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.     

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.     

Thermal treatment of plasma-synthesized goethite improves Fenton-like degradation of orange II dye

Various iron oxides are used for Fenton reactions to degrade organic pollutants. The degradation efficiency may be improved by transforming an iron oxide phase to another. Here, we report on the transformation of goethite into hematite by thermal treatment at 400 °C. The products were analyzed by X-ray diffractometry, Raman spectroscopy, scanning electron microscopy and N₂-physisorption. The catalytic activities were measured for orange II bleaching at initial concentration of 25 mg L^?1, pH 3, catalyst concentration of 0.2 g L^?1; 5 mM H₂O₂, 30 °C. Results show that the synthesized goethite was successfully transformed into hematite, and the specific surface area of the material increased from 134 to 163 m² g^?1. The bleaching efficiency of the orange II dye reached 100 % for the hematite product, versus 78 % for goethite. Therefore, a moderate thermal treatment of a plasma-synthesized goethite improves the catalytic oxidation of organic pollutants.     

Coupled electrocoagulation–electro-Fenton for efficient domestic wastewater treatment

This article reports the first use of coupled electrocoagulation and electro-Fenton (EF-EC) to clean domestic wastewater. Domestic wastewater contains high amounts of organic, inorganic and microbial pollutants that cannot be usually treated in a single step. Here, to produce an effluent suitable for discharge in a single process step, a hybrid process combining electrocoagulation and electro-Fenton was simultaneously used to decrease chemical oxygen demand (COD), turbidity and total suspended solids (TSS) from domestic wastewater. The electrocoagulation–electro-Fenton process was firstly tested for the production of H₂O₂ using Ti–IrO₂ and vitreous carbon- or graphite electrodes arranged at the anode and the cathode, respectively. The concentration of H₂O₂ recorded at 1.5 A of current intensity during 60 min of electrolysis using vitreous carbon- and graphite electrodes at the cathode was 4.18 and 1.62 mg L^?1, respectively. By comparison, when the iron electrode was used at the anode, 2.05 and 1.06 mg L^?1 of H₂O₂ were recorded using vitreous carbon and graphite, respectively. The H₂O₂ concentration decrease was attributed to hydroxyl radical formation generated by the Fenton reaction. Electro-Fenton using iron electrode at the anode and vitreous carbon at the cathode with a current density imposed of 0.34 A dm^?2 ensures the removal efficiency of 50.1 % COD_T, 70.8 % TSS and 90.4 % turbidity. The electrocoagulation–electro-Fenton technique is therefore a promising secondary treatment to simultaneously remove organic, inorganic and microbial pollutants from domestic, municipal and industrial wastewaters.     

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     

Solar-induced generation of singlet oxygen and hydroxyl radical in sewage wastewaters

Singlet oxygen (¹O₂) and hydroxyl radical (·OH) play an important role in the degradation of pollutants in surface waters. However, the mechanism underlying the photochemical generation of ¹O₂ and ·OH in wastewaters is poorly known. Here we studied the photo-induced generation of ¹O₂ and ·OH in different sewage treatment plant units. The correlation between the generation of ¹O₂ and ·OH and the water constituents was discussed. Our results show that in sewage units the ¹O₂ formation rate ranges from 2.19 × 10^?8 to 6.74 × 10^?8 mol L^?1 s^?1, and the ·OH formation rate ranges from 1.7 × 10^?11 to 3.06 × 10^?10 mol L^?1 s^?1. The average ¹O₂ formation rates in the various sewage units are similar to those in wetland and estuarine waters containing rich dissolved organic matter and 2–4 times higher than those in lake and seawater samples. The average ·OH formation rates of the sewage units are 5–50 times higher than for other water samples reported. The ·OH generation rate increased with the iron content with a correlation coefficient of 0.85, which indicates that the photo-Fenton reaction plays a dominant role in ·OH generation in sewage wastewater.     

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.     

Seasonal differences in treatment efficiency of a set of stabilization ponds in a semi-arid region

This article aims to determine the significant differences of the seasonal changes of pH, chemical oxygen demand (COD), biological oxygen demand (BOD), and total suspended solids (TSS) parameters in a wastewater stabilization pond. The variation of these parameters followed the seasonal pattern of temperature. The mean seasonal pH of the influent wastewater ranged between 7.8 (in spring) and 7.9 (in summer), while in the final effluents it was between 7.9 (in winter) and 8.3 (in summer). The mean seasonal COD of the influent wastewater ranged between 650?mg?L^?1 in spring and 600?mg?L^?1 in autumn, whereas in the effluents it was between 150?mg?L^?1 in autumn and 270?mg?L^?1 in spring. The mean seasonal BOD₅ of the influent wastewater ranged between 360?mg?L^?1 in autumn and 390?mg?L^?1 in winter, whereas in the effluents it was between 66?mg?L^?1 in summer and 130?mg?L^?1 in winter. The results showed that the percent removals of COD, BOD₅ and TSS from final effluents were maximum in summer for COD and BOD₅ (76%), summer (83%) and for TSS in winter (78%), respectively. Data analysis showed that there were significant differences between parameters of pH, COD, BOD₅ and TSS at four different seasons (p?相似文献   

Rice seedlings under cadmium stress: effect of silicon on growth,cadmium uptake,oxidative stress,antioxidant capacity and root and leaf structures

In this study, the effect of silicon (Si) addition on cadmium (Cd) toxicity in rice seedlings was investigated. After a series of screening experiments, 50 μmol·L^?1 of Cd and 10 μ mol·L^?1 of Si were selected. Treatment of rice seedlings with Cd (50 μ mol·L^?1) resulted in significant accumulation of this metal in roots and shoots. The data revealed that accumulation of Cd resulted in oxidative stress in rice seedlings as evidenced by increased accumulation of hydrogen peroxide (H₂O₂) and malondialdehyde (MDA; a peroxidation product of lipids). However, addition of Si (10 μ mol·L^?1) together with Cd prevented accumulation of Cd, H₂O₂ and MDA. Antioxidant capacity was decreased by Cd but enhanced by Si addition. Cd decreased the length and frequency of root hairs, stomatal frequency, and distorted leaf mesophyll cells and vascular bundles. However, addition of Si together with Cd reduced these abnormalities. The results showed that addition of exogenous Si protected rice seedlings against Cd toxicity by preventing Cd accumulation and oxidative stress (H₂O₂ and MDA accumulation) by increasing Si accumulation and antioxidant capacity, which maintained the structure and integrity of leaf and root.     

Removal of cyanide in aqueous solution by oxidation with hydrogen peroxide in presence of activated alumina

This work is dedicated to the removal of free cyanide from aqueous solution by oxidation with hydrogen peroxide H₂O₂ catalyzed by neutral activated alumina. Effects of initial molar ratio [H₂O₂]₀/[CN^?]₀, catalyst amount, pH, and temperature on cyanide removal have been examined. The presence of activated alumina has increased the reaction rate showing thus, a catalytic activity. The rate of removal of cyanides increases with rising initial molar ratio [H₂O₂]₀/[CN^?]₀ but decreases at pH 10 to 12. Increasing the alumina amount from 1.0 to 30 g/L has a beneficial effect, and increasing the temperature from 20 °C to 35 °C improves cyanide removal. The kinetics of cyanide removal has been found to be of pseudo-first-order with respect to cyanide and the rate constants have been determined.     

Isolation and characterisation of a carbofuran degrading Burkholderia sp. PCL3 from carbofuran-phytoremediated rhizosphere soil

A bacterial strain capable of degrading carbofuran as the sole carbon source was isolated from carbofuran-phytoremediated rhizosphere soil of rice. A 16S rRNA study identified the strain as Burkholderia sp. (isolate PCL3). Free cells of isolate PCL3 possessed inhibitory-type degradation kinetics with a q _max of 0.087 day^?1 and S _m of 248.76 mg·L^?1. Immobilised PCL3 on corncob and sugarcane bagasse possessed Monod-type degradation kinetics with a q _max of 0.124 and 0.098 day^?1, respectively. The optimal pH and temperature with the highest degradation rate coefficient of carbofuran were pH 7.5 and 35 °C, respectively.     

Polyphenol contents of five of medicinal plants from Cameroon and effects of their extracts on antioxidant capacities of human breast cancer cells

The aim of the study was to investigate the antiproliferative properties of extracts of five plants on breast cancer cells (MDA-MB-231) and their effects on antioxidant activities. The total phenol contents of the extracts were determined to establish a correlation to their antiproliferative effects which were evaluated by the 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide viability assay. Enzymes involved in oxidative stress were also determined. Total polyphenol contents of the five extracts varied from 170 to 440 mg L^?1 of gallic acid per mg of extract with the highest value for the extract of Sida cordifolia. Cell growth inhibition was observed within 24 h, with inhibitory concentration values ranging from 7.3 to 25 mg L^?1 depending on plant extract. At concentrations between 100 and 200 mg L^?1, all the extracts exhibited significant reduction of cell proliferation in time-dependent and linear manner. The activities of superoxide dismutase and catalase of cells treated for 24 h with the extract of S. cordifolia were 3.5 U per mg protein and 8 mole H₂O₂ consumed per min per mg protein higher than those of cells treated with an extract of Viscum album.     

Kinetics of the oxidation of endocrine disruptor nonylphenol by ferrate(VI)

The kinetics of the oxidation of endocrine disruptor nonylphenol (NP) by potassium ferrate(VI) (K₂FeO₄) in water as a function of pH 8.0–10.9 at 25°C is presented. The observed second-order rate constants, k _obs, decrease with an increase in pH 269–32 M^?1 s^?1. The speciation of Fe(VI) (HFeO ₄ ^? and FeO ₄ ^2? ) and NP (NP–OH and NP–O^?) species was used to explain the pH dependence of the k _obs values. At a dose of 10 mg L^?1 (50 μM) K₂FeO₄, the half-life for the removal of NP by Fe(VI), under water treatment conditions, is less than 1 min.     

Evaluation of kinetics and energy consumption of the electrochemical oxidation of Acid Red 73 in aqueous media

A laboratory scale, undivided electrolysis cell with platinum anode and cathode was used for electrochemical oxidation of the azo dye Acid Red 73 in simulated wastewater. The influence of the supporting electrolyte, applied voltage, pH, initial dye concentration and temperature was studied, and decolorization was monitored by UV/Vis spectroscopy. Energy consumption, current efficiency and the electric energy per order have been also determined. With NaCl (1.5 g L^?1) as supporting electrolyte, at a voltage of 6 V, at neutral pH (6.9) and at 25 °C, the solution of the dye (50 mg L^?1) was completely decolorized within 15 min. The apparent activation energy for electrochemical decolorization was determined as ?1.9 kJ mol^?1.     

Decomposition of perfluorooctanoic acid by microwaveactivated persulfate: Effects of temperature, pH, and chloride ions

Microwave-hydrothermal treatment of persistent and bioaccumulative perfluorooctanoic acid (PFOA) in water with persulfate (S₂O ₈ ^2? ) has been found effective. However, applications of this process to effectively remediate PFOA pollution require a better understanding on free-radical scavenging reactions that also take place. The objectives of this study were to investigate the effects of pH (pH = 2.5, 6.6, 8.8, and 10.5), chloride concentrations (0.01?C0.15 mol·L^?1), and temperature (60°C, 90°C, and 130°C) on persulfate oxidation of PFOA under microwave irradiation. Maximum PFOA degradation occurred at pH 2.5, while little or no degradation at pH 10.5. Lowering system pH resulted in an increase in PFOA degradation rate. Both high pH and chloride concentrations would result in more scavenging of sulfate free radicals and slow down PFOA degradation. When chloride concentrations were less than 0.04 mol·L^?1 at 90°C and 0.06 mol·L^?1 at 60°C, presence of chloride ions had insignificant impacts on PFOA degradation. However, beyond these concentration levels, PFOA degradation rates reduced significantly with an increase in chloride concentrations, especially under the higher temperature.     

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。     

Ultrastructural responses and oxidative stress induced by cypermethrin in the liver of Labeo rohita

The present study was conducted to establish the relationship between selected oxidative stress parameters and ultrastructural responses in liver tissue of Labeo rohita fingerlings exposed to cypermethrin. Fish were exposed to lethal (4.0 μg L^?1) and sublethal (0.4 μg L^?1) concentrations of cypermethrin for a period of 24, 48, 72 and 96 h for acute studies and 1, 5, 10 and 15 days for subacute studies, respectively. Results showed increased catalase (CAT) and protease activity, hydrogen peroxide (H₂O₂), malondialdehyde (MDA), protein carbonyls and free amino acid (FAA) levels at both concentrations. This suggests participation of free-radical-induced oxidative cell injury in mediating the hepatotoxicity of cypermethrin. In corroboration of this, ultrastructural lesions witnessed a reduction in the number of cell organelles, swollen, vacuolated and condensed mitochondria, dilated rough endoplasmic reticulum, and reduced numbers of smooth enodplasmic reticulum, peroxisomes and lysosomes at the lethal (4.0 μg L^?1) concentration. At the sublethal (0.4 μg L^?1) concentration, cytoplasmic vacuolation, condensed, vacuolated and swollen mitochondria, dilated rough endoplasmic reticulum and an absence of hepatocyte microvilli were prominent. Ultrastructural changes were exhibited as subcellular responses due to the imbalance in cellular oxidative status by means of oxidative damage.     

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.     

Metabolic responses of Azolla pinnata to cadmium stress: photosynthesis,antioxidative system and phytoremediation

This present study deals with the growth, photosynthesis, oxidative stress and phytoremediation character of Azolla pinnata L. exposed to different levels (0.05, 0.1, 0.5, 1.0, 1.5 and 2.0 mg·L^?1) of cadmium (Cd). Significant accumulation of Cd in Azolla fronds was noticed after 24 and 96 h of exposure and the accumulation rate was dose and time dependent. Growth of A. pinnata increased significantly after both exposure times with and without metal. At lower Cd doses (0.05 and 0.1 mg·L^?1), growth and photosynthesis of A. pinnata showed a marginal increase over the respective control, however, at higher Cd doses (0.5, 1.0, 1.5 and 2.0 mg·L^?1), a decreasing trend was noticed. At lower doses, Azolla fronds could counterbalance the negative effect of enhanced levels of superoxide radicals (SOR) and hydrogen peroxide (H₂O₂) through the greater activity of antioxidative enzymes. The decaresing trends in catalase and peroxidase activity at higher Cd doses suggest that Azolla fronds were not able to mitigate the negative effects of H₂O₂, hence an increase in malondialdehyde content was noticed. The study concludes that up to 0.1 ,mg·L^?1 Cd, A. pinnata can flourish and be used as biofertiliser and for phytoremedial purposes in Cd-contaminated fields; beyond this concentration poor growth may restrict its application.     

Diffusive boundary layers and photosynthesis of the epilithic algal community of coral reefs

The effects of mass transfer resistance due to the presence of a diffusive boundary layer on the photosynthesis of the epilithic algal community (EAC) of a coral reef were studied. Photosynthesis and respiration of the EAC of dead coral surfaces were investigated for samples from two locations: the Gulf of Aqaba, Eilat (Israel), and One Tree Reef on the Great Barrier Reef (Australia). Microsensors were used to measure O₂ and pH at the EAC surface and above. Oxygen profiles in the light and dark indicated a diffusive boundary layer (DBL) thickness of 180–590 μm under moderate flow (~0.08 m s^?1) and >2,000 μm under quasi-stagnant conditions. Under light saturation the oxygen concentration at the EAC surface rose within a few minutes to 200–550% air saturation levels under moderate flow and to 600–700% under quasi-stagnant conditions. High maximal rates of net photosynthesis of 8–25 mmol O₂ m^?2 h^?1 were calculated from measured O₂ concentration gradients, and dark respiration was 1.3–3.3 mmol O₂ m^?2 h^?1. From light–dark shifts, the maximal rates of gross photosynthesis at the EAC surface were calculated to be 16.5 nmol O₂ cm^?3 s^?1. Irradiance at the onset of saturation of photosynthesis, E _k, was <100 µmol photons m^?2 s^?1, indicating that the EAC is a shade-adapted community. The pH increased from 8.2 in the bulk seawater to 8.9 at the EAC surface, suggesting that very little carbon in the form of CO₂ occurs at the EAC surface. Thus the major source of dissolved inorganic carbon (DIC) must be in the form of HCO₃ ^?. Estimates of DIC fluxes across the DBL indicate that, throughout most of the daytime under in situ conditions, DIC is likely to be a major limiting factor for photosynthesis and therefore also for primary production and growth of the EAC.