Unexpected toxicity decrease during photoelectrochemical degradation of atrazine with NaCl

This report shows an unexpected toxicity decrease during atrazine photoelectrodegradation in the presence of NaCl. Atrazine is a pesticide classified as endocrine disruptor occurring in industrial effluents and agricultural wastewaters. We therefore studied the effects of the degradation method, electrochemical and electrochemical photo-assisted, and of the supporting electrolyte, NaCl and Na₂SO₄, on the residual toxicity of treated atrazine solutions. We also studied the toxicity of treated atrazine solutions using Artemia nauplii. Results show that at initial concentration of 20 mg L⁻¹, atrazine was completely removed in up to 30 min using 10 mA cm⁻² electrolysis in NaCl medium, regardless of the electrochemical method used. The total organic carbon removal by the photo-assisted method was 82% with NaCl and 95% with Na₂SO₄. The solution toxicity increased during sole electrochemical treatment in NaCl, as expected. However, the toxicity unexpectedly decreased using the photo-assisted method. This finding is a major discovery because electrochemical treatment with NaCl usually leads to the formation of toxic chlorine-containing organic degradation by-products.     

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

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

Degradation of azo dyes in water by Electro-Fenton process

The degradation of the azo dyes azobenzene, p-methyl red and methyl orange in aqueous solution at room temperature has been studied by an advanced electrochemical oxidation process (AEOPs) under potential-controlled electrolysis conditions, using a Pt anode and a carbon felt cathode. The electrochemical production of Fenton's reagent (H₂O₂, Fe²⁺) allows a controlled in situ generation of hydroxyl radicals (^·OH) by simultaneous reduction of dioxygen and ferrous ions on the carbon felt electrode. In turn, hydroxyl radicals react with azo dyes, thus leading to their mineralization into CO₂ and H₂O. The chemical composition of the azo dyes and their degradation products during electrolysis were monitored by high performance liquid chromatography (HPLC). The following degradation products were identified: hydroquinone, 1,4-benzoquinone, pyrocatechol, 4-nitrocatechol, 1,3,5-trihydroxynitrobenzene and p-nitrophenol. Degradation of the initial azo dyes was assessed by the measurement of the chemical oxygen demand (COD). Kinetic analysis of these data showed a pseudo-first order degradation reaction for all azo dyes. A pathway of degradation of azo dyes is proposed. Specifically, the degradation of dyes and intermediates proceeds by oxidation of azo bonds and aromatic ring by hydroxyl radicals. The results display the efficiency of the Electro-Fenton process to degrade organic matter. Electronic Publication     

Comparison of photoelectrochemical properties of TiO2-nanotube-array photoanode prepared by anodization in different electrolyte

Self-organized, well-crystallized and high aspect-ratio TiO₂ nanotube arrays (TNAs) have been prepared by anodic oxidation in dimethyl sulfoxide (DMSO) containing 5 wt% HF at 40 V (vs. Pt). A 50 h anodization results in a nanotube arrays approximately 19.4 μm in length, referred as long tube. As a comparison, the short titania nanotube arrays, about 500 nm in length, was obtained by anodization in HF aqueous solution, referred as short tube. Different characterization techniques (viz. FESEM, TEM, XRD and DRS) are used to study the nanotubular microstructure. The morphology of the nanotube electrodes shows an evident influence on their photocatalytic (PC) and photoelectrochemical reactivity. The long tube reveals enhanced photocurrent response and PC degradation efficiency of organic compounds. The kinetic constant of PC degradation of methylic orange (MO) for long tube electrode is found 1.55 times as high as the short tube. A significant photoelectrochemcial synergetic effect in MO degradation was observed on the long tube electrode and the photoelectrocatalytic (PEC) degradation of MO on long tube is 27% higher than its PC process.     

Efficient photoelectrochemical oxidation of rhodamine B on metal electrodes without photocatalyst or supporting electrolyte

We designed photoelectrochemical cells to achieve efficient oxidation of rhodamine B (RhB) without the need for photocatalyst or supporting electrolyte. RhB, the metal anode/cathode, and O₂ formed an energy-relay structure, enabling the efficient formation of O ₂ ^– species under ultraviolet illumination. In a single-compartment cell (S cell) containing a titanium (Ti) anode, Ti cathode, and 10 mg·mL^–1 RhB in water, the zero-order rate constant of the photoelectrochemical oxidation (k_PEC) of RhB was 0.049 mg·L^–1·min^–1, while those of the photochemical and electrochemical oxidations of RhB were nearly zero. k_PEC remained almost the same when 0.5 mol·L^–1 Na₂SO₄ was included in the reactive solution, regardless of the increase in the photocurrent of the S cell. The k_PEC of the illuminated anode compartment in the two-compartment cell, including a Ti anode, Ti cathode, and 10 mg·mL^–1 RhB in water, was higher than that of the S cell. These results support a simple, eco-friendly, and energysaving method to realize the efficient degradation of RhB.

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Preparation and characterization of a new TiO2/SiO2 composite catalyst for photocatalytic degradation of indigo carmin

The TiO₂/SiO₂ composite was prepared by means of the SiO₂-particle-entrapment method. The FTIR data showed the presence of Si–O–Ti stretching vibration band at 970 cm⁻¹ in the TiO₂/SiO₂ composite, suggesting a reaction between TiO₂ and silica on the TiO₂ particle surface during the silicagel formation around the TiO₂ particles. The photocatalytic efficiency of TiO₂ immobilized in silicagel was compared with that of the conventional TiO₂ Degussa P25 catalyst. For this purpose, the degradation of indigo carmin (IC) dye was used as model molecule in the tests. The effect of operational parameters such as catalyst loading and dye concentration on the photocatalytic degradation of the model dye was investigated. The rate of degradation increased with increasing catalyst loading, and when the concentration of the dye decreases.     

Electrochemical remediation of phenanthrene from contaminated kaolinite

In this work a two-stage process combining soil electrokinetic remediation and liquid electrochemical oxidation for the remediation of polluted soil with organic compounds has been developed and evaluated using phenanthrene-spiked kaolinite. Application of an unenhanced electrokinetic process resulted in negligible removal of phenanthrene from the kaolinite sample. Addition of co-solvents and electrolyte to the processing fluid used in the electrode chambers enhanced phenanthrene desorption from the kaolinite matrix and favoured electro-osmotic flow. Near-complete removal of phenanthrene was achieved using Na₂SO₄ and ethanol in the processing fluid. Phenanthrene was transported towards the cathode chamber where it was collected. The cathodic solution containing the pollutant was treated by electrochemical oxidation; complete degradation of phenanthrene occurred after 9 h using Na₂SO₄ as electrolyte.     

Electrochemical degradation of Acid Red I dye and its treatment by UV light

Degradation of Acid Red I (ARI) dye by electrochemical treatment and UV light irradiation was studied in this work. The effect of the current density and the concentration of NaCl and dye on the decoloration and degradation efficiency were studied and optimized. The UV irradiation was monitored by UV-Vis spectrophotometry and chemical oxygen demand. The kinetic constants for decoloration and degradation were calculated. Degradation of 86% was achieved in 160?min and the first-order kinetic constant was 0.013?min^?1. Degradation products were identified by gas chromatography/mass spectrometry. The mechanism for the degradation of ARI was proposed.     

Photocatalytic degradation of methyl orange using ZnO/TiO2 composites

ZnO/TiO₂ composites were synthesized by using the solvothermal method and ultrasonic precipitation followed by heat treatment in order to investigate their photocatalytic degradation of methyl orange (MO) in aqueous suspension under UV irradiation. The composition and surface structure of the catalyst were characterized by X-ray diffraction (XRD), field emission scanning electron microscope (FE-SEM), and transmission electron microscopy (TEM). The degradation efficiencies of MO at various pH values were obtained. The highest degradation efficiencies were obtained before 30 min and after 60 min at pH 11.0 and pH 2.0, respectively. A sample analysis was conducted using liquid chromatography coupled with electrospray ionization ion-trap mass spectrometry. Six intermediates were found during the photocatalytic degradation process of quinonoid MO. The degradation pathway of quinonoid MO was also proposed.     

Screening bamboo species for salt tolerance using growth parameters,physiological response and osmolytes accumulation as effective indicators

Bamboos are potential species for reclamation of saline soils and water. In this study, the performances of three bamboo species, namely Dendrocalamus strictus (S1), Dendrocalamus longispathus (S2) and Bambusa bambos (S3), were investigated for salinity stress tolerance. After 14 days of treatment with 100?mM NaCl, reduction in shoot length was 66%, 100%, 77%, root length was 77%, 100%, 57%, number of leaves was 50%, 100%, 73% and fresh weight was 30%, 72%, 14% in S1, S2 and S3 species, respectively. Relative water content (RWC) in S1 and S3 species was 1.26 and 1.07 folds higher in 50?mM NaCl in comparison to control. In S2 species, total chlorophyll, chlorophyll_a and chlorophyll_b degradation were the highest (40.4%, 42.7%, 16.32%, respectively) in comparison to S3 (18.18%, 23%, 16.4%) and S1 (23.5%, 25%, 19.17%) species. In S3 and S1 species, the Chl_a/Chl_b ratio was maintained showing stabilisation of the net photosynthetic rate. Proline played a more important role than glycine betaine for salt tolerance of these bamboo species. On account of vegetative growth, proline accumulation and RWC, it is inferred that S1 and S3 species are salt tolerant while S2 is a sensitive species.

Abbreviations: SL: shoot length; RL: root length; NL: number of leaves; FW: fresh weight; RWC: relative water content; Chl_a: chlorophyll_a; Chl_b: chlorophyll_b; TC: total chlorophyll; GB: glycine betaine     

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.     

A simple and cheap method for preparation of coupled ZrO2/ZnO with high photocatalytic activities

The objective of this study was to prepare a new photocatalyst with high activities for degradation of organic pollutants. Coupled ZrO₂/ZnO photocatalyst was prepared with a simple precipitation method with cheap raw materials zinc acetate and zirconium oxychloride, and was characterized by X-ray diffraction (XRD) and transmission electron microscopy (TEM). Reactive brilliant red X-3B was used as a model compound to investigate the photocatalytic activity of synthesized catalysts in water under 254 nm UV irradiation. Results show that the optimal calcination temperature and coupling molar ratio of Zr were 350°C And 2.5%, respectively. At the calcination temperature of 350°C, ZrO₂ was dispersed on the surface of hexagonal ZnO in the form of amorphous clusters. The particle size of ZrO₂/ZnO decreased with the decrease of calcination temperature and the increase of Zr coupling amount. ZrO₂/ZnO has better photocatalytic activity for degradation of reactive brilliant red (RBR) X-3B than pure ZnO and P25-TiO₂.     

Metal-free oxidation of aldehydes to acids using the 4Na<Subscript>2</Subscript>SO<Subscript>4</Subscript>·2H<Subscript>2</Subscript>O<Subscript>2</Subscript>·NaCl adduct

Oxidation of aldehydes to carboxylic acids is a major reaction. Conventionally, this reaction is carried out with oxidants and metal catalysts, thus producing unwanted metal waste. Recently, aqueous media have been used as an alternative for toxic organic solvents. Here, we tested the clathrate-structured, neutral hydrogen peroxide adduct 4Na₂SO₄·2H₂O₂·NaCl for the oxidation of aldehydes to acids in aqueous solution. We found that various aromatic, heteroaromatic and aliphatic aldehydes were selectively oxidized to corresponding acids in 70–98% yields. This simple acid–base treatment allows to separate easily the acid product in high purity without any organic solvent. Moreover, the adduct is produced using 25% H₂O₂, with inexpensive sodium sulphate, Na₂SO₄, and sodium chloride, NaCl. The adduct is a non-toxic white crystalline solid, readily soluble in water, and easy to handle.     

TiO2 photocatalyzed degradation of diazinon in an aqueous medium

The photocatalytic degradation of diazinon was studied over TiO₂ catalysts. The kinetics obtained demonstrated that powder titania (t_1/2 = 9.7 min) was more efficient compared to pure titania thin film catalysts (t_1/2 = 29.4 min). Mineralization of organic carbon to CO₂ after 360 min of irradiation was found to be 75% while heteroatoms (P, S, N) were mineralized into phosphate, sulfate and nitrate ions, respectively. A microtox test was performed to evaluate the toxicity of solutions treated by catalysts. Illumination of diazinon in the presence of TiO₂ gave rise to several intermediates that have been identified by means of solid phase extraction and gas chromatography-mass spectrometry, while a simple degradation pathway is proposed.     

Effective degradation of tetracycline by mesoporous Bi<Subscript>2</Subscript>WO<Subscript>6</Subscript> under visible light irradiation

Bi₂WO₆ was synthesized with a hydrothermal method at different pHs and used for the degradation of tetracycline (TC) in water. The mesoporous Bi₂WO₆ prepared at pH 1 (BWO-1) displayed the highest adsorption and degradation capacity to TC due to its large surface area and more efficient capacity to separate photogenerated electrons and holes. 97% of TC at 20 mg·L^?1 was removed by BWO-1 at 0.5 g·L^?1 after 120 min irradiation under simulated solar light. Only 31% of the total organic carbon (TOC) was removed after 360 min irradiation although the TC removal reached 100%, suggesting that TC was mainly transformed to intermediate products rather than completely mineralized. The intermediates were identified by high-performance liquid chromatography-time of flight-mass spectrometry (HPLC-TOF-MS) and possible photodegradation pathways were proposed.     

Solar photocatalytic decomposition of two azo dyes on multi-walled carbon nanotubes (MWCNTs)/TiO<Subscript>2</Subscript> composites

Multi-walled carbon nanotubes (MWCNTs)/TiO₂ composite photocatalysts with high photoactivity were prepared by sol-gel process and further characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier transform infrared (FT-IR), and UV-vis absorption spectra. Compared to pure TiO₂, the combination of MWCNTs with titania could cause a significant absorption shift toward the visible region. The photocatalytic performances of the MWCNTs/TiO₂ composite catalysts were evaluated for the decomposition of Reactive light yellow K-6G (K-6G) and Mordant black 7 (MB 7) azo dyes solution under solar light irradiation. The results showed that the addition of MWCNTs enhanced the adsorption and photocatalytic activity of TiO₂ for the degradation of azo dyes K-6G and MB 7. The effect of MWCNTs content, catalyst dosage, pH, and initial dye concentration were examined as operational parameters. The kinetics of photocatalytic degradation of two dyes was found to follow a pseudo-first-order rate law. The photocatalyst was used for seven cycles with photocatalytic degradation efficiency still higher than 98%. A plausible mechanism is also proposed and discussed on the basis of experimental results.     

Comparative study between using natural and synthetic zeolites for the improvement of soil salinity and crop yield

The effects of natural zeolite (clinoptilolite, NZ) and synthetic zeolite (Y, SZ) on salinity and the presence of the harmful salts in the soil were compared on Raphanus sativus L. Nine soil treatments were studied: 1 (control), 2 (NaCl), 3 (Na₂SO₄), 4 (NZ), 5 (SZ), 6 (NZ?+?NaCl), 7 (SZ?+?NaCl), 8 (NZ?+?Na₂SO₄), and 9 (SZ?+?Na₂SO₄). Five radish seeds were planted in each pot. Each treatment was repeated 10 times. After 50 days under equal conditions some parameters consisting of the number of leaves (NL), total leaf area (TLA), total fresh weight (TFW), total dry weight (TDW), root fresh weight (RFW), air fresh weight (AFW), root dry weight (RDW) and air dry weight (ADW) were determined. Results showed that adding either NZ or SZ to salinic soil (treatments NZNaCl, NZNa₂SO₄, SZNaCl and SZNa₂SO₄) increased AFW, TFW and TDW. Using both NZ and SZ in normal soil increased the weight of plants by developing AFW. Further NZ was more effective on soil with NaCl than SZ.     

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。     

ZnO薄膜光电催化降解乙酰甲胺磷

采用溶胶-凝胶法制备了ZnO薄膜,并通过光电流响应、EIS、SEM、XRD等分析方法对其光电化学性能、表面形貌和结构进行表征.以制备的ZnO薄膜为工作电极对乙酰甲胺磷进行光电催化降解.实验表明,ZnO薄膜电极在UV照射下能够有效地光电催化降解乙酰甲胺磷,加入适量H2O2后具有一定的协同作用.在H2O2浓度为9.908 mmol.L-1,外加电压为1.2 V,支持电解液Na2SO4浓度为0.01 mol.L-1,溶液pH值为5.4的条件下,对0.1 mmol.L-1的乙酰甲胺磷180 min的降解率可达到89.6%.     

Response of mussel Brachidontes variabilis to chlorination

Brachidontes variabilis is a common fouling mussel species in cooling water systems of tropical coastal power stations. However, there are hardly any data available on the response of B. variabilis to chlorine, a commonly used antifouling biocide. Therefore, lethal and sublethal responses of this mussel to chlorine are of considerable interest to the industry. The response of mussels in terms of mortality pattern (LT₅₀ and LT₁₀₀) and physiological activities (oxygen consumption, filtration rate, foot activity and byssus thread production) in different size groups (with shell lengths of 7–24 mm) of B. variabilis was studied in the laboratory under different chlorine concentrations (0.25, 0.50, 0.75 and 1.00 mg l^?1 for sublethal responses and 1, 2, 3 and 5 mg l^?1 for mortality). The results showed that the exposure time for 100% mortality of mussels decreased significantly with increasing chlorine concentration. However, mussel size was not a determinant of its chlorine tolerance: all size groups tested (with shell lengths of 7–24 mm) took comparable exposure times to reach 100% mortality at a given chlorine concentration (1–5 mg l^?1). All size groups of B. variabilis showed a progressive reduction in physiological activities such as oxygen consumption, filtration rate, foot activity and byssus thread production, when chlorine residuals were increased from 0 to 1 mg l^?1. The data generated in the present work are compared with similar data available for other tropical fouling mussel species to see how far relative chlorine toxicity could have influenced the relative distribution of the mussels inside the seawater intake tunnel of a power station at Kalpakkam in India. It is shown that in this insufficiently chlorinated system, the relative distribution of Brachidontes striatulus, B. variabilis and Modiolus philippinarum reflects the relative tolerance of the species to chlorine.