Electrochemical combustion of herbicide mecoprop in aqueous medium using a flow reactor with a boron-doped diamond anode

The anodic oxidation of 1.8l of solutions with mecoprop (2-(4-chloro-2-methylphenoxy)-propionic acid or MCPP) up to 0.64 g l(-1) in Na2SO4 as background electrolyte within the pH range 2.0-12.0 has been studied using a flow plant containing a one-compartment filter-press electrolytic reactor with a boron-doped diamond (BDD) anode and a stainless steel cathode, both of 20-cm2 area. Electrolyses carried out in batch under steady conditions and operating at constant current density between 50 and 150 mA cm(-2) always yield complete mineralization due to the great concentration of hydroxyl radical generated at the BDD anode. The degradation rate is practically independent of pH and Na2SO4 concentration, but it becomes faster with increasing MCPP concentration, current density, temperature and liquid flow rate. The effect of these parameters on current efficiency and energy cost has also been investigated. Generated weak oxidants such as H2O2 and peroxodisulfate ion have little influence on the mineralization process. The kinetics for the herbicide decay follows a pseudo first-order reaction with a higher rate constant when current density increases. Aromatic products such as 4-chloro-o-cresol, 2-methylhydroquinone and 2-methyl-p-benzoquinone, and generated carboxylic acids such as maleic, fumaric, lactic, pyruvic, tartronic, acetic and oxalic, have been identified as intermediates by chromatographic techniques. The initial chlorine is completely released in the form of chloride ion, which is slowly oxidized to Cl2 at the BDD anode. A reaction pathway for MCPP mineralization involving all products detected is proposed.     

Mineralization of paracetamol in aqueous medium by anodic oxidation with a boron-doped diamond electrode

The degradation of 100ml of solutions with paracetamol (N-(4-hydroxyphenyl)acetamide) up to 1 g l(-1) in the pH range 2.0-12.0 has been studied by anodic oxidation in a cell with a boron-doped diamond (BDD) anode and a graphite cathode, both of 3-cm2 area, by applying a current of 100, 300 and 450 mA between 25 and 45 degrees C. Complete mineralization is always achieved due to the great concentration of hydroxyl radical (*OH) generated at the BDD surface, with release of NH4+ and NO3- ions. The mineralization rate is pH-independent, increases with increasing applied current and temperature, but decreases when drug concentration raises from 315 mg l(-1). Reversed-phase chromatography revealed a similar complex paracetamol decay in acid and alkaline media. Ion-exclusion chromatography allowed the detection of oxalic and oxamic acids as ultimate carboxylic acids. When the same solutions have been comparatively treated with a Pt anode, a quite poor mineralization is found because of the production of much lower *OH concentration. Under these conditions, the degradation rate is enhanced in alkaline medium and polymerization of intermediates is favored in concentrated solutions. Paracetamol can be completely destroyed with Pt and its kinetics follows a pseudo-first-order reaction with a constant rate independent of pH.     

Electrochemical oxidation of nitrogen-heterocyclic compounds at boron-doped diamond electrode

Nitrogen-heterocyclic compounds (NHCs) are toxic and bio-refractory contaminants widely spread in environment. This study investigated electrochemical degradation of NHCs at boron-doped diamond (BDD) anode with particular attention to the effect of different number and position of nitrogen atoms in molecular structure. Five classical NHCs with similar structures including indole (ID), quinoline (QL), isoquinoline (IQL), benzotriazole (BT) and benzimidazole (BM) were selected as the target compounds. Results of bulk electrolysis showed that degradation of all NHCs was fit to a pseudo first-order equation. The five compounds were degraded with the following sequence: ID > QL > IQL > BT > BM in terms of their rates of oxidation. Quantum chemical calculation was combined with experimental results to describe the degradation character of NHCs at BDD anode. A linear relationship between degradation rate and delocalization energy was observed, which demonstrated that electronic charge was redistributed through the conjugation system and accumulated at the active sites under the attack of hydroxyl radicals produced at BDD anode. Moreover, atom charge was calculated by semi empirical PM3 method and active sites of NHCs were identified respectively. Analysis of intermediates by GC-MS showed agreement with calculation results.     

Electrochemical oxidation of benzene on boron-doped diamond electrodes

This work presents an electrochemical investigation of the benzene oxidation process in aqueous solution on boron-doped diamond (BDD) electrodes. Additionally, in order to determine the main products generated during the oxidation process, electrolysis and high performance liquid chromatography experiments were carried out. The complete degradation of this compound was performed aiming to a further application in waste water treatment. The cyclic voltammetry studies indicate that benzene is irreversibly oxidized in acid medium (H₂SO₄ 0.5 M) on the BDD electrode surface at 2.0 V versus Ag/AgCl in a diffusion controlled process. During the cycling, other products are generated, and a pair of peaks was observed that can be associated with the oxi-reduction of anyone of the following species: hydroquinone, benzoquinone, resorcinol or catechol. The electrolysis experiments were carried out at 2.4 and 2.5 V on the BDD electrode surface in a solution containing 1 × 10⁻² M of benzene (below the saturation concentration in aqueous solution), for 3 and 5 h, respectively. The main products measured were: hydroquinone, resorcinol, p-benzoquinone, catechol and phenol. The complete electrochemical benzene degradation was performed in the electrolysis experiments using a rotating BDD disc electrode (2.5 V for 5 h) and the main products detected were all measured at concentrations lower than 10⁻⁵ M in this condition. The boron-doped diamond electrode had proved to be a valuable tool for the electrochemical degradation of the benzene, a very stable chemical compound.     

A comparative study of the electrochemical oxidation of the herbicide tebuthiuron using boron-doped diamond electrodes

The thiadiazolylurea derivative tebuthiuron (TBH) is commonly used as an herbicide even though it is highly toxic to humans. While various processes have been proposed for the removal of organic contaminants of this type from wastewater, electrochemical degradation has shown particular promise. The aim of the present study was to investigate the electrochemical degradation of TBH using anodes comprising boron-doped (5000 and 30 000 ppm) diamond (BDD) films deposited onto Ti substrates operated at current densities in the range 10-200 mA cm⁻². Both anodes removed TBH following a similar pseudo first-order reaction kinetics with k_app close to 3.2 × 10⁻² min⁻¹. The maximum mineralization efficiency obtained was 80%. High-pressure liquid chromatography with UV-VIS detection established that both anodes degraded TBH via similar intermediates. Ion chromatography revealed that increasing concentrations of nitrate ions (up to 0.9 ppm) were formed with increasing current density, while the formation of nitrite ions was observed with both anodes at current densities ?150 mA cm⁻². The BDD film prepared at the lower doping level (5000 ppm) was more efficient in degrading TBH than its more highly doped counterpart. This unexpected finding may be explained in terms of the quantity of impurities incorporated into the diamond lattice during chemical vapor deposition.     

芬顿氧化法处理水中酸性品红的研究

研究了酸性品红在Fenton体系中的降解过程,反应30 min后,在[Fe2+]0=0.06 mmol/L、[H2O2]0=0.3 mmol/L、pH=3、T=30℃的条件下,初始浓度为20 mg/L的酸性品红的去除率达到97%以上。升高反应温度,有利于Fenton体系中酸性品红的降解,但影响并不显著。根据不同温度下的速率常数,并结合Arrhenius方程求出了Fenton试剂降解酸性品红的反应活化能,仅为11.63 kJ/mol。C1?的存在对酸性品红在Fenton体系中的降解表现出明显的阻碍作用,并且随着C1?浓度的增加,抑制作用越来越大;SO24-和NO3-的存在也降低了Fenton试剂的氧化性能。     

TiO2薄膜光催化降解双酚A的研究

采用sol-gel法制备TiO2薄膜。以该薄膜为催化剂，研究了在H2O2存在的条件下，对内分泌干扰物质双酚A的光催化降解反应。分别讨论了pH值、H2O2的加入量、双酚A的初始浓度以及光照时间对降解反应的影响。结果表明，在pH=4，30mg／L的H2O2中对初始浓度为50mg／L的双酚A溶液光照180min有较好的降解效果。     

TiO2薄膜光催化降解双酚A的研究

采用sol-gel法制备TiO2薄膜.以该薄膜为催化剂,研究了在H2O2存在的条件下,对内分泌干扰物质双酚A的光催化降解反应.分别讨论了pH值、H2O2的加入量、双酚A的初始浓度以及光照时间对降解反应的影响.结果表明,在pH=4,30 mg/L的H2O2中对初始浓度为50 mg/L的双酚A溶液光照180 min有较好的降解效果.     

Photoelectrocatalytic degradation of pentachlorophenol in aqueous solution using a TiO2 nanotube film electrode

Titanium dioxide (TiO2) nanotube film electrodes are fabricated by the anodic oxidation method. Scanning electron microscopy (SEM) showed that these tubes were well aligned and organized into high-density uniform arrays. XRD analysis showed the TiO2 nanotubes to be in the anatase crystal form. The TiO2 nanotube film electrode exhibited increased photoelectrocatalytic (PEC) capability compared to a traditional TiO2 film electrode fabricated using the anodizing method for pentachlorophenol (PCP) degradation in aqueous solution. The bias potential, pH value, and electrolyte concentration were shown to be important factors influencing the degradation of PCP by the PEC method using the TiO2 nanotube film electrode as the working electrode.     

The enhanced PC and PEC oxidation of formic acid in aqueous solution using a Cu-TiO2/ITO film

The photocatalytic (PC) and photoelectrocatalytic (PEC) activity of Cu-TiO2/ITO films for degrading formic acid in aqueous solution was investigated in this study. Compared with a TiO2/ITO film, the degradation efficiency of formic acid on the Cu-TiO2 films increased markedly in both the PC and PEC oxidation processes. However, it was found that the photodeposited Cu metal on the Cu-TiO2 films could electrochemically dissolute during the PEC reaction, while an electrical bias with the voltage higher than 1.48 V was applied. It is believed this is a common problem occurred for several metals deposition on the TiO2 films, which results in a poor stability of the metal-deposited TiO2 electrode in PEC processes. To improve the stability of the Cu-TiO2 electrode, an alternative process between PC and PEC reactions was investigated. It was found that the dissolute Cu metal during the PEC process was re-deposited on the Cu-TiO2 film again during the PC process. The experiments with repeated runs demonstrated that this alternative process could not only overcome the loss of Cu, but also enhance the PEC oxidation efficiency of the Cu-TiO2 films.     

Ti/SnO2-F新型电极氧化降解全氟辛酸

采用溶胶-凝胶法制备F掺杂的Ti/SnO2电极,用于水相中全氟辛酸（PFOA）的电氧化降解,实验考察了F或Sb掺杂、煅烧温度、氟掺杂量、老化时间及涂覆次数对PFOA降解效率的影响。结果表明,在煅烧温度为500℃,掺杂比Sn：F=9：0.25,老化时间10 d,涂覆20次的条件下,F掺杂的Ti/SnO2电极性能最好,反应30 min对PFOA的降解率达98%;而在相同电解条件下,Sb掺杂Ti/SnO2电极降解PFOA效率仅61.7%。因此,F掺杂可有效提高SnO2电极性能,有效氧化降解PFOA。     

Subcritical water oxidation of propham by H2O2 using response surface methodology (RSM)

This study was conducted to investigate the degradation of propham, which is a compound that pollutes water and seriously threatens human health, by subcritical water oxidation and using H₂O₂ as an oxidising agent. The maximum total organic carbon removal rate of propham was obtained as 73.65% at 40 min of treatment time and 60 mM of H₂O₂ concentration and 373 K of temperature. In addition, response surface method based on the Box-Behnken design was applied to design the degradation experiments of propham for determination of the combined effects of process variables, namely temperature, concentration of oxidising agent and treatment time. The proposed quadratic model of propham degradation, which was examined with the analysis of variance, was used for navigating the design space. The R² and adjusted R² values of the model were determined as 0.9921 and 0.9819 respectively. It was shown that propham was effectively degraded, thus could be removed from the water by using an environmentally friendly method.     

Electrochemical monitoring of methylparathion degradation in an acid aqueous medium in presence of Cu(II)

A study was undertaken to determine the effect of Cu(II) in degradation of methylparathion (o,o-dimethyl o,4-nitrophenyl phosphoriotioate) in acid medium. Initial electrochemical characterization of Cu(II) and methylparathion was done in an aqueous medium at a pH range of 2-7. Cu(II) was studied in the presence of different anions and it was observed that its electroactivity depends on pH and is independent of the anion used. Methylparathion had two reduction signals at pH < or = 6 and only one at pH > 6. The pesticide's transformation kinetic was then studied in the presence of Cu(II) in acid buffered aqueous medium at pH values of 2, 4, and 7. Paranitrophenol appeared as the only electroactive product at all three pH values. The reaction was first order and had k values of 5.2 x 10(-3) s(-1) at pH 2, 5.5 x 10(-3) s(-1) at pH 4 and 9.0 x 10(-3) s(-1) at pH 7. It is concluded that the principal degradation pathway of methylparathion in acid medium is a Cu(II) catalyzed hydrolysis reaction.     

TiO2光催化氧化降解乳酸的工艺及机理研究

以TiO2为催化剂、紫外灯为光源对乳酸进行光催化降解实验,考察了乳酸初始浓度、TiO2用量、反应时间、曝气方式等因素对乳酸降解率的影响,并在此基础上应用正交实验对降解条件进行优化,同时对乳酸的降解机理进行了探索研究。实验结果表明：以300 W紫外汞灯为光源,在乳酸初始浓度为0.5 g/L、TiO2量为0.20 g/L、反应时间120 min、持续通入空气鼓泡的条件下,乳酸降解效果最佳,乳酸降解率为99.9%;降解12 h总有机碳去除率达91.2%。乳酸光催化降解的反应途径为：乳酸脱羧生成乙醇,乙醇被氧化生成乙醛,进而氧化为乙酸,所有的中间产物被继续降解,最终矿化为CO2和H2O等小分子物质。     

UV/TiO2薄膜体系光降解酞酸酯研究

采用自制玻璃负载TiO2薄膜,研究了UV-V is/TiO2以及UV/TiO2/H2O2体系对2种酞酸酯DBP和DEHP的光催化降解情况。研究结果表明,TiO2在暗处对酞酸酯没有降解作用;UV/TiO2体系能有效光降解DBP和DEHP,TiO2具有明显的光催化作用,增强因子分别为fDBP=2.06,fDEHP=1.53;在一定浓度范围内DBP在UV/TiO2体系中的降解速率与其初始浓度成负一级动力学关系;UV/TiO2/H2O2体系对DBP的光降解能力远大于UV/TiO2和UV/H2O2体系,H2O2能显著提高TiO2的光催化活性。     

UV／TiO2薄膜体系光降解酞酸酯研究

采用自制玻璃负载TiO2薄膜，研究了UV-Vis／TiO2以及UV／TiO2／H2O2体系对2种酞酸酯DBP和DEHP的光催化降解情况。研究结果表明，TiO2在暗处对酞酸酯没有降解作用；UV／TiO2体系能有效光降解DBP和DEHP，TiO2具有明显的光催化作用，增强因子分别为，fDBP=2．06，fDEHP=1．53；在一定浓度范围内DBP在UV／TiO2体系中的降解速率与其初始浓度成负一级动力学关系；UV／TiO2／H2O2体系对DBP的光降解能力远大于UV／TiO2和UV／H2O2体系，H2O2能显著提高TiO2的光催化活性。     

Electrochemical degradation of amoxicillin in acidic aqueous medium using TiO2-based electrodes modified by oxides of transition metals

Environmental Science and Pollution Research - One of the most widely used antibiotics is amoxicillin (AMX), which is the most widely used in humans and animals, but it is discharged metabolically...     

Metabolic fate of the 14C-labeled herbicide clodinafop-propargyl in soil

The metabolic fate of ¹⁴C-phenyl-labeled herbicide clodinafop-propargyl (CfP) was studied for 28 days in lab assays using a soil from Germany (A_p horizon, silt loam, and cambisol). Mineralization amounted to 12.40% of applied ¹⁴C after 28 days showing a distinct lag phase until day 7 of incubation. Portions of radioactivity extractable by means of 0.01 M CaCl₂ solution (bioavailable fraction) decreased rapidly and were 4.41% after 28 days. Even immediately after application, only 57.31% were extracted with the aqueous solvent. Subsequent extraction using accelerated solvent extraction (ASE; acetonitrile/water 4:1, v/v) released 39.91% of applied ¹⁴C with day 0 and 26.16% with day 28 of incubation from the samples. Non-extractable portions of radioactivity thus, increased with time amounting to 11.99% (day 0) and 65.00% (day 28). A remarkable increase was observed between 14 and 28 days correlating with the distinct increase of mineralization. No correlation was found throughout incubation with general microbial activity as determined by DMSO reduction. Analysis of the CaCl₂ and ASE extracts by radio-TLC, radio-HPLC and GC/MS revealed that CfP was rapidly cleaved to free acid clodinafop (Cf), which was further (bio-) transformed; DT₅₀ values (based on radio-TLC detection of the parent compound) were far below 1 day (CfP) and about 7 days (Cf). TLC analysis pointed to 2-(4-hydroxyphenoxy)-propionic acid as further metabolite. Due to fractionation of non-extractable residues, most of the ¹⁴C was associated with fulvic and humic acids, portions in humin fractions and non-humics were moderate and low, respectively. Using a special strategy, which included pre-incubation of the soil with CfP and then mineralization of ¹⁴C-CfP as criterion, a microorganism was isolated from the soil examined. The microorganism grew using CfP as sole carbon source with concomitant evolution of ¹⁴CO₂. The bacterium was characterized by growth on commonly used carbon sources and by 16S rDNA sequence analysis. The sequence exhibited high similarity with that of Rhodococcus wratislaviensis (99.56%; DSM 44107, NCIMB 13082).