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1.
Olive oil mill wastewater (OMWW), a recalcitrant pollutant, has features including high phenolic content and dark color; thereby, several chemical or physical treatments or biological processes were not able to remediate it. In this study, the treatment efficiencies of three treatments, including adsorption, biological application, and photo-Fenton oxidation were sequentially evaluated for OMWW. Adsorption, biological treatment, and photo-Fenton caused decreasing phenolic contents of 48.69 %, 59.40 %, and 95 %, respectively. However, after three sequential treatments were performed, higher reduction percentages in phenolic (total 99 %) and organic contents (90 %) were observed. Although the studied fungus has not induced significant color reduction, photo-Fenton oxidation was considered to be an attractive solution, especially for color reduction. Besides, toxicity of OMWW treatment was significantly reduced.  相似文献   

2.
Oxidation of TNT by photo-Fenton process   总被引:4,自引:0,他引:4  
Liou MJ  Lu MC  Chen JN 《Chemosphere》2004,57(9):1107-1114
A series of photo-Fenton reactions have been performed for the degradation of 2,4,6-trinitrotoluene (TNT) in a 4.2-l reactor. The degradation reaction rate of TNT followed a pseudo-first-order behavior; and the rate constants for 2.4mW cm(-2)UV only, 2.4mW cm(-2)UV/H(2)O(2), Fenton, photo-Fenton (2.4mW cm(-2)) and photo-Fenton (4.7mW cm(-2)) were 0.002min(-1), 0.007min(-1), 0.014min(-1), 0.025min(-1) and 0.037min(-1), respectively. Increasing the intensity of UV light, and the concentrations of ferrous ions and hydrogen peroxide promoted the oxidation rate under the experimental conditions in this study. The weighting factor (f), the Fe(II)-promoted efficiency (r) and the promoted-UV light efficiency (p) were calculated to clarify their effects on the TNT oxidation. Moreover, the inhibition effect of hydroxyl radical was also observed in both Fenton and photo-Fenton oxidation when the concentration of Fe(II) were higher than 2.88mM. Solid phase micro-extraction was first applied to the separation of the organic byproducts from TNT oxidation. GC/MS was employed to identify the byproducts during the Fenton and photo-Fenton oxidation of TNT. These compounds were clarified as 1,3,5-trinitrobenzene, 1-methyl-2,4-dinitrobenzene 2,5-dinitrobenzoic acid and 1,3-dinitrobenzene. By these byproducts, the mechanisms of the methyl group oxidation, decarboxylation, aromatic ring breakage, and hydrolysis can be recognized and demonstrated. The pathway of TNT oxidation by photo-Fenton process was also proposed in this study.  相似文献   

3.
INTENTION, GOAL, SCOPE, BACKGROUND: Since the intermediate products of some compounds can be more toxic and/or refractory than the original compund itself, the development of innovative oxidation technologies which are capable of transforming such compounds into harmless end products, is gaining more importance every day. Advanced oxidation processes are one of these technologies. However, it is necessary to optimize the reaction conditions for these technologies in order to be cost-effective. OBJECTIVE: The main objectives of this study were to see if complete mineralization of 4-chlorophenol with AOPs was possible using low pressure mercury vapour lamps, to make a comparison of different AOPs, to observe the effect of the existence of other ions on degradation efficiency and to optimize reaction conditions. METHODS: In this study, photochemical advanced oxidation processes (AOPs) utilizing the combinations of UV, UV/H2O2 and UV/H2O2/Fe2+ (photo-Fenton process) were investigated in labscale experiments for the degradation and mineralization of 4-chlorophenol. Evaluations were based on the reduction of 4-chlorophenol and total organic carbon. The major parameters investigated were the initial 4-chlorophenol concentration, pH, hydrogen peroxide and iron doses and the effect of the presence of radical scavengers. RESULTS AND DISCUSSION: It was observed that the 4-chlorophenol degradation efficiency decreased with increasing concentration and was independent of the initial solution pH in the UV process. 4-chlorophenol oxidation efficiency for an initial concentration of 100 mgl(-1) was around 89% after 300 min of irradiation in the UV process and no mineralization was achieved. The efficiency increased to > 99% with the UV/H2O2 process in 60 min of irradiation, although mineralization efficiency was still around 75% after 300 min of reaction time. Although the H2O2/4-CP molar ratio was kept constant, increasing initial 4-chlorophenol concentration decreased the treatment efficiency. It was observed that basic pHs were favourable in the UV/H2O2 process. The results showed that the photo-Fenton process was the most effective treatment process under acidic conditions. Complete disappearance of 100 mgl(-1) of 4-chlorophenol was achieved in 2.5 min and almost complete mineralization (96%) was also possible after only 45 min of irradiation. The efficiency was negatively affected from H2O2 in the UV/H2O2 process and Fe2+ in the photo-Fenton process over a certain concentration. The highest negative effect was observed with solutions containing PO4 triple ions. Required reaction times for complete disappearance of 100 mgl(-1) 4-chlorophenol increased from 2.5 min for an ion-free solution to 30 min for solutions containing 100 mgl(-1) PO4 triple ion and from 45 min to more than 240 min for complete mineralization. The photodegradation of 4-chlorophenol was found to follow the first-order law. CONCLUSION: The results of this study showed that UV irradiation alone can degrade 4-CP, although at very slow rates, but cannot mineralize the compound. The addition of hydrogen peroxide to the system, the so-called UV/H2O2 process, significantly enhances the 4-CP degradation rate, but still requires relatively long reaction periods for complete mineralization. The photo-Fenton process, the combination of homogeneous systems of UV/H2O2/Fe2+ compounds, produces the highest photochemical elimination rate of 4-CP and complete mineralization is possible to achieve in quite shorter reaction periods when compared with the UV/H2O2 process. RECOMMENDATIONS AND OUTLOOK: It is more cost effective to use these processes for only purposes such as toxicity reduction, enhancement of biodegradability, decolorization and micropollutant removal. However the most important point is the optimization of the reaction conditions for the process of concern. In such a case, AOPs can be used in combination with a biological treatment systems as a pre- or post treatment unit providing the cheapest treatment option. The AOP applied, for instance, can be used for toxicity reduction and the biological unit for chemical oxygen demand (COD) removal.  相似文献   

4.
Solar photo-Fenton process has been extensively reported to be highly efficient in the remediation of complex industrial wastewater containing several families of pollutants such as pharmaceuticals, dyes, pesticides, derivatives of wine, etc. Moreover, solar photo-Fenton mathematical modelling regarded as a powerful tool for scaling-up and process control purposes is hindered by the complexity and variability of its reaction mechanism which depends on the particular wastewater under study. In this work, non-biodegradable cork boiling wastewater has been selected as a case study for solar photo-Fenton dynamic modelling by using MATLAB® software. First of all physic-chemical pretreatment was applied attaining chemical oxygen demand (COD) reductions between 43 and 70 % and total suspended solid (TSS) reductions between 23 % and 59 %. After solar photo-Fenton treatment, COD decreased between 45 and 90 % after consumptions of H2O2 varying around 1.9 and 2.4 g/L. Individual calibration of the semi-empirical model by using experimental results made it possible to perfectly predict hydrogen peroxide variations throughout the treatment. It must be highlighted that slight deviations between predictions and experimental data must be attributed to important changes in wastewater characteristics.  相似文献   

5.
The photo-Fenton reaction of an organophosphorus insecticide, dimethoate (O,O-dimethyl methylcarbamoylmethyl phosphorodithioate), was studied by following the identification and determination of the decomposition products and the total carbon removal rate. The reactions were performed in a batch recycle reactor, at room temperature, using UV radiation, H2O2 as oxidant, and FeCl3 x 6H2O as catalyst. The oxidation results were determined with a total organic carbon (TOC) analyzer and ion chromatography. The presence of reaction products was identified by gas chromatography-mass spectrometry (GC-MS). Apart from the sulfate, phosphate, and ammonium ions, the presence of dimethyl phosphite, N-methyl-acetamide, and formic acid was also detected. Excess of H2O2 concentration did not influence the reaction rate. The expression for the total carbon removal was assessed and the TOC removal rate constants were calculated.  相似文献   

6.
Abstract

The effect of fenhexamid, mepanipyrim and cyazofamid fungicides on in vitro bioavailability of antioxidant activity and phenolic compounds of Tempranillo and Graciano red wine was studied by simulating the digestive process by dialysis in semipermeable membranes. Determination of antioxidant activity was through reaction with the DPPH ? radical and the measurement of phenolic compounds was made with liquid chromatography with diode detector (HPLC-DAD). Fenhexamid, mepanipyrim and cyazofamid reduce the total polyphenol content in both wines. During dialysis there was a large loss of total polyphenols (80–90%) and of antioxidant activity (> 90%). The bioavailability of the phenolic compounds is lower than that for non-treated wines and the highest dialization percentages were found for stilbenes > 50%. While for the remaining phenolic fraction the order is the following hydroxycinnamic derivatives?>?anthocyanins?>?flavonols.  相似文献   

7.
Ferric antimonate, a cation-exchanger, has been investigated as an adsorbent for the removal of phenol and polyhydric phenols from aqueous solution. It has been found that ferric antimonate in H+ form selectively adsorbs polyhydric phenols having hydroxyl groups on adjacent positions. While phenol, resorcinol, and quinol did not show any appreciable adsorption, catechol, pyrogallol, and gallic acid having hydroxyl groups on adjacent positions exhibited considerable adsorption on ferric antimonate. Batch equilibrium experiments were carried out to study the effect of contact time, initial concentration of phenolic compounds, and temperature on the adsorption of phenolic compounds on ferric antimonate. The equilibrium time was found to be 1.5 hours for gallic acid and pyrogallol and 2 hours for catechol and salicylic acid. The adsorption data of the phenols at temperatures of 30 degrees, 40 degrees, and 50 degrees C have been described by Langmuir and Freundlich isotherm models. The best fit was obtained with the Langmuir model in the whole range of concentrations studied at all temperatures, indicating a monolayer adsorption onto a homogeneous adsorption surface. On the basis of the Langmuir isotherm, the maximum adsorption capacity of ferric antimonate for gallic acid, pyrogallol, catechol, and salicylic acid was found to be 3.915, 3.734, 2.397, and 2.758 mg/g, respectively at 30 degrees C. The maximum sorption capacity of ferric antimonate for the phenolic compounds studied is in the following order: gallic acid > pyrogallol > salicylic acid > catechol. The adsorption of phenolic compounds was found to decrease with an increase in temperature. Thermodynamic parameters like free energy, enthalpy, and entropy changes were calculated and discussed. The adsorption of polyhydric phenols on ferric antimonate is exothermic and spontaneous in nature.  相似文献   

8.

The adsorption and photo-Fenton degradation of tetracycline (TC) over Fe-saturated nanoporous montmorillonite was analyzed. The synthesized samples were characterized using XRD, FTIR, SEM, and XRF analysis, and the adsorption and desorption of TC onto these samples, as well as the antimicrobial activity of TC during these processes, were analyzed at different pH. Initially, a set of adsorption/desorption experiments was conducted, and surprisingly, up to 50% of TC adsorbed was released from Mt structure. Moreover, the desorbed TC had strong antibacterial activity. Then, an acid treatment (for the creation of nanoporous layers) and Fe saturation of the montmorillonite were applied to improve its adsorption and photocatalytic degradation properties over TC. Surprisingly, the desorption of TC from modified montmorillonite was still high up to 40% of adsorbed TC. However, simultaneous adsorption and photodegradation of TC were detected and almost no antimicrobial activity was detected after 180 min of visible light irradiation, which could be due to the photo-Fenton degradation of TC on the modified montmorillonite surface. In the porous structures of modified montmorillonite high, ˙OH radicals were created in the photo-Fenton reaction and were measured using the Coumarin technique. The ˙OH radicals help the degradation of TC as proposed in an oxidation process. Surprisingly, more than 90% of antimicrobial activity of the TC decreased under visible light (after 180 min) when desorbed from nanoporous Fe-saturated montmorillonite compared to natural montmorillonite. To the best of our knowledge, this is the first time that such a high TC desorption rate from an adsorbent with the least residual antimicrobial activity is reported which makes nanoporous Fe-saturated montmorillonite a perfect separation substance of TC from the environment.

  相似文献   

9.
《Chemosphere》1987,16(4):681-694
Rate constants for some environmentally important organic model compounds reacting with singlet oxygen in water have been determined in laboratory experiments using rose bengal as a sensitizer. Dimethylfuran, furfuryl alcohol, 2,3-dimethyl-2-butene and diethylsulfide react about three times faster in water than in non-aqueous solutions. Phenolic compounds react faster at higher pH values. Their rate constants exactly increase with their degree of dissociation. Rate constants for the ionized species of these phenolic compounds are greater than 108M−1s−1. In natural surface water under solar irradiation reaction with singlet oxygen is important only for a few classes of especially reactive organic compounds.  相似文献   

10.
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   

11.
A novel process for degradation of toluene in the gas-phase using heterogeneous gas-liquid photocatalytic oxidation has been developed. The degradation of toluene gas by photo-Fenton reaction in the liquid-phase has experimentally examined. The photo-Fenton reaction in the liquid-phase could improve the overall toluene absorption rate by increasing the driving force for mass transfer and as a result enhance the removal of toluene in the exhaust gas. The toluene concentrations in the inlet gas were varied in the range from 0.0968 to 8.69gm(-3) with initial hydrogen peroxide concentration of 400mgl(-1) and Fe dose of 5.0mgl(-1). It was found that toluene in the inlet gas was almost completely dissolved into water and degraded in the liquid-phase for the inlet toluene gas concentration of less than 0.42gm(-3). The dynamic process of toluene gas degradation by the photo-Fenton reaction providing information for reaction kinetics and mass transfer rate was examined. Toluene removal kinetic analysis indicated that photo-Fenton degradation was significantly affected by H(2)O(2) concentration. The experimental results were satisfactorily described by the predictions simulated using the simplified tanks-in-series model combined with toluene removal kinetic analysis. The present results showed that the proposed chemical absorption process using the photo-Fenton heterogeneous gas-liquid photocatalytic oxidation is very effective for degradation of volatile organic gases.  相似文献   

12.
Kinetic model for phenolic compound oxidation by Fenton's reagent   总被引:6,自引:0,他引:6  
A kinetic model is developed for the oxidation of phenolic compounds by Fenton's reagent. In the first stage a rigorous kinetic model is applied to calculate the different kinetic rate constants for the oxidation process of p-hydroxybenzoic acid. In a second phase a competitive method is applied to calculate these kinetic constants for another 10 phenolic compounds present in agroindustrial and pulp paper wastewaters. These 10 phenolic compounds were: beta-resorcylic acid, 3-(4-hydroxyphenyl)-propionic acid, ferulic acid, protocatechuic acid, caffeic acid, p-coumaric acid, vanillic acid, syringic acid, veratric acid and 3,4,5-trimethoxybenzoic acid.  相似文献   

13.
Cyanide has been detected in the effluents of some publicly owned treatment works (POTWs) at levels exceeding the influent concentration. The presence of nitrite ion (NO2-) as a common constituent in domestic wastewater effluents may play an important role in the formation of cyanide through reaction with certain kinds of organic compounds, especially aromatic compounds. Laboratory studies with seven organic compounds (aniline. p-toluidine, phenol, 1,2,4-trihydroxybenzene, L-serine, glycine, and benzoic acid) revealed that cyanide can be formed by reaction of nitrite with some of these compounds. The most substantial free cyanide (HCN. CN-) production observed at 25 degrees C was 0.15 mg/L from reaction of 0.01 mM 1.2.4-trihydroxybenze with 5 mg/L nitrite for 72 hours. Substantial free cyanide formation was also observed at pH 2-4 in experiments with POTW effluents when reactive organics and nitrite were both added to wastewater. Formation of cyanide through nitrosation was strongly pH dependent, being most significant at low pH (2 to 4) and negligible at neutral-to-high pH. This result points to nitrous acid (HNO2) as being more reactive than the dissociated NO2- ion. The reaction of these nitrite species with organics also occurs in conventional analyses for total cyanide which involve distillation under strongly acidic conditions. Sufficient sample pretreatment with sulfamic acid at the time of sampling, not at the time of analysis. is highly recommended to prevent biasing analytical measurement of total cyanide in POTW effluents.  相似文献   

14.
Paterlini WC  Nogueira RF 《Chemosphere》2005,58(8):1107-1116
The degradation of herbicides in aqueous solution by photo-Fenton process using ferrioxalate complex (FeOx) as source of Fe2+ was evaluated under blacklight irradiation. The commercial products of the herbicides tebuthiuron, diuron and 2,4-D were used. The multivariate analysis, more precisely, the response surface methodology was applied to evaluate the role of FeOx and hydrogen peroxide concentrations as variables in the degradation process, and in particular, to define the concentration ranges that result in the most efficient degradation of the herbicides. The degradation process was evaluated by the determination of the remaining total organic carbon content (TOC), by monitoring the decrease of the concentrations of the original compounds using HPLC and by the chloride ion release in the case of diuron and 2,4-D. Under optimized conditions, 20 min were sufficient to mineralize 93% of TOC from 2,4-D and 90% of diuron, including oxalate. Complete dechlorination of these compounds was achieved after 10 min reaction. It was found that the most recalcitrant herbicide is tebuthiuron, while diuron shows the highest degradability. However, under optimized conditions the initial concentration of tebuthiuron was reduced to less than 15%, while diuron and 2,4-D were reduced to around 2% after only 1 min reaction. Furthermore, it was observed that the ferrioxalate complex plays a more important role than H2O2 in the photodegradation of these herbicides in the ranges of concentrations investigated.  相似文献   

15.
Tryba B  Morawski AW  Inagaki M  Toyoda M 《Chemosphere》2006,64(7):1225-1232
Fe-C-TiO(2) photocatalysts which contained the residue carbon (0.2-3.3 mass%) were prepared from a mixture of TiO(2) and FeC(2)O(4) through the heating at 673-1173 K in Ar. These photocatalysts did not show a high adsorption of phenol, but they were active in photo-Fenton reactions during decomposition of phenol under UV irradiation with addition of H(2)O(2). It was proved that Fe(2+) governed the photoactivity of Fe-C-TiO(2) photocatalysts, it decreased with heat-treatment temperature above 773 K. For comparison, Fe-TiO(2) photocatalyst was prepared by heating TiO(2) and FeC(2)O(4) at 823 K in air for 3h. Phenol decomposition was going much slower on Fe-TiO(2) photocatalyst in comparison with Fe-C-TiO(2), of which mechanism was different, on the former phenol was decomposed by the radical reaction, on the latter through a complex reaction with iron and intermediates of phenol decomposition. Therefore carbon-coating TiO(2) was found to be advantageous for mounting iron and its application for the phenol decomposition via photo-Fenton process.  相似文献   

16.
The homogeneous degradation of the polychlorinated n-alkane, 1,2,9,10-tetrachlorodecane (T4C10), was studied in aqueous solutions of hydrogen peroxide, including Fenton and photo-Fenton reaction conditions. All solutions were adjusted to a pH of 2.8 and an ionic strength of 0.1 M NaClO4 prior to photolysis. T4C10 (2 x 10(-6) M) was substantially degraded by the H2O2/UV system (1.0 x 10(-2) M H2O2), with 60% disappearance in 20 min of irradiation in a photoreactor equipped with 300 nm lamps of light intensity 3.6 x 10(-5) Ein L(-1) min(-1) (established by ferrioxalate actinometry). The reaction produced stoichiometric amounts of chloride ion indicating complete dechlorination of the chlorinated n-alkane. T4C10 degraded very slowly under Fenton (Fe2+/H2O2/dark) and Fenton-like (Fe3+/H2O2/dark) conditions. However, when the same solutions were irradiated, T4C10 degraded more rapidly than in the H2O2/UV system, with 61% disappearance in 10 min of exposure. The rapid degradation is related to the enhanced degradation of hydrogen peroxide to oxidizing *OH radicals under photo-Fenton conditions. Degradation was inhibited in both the H2O2/UV and photo-Fenton systems by the addition of KI and tert-butyl alcohol due to *OH scavenging.  相似文献   

17.
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   

18.
Growth and utilization of different phenolic acids present in olive mill wastewater (OMW) by Azotobacter chroococcum were studied in chemically defined media. Growth and utilization of phenolic acids were only detected when the microorganism was cultured on p-hydroxybenzoic acid at concentration from 0.01% to 0.5% (w/v) and protocatechuic acid at concentration from 0.01% to 0.3% (w/v) as sole carbon sources suggesting that only these phenolic compounds could be utilized as a carbon source by A. chroococcum. Moreover when culture media were added with a mixture of 0.3% of protocatechuic acid and 0.3% p-hydroxybenzoic acid, the microorganism degradated in first place protocatechuic acid and once the culture medium was depleted of this compound, the degradation of p-hydroxybenzoic acid commenced very fast.  相似文献   

19.
20.
In this study, the effects of experimental variables such as type of solvent, sample/solvent ratio, and time of extraction have been evaluated to individuate the best results in phenolic recovery by Olive Pomaces (OP) belonging to Carolea and Ottobratica cultivars. Folin–Ciocaulteu procedure and DPPH and ABTS assays were used, respectively, for total phenol quantification and total antioxidant activity of pomace extracts. The ethanol/water mixture was resulted the most efficient extraction solvent for both olive cultivars. The highest amount of phenolic compounds (171 ± 4 mg of gallic acid 100 g?1 of dry pomace) was obtained after extraction at 120 min with 2:1 solvent/OP (v/w) of Ottobratica Olive Pomace. The recovery of phenol compounds from olive wastes increases the sustainability of sector, allowing obtaining an extract that could be a suitable alternative in the food industry to the use of synthetic antioxidants in order to improve the quality of foods.  相似文献   

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