Study of the Oxidation Rate of Fe<Superscript>2+</Superscript> Ions in Water during Air Bubbling

The influence of the specific surface area of air bubbles in the process of bubbling on the oxidation rate of Fe²⁺ ions of model solutions prepared using distilled water with the addition of Fe²⁺ ions in the form of iron(II) sulfate (pure grade). The dependences of the rate of Fe²⁺ oxidation in water during air bubbling have been found.     

Comparison between Fenton oxidation process and electrochemical oxidation for PAH removal from an amphoteric surfactant solution

The decomposition of polycyclic aromatic hydrocarbons in a creosote oily solution and in synthetic solutions containing naphthalene and pyrene was investigated in the presence of an amphoteric surfactant using electrooxidation by comparison to Fenton oxidation process. Electrolysis was carried out using a parallelepipedic electrolytic 1.5-L cell containing five anodes (expanded titanium covered with ruthenium) and five cathodes (stainless steel) alternated in the electrode pack, whereas Fenton oxidation process was carried out in 500 mL Erlenmeyer glass-flasks in which H₂O₂ and Fe²⁺ were added. Using electrochemical oxidation, the sum concentration of 16 polycyclic aromatic hydrocarbons investigated could be optimally diminished by up to 80–82% by applying a current density of 9.23 mA cm⁻² and a pH of 4.0 or 7.0 for 90-min reaction period. By comparison, the best yield (46%) of Fenton oxidation process for polycyclic aromatic hydrocarbons degradation was recorded by using H₂O₂/Fe²⁺ molar ratio of 11.0 and a pH of 4.0.     

Removal of metsulfuron methyl by Fenton reagent

The removal of metsulfuron methyl (MeS)—a sulfonyl urea herbicide from contaminated water was investigated by advanced oxidation process (AOP) using Fenton method. The optimum dose of Fenton reagent (Fe²⁺/H₂O₂) was 10 mg/L Fe²⁺ and 60 mg/L H₂O₂ for an initial MeS concentration ([MeS]₀) range of 0–80 mg/L. The Fenton process was effective under pH 3. The degradation efficiency of MeS decreased by more than 70% at pH > 3 (pH 4.5 and 7). The initial Fe²⁺ concentration ([Fe²⁺]₀) in the Fenton reagent affected the degradation efficiency, rate and kinetics. The degradation of MeS at optimum dose of Fenton reagent was more than 95% for [MeS] ₀ of 0–40 mg/L and the degradation time was less than 30 min. The determination of residual MeS concentration after Fenton oxidation by UV spectrophotometry was affected by the interferences from Fenton reagent. The estimation of residual MeS concentration after Fenton oxidation by high pressure/performance liquid chromatograph (HPLC) was interference free and represented the actual concentration of MeS and does not include the by-products of Fenton oxidation. The degradation kinetics of MeS was modelled by second order reactions involving 8 rate constants. The two reaction constants directly involving MeS were fitted using the experimental data and the remaining constants were selected from previously reported values. The model fit for MeS and the subsequent prediction of H₂O₂ were found to be within experimental error tolerances.     

Synthesis and photophysical behavior of a water-soluble fluorescein-bearing polymer for Fe<Superscript>3+</Superscript> ion sensing

An acrylic monomer bearing xanthene group, acryloylfluorescein (Ac-Flu) was synthesized from fluorescein and acryloyl chloride in the presence of triethylamine in dry dichloromethane (CH₂Cl₂) at room temperature. The synthesized Ac-Flu was identified by IR, MS and ¹HNMR spectra. Copolymer of Ac-Flu and acrylamide (AM) was synthesized with thermal initiator and it was characterized by the method of IR, UV–Vis and DSC. The photophysical behaviors of Ac-Flu and its copolymer were explored by recording the fluorescence spectra in solution, solid state and film in detail. In addition, the ability of the copolymer to detect different metal cations (Mn²⁺, Fe³⁺, Fe²⁺, Co²⁺, Ni²⁺, Cu²⁺, Zn²⁺) in aqueous solution was investigated. The results showed that poly(Ac-Flu-co-AM) had a good linear response between the logarithm of concentration of Fe³⁺ (lg[Fe³⁺]) against the relative fluorescence intensity for Fe³⁺ concentration. The results suggest that this copolymer may offer potential as a reusable polymer sensor for Fe³⁺ ion in aqueous solution.     

Influence of process variables on biooxidation of ferrous sulfate by an indigenous Acidithiobacillus ferrooxidans. Part II: Bioreactor experiments

The oxidation of ferrous iron in solution using Acidithiobacillus ferrooxidans has industrial applications in the regeneration of ferric iron as an oxidant agent for the removal of hydrogen sulfide from waste gases, desulphurization of coal, leaching of non-ferrous metallic sulfides and treatment of acid mine drainage. The aim of this attempt was to increase the biooxidation rate of ferrous sulfate by using immobilized cells. Rate of ferrous iron oxidation was determined in a packed-bed reactor configuration with low density polyethylene (LDPE) particles as support material in order to find the most practical system for scale-up. The present work studies the influence of basic parameters on the ferrous iron biooxidation process using an indigenous iron-oxidizing microorganism, namely A. ferrooxidans, in a 2 L packed-bed bioreactor. Effects of several process variables such as initial pH, temperature, dilution rate, initial concentrations of ferrous and ferric ions on oxidation of ferrous sulfate were investigated. Experimental results indicate that in the temperature range of 31–34 °C the biooxidation of ferrous ions to ferric ions could be resulted efficiently. A pH range of 2–2.2 was optimum for the growth of the culture and effective bacterial activity for oxidation of ferrous ions to ferric ions. The highest oxidation rate of 2.9 g Fe²⁺ L⁻¹ h⁻¹ was obtained using a culture initially containing 25 g L⁻¹ Fe⁺² at the dilution rate of 0.4 h⁻¹. This rate is very high compared to that achieved in other bioreactors found in the literature. In addition the biooxidation of Fe²⁺ to Fe³⁺ conversion could be achieved effectively in the presence of the Fe³⁺ in the concentration range of 0.1–0.7 g/L.     

Optimization of the operating parameters using RSM for the Fenton oxidation process and adsorption on vegetal carbon of MO solutions

This study focused on the application of RSM on the Fenton process and the adsorption of vegetal carbon (VC) to obtain the optimal conditions for the minimization of the colored synthetic wastewater. Methyl orange (MO) with an azo dye was used as the model organic compound. Fenton processes were investigated to establish the optimal conditions. The Fe²⁺/H₂O₂ ratio was studied to establish the major MO degradation when 100 and 200 mg/L of MO were treated. For the adsorption process, to determine the optimal conditions, the principal variables studied were the vegetal carbon mass dosage, degradation time and dye concentration.     

Electrocatalytic activity of [Ru(bpy)<Subscript>3</Subscript>]<Superscript>2+</Superscript> toward guanine oxidation upon incorporation of surfactants and SWCNTs

The homogeneous and mediated oxidation of guanine by [Ru(bpy)₃]²⁺ (2,2′-bipypyridine) in the presence of surfactants and single-walled carbon nanotubes (SWCNTs) has been investigated using cyclic voltammetry, repetitive differential pulse voltammetry and rotating electrode method. In acidic medium, the oxidation of guanine was controlled by mass transport process of [Ru(bpy)₃]²⁺ in solution, leading to a homogeneous electrocatalysis. In neutral medium, the result from emission spectroscopy suggested the formation of the aggregates containing [Ru(bpy)₃]²⁺, dihexadecyl phosphate (DHP) and guanine. The electrocatalysis of [Ru(bpy)₃]²⁺ toward guanine oxidation was promoted by anionic surfactant DHP and, however, hindered by an excess amount of hexadecyl trismethyl ammonium chloride (HTAC) or SWCNTs added to solutions. The electrocatalytic mechanism of [Ru(bpy)₃]²⁺ for guanine oxidation becomes evident, strongly depending on the presence of anionic or cationic surfactants and SWCNTs.     

Solar photoassisted anodic oxidation of carboxylic acids in presence of Fe using a boron-doped diamond electrode

This paper reports a comparative study on the anodic oxidation of 2.5 l of 50 mg l⁻¹ TOC of formic, oxalic, acetic, pyruvic or maleic acid in 0.1 M Na₂SO₄ solutions of pH 3.0 with and without 1.0 mM Fe³⁺ as catalyst in the dark or under solar irradiation. Experiments have been performed with a batch recirculation flow plant containing a one-compartment filter-press electrolytic reactor equipped with a 20 cm² boron-doped diamond (BDD) anode and a 20 cm² stainless steel cathode, and coupled to a solar photoreactor. This system gradually accumulates H₂O₂ from dimerization of hydroxyl radical (OH) formed at the anode surface from water oxidation. Carboxylic acids in direct anodic oxidation are mainly oxidized by direct charge transfer and/or OH produced on BDD, while their Fe(III) complexes formed in presence of Fe³⁺ can also react with OH produced from Fenton reaction between regenerated Fe²⁺ with electrosynthesized H₂O₂ and/or photo-Fenton reaction. Fast photolysis of Fe(III)-oxalate and Fe(III)-pyruvate complexes under the action of sunlight also takes place. Chemical and photochemical trials of the same solutions have been made to better clarify the role of the different catalysts. Solar photoassisted anodic oxidation in presence of Fe³⁺ strongly accelerates the removal of all carboxylic acids in comparison with direct anodic oxidation, except for acetic acid that is removed at similar rate in both cases. This novel electrochemical advanced oxidation process allows more rapid mineralization of formic, oxalic and maleic acids, without any significant effect on the conversion of acetic acid into CO₂. The synergistic action of Fe³⁺ and sunlight in anodic oxidation can then be useful for wastewater remediation when oxalic and formic acids are formed as ultimate carboxylic acids of organic pollutants, but its performance is expected to strongly decay in the case of generation of persistent acetic acid during the degradation process.     

Characterization of nanostructured allophane clays and their use as support of iron species in a heterogeneous electro-Fenton system

Nanostructured allophane clays supported with iron oxide (AlSi2Fe6) were characterized by X-ray photoelectron spectroscopy (XPS) and Mössbauer spectroscopy showing the presence of both Fe^3 + and Fe^2 + species on the allophane surface. A glassy carbon disk (GC) modified with a film obtained by the deposition of drops of a dispersion formed by graphite and AlSi2Fe6 in water was used as working electrode in a heterogeneous electro-Fenton system (HE-Fenton) for the oxidation of atrazine. The effect of the initial pHs and the proportion of AlSi2Fe6/graphite in the mixture were studied and compared with the heterogeneous Fenton process. The HE-Fenton system using AlSi2Fe6-GC electrodes showed higher efficiency towards the oxidation of atrazine than the heterogeneous Fenton one; mainly due to the continuous and simultaneous electro-regeneration of iron species (Fe^3 +/Fe^2 +) and electro-generation of hydrogen peroxide by the oxygen reduction process. The degradation of atrazine in this HE-Fenton system reached almost 100% at pH 3.0 after 8 h, whereas at more neutral pH (~ 6) a 76% of degradation was obtained. Two reaction products were identified by HPLC: desethyl-atrazine (DEA) and desethyl-desisopropyl-atrazine (DEIA).     

Functionalized Mesoporous SBA-15 with CeF<Subscript>3</Subscript>: Eu<Superscript>3+</Superscript> Nanoparticle by Three Different Methods: Synthesis,Characterization, and Photoluminescence

Luminescence functionalization of the ordered mesoporous SBA-15 silica is realized by depositing a CeF₃: Eu³⁺ phosphor layer on its surface (denoted as CeF₃: Eu³⁺/SBA-15/IS, CeF₃: Eu³⁺/SBA-15/SI and CeF₃: Eu³⁺/SBA-15/SS) using three different methods, which are reaction in situ (I-S), solution impregnation (S-I) and solid phase grinding synthesis (S-S), respectively. The structure, morphology, porosity, and optical properties of the materials are well characterized by X-ray diffraction, Fourier transform infrared spectroscopy, transmission electron microscopy, N₂ adsorption, and photoluminescence spectra. These materials all have high surface area, uniformity in the mesostructure and crystallinity. As expected, the pore volume, surface area, and pore size of SBA-15 decrease in sequence after deposition of the CeF₃: Eu³⁺ nanophosphors. Furthermore, the efficient energy transfer in mesoporous material mainly occurs between the Ce³⁺ and the central Eu³⁺ ion. They show the characteristic emission of Ce³⁺ 5d → 4f (200–320 nm) and Eu^{3+ 5}D₀ → ⁷F _J (J = 1–4, with ⁵D₀ → ⁷F₁ orange emission at 588 nm as the strongest one) transitions, respectively. In addition, for comparison, the mesoporous material CeF₃: Eu³⁺/SBA-15/SS exhibits the characteristic emission of Eu³⁺ ion under UV irradiation with higher luminescence intensity than the other materials.     

Garlic's ability to prevent <Emphasis Type="Italic">in vitro</Emphasis> Cu<Superscript>2+</Superscript>-induced lipoprotein oxidation in human serum is preserved in heated garlic: effect unrelated to Cu<Superscript>2+</Superscript>-chelation

Background  

It has been shown that several extracts and compounds derived from garlic are able to inhibit Cu²⁺-induced low density lipoprotein oxidation. In this work we explored if the ability of aqueous garlic extract to prevent in vitro Cu²⁺-induced lipoprotein oxidation in human serum is affected by heating (a) aqueous garlic extracts or (b) garlic cloves. In the first case, aqueous extract of raw garlic and garlic powder were studied. In the second case, aqueous extract of boiled garlic cloves, microwave-treated garlic cloves, and pickled garlic were studied. It was also studied if the above mentioned preparations were able to chelate Cu²⁺.     

Effect of Fe<Superscript>3+</Superscript> doping on the performance of TiO<Subscript>2</Subscript> mechanocoated alumina bead photocatalysts

Ferric ion was introduced to the commercial photocatalyst P25 (Degussa) by ultrasonic wet impregnation technique. The concentration of the dopant was varied from 0.0 to 3.0% Fe/Ti ratio. The doped TiO₂ was then loaded to alumina balls using mechanical coating technique and followed by calcination in air at 400, 450, 500 and 550 °C. The fabricated photocatalyst was characterized by X-ray diffraction, N₂ adsorption-desorption isotherms, scanning electron microscopy, UV-Vis diffuse reflectance spectroscopy, X-ray adsorption near edge structure and photoluminescence spectroscopy. The photocatalytic activity was tested by following the degradation of methylene blue (MB). It was found that the Fe³⁺ doped TiO₂/Al₂O₃ has a combination of anatase and rutile phase and free of iron oxide phases. The optimum calcination temperature is 400 °C with 0.1% Fe³⁺ concentration. The catalyst addresses the entrainment in photocatalytic reactors, eliminating the need for a post filtration process.     

UV-LEDs assisted peroxymonosulfate/Fe<Superscript>2+</Superscript> for oxidative removal of carmoisine: The effect of chloride ion

The performance of UVA-LEDs assisted peroxymonosulfate (PMS)/Fe²⁺ system was evaluated on carmoisine (E122) decolorization. Complete color removal was obtained under the conditions of pH=3.0, PMS=1.5 mM, Fe²⁺=1 mM and 25 min reaction time. UVA-LEDs were preferable compared to conventional UVA lamp in terms of decolorization. The functions of Co²⁺, Cu²⁺, Mn²⁺ and Fe²⁺ were compared and their results showed that Co²⁺ and Fe²⁺ had the highest efficiencies. Moreover, the presence of chloride ion showed a double role in different concentrations in which promotional effect was observed in 100 mM Cl^?<, while inhibitory effect occurred in 1–10 mM Cl^?. However, the high concentration of chloride had no influence on mineralization of E122. The scavenging results demonstrated that the UV irradiation increased the contribution of HO^?. In addition, in the presence of chloride ion, HOCl along with sulfate and hydroxyl radicals were the major oxidative agents.     

Study on an iron–manganese Fischer–Tropsch synthesis catalyst prepared from ferrous sulfate

A systematic study was undertaken to investigate the effects of the initial oxidation degree of iron on the bulk phase composition and reduction/carburization behaviors of a Fe–Mn–K/SiO₂ catalyst prepared from ferrous sulfate. The catalyst samples were characterized by powder X-ray diffraction (XRD), Mössbauer spectroscopy, X-ray photoelectron spectroscopy (XPS) and H₂ (or CO) temperature-programmed reduction (TPR). The Fischer–Tropsch synthesis (FTS) performance of the catalysts was studied in a slurry-phase continuously stirred tank reactor (CSTR). The characterization results indicated that the fresh catalysts are mainly composed of α-Fe₂O₃ and Fe₃O₄, and the crystallite size of iron oxides is decreased with the increase of the initial oxidation degree of iron. The catalyst with high content of α-Fe₂O₃ in its as-prepared state has high content of iron carbides after being reduced in syngas. However, the catalyst with high content of Fe₃O₄ in its as-prepared state cannot be easily carburized in CO and syngas. FTS reaction study indicates that Fe-05 (Fe³⁺/Fe_total = 1.0) has the highest CO conversion, whereas Fe-03 (Fe³⁺/Fe_total = 0.55) has the lowest activity. The catalyst with high CO conversion has a high selectivity to gaseous hydrocarbons (C₁–C₄) and low selectivity to heavy hydrocarbons (C₅₊).     

Electro-catalytic degradation of methylene blue wastewater assisted by Fe2O3-modified kaolin

The electrochemical oxidation of methylene blue (MB) wastewater assisted by Fe₂O₃-modified kaolin in a 200 mL electrolytic batch reactor with graphite plate as electrodes was investigated. The catalyst was characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The effects of pH, current density and introduction of NaCl on the efficiency of the electrochemical degradation process were also studied. It was found that Fe₂O₃-modified kaolin has higher catalytic activity in the electrochemical degradation of MB wastewater. 96.47% chemical oxygen demand (COD) removal was obtained in 40 min of electrochemical treatment of MB wastewater at pH 3, current density was equal to 69.23 mA cm⁻².     

3D rectangular WO3 hybridized by PrFeO3 nanoparticles with efficient dual charge transfer for enhanced photo-Fenton-like activity

In this work, zero-dimensional (0D) high crystalline PrFeO₃ worm nanocrystals were loaded over a three-dimensional (3D) rectangular WO₃ to construct a 0D/3D PFO/W Z-scheme heterojunction by an in situ ultrasonic synthetic process. This heterojunction exhibited excellent photocatalytic activities towards the degradation of organic pollutants such as rhodamine B (RhB), Methylene blue (MB), and tetracycline hydrochloride (TC) in the presence of small amounts of H₂O₂ under visible-light irradiation. For example, the k value of PFO/W + H₂O₂ was about 67, 107, 45, 27, 11 and 14 times higher than pure H₂O₂, PrFeO₃, WO₃, PFO/W nanocomposite, PrFeO₃+ H₂O₂ and WO₃+H₂O₂ respectively during the degradation of MB. The trapping experiments and ESR measurements identified that the generated ·OH, ·O₂⁻, and h⁺ were the active species involved in the catalysis. Further, the ·OH radical could be continuously generated by Fe³⁺/Fe²⁺ and W⁶⁺/W⁵⁺ conversion and played the dominant role in the degradation of organic pollutants. The superior photocatalytic performance of the PFO/W + H₂O₂ system was derived from the synergistic effect of the Z-scheme heterostructure and dual photo-Fenton-like oxidation (Fe³⁺/Fe²⁺ and W⁶⁺/W⁵⁺). A possible mechanism was postulated based on the results obtained. In summary, this study provided new insights into synthesizing an effectively heterogeneous 0D/3D Z-scheme dual photo-Fenton-like catalyst for water clarification.     

Optimization of Oil Oxidation by Response Surface Methodology and the Application of this Model to Evaluate Antioxidants

The oxidative stability of oils is a complex process influenced by several factors, making the evaluation of antioxidant effects of new compounds difficult. Thus, the objective of this study was to apply a factorial design to obtain the combination of factors that maximizes the formation of oil oxidation products, and use this model to evaluate the antioxidant activity of different compounds. Temperature, Fe²⁺ and ascorbyl palmitate were evaluated in two full-factorial designs (2³ and 3²). The validated optimized oxidation model was obtained by adding 1.47 mmol/L of Fe²⁺ and 1.54 mmol/L of ascorbyl palmitate to flaxseed oil stripped of tocopherol kept at 40 °C for 8 days. Antioxidant activities of six compounds were evaluated using this model. All antioxidant samples were statistically different (p < 0.001) at 200 ppm concentration, indicating the efficiency of the optimized model to evaluate the antioxidant action of natural and synthetic compounds.     

Mineralization of aniline and 4-chlorophenol in acidic solution by ozonation catalyzed with Fe2+ and UVA light

Solutions with 1.07 mmol dm⁻³ aniline or with 1.38 mmol dm⁻³ 4-chlorophenol at pH ca. 3 have been treated with ozone and ozonation catalyzed with Fe²⁺ and/or UVA. The initial mineralization rate increases as more oxidizing hydroxyl radical is produced in the medium by the catalyzed ozonations. Direct ozone treatment leads to stable oxidation products, which are quickly destroyed under UVA illumination. In the presence of Fe²⁺ as catalyst, the degradation process is inhibited by the formation of Fe³⁺ complexes with short organic diacids, being photodecomposed by UVA light. Each initial pollutant is destroyed at similar rate in all processes. p-Benzoquinone and nitrobenzene are identified as intermediates of aniline oxidation. The former product is only detected when high amounts of hydroxyl radical are produced by the action of Fe²⁺. Ammonium ion released during p-benzoquinone formation is also generated in larger extension under the same conditions. Nitrate ion reaches maximum production under UVA irradiation, indicating that generation of nitrobenzene from selective attack of O₃ on the amino group of aniline is photocatalyzed. Reaction of 4-chlorophenol with ozone leads to 4-chloro-1,3-dihydroxybenzene and 4-chloro-1,2-dihydroxybenzene. The last product is produced in larger extension when high amounts of hydroxyl radical can selectively attack the initial pollutant. Chloride ion is completely lost during the further degradation of both dihydroxylated derivatives. Oxidation of all aromatic intermediates detected during aniline and 4-chlorophenol degradation gives maleic acid, which is further mineralized via oxalic acid. A general reaction pathway for the degradation of each pollutant is proposed.     

Synergistic effects of doped Fe3+ and deposited Au on improving the photocatalytic activity of TiO2

Fe³⁺ doped together with Au deposited TiO₂ (Au/Fe³⁺–TiO₂) was successfully prepared, which shows excellent photocatalytic activity for degradation of methyl orange (MO) under both UV and visible light (λ > 420 nm) illumination. Fe³⁺ has been confirmed by EPR to substitute for Ti⁴⁺ in the TiO₂ lattice, and Au exists as Au⁰ on the surface of the photocatalyst indicated by the results of XRD. Fe³⁺ and Au have synergistic effects on improving the photocatalytic activity of TiO₂. A proposed mechanism concerning the synergistic effects is discussed to explain the improvement of the photocatalytic activities.