Effect of inorganic, synthetic and naturally occurring chelating agents on Fe(II) mediated advanced oxidation of chlorophenols

This study examines the feasibility and application of Advanced Oxidation Technologies (AOTs) for the treatment of chlorophenols that are included in US EPA priority pollutant list. A novel class of sulfate/hydroxyl radical-based homogeneous AOTs (Fe(II)/PS, Fe(II)/PMS, Fe(II)/H₂O₂) was successfully tested for the degradation of series of chlorophenols (4-CP, 2,4-CP, 2,4,6-CP, 2,3,4,5-CP). The major objective of the present study was to evaluate the effectiveness of three representative chelating agents (citrate, ethylenediaminedisuccinate (EDDS), and pyrophosphate) on Fe(II)-mediated activation of three common peroxide (peroxymonosulfate (PMS), persulfate (PS), and hydrogen peroxide (H₂O₂)) at neutral pH conditions. Short term (4 h) and long term (7 days) experiments were conducted to evaluate the kinetics and longevity of different oxidative systems for 4-chlorophenol degradation. Results showed that each of the iron-chelating agent couple was superior in activating a particular oxidant and consequently for 4-CP degradation. In case of Fe(II)/PMS system, the inorganic chelating agent pyrophosphate showed effective activation of PMS whereas very fast dissociation of PMS was recorded in the case of EDDS without any apparent 4-CP degradation. In Fe(II)/H₂O₂ system, EDDS was proven to be the most effective whereas pyrophosphate showed negligible activation of H₂O₂. Fe(II)/Citrate system showed moderate activation of all three oxidants. PMS was found to be the most universal oxidant, which was activated by all three iron-chelating agent systems and Fe(II)/Citrate was the most universal chelating agent system, which was able to activate all three oxidants to a certain extent.     

Preparation and photocatalytic performance of Fe (III)-amidoximated PAN fiber complex for oxidative degradation of azo dye under visible light irradiation

Polyacrylonitrile (PAN) fiber was modified with hydroxylamine hydrochloride to introduce amidoxime groups onto the fiber surface. These amidoxime groups were used to react with Fe (III) ions to prepare Fe (III)-amidoximated PAN fiber complex, which was characterized using SEM, XRD, FTIR, XPS, DMA, and DRS respectively. Then the photocatalytic activity of Fe-AO-PAN was evaluated in the degradation of a typical azo dye, C. I. Reactive Red 195 in the presence of H₂O₂ under visible light irradiation. Moreover, the effect of the Fe content of Fe-AO-PAN on dye degradation was also investigated. The results indicated that Fe (III) ions can crosslink between the modified PAN fiber chains by the coordination of Fe (III) ions with the amino nitrogen atoms and hydroxyl oxygen atoms of the amidoximation groups to form Fe (III)-amidoximated PAN fiber complex, and the Fe content of which is mainly determined by Fe (III) ions and amidoximation groups. Fe (III)-amidoximated PAN fiber complex is found to be activated in the visible light region. Moreover, Fe (III)-amidoximated PAN fiber complex shows the catalytic activity for dye degradation by H₂O₂ at pH = 6.0 in the dark, and can be significantly enhanced by increasing light irradiation and Fe content, therefore, it can be used as a new heterogeneous Fenton photocatalyst for the effective decomposition of the dye in water. In addition, ESR spectra confirm that Fe (III)-amidoximated PAN fiber complex can generate more OH radicals from H₂O₂ under visible light irradiation, leading to dye degradation. A possible mechanism of photocatalysis is proposed.     

Nitrite reduction with hydrous ferric oxide and Fe(II): Stoichiometry, rate, and mechanism

Fe(II)/Fe(III) oxide is an important redox couple in environmental systems. Recent studies have revealed unique characteristics of Fe(II)/Fe(III) oxide and reactions with oxidizing or reducing agents. Nitrite was used as an oxidizing agent in this study in order to probe details of these reactions and hydrous ferric oxide (HFO) was used as the Fe(III) oxide phase. Abiotic nitrite reduction is a significant global producer of nitric oxide (a catalyst for production of tropospheric ozone) and nitrous oxide (a greenhouse gas and contributor to stratospheric ozone depletion). All experiments were conducted at pH 6.8 using a strictly anoxic environment with mass-balance measurements for Fe(II). Oxidation of Fe(II) was negligible in the absence of HFO. The reaction was fast in the presence of HFO and was described by d[Fe(II)]/dt = −k_overall [Fe(II)_diss] [Fe(II)_solid-bound] [NO₂⁻] (k_overall = 2.59 × 10⁻⁷ μM⁻² min⁻¹) for Fe(II)/Fe(III) molar ratios less than 0.30. The reaction was inhibited for higher Fe(II)/HFO ratios. The concentration of solid-bound Fe(II) was constant after an initial equilibration period and the reaction stopped when dissolved Fe(II) was depleted even though substantial solid-bound Fe(II) and nitrite remained. The results regarding rate-dependence and conservation of solid-bound Fe(II) and inhibition of reaction at high Fe(II)/Fe(III) ratios were similar to our earlier results for the Fe(II)/HFO/O₂ system [Park, B., Dempsey, B.A., 2005. Heterogeneous oxidation of Fe(II) on ferric oxide at neutral pH and a low partial pressure of O₂. Environmental Science and Technology 39(17), 6494-6500.].     

Effect of some parameters on the rate of the catalysed decomposition of hydrogen peroxide by iron(III)-nitrilotriacetate in water

The decomposition rate of H₂O₂ by iron(III)-nitrilotriacetate complexes (Fe^IIINTA) has been investigated over a large range of experimental conditions: 3 < pH < 11, [Fe(III)]_T,0: 0.05-1 mM; [NTA]_T,0/[Fe(III)]_T,0 molar ratios : 1-250; [H₂O₂]₀: 1 mM-4 M) and concentrations of HO radical scavengers: 0-53 mM. Spectrophotometric analyses revealed that reactions of H₂O₂ with Fe^IIINTA (1 mM) at neutral pH immediately lead to the formation of intermediates (presumably peroxocomplexes of Fe^IIINTA) which absorb light in the region 350-600 nm where Fe^IIINTA and H₂O₂ do not absorb. Kinetic experiments showed that the decomposition rates of H₂O₂ were first-order with respect to H₂O₂ and that the apparent first-order rate constants were found to be proportional to the total concentration of Fe^IIINTA complexes, were at a maximum at pH 7.95 ± 0.10 and depend on the [NTA]_T,0/[Fe(III)]_T,0 and [H₂O₂]₀/[Fe(III)]_T,0 molar ratios. The addition of increasing concentrations of tert-butanol or sodium bicarbonate significantly decreased the decomposition rate of H₂O₂, suggesting the involvement of HO radicals in the decomposition of H₂O₂. The decomposition of H₂O₂ by Fe^IIINTA at neutral pH was accompanied by a production of dioxygen and by the oxidation of NTA. The degradation of the organic ligand during the course of the reaction led to a progressive decomplexation of Fe^IIINTA followed by a subsequent precipitation of iron(III) oxyhydroxides and by a significant decrease in the catalytic activity of Fe(III) species for the decomposition of H₂O₂.     

Degradation of the emerging contaminant ibuprofen in water by photo-Fenton

In this study the degradation of the worldwide Non-Steroidal Anti-Inflammatory Drug (NSAID) ibuprofen (IBP) by photo-Fenton reaction by use of solar artificial irradiation was carried out. Non-photocatalytic experiments (complex formation, photolysis and UV/Vis-H₂O₂ oxidation) were executed to evaluate the isolated effects and additional differentiated degradation pathways of IBP. The solar photolysis cleavage of H₂O₂ generates hydroxylated-IBP byproducts without mineralization. Fenton reaction, however promotes hydroxylation with a 10% contamination in form of a mineralization. In contrast photo-Fenton in addition promotes the decarboxylation of IBP and its total depletion is observed. In absence of H₂O₂ a decrease of IBP was observed in the Fe(II)/UV-Vis process due to the complex formation between iron and the IBP-carboxylic moiety. The degradation pathway can be described as an interconnected and successive principal decarboxylation and hydroxylation steps. TOC depletion of 40% was observed in photo-Fenton degradation. The iron-IBP binding was the key-point of the decarboxylation pathway. Both decarboxylation and hydroxylation mechanisms, as individual or parallel process are responsible for IBP removal in Fenton and photo-Fenton systems. An increase in the biodegradability of the final effluent after photo-Fenton treatment was observed. Final BOD₅ of 25 mg L⁻¹ was reached in contrast to the initial BOD₅ shown by the untreated IBP solution (BOD₅ < 1 mg L⁻¹). The increase in the biodegradability of the photo-Fenton degradation byproducts opens the possibility for a complete remediation with a final post-biological treatment.     

Inactivation of MS2 coliphage by Fenton's reagent

Fenton's reagent (i.e., Fe[II]/H₂O₂) is known to generate strong oxidants capable of oxidizing a broad spectrum of organic compounds in aqueous solution. This study demonstrates the successful inactivation of MS2 coliphage (MS2) by the oxidants produced from Fenton's reagent. The inactivation process of MS2 by Fenton's reagent was found to proceed in two distinct stages. The first stage inactivation, which took place rapidly within 1 min reaction time, was mainly achieved by the reaction of Fe(II) with H₂O₂ (i.e., the Fenton reaction). The second stage, which occurred by the catalytic reactions of Fe(III) with H₂O₂, exhibited much slower inactivation than the first stage. The rate of MS2 inactivation increased as pH decreased from 8.0 to 6.0. The addition of oxalate and humic acids significantly inhibited the MS2 inactivation, whereas 1,10-phenanthroline and bipyridine resulted in a gradual and steady inactivation of MS2. These observations on the effects of pH and iron-chelating agents indicate that oxidants formed on the surface or inside MS2 are responsible for the inactivation.     

Oxidation of 2,4-dichlorophenol and 3,4-dichlorophenol by means of Fe(III)-homogeneous photocatalysis and algal toxicity assessment of the treated solutions

Chlorophenols are used worldwide as broad-spectrum biocides and fungicides. They have half-life times in water from 0.6 to 550 h and in sediments up to 1700 h and, due to their numerous origins, they can be found in wastewaters, groundwaters or soils. Moreover, chlorophenols are not readily biodegradable.Recently, classic Advanced Oxidation Processes (AOP) have been proposed for their abatement in an aqueous solution. This paper investigates the oxidation of 2,4-dichlorophenol and 3,4-dichlorophenol, at starting concentrations of 6.1 · 10⁻⁵ mol L⁻¹, in aqueous solutions through Fe(III)/O₂ homogeneous photocatalysis under UV light (303 ÷ 366 nm). The Fe(III)/O₂ homogeneous photocatalysis is less expensive than using H₂O₂ due to the capability of Fe(III) to produce OH radicals, if irradiated with an UVA radiation, and of oxygen to re-oxidize ferrous ions to ferric ones when dissolved in solution. The results show that the best working conditions, for both compounds, are found for pH = 3.0 and initial Fe(III) concentration equal to 1.5·10⁻⁴ mol L⁻¹ although the investigated oxidizing system can be used even at pH close to 4.0 but with slower abatement kinetics. Toxicity assessment on algae indicates that treated solutions of 2,4-dichlorophenol are less toxic on algae Pseudokirchneriella subcapitata if compared to not treated solutions whereas in the case of 3,4-dichlorophenol only the samples collected during the runs at 20 and 60 min are capable of inhibiting the growth of the adopted organism.The values of the kinetic constant for the photochemical re-oxidation of iron (II) to iron (III) and for HO attack to intermediates are evaluated by a mathematical model for pH range of 2.0-3.0 and initial Fe(III) concentrations range of 1.5 · 10⁻⁵-5.2 · 10⁻⁴ mol L⁻¹.     

Comparison of UV/H(2)O(2) and UV/TiO(2) for the degradation of metaldehyde: Kinetics and the impact of background organics

The kinetics of photodegradation of the pesticide metaldehyde by UV/H₂O₂ and UV/TiO₂ in laboratory grade water and a natural surface water were studied. Experiments were carried out in a bench scale collimated beam device using UVC radiation. Metaldehyde was efficiently degraded by both processes in laboratory grade water at identical rates of degradation (0.0070 and 0.0067 cm² mJ⁻¹ for UV/TiO₂ and UV/H₂O₂ respectively) when optimised doses were used. The ratio between oxidant and metaldehyde was significantly higher for H₂O₂ due to its low photon absorption efficiency at 254 nm. However, the presence of background organic compounds in natural water severely affected the rate of degradation, and whilst the pseudo first-order rate constant of degradation by UV/H₂O₂ was slowed down (0.0020 cm² mJ⁻¹), the degradation was completely inhibited for the UV/TiO₂ process (k′ = 0.00007 cm² mJ⁻¹) due to the blockage of active sites on TiO₂ surface by the background organic material.     

Photodegradation of phenol red in the presence of oxyhydroxide of Fe(III) (Goethite) under artificial and a natural light

The (α‐FeOOH) Goethite composite is a stable and an efficient catalyst in aqueous suspension under irradiation at 365 nm and by solar light. The photocatalytic activities of this composite were evaluated using Phenol Red (PR) dye (phenolsulfonphthalein class). In the dark, controlling factors, such as the pH and the adsorption of PR on Goethite surface were evaluated (before starting the photochemical experiments). It was found that the system PR‐Goethite present a small decrease in the main band of the dye (435 nm) which was explained by the low rate of adsorption of this dye on the Goethite. Also, we note that 40% of PR decolourisation was obtained after 200 min by the system PR‐Goethite‐hydrogen peroxide (H₂O₂) in dark due to the formation of ^?OH by thermal decomposition of H₂O₂ on the surface of Goethite. The effects of various experimental parameters, such as initial dye concentration, pH, photocatalyst amount, tert‐Butyl alcohol effect and H₂O₂ addition were investigated in the study of photodegradation of the dye. The results showed that the photodegradation of PR under UV‐A (365 nm) irradiation could be enhanced greatly in the presence of H₂O₂. Natural radiation tests (under sunlight) showed that degradation was faster comparing with that obtained using the artificial one at 365 nm. Studies of the mineralization using total organic carbon method under naturel light certify that this method, compatible with the environment, may be considered in the treatment of wastewater and generally in the process of removal of this kind of pollutant.     

Removal of arsenic from water: Effect of calcium ions on As(III) removal in the KMnO4–Fe(II) process

A novel KMnO₄–Fe(II) process was developed in this study for As(III) removal. The optimum As(III) removal was achieved at a permanganate dosage of 18.6 μM. At the optimum dosage of permanganate, the KMnO₄–Fe(II) process was much more efficient than the KMnO₄–Fe(III) process for As(III) removal by 15–38% at pH 5–9. The great difference in As(III) removal in these two processes was not ascribed to the uptake of arsenic by the MnO₂ formed in situ but to the different properties of conventional Fe(III) and the Fe(III) formed in situ. It was found that the presence of Ca²⁺ had limited effects on As(III) removal under acidic conditions but resulted in a significant increase in As(III) removal under neutral and alkaline conditions in the KMnO₄–Fe(II) process. Moreover, the effects of Ca²⁺ on As(III) removal in the KMnO₄–Fe(II) process were greater at lower permanganate dosage when Fe(II) was not completely oxidized by permanganate. This study revealed that the improvement of As(III) removal at pH 7–9 in the KMnO₄–Fe(II) process by Ca²⁺ was associated with three reasons: (1) the specific adsorption of Ca²⁺ increased the surface charge; (2) the formation of amorphous calcium carbonate and calcite precipitate that could co-precipitate arsenate; (3) the introduction of calcium resulted in more precipitated ferrous hydroxide or ferric hydroxide. On the other hand, the enhancement of arsenic removal by Ca²⁺ under acidic conditions was ascribed to the increase of Fe retained in the precipitate. FTIR tests demonstrated that As(III) was removed as arsenate by forming monodentate complex with Fe(III) formed in situ in the KMnO₄–Fe(II) process when KMnO₄ was applied at 18.6 μM. The strength of the “non-surface complexed” As–O bonds of the precipitated arsenate species was enhanced by the presence of Ca²⁺ and the complexation reactions of arsenate with Fe(III) formed in situ in the presence or absence of Ca²⁺ were proposed.     

Effect of moderate pre-oxidation on the removal of Microcystis aeruginosa by KMnO4-Fe(II) process: significance of the in-situ formed Fe(III)

This study developed a novel KMnO₄-Fe(II) process to remove the cells of Microcystis aeruginosa, and the mechanisms involved in have been investigated. At KMnO₄ doses of 0-10.0 μM, the KMnO₄-Fe(II) process showed 23.4-53.3% higher efficiency than the KMnO₄-Fe(III) process did. This was first attributed to the moderate pre-oxidation of M. aeruginosa by KMnO₄, achieved by dosing Fe(II) after a period of pre-oxidation, to cease the further release of intracellular organic matter (IOM) and the degradation of dissolved organic matter (DOM). The extensive exposure of M. aeruginosa to KMnO₄ in KMnO₄-Fe(III) process led to high levels and insufficient molecular weight of DOM, inhibiting the subsequent Fe(III) coagulation. Additionally, Fe(II) contributed to lower levels of the in-situ formed MnO₂, the reduction product of KMnO₄ which adversely affected algae removal by Fe(III) coagulation. However, the in-situ formed Fe(III), which was derived from the oxidation of Fe(II) by KMnO₄, in-situ MnO₂, and dissolved oxygen, dominated the remarkably high efficiency of KMnO₄-Fe(II) process with respect to the removal of M. aeruginosa. On one hand, in-situ formed Fe(III) had more reactive surface area than pre-formed Fe(III). On the other hand, the continuous introduction of fresh Fe(III) coagulant showed higher efficiency than one-off dosage of coagulant to destabilize M. aeruginosa cells and to increase the flocs size. Moreover, the MnO₂ precipitated on algae cell surfaces and contributed to the formation of in-situ formed Fe(III), which may act as bridges to enhance the removal of M. aeruginosa.     

Sonophotolytic degradation of azo dye reactive black 5 in an ultrasound/UV/ferric system and the roles of different organic ligands

The sonophotolytic advance oxidation system (US/UV/Fe³⁺) could achieve synergistic degradation of reactive black 5 (RB5), as compared to UV/Fe³⁺ and US/Fe³⁺ systems. A synergy factor of 2.5 based on the pseudo-first-order degradation rate constant (k_obs) was found, along with enhancements in organic detoxification and mineralization. The presence of organic ligands could affect the US/UV/Fe³⁺ system differently. Oxalate, citrate, tartrate and succinate could enhance the RB5 degradation, while NTA and EDTA exhibited strong inhibitions. The influence of these ligands on k_obs(RB5) in the US/UV/Fe(III)-ligand systems followed the sequence of oxalate > tartrate > succinate > citrate > without ligand > NTA > EDTA, while they could be degraded simultaneously with the k_obs(ligand) order of oxalate > citrate > tartrate > succinate > NTA > EDTA. Monitoring of iron species and the generated H₂O₂ and •OH revealed that the ligands in the US/UV/Fe(III)-ligand system could play different mechanistic roles: (1) promoting H₂O₂ production, (2) accelerating Fenton reaction, and (3) competing with RB5 for reacting with •OH. Among the ligands, oxalate exhibited the most significant enhancement of RB5 oxidation in the sonophotolytic system, and the process was pH-dependent. An initial reaction lag in RB5 degradation was observed when Fe²⁺ was used in lieu of Fe³⁺ as the catalyst in the sonophotolytic system.     

Removal of refractory compounds from stabilized landfill leachate using an integrated H2O2 oxidation and granular activated carbon (GAC) adsorption treatment

This study investigated the treatment performances of H₂O₂ oxidation alone and its combination with granular activated carbon (GAC) adsorption for raw leachate from the NENT landfill (Hong Kong) with a very low biodegradability ratio (BOD₅/COD) of 0.08. The COD removal of refractory compounds (as indicated by COD values) by the integrated H₂O₂ and GAC treatment was evaluated, optimized and compared to that by H₂O₂ treatment alone with respect to dose, contact time, pH, and biodegradability ratio. At an initial COD concentration of 8000 mg/L and NH₃-N of 2595 mg/L, the integrated treatment has substantially achieved a higher removal (COD: 82%; NH₃-N: 59%) than the H₂O₂ oxidation alone (COD: 33%; NH₃-N: 4.9%) and GAC adsorption alone (COD: 58%) at optimized experimental conditions (p ≤ 0.05; t-test). The addition of an Fe(II) dose at 1.8 g/L further improved the removal of refractory compounds by the integrated treatment from 82% to 89%. Although the integrated H₂O₂ oxidation and GAC adsorption could treat leachate of varying strengths, treated effluents were unable to meet the local COD limit of less than 200 mg/L and the NH₃-N of lower than 5 mg/L. However, the integrated treatment significantly improved the biodegradability ratio of the treated leachate by 350% from 0.08 to 0.36, enabling the application of subsequent biological treatments for complementing the degradation of target compounds in the leachate prior to their discharge.     

The generation of hydrogen peroxide in the processes of oxidation of aliphatic alcohols in the UV/H<Subscript>2</Subscript>O<Subscript>2</Subscript> system

The article has studied the impact of various physicochemical factors (the concentration of H₂O₂: alcohol ratio, the presence of oxygen, of Fe(III) ions, etc.) on the consumption and buildup of H₂O₂ in oxidation of aliphatic alcohols in aqueous solutions under the effect of UV light (200–360 nm). Based on the obtained data the kinetic model of generating H₂O₂ has been proposed in the processes being considered.     

Degradation of azo dye by an UV/H2O2 advanced oxidation process using an amalgam lamp

The discharge of dyes into water is an ecological problem that can be alleviated by advanced oxidation processes (AOPs), such as UV/H₂O₂ treatments. Searching for more efficient light sources is a way to improve AOPs’ efficiency. This work tested the efficiency of an amalgam lamp on the degradation of an azo dye, studying the effect of dye and H₂O₂ concentrations and pH, and the influence of some salts on the decolouration rate of methyl orange. Actinometry showed that the amalgam lamp system was able to provide a high incident photon irradiance (6.30·10^?5 mol/cm² s). The amalgam lamp‐driven AOP was able to decolourize the dye at pseudo‐first‐order rates of 0.654–4.008 1/min, with increasing rates at low dye concentration and low pH and at high H₂O₂ concentrations until a maximum value is reached. The results show that the amalgam lamp can be an alternative light source for fast dye degradation by AOPs.     

Fenton's oxidation of pentachlorophenol

The combination of H₂O₂ and Fe(II) (Fenton's reaction) has been demonstrated to rapidly degrade many organics via hydroxyl radicals. However, few studies have related hydroxyl radical generation rates with measured organic chemical degradation data. The goals of this work were to investigate the kinetics, stoichiometry, and intermediates of pentachlorophenol (PCP) degradation in the Fenton's reaction and to develop a mathematical model of this reaction system. Batch reaction experiments were performed to assess both initial transients and steady states, and special attention was given to the analysis of intermediates. Solutions of PCP (55 μM) and Fe(II) (200 μM) were treated with variable levels of H₂O₂ (<850 μM), and the concentrations of these reactants and their products were measured. Partial PCP degradation and near stoichiometric dechlorination were observed at low initial H₂O₂ concentrations. Higher H₂O₂ doses achieved at most 70% dechlorination even though nearly all of the PCP was degraded. The reaction intermediates tetrachlorohydroquinone and dichloromaleic acid accounted for up to 5% of the PCP degraded. Organic carbon mineralization (transformation to CO₂) was not observed. The OH scavenging effects of the PCP-by-products mixture were characterized as a lumped parameter in the reaction kinetics model, which provided reasonable predictions of experimental results at different oxidant concentrations and reaction time.     

Iron speciation and iron species transformation in activated sludge membrane bioreactors

Iron speciation and iron species transformation were investigated in three membrane bioreactors (MBRs) differing in feed iron concentration (and oxidation state) and the presence or absence of an anoxic chamber to simulate various feed stream conditions and operational configurations. The concentration of dissolved Fe(II) was below detection limit (i.e., <0.1 μM) in all chambers while the concentration of dissolved Fe(III) was found to be around 0.25 μM. H₂O₂ was detected as a quasi-stable reactive oxygen species with concentrations in the μM range in all MBR chambers. H₂O₂ acted as the primary potential oxidant of Fe(II) in the anoxic chamber. Batch experiments showed that the rate constant for oxygenation of dissolved Fe(II) in the liquid phase of the activated sludge compartment was as high as 78 M⁻¹ s⁻¹. The half-life time of dissolved Fe(II) in all chambers was found to be no longer than 1 min. The stability constants of the Fe(III)SMP complexes were far from uniform. A large quantity of Fe(II) (over 0.036% of the sludge dry mass) was found to be adsorbed by the bacterial flocs suggesting the active reduction of adsorbed Fe(III). The content of adsorbed Fe(II) was found to increase if the MBR was supplied with iron in the Fe(II) form. Over 60% of iron fed to the reactors was converted to highly insoluble ferric oxyhydroxide in all MBRs. A model has been developed which satisfactorily describes the oxidation of Fe(II) in the activated sludge liquid phase and which provides valuable insight into the relative importance of redox processes occurring which mediate the speciation of iron in the system.     

Solar Fenton and solar TiO2 catalytic treatment of ofloxacin in secondary treated effluents: Evaluation of operational and kinetic parameters

Two different technical approaches based on advanced oxidation processes (AOPs), solar Fenton homogeneous photocatalysis (hv/Fe²⁺/H₂O₂) and heterogeneous photocatalysis with titanium dioxide (TiO₂) suspensions were studied for the chemical degradation of the fluoroquinolone ofloxacin in secondary treated effluents. A bench-scale solar simulator in combination with an appropriate photochemical batch reactor was used to evaluate and select the optimal oxidation conditions of ofloxacin spiked in secondary treated domestic effluents. The concentration profile of the examined substrate during degradation was determined by UV/Vis spectrophotometry. Mineralization was monitored by measuring the dissolved organic carbon (DOC). The concentrations of Fe²⁺ and H₂O₂ were the key factors for the solar Fenton process, while the most important parameter of the heterogeneous photocatalysis was proved to be the catalyst loading. Kinetic analyses indicated that the photodegradation of ofloxacin can be described by a pseudo-first-order reaction. The rate constant (k) for the solar Fenton process was determined at different Fe²⁺ and H₂O₂ concentrations whereas the Langmuir-Hinshelwood (LH) kinetic expression was used to assess the kinetics of the heterogeneous photocatalytic process. The conversion of ofloxacin depends on several parameters based on the various experimental conditions, which were investigated. A Daphnia magna bioassay was used to evaluate the potential toxicity of the parent compound and its photo-oxidation by-products in different stages of oxidation. In the present study solar Fenton has been demonstrated to be more effective than the solar TiO₂ process, yielding complete degradation of the examined substrate and DOC reduction of about 50% in 30 min of the photocatalytic treatment.     

Photocatalytic degradation of 2,4-dinitrophenol (DNP) by multi-walled carbon nanotubes (MWCNTs)/TiO2 composite in aqueous solution under solar irradiation

Nanosized multi-walled carbon nanotubes (MWCNTs)/TiO₂ composite and neat TiO₂ photocatalysts were synthesized by sol-gel technique using tetrabutyl titanate as a precursor. The as prepared photocatalysts were characterized using XRD, SEM, FTIR and UV-vis spectra. The samples were evaluated for their photocatalytic activity towards the degradation of 2,4-dinitrophenol (DNP) under solar irradiation. The results indicated that the addition of an appropriate amount of MWCNTs could remarkably improve the photocatalytic activity of TiO₂. An optimal MWCNTs:TiO₂ ratio of 0.05% (w/w) was found to achieve the maximum rate of DNP degradation. The effects of pH, irradiation time, catalyst concentration, DNP concentration, etc. on the photocatalytic activity were studied and the results obtained were fitted to the Langmuir-Hinshelwood model to study the degradation kinetics. The optimal conditions were an initial DNP concentration of 38.8 mg/L at pH 6.0 with catalyst concentration of 8 g/L under solar irradiation for 150 min with good recyclisation of catalyst. The degree of photocatalytic degradation of DNP increased with an increase in temperature. The MWCNTs/TiO₂ composite was found to be very effective in the decolorization and COD reduction of real wastewater from DNP manufacturing. Thus, this study showed the feasible and potential use of MWCNTs/TiO₂ composite in degradation of various toxic organic contaminants and industrial effluents.     

Lethal synergy of solar UV-radiation and H2O2 on wild Fusarium solani spores in distilled and natural well water

Environmentally-friendly disinfection methods are needed in many industrial applications. As a natural metabolite of many organisms, hydrogen peroxide (H₂O₂)-based disinfection may be such a method as long as H₂O₂ is used in non-toxic concentrations. Nevertheless, when applied alone as a disinfectant, H₂O₂ concentrations need to be high enough to achieve significant pathogen reduction, and this may lead to phytotoxicity. This paper shows how H₂O₂ disinfection concentrations could be significantly reduced by using the synergic lethality of H₂O₂ and sunlight the first time for fungi and disinfection. Experiments were performed on spores of Fusarium solani, the ubiquitous, pytho- and human pathogenic fungus. Laboratory (250-mL bottles) and pilot plant solar reactors (2 × 14 L compound parabolic collectors, CPCs) were employed with distilled water and real well water under natural sunlight. This opens the way to applications for agricultural water resources, seed disinfection, curing of fungal skin infections, etc.