Effect of ethylenediamine-N,N′-disuccinic acid on Fenton and photo-Fenton processes using goethite as an iron source: optimization of parameters for bisphenol A degradation

The main disadvantage of using iron mineral in Fenton-like reactions is that the decomposition rate of organic contaminants is slower than in classic Fenton reaction using ferrous ions at acidic pH. In order to overcome these drawbacks of the Fenton process, chelating agents have been used in the investigation of Fenton heterogeneous reaction with some Fe-bearing minerals. In this work, the effect of new iron complexing agent, ethylenediamine-N,N'-disuccinic acid (EDDS), on heterogeneous Fenton and photo-Fenton system using goethite as an iron source was tested at circumneutral pH. Batch experiments including adsorption of EDDS and bisphenol A (BPA) on goethite, H₂O₂ decomposition, dissolved iron measurement, and BPA degradation were conducted. The effects of pH, H₂O₂ concentration, EDDS concentration, and goethite dose were studied, and the production of hydroxyl radical (^?OH) was detected. The addition of EDDS inhibited the heterogeneous Fenton degradation of BPA but also the formation of ^?OH. The presence of EDDS decreases the reactivity of goethite toward H₂O₂ because EDDS adsorbs strongly onto the goethite surface and alters catalytic sites. However, the addition of EDDS can improve the heterogeneous photo-Fenton degradation of BPA through the propagation into homogeneous reaction and formation of photochemically efficient Fe-EDDS complex. The overall effect of EDDS is dependent on the H₂O₂ and EDDS concentrations and pH value. The high performance observed at pH 6.2 could be explained by the ability of O ₂ ^?? to generate Fe(II) species from Fe(III) reduction. Low concentrations of H₂O₂ (0.1 mM) and EDDS (0.1 mM) were required as optimal conditions for complete BPA removal. These findings regarding the capability of EDDS/goethite system to promote heterogeneous photo-Fenton oxidation have important practical implications for water treatment technologies.     

溴酸钾对二茂铁(Fc)非均相Fenton效能的影响

研究了KBrO3对二茂铁(Fc)非均相Fenton效能的影响,深入考察了KBrO3对体系中Fc溶解、H2O2分解和羟基自由基(·OH)生成的影响。结果表明,KBrO3的加入对不同反应阶段Fc/Fenton体系的效能均有明显的促进作用,初始阶段主要是由于KBrO3对·OH产生的促进作用所致,后期主要是由于KBrO3促进了体系中Fc的溶解,使得体系中溶解态的Fc催化的均相Fenton反应的比例增加,体系中H2O2的分解加快,·OH的表观生成率增加,进而促进了反应的进行。无KBrO3添加,pH=4,MB初始浓度为10 mg/L,Fc的量为1.6×10-3mol/L,[H2O2]/[MB]=3.14时,45 min时,MB的剩余率为9.1%,105 min时为0。当KBrO3的用量为3×10-4mol/L时,反应45 min后MB的去除率即可达到100%。随着KBrO3浓度的增加,其对Fc/Fenton效能的促进作用增强。     

Degradation of Acid Orange 7 in aqueous solution by dioxygen activation in a pyrite/H2O/O2 system

Increasing attention has been paid to pyrite due to its ability to generate hydroxyl radicals in air-saturated solutions. In this study, the mineral pyrite was studied as a catalyst to activate molecular oxygen to degrade Acid Orange 7 (AO7) in aqueous solution. A complete set of control experiments were conducted to optimize the reaction conditions, including the dosage of pyrite, the AO7 concentration, as well as the initial pH value. The role of reactive oxygen species (ROS) generated by pyrite in the process was elucidated by free radical quenching reactions. Furthermore, the concentrations of Fe(II) and total Fe formed were also measured. The mechanism for the production of ROS in the pyrite/H₂O/O₂ system was that H₂O₂ was formed by hydrogen ion and superoxide anion (O₂ ^·?) which was produced by the reaction of pyrite activating O₂ and then reacted with Fe(II) dissolved from pyrite to produce ^·OH through Fenton reaction. The findings suggest that pyrite/H₂O/O₂ system is potentially practical in pollution treatment. Moreover, the results provide a new insight into the understanding of the mechanism for degradation of organic pollutants by pyrite.     

Fe(III)–EDDS complex in Fenton and photo-Fenton processes: from the radical formation to the degradation of a target compound

The present work compares the efficiency of homogenous Fenton and photo-Fenton processes in the presence of Fe(III)–EDDS complex under different experimental conditions. 4-tert-Butylphenol (4-t-BP), which is one of the endocrine disrupting chemicals, was used as a model pollutant to investigate the Fenton and photo-Fenton application. The efficiency of homogenous photo-Fenton process was significantly much higher than homogenous Fenton process, which is due to the rapid formation of Fe²⁺ under UV irradiation of the iron complex and the photochemical formation of HO^? from the photolysis of the complex Fe(III)–EDDS. Through the degradation of 4-t-BP, the effect of Fe(III)–EDDS concentration, H₂O₂ concentration, pH, and oxygen was investigated in both processes. Such trend was also correlated with pH calculating the polychromatic Fe²⁺ quantum yield formation at pH 4.0, 6.0, and 8.6. The results showed that at high Fe(III)–EDDS and H₂O₂ concentrations, a negative effect was found. By the way, the Fenton process was found to be enhanced at basic pH. These results can be very useful for the use and optimization of such iron complex in water treatment process as function of different physico-chemical conditions.     

Influence of operational key parameters on the photocatalytic decolorization of Rhodamine B dye using Fe2+/H2O2/Nb2O5/UV system

The present research deals with the development of a new heterogeneous photocatalysis and Fenton hybrid system for the removal of color from textile dyeing wastewater as Rhodamine B (RhB) solutions by using Fe²⁺/H₂O₂/Nb₂O₅ as a photocatalytic system. The application of this photocatalytic system for the decolorization of dye contaminants is not reported in the literature yet. Different parameters like dye concentration, Nb₂O₅/Fe²⁺ catalyst amount, pH, and H₂O₂ concentration have been studied. The optimum conditions for the decolorization of the dye were initial concentration of 10 mg L^?1 of dye, pH 4, and Nb₂O₅/Fe²⁺ catalyst concentration of 0.5 g L^?1/50 mg L^?1. The optimum value of H₂O₂ concentration for the conditions used in this study was 700 mg L^?1. Moreover, the efficiency of the Nb₂O₅/photo-Fenton hybrid process in comparison to photo-Fenton alone and a dark Fenton process as a control experiment to decolorize the RhB solution has been investigated. The combination of photo-Fenton and Nb₂O₅ catalysts has been proved to be the most effective for the treatment of such type of wastewaters. The results revealed that the RhB dye was decolorized in a higher percent (78 %) by the Nb₂O₅/photo-Fenton hybrid process (Fe²⁺/H₂O₂/Nb₂O₅/UV) than by the photo-Fenton process alone (37 %) and dark Fenton process (14 %) after 120 min of treatment. Moreover, the Nb₂O₅ catalyst as a heterogeneous part of the photocatalytic system was demonstrated to have good stability and reusability.     

Kinetic degradation of the pollutant guaiacol by dark Fenton and solar photo-Fenton processes

This work is first intended to optimize the experimental conditions for the maximum degradation of guaiacol (2-methoxyphenol) by Fenton’s reagent, and second, to improve the process efficiency through the use of solar radiation. Guaiacol is considered as a model compound of pulp and paper mill effluent. The experiments were carried out in a laboratory-scale reactor subjected or not to solar radiation. Hydrogen peroxide solution was continuously introduced into the reactor at a constant flow rate. The kinetics of organic matter decay was evaluated by means of the chemical oxygen demand (COD) and the absorbance measurements. The experimental results showed that the Fenton and solar photo-Fenton systems lead successfully to 90% elimination of COD and absorbance at 604 nm from a guaiacol solution under particular experimental conditions. The COD removal always obeyed a pseudo-first-order kinetics. The effect of pH, temperature, H₂O₂ dosing rate, initial concentration of Fe²⁺, and initial COD was investigated using the Fenton process. The solar photo-Fenton system needed less time and consequently less quantity of H₂O₂. Under the optimum experimental conditions, the solar photo-Fenton process needs a dose of H₂O₂ 40% lower than that used in the Fenton process to remove 90% of COD.     

Factors that have an effect on degradation of diclofenac in aqueous solution by gamma ray irradiation

Purpose  

Gamma ray irradiation is considered as an effective way to degrade diclofenac. However, due to the extensive coexisting substances in natural waters, the use of gamma ray irradiation for degradation is often influenced by multiple factors. The various factors that affect degradation efficiency, such as initial diclofenac concentration, initial pH, and the concentration of the additives including H₂O₂ (·OH radical promoter), CH₃OH (·OH radical scavenger), thiourea (·OH, H·, and e_aq⁻ scavenger), humic acid, and NO₃⁻ (coexisting substances in natural waters), are investigated. Furthermore, possible intermediate products are identified and corresponding transformation pathways are proposed.     

Degradation of rhodamine B by Fe(0)-based Fenton process with H2O2

Degradation of rhodamine B by Fe(0)-based Fenton process with H₂O₂ was investigated. The effects of H₂O₂ dose, Fe(0) dose, initial concentration of rhodamine B and initial pH value on the degradation of rhodamine B were examined. The results showed that the degradation and mineralization of rhodamine B occurred with low dose of H₂O₂ and Fe(0). The intermediates of rhodamine B were analyzed with UV-Vis spectrophotometry and ion chromatography and the mechanism of oxidative degradation of rhodamine B was also discussed. The reactive oxygen species (·OH) produced in Fe(0)-based Fenton process with H₂O₂ is the key to the degradation of rhodamine B by ways of N-de-ethylation, chromophore cleavage, ring-opening and mineralization.     

Fenton氧化法对磺胺类抗生素的降解动力学

采用Fenton氧化法同时降解水溶液中磺胺吡啶(SPY)、磺胺二甲基嘧啶(SMZ)和磺胺甲噁唑(SMX)。系统考查了初始H2O2浓度、Fe2+浓度、pH对3种磺胺类抗生素降解性能的影响。结果表明,3种磺胺抗生素被完全降解的最佳Fenton氧化条件是:H2O2浓度为2.0 mmol/L,Fe2+浓度为0.10 mmol/L,pH为3.0~3.5,反应时间为20 min。Fenton试剂对3种磺胺类抗生素的降解符合一级反应动力学,速度常数为0.0318~0.2002 min-1。     

Fenton氧化活性深蓝染料B-2GLN的动力学

为了考查H2O2/Fe2+的摩尔比和H2O2的初始剂量、pH值以及活性深蓝染料B-2GLN(RDB B-2GLN)的初始浓度对活性深蓝染料B-2GLN降解过程的影响,采用在线分光光度法对活性深蓝染料B-2GLN的Fenton氧化过程进行了研究,探讨了其动力学过程,并利用气相色谱-质谱联用分析降解中间产物。结果显示,采用Fenton氧化降解水溶液中活性深蓝染料B-2GLN,在H2O2的剂量为2.635 mmol/L,pH值为2.7,H2O2/Fe2+的摩尔比为37.80和活性深蓝染料B-2GLN的初始浓度16 mg/L的条件下,得到300 s后活性深蓝染料B-2GLN的最大色度去除率为85.04%。水溶液中活性深蓝染料B-2GLN与·OH的反应速率常数为2.62×1011L/(mol·s)。活性深蓝B-2GLN染料的分子结构被Fenton试剂分解而未被完全矿化,同时对活性深蓝染料降解产物进行了分析。在线分光光度法是研究染料色度去除率的一种精确、快速与可行的方法。     

Parathion degradation and its intermediate formation by Fenton process in neutral environment

The purpose of this study is to investigate parathion degradation by Fenton process in neutral environment. The initial parathion concentration for all the degradation experiments was 20 ppm. For hydrogen ion effect on Fenton degradation, the pH varied from 2 to 8 at the [H₂O₂] to [Fe²⁺] ratio of 2-2 mM, and the result showed pH 3 as the most effective environment for parathion degradation by Fenton process. Apparent degradation was also observed at pH 7. The subsequent analysis for parathion degradation was conducted at pH 7 because most environmental parathion exists in the neutral environment. Comparing the parathion degradation results at various Fenton dosages revealed that at Fe²⁺ concentrations of 0.5, 1.0 and 1.5 mM, the Fenton reagent ratio ([H₂O₂]/[Fe²⁺]) for best-removing performance were found as 4, 3, and 2, resulting in the removal efficiencies of 19%, 48% and 36%, respectively. Further increase in Fe²⁺ concentration did not cause any increase of the optimum Fenton reagent ratio for the best parathion removal. The result from LC-MS also indicated that hydroxyl radicals might attack the PS double bond, the single bonds connecting nitro-group, nitrophenol, or the single bond within ethyl groups of parathion molecules forming paraoxons, nitrophenols, nitrate/nitrite, thiophosphates, and other smaller molecules. Lastly, the parathion degradation by Fenton process at the presence of humic acids was investigated, and the results showed that the presence of 10 mg L⁻¹ of humic acids in the aqueous solution enhanced the parathion removal by Fenton process twice as much as that without the presence of humic acids.     

Application of Fenton, photo-Fenton, solar photo-Fenton, and UV/H2O2 to degradation of the antineoplastic agent mitoxantrone and toxicological evaluation

In the present study, selected advanced oxidation processes (AOPs)—namely, photo-Fenton (with Fe²⁺, Fe³⁺, and potassium ferrioxalate—FeOx—as iron sources), solar photo-Fenton, Fenton, and UV/H₂O₂—were investigated for degradation of the antineoplastic drug mitoxantrone (MTX), frequently used to treat metastatic breast cancer, skin cancer, and acute leukemia. The results showed that photo-Fenton processes employing Fe(III) and FeOx and the UV/H₂O₂ process were most efficient for mineralizing MTX, with 77, 82, and 90 % of total organic carbon removal, respectively. MTX probably forms a complex with Fe(III), as demonstrated by voltammetric and spectrophotometric measurements. Spectrophotometric titrations suggested that the complex has a 2:1 Fe³⁺:MTX stoichiometric ratio and a complexation constant (K) of 1.47 × 10⁴ M^–1, indicating high MTX affinity for Fe³⁺. Complexation partially inhibits the involvement of iron ions and hence the degradation of MTX during photo-Fenton. The UV/H₂O₂ process is usually slower than the photo-Fenton process, but, in this study, the UV/H₂O₂ process proved to be more efficient due to complexing of MTX with Fe(III). The drug exhibited no cytotoxicity against NIH/3T3 mouse embryonic fibroblast cells when oxidized by UV/H₂O₂ or by UV/H₂O₂/FeOx at the concentrations tested.     

粉煤灰负载铁离子催化氧化活性黄染料废水

以粉煤灰为载体,制备铁/粉煤灰负载型催化剂,并利用该催化剂催化H2O2氧化降解活性黄染料废水,探讨了H2O2投加量、催化剂投加量、染料初始浓度和初始pH值等因素对染料废水COD去除率和脱色率的影响。结果表明,当染料废水COD初始浓度为200 mg/L,初始pH值为1.7,投加0.5 g/100 mL催化剂及加入1.0 mL浓度为1.13 mol/L的H2O2溶液时,处理效果最好,此时染料废水的COD去除率和脱色率分别达到63%和99%,并且废水的可生化性得到很大的提高。利用该负载催化剂能够有效地减少活性黄染料废水中Fe3+的残留量。     

The use of artificial neural network (ANN) for the prediction and simulation of oil degradation in wastewater by AOP

The application of advanced oxidation process (AOP) in the treatment of wastewater contaminated with oil was investigated in this study. The AOP investigated is the homogeneous photo-Fenton (UV/H₂O₂/Fe⁺²) process. The reaction is influenced by the input concentration of hydrogen peroxide H₂O₂, amount of the iron catalyst Fe⁺², pH, temperature, irradiation time, and concentration of oil in the wastewater. The removal efficiency for the used system at the optimal operational parameters (H₂O₂?=?400 mg/L, Fe⁺²?=?40 mg/L, pH?=?3, irradiation time?=?150 min, and temperature?=?30 °C) for 1,000 mg/L oil load was found to be 72 %. The study examined the implementation of artificial neural network (ANN) for the prediction and simulation of oil degradation in aqueous solution by photo-Fenton process. The multilayered feed-forward networks were trained by using a backpropagation algorithm; a three-layer network with 22 neurons in the hidden layer gave optimal results. The results show that the ANN model can predict the experimental results with high correlation coefficient (R ²?=?0.9949). The sensitivity analysis showed that all studied variables (H₂O₂, Fe⁺², pH, irradiation time, temperature, and oil concentration) have strong effect on the oil degradation. The pH was found to be the most influential parameter with relative importance of 20.6 %.     

Arsenic(III) and iron(II) co-oxidation by oxygen and hydrogen peroxide: Divergent reactions in the presence of organic ligands

Iron-catalyzed oxidation of As(III) to As(V) can be highly effective for toxic arsenic removal via Fenton reaction and Fe(II) oxygenation. However, the contribution of ubiquitous organic ligands is poorly understood, despite its significant role in redox chemistry of arsenic in natural and engineered systems. In this work, selected naturally occurring organic ligands and synthetic ligands in co-oxidation of Fe(II) and As(III) were examined as a function of pH, Fe(II), H₂O₂, and radical scavengers (methanol and 2-propanol) concentration. As(III) was not measurably oxidised in the presence of excess ethylenediaminetetraacetic acid (EDTA) (i.e. Fe(II):EDTA < 1:1), contrasting with the rapid oxidation of Fe(II) by O₂ and H₂O₂ at neutral pH under the same conditions. However, partial oxidation of As(III) was observed at a 2:1 ratio of Fe(II):EDTA. Rapid Fe(II) oxidation in the presence of organic ligands did not necessarily result in the coupled As(III) oxidation. Organic ligands act as both iron speciation regulators and radicals scavengers. Further quenching experiments suggested both hydroxyl radicals and high-valent Fe species contributed to As(III) oxidation. The present findings are significant for the better understanding of aquatic redox chemistry of iron and arsenic in the environment and for optimization of iron-catalyzed arsenic remediation technology.     

Catalytic degradation of Orange II by UV-Fenton with hydroxyl-Fe-pillared bentonite in water

Although homogeneous photo-Fenton system is a very efficient method for organic wastewater treatment, it suffers from costly pH adjustment as well as difficult separation of catalysts from aqueous in practical application. Through cation exchange reaction, hydroxyl-Fe-pillared bentonite (H-Fe-P-B) was successfully prepared as a solid catalyst for UV-Fenton to degrade non-biodegradable azo-dye Orange II. Compared with raw bentonite, the content of iron, interlamellar distance and external surface area of H-Fe-P-B increased remarkably. H-Fe-P-B had good photosensitivity and catalyst reactivity. And the catalytic activity of H-Fe-P-B for H(2)O(2) came from hydroxyl-Fe between sheets rather than Fe(3+) or Fe(2+) in tetrahedral or octahedral sheets of bentonite. In UVA-H(2)O(2) system, H(2)O(2) could destroy the azo bond of excited Orange II molecules but could not effectively mineralize it. After 120 min treatment, 83% discoloration was obtained while only 2% of TOC was removed. When H-Fe-P-B was used as catalyst, a significant degradation of Orange II was observed at the same condition as UVA-H(2)O(2) system. Almost 100% discoloration and more than 60% TOC removal of Orange II could be achieved after 120 min treatment. Because of the strong surface acidity and the electronegativity of H-Fe-P-B, the pH range of this catalyst in the Orange II discoloration could be extended up to 9.5. And this catalyst showed good stability during Orange II degradation in water in wide range of pH (3.0-9.5). These results indicated that the H-Fe-P-B was a promising catalyst for UV-Fenton system.     

超声降解水中的磺胺嘧啶

以磺胺嘧啶(SD)为研究对象,探讨了超声功率、初始浓度、pH值以及超声协同H2O2、Fenton、TiO2等组合工艺对超声降解SD效率的影响。实验结果表明,超声可有效降解水中低浓度的SD,尤其在酸性条件下,超声降解更为显著,降解过程遵循准二级反应动力学模型。加入H2O2或TiO2可在一定程度上促进SD的超声降解,加入Fenton试剂则显著提升SD的去除率。依据量化计算以及LC-MS测定结果,探讨了SD的超声降解机理。超声降解水中SD主要是基于.OH自由基的氧化过程。     

A novel application of H2O2-Fe(II) process for arsenate removal from synthetic acid mine drainage (AMD) water

Batch experiments were carried out to investigate the influences of H₂O₂/Fe(II) molar ratio, pH, sequence of pH adjustment, initial As(V) concentration, and interfering ions on As(V) removal in H₂O₂-Fe(II) process from synthetic acid mine drainage (AMD). The optimum H₂O₂/Fe(II) molar ratio was one for arsenate removal over the pH range of 4-7. Arsenate removal at pH 3 was poor even at high Fe(II) dosage due to the high solubility of Fe(III) formed in situ. With the increase of Fe(II) dosage, arsenate removal increased progressively before a plateau was reached at pH 5 as arsenate concentration varied from 0.05 to 2.0 mg L⁻¹. However, arsenate removal was negligible at Fe/As molar ratio <3 and then experienced a striking increase before a plateau was reached at pH 7 and arsenate concentration ≥1.0 mg L⁻¹. The co-occurring ions exerted no significant effect on arsenate removal at pH 5. The experimental results with synthetic AMD revealed that this method is highly selective for arsenate removal and the co-occurring ions either improved arsenate removal or slightly depressed arsenate removal at pH 5-7. The extended X-ray absorption fine structure (EXAFS) derived As-Fe length, 3.27-3.30 Å, indicated that arsenate was removed by forming bidentate-binuclear complexes with FeO(OH) octahydra. The economic analysis revealed that the cost of the H₂O₂-Fe(II) process was only 17-32% of that of conventional Fe(III) coagulation process to achieve arsenate concentration below 10 μg L⁻¹ in treated solution. The results suggested that the H₂O₂-Fe(II) process is an efficient, economical, selective and practical method for arsenate removal from AMD.     

Degradation of ethylenethiourea pesticide metabolite from water by photocatalytic processes

In this study, photocatalytic (photo-Fenton and H₂O₂/UV) and dark Fenton processes were used to remove ethylenethiourea (ETU) from water. The experiments were conducted in a photo-reactor with an 80 W mercury vapor lamp. The mineralization of ETU was determined by total organic carbon analysis, and ETU degradation was qualitatively monitored by the reduction of UV absorbance at 232 nm. A higher mineralization efficiency was obtained by using the photo-peroxidation process (UV/H₂O₂). Approximately 77% of ETU was mineralized within 120 min of the reaction using [H₂O₂]₀ = 400 mg L^?1. The photo-Fenton process mineralized 70% of the ETU with [H₂O₂]₀ = 800 mg L^?1 and [Fe²⁺] = 400 mg L^?1, and there is evidence that hydrogen peroxide was the limiting reagent in the reaction because it was rapidly consumed. Moreover, increasing the concentration of H₂O₂ from 800 mg L^?1 to 1200 mg L^?1 did not enhance the degradation of ETU. Kinetics studies revealed that the pseudo-second-order model best fit the experimental conditions. The k values for the UV/H₂O₂ and photo-Fenton processes were determined to be 6.2 × 10^?4 mg L^?1 min^?1 and 7.7 × 10^?4 mg L^?1 min^?1, respectively. The mineralization of ETU in the absence of hydrogen peroxide has led to the conclusion that ETU transformation products are susceptible to photolysis by UV light. These are promising results for further research. The processes that were investigated can be used to remove pesticide metabolites from drinking water sources and wastewater in developing countries.     

微波-Fenton对沼液中抗生素和激素的高级氧化

采用微波强化Fenton氧化处理系统,研究H2O2浓度、Fe2+浓度、初始pH、微波辐射时间和微波辐射功率对沼液中喹乙醇、土霉素、四环素及金霉素降解效果的影响.结果发现,采用微波强化Fenton氧化降解沼液中抗生素与激素的最优条件是:H2O2浓度为40 mg/L、Fe2+浓度为12 mg/L、初始pH为4、微波辐射时间为2 min、微波辐射功率为中火(445W),沼液中喹乙醇、土霉素、四环素、金霉素和COD的去除率分别达到67％、93％、91％、88％和46％.在水浴条件下,与单独微波辐射和单独Fenton相比,微波强化Fenton氧化有明显的优越性.