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1.
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.  相似文献   

2.
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.  相似文献   

3.
Most studies on the treatment of chlorinated contaminants by Fe(0) focus on aqueous system tests. However, few is known about the effectiveness of these tests for degrading chlorinated contaminants such as 1,1,1-trichloroethane (TCA) in soil. In this work, the reductive degradation performance of 1,1,1-TCA by Fe(0) was thoroughly investigated in a soil slurry system. The effects of various factors including acid-washed iron, the initial 1,1,1-TCA concentration, Fe(0) dosage, slurry pH, and common constituents in groundwater and soil such as Cl?, HCO3 ?, SO4 2?, and NO3 ? anions and humic acid (HA) were evaluated. The experimental results showed that 1,1,1-TCA could be effectively degraded in 12 h for an initial Fe(0) dosage of 10 g L?1 and a soil/water mass ratio of 1:5. The soil slurry experiments showed two-stage degradation kinetics: a slow reaction in the first stage and a fast reductive degradation of 1,1,1-TCA in the second stage. The reductive degradation of 1,1,1-TCA was expedited as the mass concentration of Fe(0) increased. In addition, high pHs adversely affected the degradation of 1,1,1-TCA over a pH range of 5.4–8.0 and the reductive degradation efficiency decreased with increasing slurry pH. The initial 1,1,1-TCA concentration and the presence of Cl? and SO4 2? anions had negligible effects. HCO3 ? anions had a accelerative effect on 1,1,1-TCA removal, and both NO3 ? and HA had inhibitory effects. A Cl? mass balance showed that the amount of Cl? ions released into the soil slurry system during the 1,1,1-TCA degradation increased with increasing reaction time, suggesting that the main degradation mechanism of 1,1,1-TCA by Fe(0) in a soil slurry system was reductive dechlorination with 1,1-DCA as the main intermediate. In conclusion, this study provides a theoretical basis for the practical application of the remediation of contaminated sites containing chlorinated solvent.  相似文献   

4.
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 %.  相似文献   

5.
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.  相似文献   

6.

Extracts of copoazu (Theobroma gramdiflorum), canangucha (Maurita Flexuosa), and coffee (Coffea arabica) were explored as enhancers of the solar photo-Fenton process to eliminate acetaminophen, sulfamethoxazole, carbamazepine, and diclofenac in raw municipal wastewater. The process, at pH 6.2 and 5 mg L?1 of iron without the presence of extracts, had a very limited action (~35% of the pollutants degradation at 90 min of treatment) due to the iron precipitation. Interestingly, the extract addition increased the soluble iron forms, but only copoazu extract improved the pollutant degradation (~95% of elimination at 20 min of the process action). The copoazu extract components acted as natural complexing agents, maintaining the soluble iron up to 2 mg L?1 even after 90 min and, consequently, enhancing the pollutant degradation. The effect of copoazu extract dose on the process performance was also assessed, finding that an iron:polyphenols (from the copoazu extract) at a molar ratio equal to 1:0.16 was the most favorable condition. Then, the process improved by copoazu extract was applied to raw municipal wastewater. Remarkably, the process led to ~90% of total pharmaceuticals degradation at 20 min of treatment. This work evidenced the feasibility of amazonian fruit extracts to improve the solar photo-Fenton process to degrade pharmaceuticals in aqueous matrices at near-neutral pH.

  相似文献   

7.
In this paper, for the first time, faujasite Y zeolite impregnated with iron (III) was employed as a catalyst to remove a real cocktail of micropollutants inside real water samples from the Meurthe river by the means of the heterogeneous photo-Fenton process. The catalyst was prepared by the wet impregnation method using iron (III) nitrate nonahydrate as iron precursor. First, an optimization of the process parameters was conducted using phenol as model macro-pollutant. The hydrogen peroxide concentration, the light wavelength (UV and visible) and intensity, the iron loading immobilized, as well as the pH of the solution were investigated. Complete photo-Fenton degradation of the contaminant was achieved using faujasite containing 20 wt.% of iron, under UV light, and in the presence of 0.007 mol/L of H2O2 at pH 5.5. In a second step, the optimized process was used with real water samples from the Meurthe river. Twenty-one micropollutants (endocrine disruptors, pharmaceuticals, personal care products, and perfluorinated compounds) including 17 pharmaceutical compounds were specifically targeted, detected, and quantified. All the initial concentrations remained in the range of nanogram per liter (0.8–88 ng/L). The majority of the micropollutants had a large affinity for the surface of the iron-impregnated faujasite. Our results emphasized the very good efficiency of the photo-Fenton process with a cocktail of a minimum of 21 micropollutants. Except for sulfamethoxazole and PFOA, the concentrations of all the other microcontaminants (bisphenol A, carbamazepine, carbamazepine-10,11-epoxide, clarithromycin, diclofenac, estrone, ibuprofen, ketoprofen, lidocaine, naproxen, PFOS, triclosan, etc.) became lower than the limit of quantification of the LC-MS/MS after 30 min or 6 h of photo-Fenton treatment depending on their initial concentrations. The photo-Fenton degradation of PFOA can be neglected. The photo-Fenton degradation of sulfamethoxazole obeys first-order kinetics in the presence of the cocktail of the other micropollutants.  相似文献   

8.

The objective of this study was to quantify the effectiveness of different pretreated iron byproducts from the automotive industry to degrade DDT [(1,1,1-trichloro-2,2-bis(4-chlorophenyl) ethane] in aqueous solutions and soil slurry. Iron byproducts from automotive manufacturing were pretreated by three different methods (heating, solvent and 0.5N HCl acid washing) prior to experimentation. All pretreated irons were used at 5% (wt v? 1) to treat 0.014 mM (5 mgL? 1) of DDT in aqueous solution. Among the pretreated irons, acid pretreated iron results in the fastest destruction rates, with a pseudo first-order degradation rate of 0.364 d? 1. By lowering the pH of the DDT aqueous solution from 9 to 3, destruction kinetic rates increase more than 20%. In addition, when DDT-contaminated soil slurry (3.54 mg kg? 1) was incubated with 5% (wt v? 1) acid-pretreated iron, more than 90% destruction of DDT was observed within 8 weeks. Moreover, DDT destruction kinetics were enhanced when Fe(II), Fe(III) or Al(III) sulfate salts were added to the soil slurry, with the following order of destruction kinetics: Al(III) sulfate > Fe(III) sulfate > Fe(II) sulfate. These results provide proof-of concept that inexpensive iron byproducts of the automotive industry can be used to remediate DDT-contaminated water and soil.  相似文献   

9.
Intensive use of chlorinated pesticides from the 1960s to the 1990s has resulted in a diffuse contamination of soils and surface waters in the banana-producing areas of the French West Indies. The purpose of this research was, for the first time, to examine the degradation of two of these persistent pollutants – chlordecone (CLD) and beta-hexachlorocyclohexane (β-HCH) in 1 mg L?1 synthetic aqueous solutions by means of photolysis, (photo-) Fenton oxidation and ozonation processes. Fenton oxidation is not efficient for CLD and yields less than 15% reduction of β-HCH concentration in 5 h. Conversely, both molecules can be quantitatively converted under UV-Vis irradiation reaching 100% of degradation in 5 h, while combination with hydrogen peroxide and ferrous iron does not show any significant improvement except in high wavelength range (>280 nm). Ozonation exhibits comparable but lower degradation rates than UV processes. Preliminary identification of degradation products indicated that hydrochlordecone was formed during photo-Fenton oxidation of CLD, while for β-HCH the major product peak exhibited C3H3Cl2 as most abundant fragment.  相似文献   

10.
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.  相似文献   

11.
The degradation of ciprofloxacin was studied in aqueous solutions by using a continuous flow homogeneous photo-Fenton process under simulated solar light. The effect of different operating conditions on the degradation of ciprofloxacin was investigated by changing the hydrogen peroxide (0–2.50 mM) and iron(II) sulphate (0–10 mg Fe L?1) concentrations, as well as the pH (2.8–10), irradiance (0–750 W m?2) and residence time (0.13–3.4 min) of the process. As expected, the highest catalytic activity in steady state conditions was achieved at acidic pH (2.8), namely 85 % of ciprofloxacin conversion, when maintaining the other variables constant (i.e. 2.0 mg L?1 of iron(II), 2.50 mM of hydrogen peroxide, 1.8 min of residence time and 500 W m?2 of irradiance). Additionally, magnetite magnetic nanoparticles (ca. 20 nm of average particle size) were synthesized, characterized and tested as a possible catalyst for this reaction. In this case, the highest catalytic activity was achieved at natural pH, namely a 55 % average conversion of ciprofloxacin in 1.8 min of residence time and under 500 W m?2. Some of the photocatalytic activity was attributed to Fe2+ leaching from the magnetic nanoparticles to the solution.  相似文献   

12.
改性TiO2光催化降解三苯甲烷类污染物   总被引:1,自引:0,他引:1  
张一兵  陈博  谈军 《环境工程学报》2012,6(9):3101-3105
以硫酸钛为原料采用水热法制备了掺Fe3+TiO2晶体粉末,采用X射线衍射仪(XRD)对样品的结构进行了表征。在可见光条件下,用溴酚蓝、甲基绿、甲基蓝、孔雀石绿、甲基紫和碱性品红等6种典型三苯甲烷类化合物为目标降解物,研究了以自制的掺Fe3+TiO2晶体粉末对它们的催化降解作用。实验结果表明,制备的掺Fe3+TiO2晶体属于锐钛矿型。6种化合物的光催化降解反应遵循拟一级动力学规律,且可用Langmuir-Hinshelwood(L-H)动力学模型描述,其表观反应速度常数(k)的大小顺序为:溴酚蓝<甲基绿<甲基蓝<孔雀石绿<甲基紫<碱性品红,大小变化次序与其半衰期t1/2成反比,并从分子结构上对它们的降解规律进行定性解释。  相似文献   

13.
The photo-Fenton reaction was applied as a novel method for the removal of volatile organic compounds (VOCs) in the gas phase, and its effectiveness was experimentally examined. In conventional VOCs removal methods using a photocatalyst or ozone, VOCs are oxidized in the gas phase. Therefore, incompletely oxidized intermediates, which may have adverse effects on health, are likely to contaminate the treated air. On the other hand, in the VOCs removal method developed in this study, because the VOCs are oxidized in the liquid phase by the photo-Fenton reaction, any incompletely oxidized intermediates produced are confined to the liquid phase. As a result, the contamination of the treated air by these harmful intermediates can be prevented. Using a semi-batch process, it was found that the removal efficiency for toluene in a one-pass test (residence time of 17 s) was 61%, for an inlet toluene gas concentration of 930 ppbv, an initial iron ion concentration of 20 mg L−1, and an initial hydrogen peroxide concentration of 630 mg L−1. The removal efficiency was almost constant as long as H2O2 was present in the solution. Proton transfer reaction mass spectrometry analysis confirmed the absence of any incompletely oxidized intermediates in the treated air.  相似文献   

14.
Zero-valent iron nanoparticles (nZVI, diameter < 90 nm, specific surface area = 25 m2 g?1) have been used under anoxic conditions for the remediation of pesticides alachlor and atrazine in water. While alachlor (10, 20, 40 mg L?1) was reduced by 92–96% within 72 h, no degradation of atrazine was observed. The alachlor degradation reaction was found to obey first-order kinetics very closely. The reaction rate (35.5 × 10?3–43.0 × 10?3 h?1) increased with increasing alachlor concentration. The results are in conformity with other researchers who worked on these pesticides but mostly with micro ZVI and iron filings. This is for the first time that alachlor has been degraded under reductive environment using nZVI. The authors contend that nZVI may prove to be a simple method for on-site treatment of high concentration pesticide rinse water (100 mg L?1) and for use in flooring materials in pesticide filling and storage stations.  相似文献   

15.
Degradation of atrazine by catalytic ozonation in the presence of iron scraps (ZVI/O3) was carried out. The key operational parameters (i.e., initial pH, ZVI dosage, and ozone dosage) were optimized by the batch experiments, respectively. This ZVI/O3 system exhibited much higher degradation efficiency of atrazine than the single ozonation, ZVI, and traditional ZVI/O2 systems. The result shows that the pseudo-first-order constant (0.0927?min?1) and TOC removal rate (86.6%) obtained by the ZVI/O3 process were much higher than those of the three control experiments. In addition, X-ray diffraction (XRD) analysis indicates that slight of γ-FeOOH and Fe2O3 were formed on the surface of iron scrap after ZVI/O3 treatment. These corrosion products exhibit high catalytic ability for ozone decomposition, which could generate more hydroxyl radical (HO?) to degrade atrazine. Six transformation intermediates were identified by liquid chromatography-mass spectrometry (LC-MS) analysis in ZVI/O3 system, and the degradation pathway of atrazine was proposed. Toxicity tests based on the inhibition of the luminescence emitted by Photobacterium phosphoreum and Vibrio fischeri indicate the detoxification of atrazine by ZVI/O3 system. Finally, reused experiments indicate the approving recyclability of iron scraps. Consequently, the ZVI/O3 system could be as an effective and promising technology for pesticide wastewater treatment.  相似文献   

16.
In this study, the degradation of molinate through heterogeneous photocatalysis, using two different types of the semiconductor TiO2 as photocatalyst, as well as through homogeneous treatment, applying the photo-Fenton reaction, has been investigated. As far as heterogeneous photocatalysis is concerned, the degradation of the pesticide follows apparent first-order kinetics, while the type of the catalyst and the pH value of the solution affect the degradation rate. The effect of the addition of electron scavengers (H2O2 and K2S2O8) was also studied. In the case of photo-Fenton-assisted system, the degradation also follows pseudo-first-order kinetics. Parameters such as iron’s and electron scavenger’s concentration and inorganic ions strongly affect the degradation rate. The extent of pesticide mineralization was investigated using dissolved organic carbon (DOC) measurements. The toxicity of the treated solution was evaluated using the Microtox test based on the luminescent bacteria Vibrio fischeri. The detoxification and mineralization efficiency was found to be dependent on the system studied, and although it did not follow the rate of pesticide disappearance, it took place in considerable extent. The study of the photodegradation treatment was completed by the determination of the intermediate by-products formed during the process, which was carried out using LC-MS/MS technique and led to similar compounds with both processes.  相似文献   

17.
The ability of free ferrous ion activated persulfate (S2O82−) to generate sulfate radicals (SO4) for the oxidation of trichloroethylene (TCE) is limited by the scavenging of SO4 with excess Fe2+ and a quick conversion of Fe2+ to Fe3+. This study investigated the applicability of ethylene-diamine-tetra-acetic acid (EDTA) chelated Fe3+ in activating persulfate for the destruction of TCE in aqueous phase under pH 3, 7 and 10. Fe3+ and EDTA alone did not appreciably degrade persulfate. The presence of TCE in the EDTA/Fe3+ activated persulfate system can induce faster persulfate and EDTA degradation due to iron recycling to activate persulfate under a higher pH condition. Increasing the pH leads to increases in pseudo-first-order-rate constants for TCE, S2O82− and EDTA degradations, and Cl generation. Accordingly, the experiments at pH 10 with different EDTA/Fe3+ molar ratios indicated that a 1/1 ratio resulted in a remarkably higher degradation rate at the early stage of reaction as compared to results by other ratios. Higher persulfate dosage under the EDTA/Fe3+ molar ratio of 1/1 resulted in greater TCE degradation rates. However, increases in persulfate concentration may also lead to an increase in the rate of persulfate consumption.  相似文献   

18.
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.  相似文献   

19.
Parameters that influence the zero valent iron mediated degradation of the pharmaceutical diazepam (DZP) were evaluated including the iron concentration and its pre-treatment, the effect of complexation with EDTA and oxic versus anoxic condition. It was observed that acid pre-treatment of iron particles is important for degradation efficiency and that H2SO4 is a better choice than HCl, resulting in higher degradation of DZP. Under oxic conditions, the degradation of DZP achieved 96% after 60 min using Fe0 (25 g L−1) pre-treated with H2SO4 in the presence of EDTA (119 mg L−1), while mineralization achieved around 60% after the same time. Under anoxic conditions, degradation occurred, however at lower extent, achieving 67% after 120 min. The addition of EDTA improved the treatment efficiency in 20% leading to 99% DZP degradation after 120 min. The first intermediates formed during DZP degradation were identified using LC/MS analysis and revealed the formation of mono- and di-hydroxylated products from DZP during Fe0/EDTA/O2 degradation, which evidences that OH was the main oxidizing species formed in this process.  相似文献   

20.
The aims of this study were (a) to evaluate the degradation of acetamiprid with the use of Fenton reaction, (b) to investigate the effect of different concentrations of H2O2 and Fe2+, initial pH and various iron salts, on the degradation of acetamiprid and (c) to apply response surface methodology for the evaluation of degradation kinetics.  相似文献   

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