixing and radiation were shown to control the depth reached by H2O2 following addition to the ponds. The synergistic effect of H2O2 addition with environmental factors increased the effectiveness of cyanobacterial removal compared with laboratory experiments. The concentration of H2O2 required for the removal of cyanobacteria under field conditions may be decreased from laboratory studies by an order of magnitude.     

利用含锌粉尘和铁鳞中锌和铁制备合成Ni-Zn铁氧体

以电炉粉尘(EAFD)中提取的Zn2+、铁鳞中提取的Fe3+和六水合氯化镍(NiCl2·6 H2 O)为原料,采用水热法直接制备合成尖晶石型Ni-ZnFe2 O4.首先探讨了焙烧温度、NaOH与EAFD质量比和焙烧时间对电炉粉尘中Zn2+提取率以及HCl浓度对铁鳞中Fe3+浸出率的影响,然后分析了Ni-ZnFe2 O4...     

锌精矿浸出液中铟铁分离工艺研究

利用软锰矿在酸性(硫酸体系)条件下氧化浸出闪锌矿,对其浸出液进行萃取铟分离铁。以P507-煤油为萃取体系,考察酸度、萃取剂的浓度、温度、相比(体积比)、时间等对铟铁萃取率的影响。在室温条件下,酸度1.5 mol/L、P507体积分数30%、萃取相比1∶1、萃取时间10 min、铟的一级萃取率可达到99%以上,而铁的一级萃取率为20%。对负载有机相进行草酸(30 g/L)洗涤,铁洗涤率为99.99%,而铟的洗涤率仅为0.000 1%。达到了萃取富集铟分离杂质的目的。     

Pretreatment by Fenton Oxidation of an Amoxillin Wastewater

Relatively few reported works have dealt with wastewaters arising from amoxillin manufacture. To develop a treatment process for one such wastewater, several physicochemical methods such as coagulation, ultrafiltration, and Fenton oxidation (FO), have been investigated. Among these methods, FO proved effective. Consequently the method was further investigated to identify the appropriate H2O2/FeSO4 ratio, FeSO4 and H2O2 concentrations, and reaction pH and temperature. In relation to the wastewater, a suitable H2O2/FeSO4 weight ratio was 5:1 (molar ratio: 22.4:1) with H2O2 and FeSO4 concentrations at 20?g/L, 4?g/L, respectively. The corresponding pH range was 2.0–4.0 while the reaction temperature was 60°C. Given these conditions, wastewater total organic carbon was reduced by 48.8–49.4%. After FO treatment, reverse osmosis (RO) effectively reduced the dissolved salt content. The contribution of FO and RO pretreatment improved the wastewater’s biodegradability thus making a downstream biotreatment polishing process viable.     

Gliotoxicity, reverse transcriptase activity and retroviral RNA in monocyte/macrophage culture supernatants from patients with multiple sclerosis

Utilizing cultured lenses from normal and homozygous glutathione peroxidase (GSHPx-1) knockout mice and inhibitors for GSSG Reductase (GSSG Red), 1,3-bis(2-chlorethyl)-1-nitrosourea (BCNU) and catalase (Cat), 3-aminotriazole (3-AT), the ability to degrade H2O2 was examined at two H2O2 concentrations, 300 microM and 80 microM. It was found that GSHPx-1 contributed about 15% to the H2O2 degradation. The Cat contribution was concentration dependent being about 30% at 300 microM H2O2 and approximately 8% to 15% at 80 microM H2O2. GSH loss measured as nonprotein thiol (NP-SH) was shown to be linked to most of the remaining H2O2 degradation accounting for about 54% to 72% of the H2O2 degradation at 300 microM and 80 microM, respectively. However, based on evaluation of the ability of GSH to nonenzymatically degrade H2O2, it can only account for about 36% at 300 microM and 19% at 80 microM H2O2 of the observed lens H2O2 degradation. It is, therefore, concluded that lens GSH must be involved in other reactions either directly or indirectly related to H2O2 degradation.     

Oxidative and Reductive Pathways in Manganese-Catalyzed Fenton’s Reactions

Soluble manganese (II) and amorphous and crystalline manganese (IV) oxides were investigated as catalysts for the Fenton-like decomposition of hydrogen peroxide into oxidants and reductants. 1-Hexanol was used as a hydroxyl radical probe and carbon tetrachloride (CT) was used as a reductant probe. Soluble manganese (II)-catalyzed reactions at acidic pH resulted in >99% degradation of 1-hexanol and no measurable transformation of CT, indicating that hydroxyl radicals were generated but reductants were not. However, when these reactions were conducted at near-neutral pH, an amorphous manganese oxide precipitate formed and 89% of the CT degraded in 60?min, while 1-hexanol degradation was negligible. Using an amorphous manganese oxide synthesized in a separate reactor, CT was rapidly degraded while 1-hexanol oxidation was undetectable. Reactions catalyzed by the crystalline manganese oxide pyrolusite(β-MnO2) at near-neutral pH also resulted in significant CT degradation, indicating that reductants are generated by both the crystalline and amorphous manganese oxide-catalyzed decomposition of H2O2. The presence of manganese oxides in the subsurface and their ability to catalyze the generation of reductants in modified Fenton’s reactions has important implications for hydrogen peroxide stability and contaminant transformation pathways during the in situ Fenton’s treatment of contaminated soils and groundwater.     

Transformation of DDT and Its Metabolites by Various Abiotic Methods

This work looks at several new abiotic treatment methods for transformation of DDT in an aqueous solution. Various combinations of calcium peroxide (CaO2), zero-valent iron (Fe0), iron sulfide (FeS), and hydrogen peroxide (H2O2) were utilized to promote the abiotic transformation of 1,1,1-trichloro-2,2-bis(p-chlorophenyl)ethane (DDT) in electrolyte, hydroquinone, and nonionic surfactant (Triton X-114) systems. Treatment with CaO2 resulted in 86% DDT mass reduction within 10?days of treatment with only traces of 1,1-dichloro-2,2-bis(p-chlorophenyl)ethane (DDD) , 1,1-dichloro-2,2-bis(p-chlorophenyl)ethylene (DDE), and 1,1-dichloro-2,2-bis(4-chlorophenyl)ethylene (DDMU) being generated. Treatments with 1:1 mixtures of Fe0:CaO2 and FeS:CaO2 resulted in 86 and 85% DDT mass transformation, respectively, within 8?days. A mixture of 0.75?g?Fe0:0.1?g?CaO2 showed similar results with 79% DDT mass transformed within 8?days. A mixture of 0.75–0.1?g of Fe0:FeS resulted in 85 and 97% transformation in the total mass of DDT in an electrolyte solution and a hydroquinone solution, respectively. The treatment of DDT in aqueous solution by CaO2, in the presence of Triton X-114, resulted in the transformation of 97% of the total mass of DDT within 30?days, albeit, large amounts of DDE (402?μM) were generated.