Degradation of endocrine disruptor bisphenol A in drinking water by ozone oxidation

The ozone oxidation of endocrine disruptor bisphenol A in drinking water was investigated. A stainless completely mixed reactor was employed to carry out the degradation experiments by means of a batch model. With an initial concentration of 11.0 mg/L, the removal efficiencies of BPA (bisphenol A) could be measured up to 70%, 82%, and 90% when the dosages of ozone were 1, 1.5, and 2 mg/L, respectively. The impacts on BPA degradation under the conditions of different ozone dosages, water background values, BPA initial concentrations, and ozone adding time were analyzed. The results showed that ozone dosage plays a dominant role during the process of BPA degradation, while the impact of the contact time could be ignored. UV wavelength scanning was used to confirm that the by-products were produced, which could be absorbed at UV254. The value of UV254 was observed to have changed during the ozonation process. Based on the change of UV254, it could be concluded that BPA is not completely degraded at low ozone dosage, while shorter adding time of total ozone dosage, high ozone dosage, and improvement of dissolved ozone concentration greatly contribute to the extent of BPA degradation. The effects of applied H₂O₂ dose in ozone oxidation of BPA were also examined in this study. The O₃-H₂O₂ processes proved to have similar effects on the degradation of BPA by ozone oxidation.     

Study on degradation process of famotidine hydrochloride in aqueous samples

The kinetics of famotidine (FAM) transformation under the influence of various factors, important from the environmental point of view, was investigated in aqueous solutions. The degradation processes using UV, H₂O₂, UV/H₂O₂, H₂O₂/Fe²⁺, and UV/H₂O₂/Fe²⁺ were studied. Direct photolysis and H₂O₂-assisted photolysis showed a pseudo-first-order kinetics, while the Fenton and the photo-Fenton processes fit second-order kinetics. The provided experiments proved a high resistance of FAM to direct photolysis. Its stability depends highly on the pH of the reaction solutions. The rate of FAM direct photolysis in acidic solutions was almost negligible. The reaction rate of FAM photolysis at pH 8–9 was 3.7 × 10^?3 min^?1 with DT₅₀ about 3 h 7 min. It was found that the presence of H₂O₂ in the reaction environment enhances the rate of photolysis of FAM. The observed rates of reaction were 5.1 × 10^?3 min^?1 and 3.7 × 10^?3 min^?1 in acidic and basic solutions, respectively. The used Fenton systems appeared to be the most efficient in FAM removal. The rate of reaction depends on concentration of Fe²⁺ and H₂O₂. It was observed that the presence of UV-light enhances the reaction rate by two to six times in comparison to the classical Fenton system. Additionally, FAM behavior in natural water under solar irradiation was examined. The irradiation experiments were carried out in batch experiments with simulated sunlight.     

Effect of natural aquatic humic substances on the photodegradation of bisphenol A

The photochemical degradation of bisphenol A (BPA) was studied in the presence of natural humic substances from different origins under simulated solar irradiation. BPA underwent insignificant direct photolysis in neutral water, but rapid photosensitized degradation in four humic substances solutions via pseudo-first-order reaction occurred. The photo-degradation rate of BPA was insensitive to the different initial BPA concentrations and was inhibited in aerated solution compared with the deoxygenated medium. The reactive oxygen species (ROS) such as ·OH and ¹O₂ produced from excitation of humic substances under irradiation was determined from the quenching kinetic experiment using molecular probe. The five main intermediate photoproducts of BPA in Nordic lake fulvic acid (NOFA) were tentatively identified using gas chromatography/mass spectrometer (GC/MS). Based on the identification of ROS and the analysis of photoproduct formation, the possible phototransformation pathways of BPA were proposed, involving the direct photolysis due to the energy transfer from the triplet state humic substance (³HS*) to BPA molecules and hydroxyl radical addition and oxidation as well.     

Degradation of trace nitrobenzene in water by microwave-enhanced H2O2-based process

To evaluate possible use of microwave-enhanced H₂O₂-based (MW/H₂O₂) process to degrade trace nitrobenzene (NB) in water, a series of batch experiments were conducted. The results showed that 2450MHz microwave irradiation significantly enhanced oxidative decomposition of nitrobenzene (NB) in a H₂O₂ system. About 90% NB was degraded by the MW/ H₂O₂ process in 30 min. Moreover, the MW/ H₂O₂ process could enhanced the oxidative degradation of NB even at relatively low temperature (50°C). When the initial concentration of NB was 300??g/L, the optimum ratio of H₂O₂ to NB and MW power were 70 and 300W respectively. The presence of humic acid significantly increased H₂O₂ dosage. The ultraviolet absorbance at 254 nm (UV₂₅₄) indicated degradation of NB was stepwise and some intermediates were produced. The gas chromatography-mass spectrometric (GC-MS) analysis showed that main intermediates were nitrophenolic and carbonyl compounds.     

Iron-doped copper 1,4-benzenedicarboxylate as photo-Fenton catalyst for degradation of methylene blue

Abstract

A metal-organic framework of iron-doped copper 1,4-benzenedicarboxylate was synthesized and, for the first time, utilized as a heterogeneous photo-Fenton catalyst for degradation of methylene blue dye in aqueous solution under visible light irradiation. The synthesized materials were characterized by scanning electron microscopy, Fourier-transform infrared spectroscopy, X-ray diffraction and energy-dispersive X-ray spectroscopy. The influence factors, kinetics, and stability of the synthesized catalysts were investigated in detail. Iron-doped copper 1,4-benzenedicarboxylate showed higher degradation efficiency than pure copper 1,4-benzenedicarboxylate. An almost complete degradation was achieved within 70?min under visible light irradiation at a solution pH of 6, a catalyst loading of 1?g?L^?1, a H₂O₂ dosage of 0.05?mol L^?1 and methylene blue concentration of 50?mg?L^?1. Recycling studies demonstrated that the iron-doped copper 1,4-benzenedicarboxylate is a promising heterogeneous photo-Fenton catalyst for long-term removal of methylene blue dye from industrial wastewater.     

Complexation of iron by salicylic acid and its effect on atrazine photodegradation in aqueous solution

The photodegradation of atrazine and the photochemical formation of Fe(II) and H₂O₂ in aqueous solutions containing salicylic acid and Fe(III) were studied under simulated sunlight irradiation. Atrazine photolysis followed first-order reaction kinetics, and the rate constant (k) corresponding to the solution of Fe(III)-salicylic acid complex (Fe(III)-SA) was only 0.0153 h^?1, roughly one eighth of the k observed in the Fe(III) alone solution (0.115 h^?1). Compared with Fe(III) solution, the presence of salicylic acid significantly enhanced the formation of Fe(II) but greatly decreased H₂O₂ generation, and their subsequent product, hydroxyl radical (˙OH), was much less, accounting for the low rate of atrazine photodegradation in Fe(III)-SA solution. The interaction of Fe(III) with salicylic acid was analyzed using Fourier-transform infrared (FTIR) spectroscopy and UV-visible absorption, indicating that Fe(III)-salicylic acid complex could be formed by ligand exchange between the hydrogen ions in salicylic acid and Fe(III) ions.     

五氧化二钒类Fenton降解邻苯二甲酸二乙酯的机制研究

发展了基于五氧化二钒(V_2O_5)和过氧化氢(H_2O_2)的新型类Fenton体系,探索了此体系产生羟基(·OH)的机制及降解邻苯二甲酸二乙酯(DEP)的效率;并考察了V_2O_5投加量、H_2O_2浓度,以及草酸对DEP降解的影响。结果表明,当V_2O_5投加量为0.1 g·L-1,H_2O_2浓度为2.0 mmol·L-1,反应24 h后,对DEP(25 mg·L-1)的降解率可达61.1%,增加或降低V_2O_5投加量和H_2O_2浓度均不利于DEP的降解。利用电子顺磁共振技术(Electron Paramagnetic Resonance,EPR)耦合5,5-二甲基-1-吡咯啉氮氧化物(DMPO)为捕获剂对反应体系中的主导自由基进行鉴定,发现·OH是体系降解DEP的主要活性物种,利用苯甲酸作为探针分子实现了·OH的间接定量,并初步推测了V_2O_5活化H_2O_2的过程。     

Effect of humic acids on the Fenton degradation of phenol

We show that the degradation of phenol by Fe(III) and hydrogen peroxide is faster in the presence of humic acids. This is most likely due to faster reduction of Fe(III)-humate complexes by H₂O₂/HO₂^·/O₂^–· when compared with Fe(III)-H₂O complexes. The fact that humic acids, a major class of naturally occurring compounds, favour the Fenton reaction has great relevance in the field of water and soil decontamination, where organic compounds usually have a negative effect. Furthermore, it adds insight into the self-depuration processes of natural aquifers.     

Degradation of dye rhodamine B under visible irradiation with Prussian blue as a photo-Fenton reagent

Rhodamine B can be degraded using Prussian blue as a photo-Fenton like reagent under λ > 420 nm visible irradiation. Kinetic studies show ln(C _o/C _t ) is linearly proportional to the reaction time during the photo-degradation process; thus, the degradation reaction obeys a pseudo-first order kinetic law. It is very interesting that the presence of salinity such as 0.1 M KCl can speed up greatly the degradation rate: the time to achieve 90.0% degradation ratio is shortened from 120.0 to 40.0 min under comparable conditions, which is very useful in the treatment of wastewaters with high content of salinity.     

Characteristics and mechanisms of 4A zeolite supported nanoparticulate zero-valent iron as Fenton-like catalyst to degrade methylene blue

4A zeolite supported nanoparticulate zero-valent iron (nZVI/4A zeolite), synthesized through borohydride reduction method, was used as a catalyst with H₂O₂ to build Fenton-like reaction system to degrade methylene blue (MB) in model wastewater. The characteristics and primary mechanisms of the catalyst were investigated. The results show that nZVI/4A zeolite has the potential as a Fenton-like catalyst, and (about 30 mg/L) MB was degraded completely in 3 h with 10 mM H₂O₂, 0.2 g/L catalyst, and initial pH of 3.0. The MB degradation rates were obtained at least 70% in the tests with initial pH ranged from 2.0 to 9.0 and the catalyst dose rose from 0.2 to 5.0 g/L. Importantly, the catalyst also has a distinctive ability to increase the solution pH value from its initial acidic pH and then maintain the value at close to neutrality. This ability was controlled by both the initial pH and the catalyst dose. MB degradation clarified that hydroxyl radical was the dominated active oxidative specie in the tests with initial acidic pH and low catalyst dose (less 2.5 g/L); otherwise, Fe(VI) oxidation was the main mechanism for MB degradation; and the two processes shared synergistic effect in MB degradation in the present test. The catalyst has high operational stability in both of the composites with low iron leaching (less 2%) and catalyzing ability. Therefore, nZVI/4A zeolite has great potential as a Fenton-like catalyst and is used with H₂O₂ to build Fenton-like system which could be used to degrade MB efficiently.     

Fenton degradation of dialkylphthalates: products and mechanism

Contamination of wastewater by organic pollutants is a major worldwide issue. For instance plastic additives such as phthalates are found in wastewater. Efficient techniques are thus needed to clean wastewaters. The Fenton reaction involving H₂O₂ and Fe(II) salts can be used to treat polluted water. During the Fenton reaction pollutants are decomposed directly by hydroxyl radicals. In some cases toxic by-products are produced. Here dimethyl phthalate, diethyl phthalate, and dipropyl phthalate by-products formed during the Fenton reaction were studied. Fenton degradation of selected phthalates yielded numerous transformation products such as hydroxylated phthalates. The hydroxylation reaction occurred at the aromatic ring of phthalates and yielded mono- and dihydroxylated phthalates. For monohydroxylated phthalate, 3-hydroxy- and 4-hydroxydialkylphthalates are the main transformation products. In addition to hydroxylated derivatives, aliphatic chain degraded mono- and dihydroxylated phthalates were also detected.     

Microwave and Fenton's reagent oxidation of wastewater

We compared two H₂O₂ oxidation methods for the treatment of industrial wastewater: oxidation using Fenton's reagent [H₂O₂/Fe(II)] and microwave irradiation. Both methods were applied to the treatment of synthetic phenol solutions (100 mg L⁻¹) and of an industrial effluent containing a mixture of ionic and non-ionic surfactants at high load (20 g L⁻¹ of COD). The effects of initial pH, initial H₂O₂ concentration, Fenton catalyst amount and irradiation time were assessed. According to the oxidation of phenol, it has been found that the oxidation by Fenton's reagent is dependent on the pH, contrary to the microwave system, which is not influenced by this parameter. For both systems, a limiting amount of oxidant has been found; above this point the oxidation of phenol is not improved by a further addition of peroxide. The oxidation of the industrial surfactant effluent has only been successful with the Fenton's reagent. In this case, large amounts of ferrous ions are necessary for the precipitation of the ionic surfactants of the effluent, followed by the oxidation of the non-ionic constituents of the solution. Electronic Publication     

Hydroxyl radical generation by redox cycling of some chemotherapeutic antibiotics

The anticancer drugs: adriamycin, farmorubicin and mitomycin C greatly enhance the generation of hydroxyl radicals (HO^.) from H₂O₂ in the presence of Co(II) ions (CoCl2) at pH 7.4 and 8, as measured by the deoxyribose assay. Catalase, hydroxyl radical scavengers (mannitol, cysteine, glutathione, thiourea, lactic dehydrogenase) inhibited the degradation of deoxyribose confirming that HO‐radicals are responsible for the degradation of the carbohydrate.     

Enhanced heterogeneous Fenton-like activity by Cu-doped BiFeO<Subscript>3</Subscript> perovskite for degradation of organic pollutants

Heterogeneous Fenton-like reaction has been extensively investigated to eliminate refractory organic contaminants in wastewater, but it usually shows low catalytic performance due to difficulty in reduction from Fe(III) to Fe(II). In this study, enhanced catalytic efficiency was obtained by employing Cu-doped BiFeO₃ as heterogeneous Fenton-like catalysts, which exhibited higher catalytic performance toward the activation of H₂O₂ for phenol degradation than un-doped BiFeO₃. BiFe_0.8Cu_0.2O₃ displayed the best performance, which yielded 91% removal of phenol (10 mg L^–1) in 120 min. The pseudo first-order kinetic rate constant of phenol degradation in BiFe_0.8Cu_0.2O₃ catalyzed heterogeneous Fenton-like reaction was 5 times higher than those of traditional heterogeneous Fenton-like catalysts, such as Fe₃O₄ and goethite. The phenol degradation efficiency could still reach 83% after 4 cycles, which implied the good stability of BiFe_0.8Cu_0.2O₃. The high catalytic activity of BiFe_0.8Cu_0.2O₃ was attributed to the fact that the doping Cu into BiFeO₃ could promote the generation of Fe(II) in the catalyst and then facilitate the activation of H₂O₂ to degrade the organic pollutants.

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Treatment of organic pollutants by homogeneous and heterogeneous Fenton reaction processes

Nowadays, the water ecosystem is being polluted due to the rapid industrialization and massive use of antibiotics, fertilizers, cosmetics, paints, and other chemicals. Chemical oxidation is one of the most applied processes to degrade contaminants in water. However, chemicals are often unable to completely mineralize the pollutants. Enhanced pollutant degradation can be achieved by Fenton reaction and related processes. As a consequence, Fenton reactions have received great attention in the treatment of domestic and industrial wastewater effluents. Currently, homogeneous and heterogeneous Fenton processes are being investigated intensively and optimized for applications, either alone or in a combination of other processes. This review presents fundamental chemistry involved in various kinds of homogeneous Fenton reactions, which include classical Fenton, electro-Fenton, photo-Fenton, electro-Fenton, sono-electro-Fenton, and solar photoelectron-Fenton. In the homogeneous Fenton reaction process, the molar ratio of iron(II) and hydrogen peroxide, and the pH usually determine the effectiveness of removing target pollutants and subsequently their mineralization, monitored by a decrease in levels of total organic carbon or chemical oxygen demand. We present catalysts used in heterogeneous Fenton or Fenton-like reactions, such as H₂O₂–Fe³⁺(solid)/nano-zero-valent iron/immobilized iron and electro-Fenton-pyrite. Surface properties of heterogeneous catalysts generally control the efficiency to degrade pollutants. Examples of Fenton reactions are demonstrated to degrade and mineralize a wide range of water pollutants in real industrial wastewaters, such as dyes and phenols. Removal of various antibiotics by homogeneous and heterogeneous Fenton reactions is exemplified.     

Pathway of the ozonation of 2,4,6-trichlorophenol in aqueous solution

The reaction mechanism and pathway of the ozonation of 2,4,6-trichlorophenol (2,4,6-TCP) in aqueous solution were investigated. The removal efficiency and the variation of H₂O₂, Cl^? formic acid, and oxalic acid were studied during the semi-batch ozonation experiments (continuous for ozone gas supply, fixed volume of water sample). The results showed that when there was no scavenger, the removal efficiency of 0.1 mmol/L 2,4,6-TCP could reach 99% within 6 min by adding 24 mg/L ozone. The reaction of molecular ozone with 2,4,6-TCP resulted in the formation of H₂O₂. The maximal concentration of H₂O₂ detected during the ozonation could reach 22.5% of the original concentration of 2,4,6-TCP. The reaction of ozone with H₂O₂ resulted in the generation of a lot of OH? radicals. Therefore, 2,4,6-TCP was degraded to formic acid and oxalic acid by ozone and OH? radicals together. With the inhibition of OH? radicals, ozone molecule firstly degraded 2,4,6-TCP to form chlorinated quinone, which was subsequently oxidized to formic acid and oxalic acid. Two reaction pathways of the degradation of 2,4,6-TCP by ozone and O₃/OH? were proposed in this study.     

Experimental and computational assessment of 1,4-Dioxane degradation in a photo-Fenton reactive ceramic membrane filtration process

• 1,4-Dioxane was degraded via the photo-Fenton reactive membrane filtration. • Degradation efficiency and AQY were both enhanced in photocatalytic membrane. • There is a tradeoff between photocatalytic degradation and membrane permeation flux. • Degradation pathways of 1,4-Dioxane is revealed by DFT analysis. The present study evaluated a photo-Fenton reactive membrane that achieved enhanced 1,4-Dioxane removal performance. As a common organic solvent and stabilizer, 1,4-Dioxane is widely used in a variety of industrial products and poses negative environmental and health impacts. The membrane was prepared by covalently coating photocatalyst of goethite (α-FeOOH) on a ceramic porous membrane as we reported previously. The effects of UV irradiation, H₂O₂ and catalyst on the removal efficiency of 1,4-Dioxane in batch reactors were first evaluated for optimized reaction conditions, followed by a systematical investigation of 1,4-Dioxane removal in the photo-Fenton membrane filtration mode. Under optimized conditions, the 1,4-Dioxane removal rate reached up to 16% with combination of 2 mmol/L H₂O₂ and UV₃₆₅ irradiation (2000 µW/cm²) when the feed water was filtered by the photo-Fenton reactive membrane at a hydraulic retention time of 6 min. The removal efficiency and apparent quantum yield (AQY) were both enhanced in the filtration compared to the batch mode of the same photo-Fenton reaction. Moreover, the proposed degradation pathways were analyzed by density functional theory (DFT) calculations, which provided a new insight into the degradation mechanisms of 1,4-Dioxane in photo-Fenton reactions on the functionalized ceramic membrane.     

Sonocatalytic degradation of tetracycline antibiotic in aqueous solution by sonocatalysis

Tetracycline (TC), one of the most common antibiotics, is often poorly bio-degraded in conventional wastewater treatment plants. In this study, the sonocatalytic degradation of TC was investigated using TiO₂ nano-particles as catalyst. The effect of pH, initial TC concentrations, reaction times, and H₂O₂ concentrations were evaluated. The efficacy of ultrasonic irradiation alone in the removal of this pollutant was negligible but removal efficiency increased upon addition of TiO₂ up to 250 mg L^?1; increase of pH and initial TC concentration attenuated TC degradation. Addition of H₂O₂ raised the removal efficiency so that complete removal of TC was achieved within 75 min.     

Preparation of effective TiO<Subscript>2</Subscript>/Bi<Subscript>2</Subscript>O<Subscript>3</Subscript> photocatalysts for water treatment

Photocatalytic oxidation using semiconductors is one of the advanced oxidation processes for degradation of organic pollutants in water and air. TiO₂ is an excellent photocatalyst that can mineralize a large range of organic pollutants such as pesticides and dyes. The main challenge is to improve the efficiency of the TiO₂ photocatalyst and to extend TiO₂ light absorption spectra to the visible region. A potential solution is to couple TiO₂ with a narrow band gap semiconductor possessing a higher conduction band such as bismuth oxide. Therefore, here we prepared Bi₂O₃/TiO₂ heterojunctions by the impregnation method with different Bi/Ti ratio. The prepared composites have been characterized by UV–Vis diffused reflectance spectra and X-ray diffraction. The photocatalytic activity of the heterojunction has been determined from the degradation of orange II under visible and UV light. Results show that Bi₂O₃/TiO₂ heterojunctions are more effective than pure TiO₂-anatase under UV-A irradiation, with an optimum for the Bi/Ti ratio of 5 %, for the photocatalytic degradation of Orange II. However, the photocatalytic activity under irradiation at λ higher than 420 nm is not much improved. Under UV–visible radiation, the two semiconductors are activated. We propose a mechanism explaining why our products are more effective under UV–visible irradiation. In this case the charge separation is enhanced because a part of photogenerated electrons from the conduction band of TiO₂ will go to the conduction band of bismuth oxide. In this composite, titanium dioxide is the main photocatalyst, while bismuth oxide acts as adsorbent photosensitizer under visible light.