Remediation of 2,4-dichlorophenol-contaminated groundwater using nano-sized CaO2 in a two-dimensional scale tank

• Nano CaO₂ is evaluated as a remediation agent for 2,4-DCP contaminated groundwater. • 2,4-DCP degradation mechanism by different Fe²⁺ concentration was proposed. • 2,4-DCP was not degraded in the system for solution pH>10. • The 2,4-DCP degradation area is inconsistent with the nano CaO₂ distribution area. This study evaluates the applicability of nano-sized calcium peroxide (CaO₂) as a source of H₂O₂ to remediate 2,4-dichlorophenol (2,4-DCP) contaminated groundwater via the advanced oxidation process (AOP). First, the effect and mechanism of 2,4-DCP degradation by CaO₂ at different Fe concentrations were studied (Fenton reaction). We found that at high Fe concentrations, 2,4-DCP almost completely degrades via primarily the oxidation of •OH within 5 h. At low Fe concentrations, the degradation rate of 2,4-DCP decreased rapidly. The main mechanism was the combined action of •OH and O₂^•−. Without Fe, the 2,4-DCP degradation reached 13.6% in 213 h, primarily via the heterogeneous reaction on the surface of CaO₂. Besides, 2,4-DCP degradation was significantly affected by solution pH. When the solution pH was>10, the degradation was almost completely inhibited. Thus, we adopted a two-dimensional water tank experiment to study the remediation efficiency CaO₂ on the water sample. We noticed that the degradation took place mainly in regions of pH<10 (i.e., CaO₂ distribution area), both upstream and downstream of the tank. After 28 days of treatment, the average 2,4-DCP degradation level was ≈36.5%. Given the inadequacy of the results, we recommend that groundwater remediation using nano CaO₂: (1) a buffer solution should be added to retard the rapid increase in pH, and (2) the nano CaO₂ should be injected copiously in batches to reduce CaO₂ deposition.     

Study of Fishes in the Chung-Kung Stream: Species Distribution and Organochlorine Pesticide Residues

Abstract

In this study, we investigated the potential for reductive dechlorination of 2,4-dichlorophenol (2,4-DCP), 2,4,6-trichlorophenol (2,4,6-TCP), and pentachlorophenol (PCP) by municipal sewage sludge adapted to 2,4-DCP at different concentrations. 2,4-DCP was completely dechlorinated within 4 weeks. After 18 weeks' incubation, 2,4,6-TCP was also completely dechlorinated and the residue of PCP was 0, 44.46, 51.96% at 0.5, 5, and 50 μg ml¹ respectively. the 2,4-DCP adapted communities initially removed the ortho-chlorine from PCP of 5.0, 50 μg ml¹, following an ortho < para < meta order of chlorine removal. Intermediate products were 3,4,5-TCP, 3,5-DCP, 3-CP (3-chlorophenol), phenol, benzoate and hexanoic acids, whereas PCP (0.5 μg ml¹) indicated a preference for meta-chlorine removal. the intermediate product of 2,4,6-TCP at three concentrations were 2,4-DCP, phenol, benzoate and hexanoic acid. These products were identified by GC-MASS spectrometry. the effects of supplements, including sodium citrate (0.08 mM), sodium pyruvate (0.18 mM), sodium sulphate (0.14 mM) had a direct stimulatory effect on the dechlorination of 2,4,6-TCP and PCP after treatment for 4 weeks, but dechlorination was inhibited after 8 weeks.     

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.     

Biotransformations of Chlorophenols in River Sediments

Abstract

The accumulation of chlorophenols, including 2,4-dichlorophenol (2,4-DCP), 2,4,6-trichlorophenol (2,4,6-TCP) and pentachlorophenol (PCP), from river sediments from southern Taiwan were studied. Through simple or more exhaustive extractions, the results showed that 99% of the samples containing 2,4,6-TCP and PCP could be removed by simple extraction. the concentrations were found to range from non-detectable to 16.60 ngg¹ for 2,4,6-TCP and to 25.02 ngg¹ for PCP. Partition coefficients (K_p) were 0.71, 0.74 mlg¹ for 2,4,6-TCP, 1.35 and 1.41 mlg¹ for PCP. Biodegradation by DCP-adapted or unadapted anaerobes in sediment was carried out. During 21 days' incubation, the complete degradation time for 2,4,6-TCP in DCP-adapted anaerobic, unadapted anaerobic, and unadapted aerobic conditions were found to be 9, 10, 12 days for N3 sediment, and 8, 10, 11 days for N6 sediment, respectively; for PCP it was 19 days, without degradation, 14 days for N3 sediment, and 13, 17, 10 days for N6 sediment, respectively. the biodegradable products were identified as 2,3,4,5-tetrachlorophenol (2,3,4,5-TeCP), 3,4,5-TCP, 3,5-DCP, 3-MCP, phenol, methylphenol, and benzoate for PCP, and 2,4-DCP, 4-MCP, phenol, methylphenol, and benzoate for 2,4,6-TCP.     

三维电催化氧化处理难生化降解有机废水研究进展

难降解有机废水成分复杂、危害大,易导致癌变、畸变,对人类健康产生重大影响,是需要优先治理的环境问题.在许多情况下,采用传统生物法和物理化学法来处理难生化处理有机废水很难达到理想的处理效果,并且其操作工艺复杂,成本相对较高.三维电催化氧化技术的出现为难降解有机废水的处理提供了一种绿色环保高效的方法.三维电催化氧化体系具有...     

Unprecedented total mineralization of atrazine and cyanuric acid by anodic oxidation and electro-Fenton with a boron-doped diamond anode

This article reports the complete mineralization of atrazine. Atrazine has been the most widely used s-triazine herbicide. Atrazine occurs in natural waters and presents a potential danger for public health because atrazine is considered as an endocrine disruptor. The use of chemical, photochemical and photocatalytic advanced oxidation processes (AOPs) to decontaminate waters containing atrazine only allowed its conversion into the cyanuric acid as ultimate end products, since it cannot be completely degraded by hydroxyl radicals (^•OH) produced by these techniques. The same behavior was previously reported for anodic oxidation and electro-Fenton with Pt anode, although better performances were found using boron-doped diamond (BDD) anode but without explaining the role of generated ^•OH. Here, the oxidative action of these radicals in such electrochemical AOPs has been clarified by studying the mineralization process and decay kinetics of atrazine and cyanuric acid in separated solutions by anodic oxidation with BDD and electro-Fenton with Pt or BDD anode using an undivided cell with a carbon-felt cathode under galvanostatic conditions. Results showed that electro-Fenton with BDD anode was the more powerful treatment to degrade both compounds. Almost total mineralization, 97% total organic carbon (COT) removal, of atrazine was only feasible by this method with a faster removal of its oxidation intermediates by ^•OH formed at the BDD surface than that formed in the bulk from Fenton reaction, although the latter process caused a more rapid decay of the herbicide. Cyanuric acid was much slowly mineralized mainly with ^•OH produced at the BDD surface, and it was not degraded by electro-Fenton with Pt anode. These results highlight that electrochemical advanced oxidation processes (EAOPs) using a BDD anode are more powerful than the classical electro-Fenton process with Pt or PbO₂ anodes.     

Up to 95 % reduction of chemical oxygen demand of slaughterhouse effluents using Fenton and photo-Fenton oxidation

Meat industries produce effluents containing high concentrations of organic and inorganic compounds, which must be removed before being discharged or reused. Advanced oxidation processes using Fenton reaction coupled with UV, solar radiation, and electrochemical oxidation are promising methods. Here, we treated the effluent from an anaerobic digester using: (a) the photoelectro-Fenton process, using a system with a Ti-RuO₂ anode and a carbon felt cathode, (b) the solar photo-Fenton process, using a batch reactor and a compound parabolic collector, and (c) a combination of Fenton and solar photo-Fenton processes. The effluent had an initial chemical oxygen demand (COD) of 1159 mgL^?1, and we obtained high removal efficiencies of COD, up to 95 %, using the combination of Fenton and solar photo-Fenton processes.     

Electrochemical treatment of wastewater to remove contaminants from the production and disposal of plastics: a review

Wastewater is major source of contaminants originating from the production, usage, and disposal of plastic materials. Due to their poor biodegradability of these contaminants in municipal wastewater treatment plants, additional advanced oxidation processes such as electrochemical treatments have been developed to improve the standard biological treatment. Here we review the applications of electrochemical treatments of wastewater for the removal of the following plastic contaminants: bisphenol A, phthalic acid esters, and benzotriazoles. We present the effectiveness of treatment in terms of contaminant removal and mineralization; the identification of transformation products; toxicity assessment; and process energy requirements. In the present review, we have focused on the applications of electrochemical treatments of wastewater for the removal of three important groups of contaminants originating mainly from plastics: bisphenol A, phthalic acid esters, and benzotriazoles. The review focuses on the research of electrochemical treatments for these contaminants from the last five years. The papers are assessed from the point of i) effectiveness of treatment in terms of contaminant removal and mineralization; ii) identification of transformation products; iii) toxicity assessment; iv) processes’ energy requirements. Electrochemical treatments were confirmed to be a viable option for the removal of selected contaminants from wastewater.

     

Wet oxidation of recalcitrant lignin water solutions: experimental and reaction kinetics

The purpose of the research was to study the behavior of lignin degradation under different conditions (T 110–190°C, pO₂ 0.5–1.5 MPa, pH 5, 9 and 12) and to develop a predictive model. Temperature increase improved lignin removal from 75% at 110°C to 100% at 190°C (experimental). Increasing the pH enhanced the lignin removal efficiency from 30 to 97% (experimental). The developed model predicted the lignin degradation and changes in COD, BOD and TOC. The model agreed well with the experimental data (R ² = 0.93 at pH 5 and 12).     

Decomposition of aqueous chlorinated contaminants by UV irradiation with H2O2

In the present study, the decomposition rates of carbon tetrachloride (CCl₄) and 2,4-dichlorophenol (2,4-DCP) in water by the ultraviolet (UV) light irradiation alone and H₂O₂/UV were experimentally investigated. The detailed experimental studies have been conducted for examining treatment capacities of the two different ultraviolet light sources (low and medium pressure Hg arc) in H₂O₂/UV processes. The low or medium UV lamp alone resulted in a 60%–90% decomposition of 2,4-DCP while a slight addition of H₂O₂ resulted in a drastic enhancement of the 2,4-DCP decomposition rate. The decomposition rate of 2,4-DCP with the medium pressure UV lamp alone was about 3–6 times greater than the low pressure UV lamp alone. In the direct photolysis of aqueous CCl₄, the medium pressure UV lamp had advantage over the low pressure UV lamp because the molar extinction coefficient of CCl₄ at shorter wavelength (210–220 nm) is about 20 to 50 times higher than that at 254 nm. However, adding H₂O₂ to the medium pressure UV lamp system rendered a negative oxidation rate because H₂O₂ acted as a UV absorber being competitive with CCl₄ due to negligible reaction between CCl₄ and OH radicals. The results from the present study indicated significant influence of the photochemical properties of the target contaminants on the photochemical treatment characteristics for designing cost-effective UV-based degradation of toxic contaminants.     

Optimization of electrochemical process for phenanthrene removal from aqueous medium by Taguchi

Discharge of refinery effluents containing phenanthrene (Phe) may exert carcinogenic effects on aquatic organisms. The aim of the current investigation was to investigate electrochemical removal of Phe from urban drinking water using a batch reactor. Phe removal efficiency was examined under different operating conditions including current density (1–8 mA/cm²), electrode composition materials such as aluminum (Al), copper (Cu), iron (Fe), steel (AS), or zinc (Zn), pH (4–10), and duration (20–60 min). Phe concentration was determined utilizing standard techniques. Steel–Steel (AS–AS) as anode–cathode electrodes resulted in the least Phe removal (not detected), while Zn–Cu anode–cathode electrodes produced the highest Phe removal (100%) under similar experimental conditions. The increase in current density from 1 to 8 mA/cm² at optimum electrode and pH enhanced Phe removal from 56% to 100%. The rise in duration from 20 to 60 min at optimum electrode and pH increased Phe removal from 32% to 100%. These findings indicated that Phe removal efficiency was elevated with increasing current density, electrolysis time, and pH. Batch experiments indicated that the electrochemical reactor might be effective in removing Phe from drinking water.     

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     

Biotransformations of Chlorophenols in River Sediments

The accumulation of chlorophenols, including 2,4-dichlorophenol (2,4-DCP), 2,4,6-trichlorophenol (2,4,6-TCP) and pentachlorophenol (PCP), from river sediments from southern Taiwan were studied. Through simple or more exhaustive extractions, the results showed that 99% of the samples containing 2,4,6-TCP and PCP could be removed by simple extraction. the concentrations were found to range from non-detectable to 16.60 ngg¹ for 2,4,6-TCP and to 25.02 ngg¹ for PCP. Partition coefficients (K_p) were 0.71, 0.74 mlg¹ for 2,4,6-TCP, 1.35 and 1.41 mlg¹ for PCP. Biodegradation by DCP-adapted or unadapted anaerobes in sediment was carried out. During 21 days' incubation, the complete degradation time for 2,4,6-TCP in DCP-adapted anaerobic, unadapted anaerobic, and unadapted aerobic conditions were found to be 9, 10, 12 days for N3 sediment, and 8, 10, 11 days for N6 sediment, respectively; for PCP it was 19 days, without degradation, 14 days for N3 sediment, and 13, 17, 10 days for N6 sediment, respectively. the biodegradable products were identified as 2,3,4,5-tetrachlorophenol (2,3,4,5-TeCP), 3,4,5-TCP, 3,5-DCP, 3-MCP, phenol, methylphenol, and benzoate for PCP, and 2,4-DCP, 4-MCP, phenol, methylphenol, and benzoate for 2,4,6-TCP.     

Photoelectrocatalytic degradation of camphor on TiO2/RuO2 electrodes

The degradation of camphor using titanium/ruthenium dioxide (TiO₂/RuO₂; 70:30) electrodes was investigated in a photoelectrochemical thin-film reactor under near UV light irradiation. Two different electrolytes (Na₂SO₄ and NaCl) were used in this work. Camphor degradation was monitored by solvent extraction methods and gas chromatography (GC) analysis. Comparative studies between photoelectrochemical, electrochemical, photolytic, and heterogeneous photocatalytical process were carried out. When NaCl was used, the degradation efficiency of camphor was improved, probably on account of electrochemical generation of active chlorine species and their photochemical conversion to chlorine radicals. Under these conditions camphor was completely mineralized at reaction times of 30 min.     

Color removal efficiency of dyes using nanozerovalent iron treatment

In this study, zerovalent iron nanoparticles (Fe⁰) were synthesized by chemical reduction method using ferric chloride hexahydrate (FeCl₃?·?6H₂O) as a starting material. Sodium borohydride (NaBH₄) was used as a reducer. The synthesized nanozerovalent iron (NZVI) was separated using magnets. The X-ray diffraction pattern of iron (Fe) nanoparticles showed that the presence of intensive diffraction peak at 2θ value of 45.33° from the lattice plane of face-centered cubic Fe unequivocally indicates that the particles are made of pure Fe. The size of the synthesized NZVI was found to be 16.64?nm. The scanning electron micrograph revealed that the particles have a hexagonal and spherical shape in nature. EDX showed the surface atomic distribution and chemical composition of NZVI. The decolorization efficiency rose with increasing concentration of nanoparticles as well as with time. Maximal color removal efficiency was 90.72% when using 0.5?g/100?mL Fe nanoparticle for acridine orange. Data revealed that the function of NZVI on color removal efficiency was statistically significant. The correlation coefficient between NZVI concentration and time showed a strong negative correlation for dyes used in the experiment.     

Photo detoxification of solubilized vat dye effluent using different pH ranges

The removal of solubilized vat dye effluent using photo detoxification method was studied at various pH ranges. Experiments were carried out with synthetic effluent using total dye concentrations of 50, 100, 200, 300, and 350 mg/L. In sunlight photo oxidation, the original soluble vat dye is precipitated and can be filtered and reused by the textile industries. The effect of the different concentrations (1,000, 2,000, 3,000 mg/L) of total dissolved solids on the removal of vat dye was also carried out in the photo detoxification process. The efficiency of the dye removal was found to be 99 %.     

多通道网状电极电化学预处理垃圾渗滤液反渗透浓缩液

反渗透(Reverse Osmosis,RO)因出水水质好、运行成本低等优势常用于垃圾渗滤液的处理,但产生的RO浓缩液具有COD高、色度高、盐分高、难降解等特点,其处理存在效果差、能耗和成本均较高等问题.本工作采用氧化钌/氧化铱涂层电极(RuO2/IrO2-Ti)的钛网为阳极,以304不锈钢电极为阴极,设计制作了6通道的电化学反应器,通过电化学氧化处理RO浓缩液,研究考查了电流密度、循环流速、比电极面积等参数对COD去除效果的影响,分析了电化学氧化去除难降解有机物并同时脱盐的过程机理与能耗.结果表明,在电流密度32.89 mA·cm^-2,循环流速0.46 cm·s^-1,比电极面积65.10 m²·m^-3的条件下,电化学氧化处理RO浓缩液3 h,COD去除率可达68.0%,TOC去除率可达40.6%,脱盐率可达72.1%,去除单位质量COD能耗仅为常规的板状电极电化学反应器的25.5%.本工作可为垃圾渗滤液RO浓缩液的预处理提供新思路.     

Photocatalytic degradation of indole in UV/TiO2: optimization and modelling using the response surface methodology (RSM)

The aim of our research is to apply experimental design methodology to the optimization of photocatalytic degradation of indole present in wastewater. Heterogeneous photocatalysis for the oxidation of organic biorecalcitrant pollutants in water is an environmental promising method. We used the response surface methodology (RSM) for the modelization and optimization of the photodegradation of indole in the presence of titanium dioxide. The effect of indole concentration, UV intensity and stirring speed on the yield of indole degradation was determined. According to the mathematic optimization of the process, the optimum point when 100% of degradation is achieved is given by the following values: UV intensity = 250 W/m², stirring speed = 536.36 tr/min and initial indole concentration = 10.10 mg/l.     

Degradation of pharmaceuticals by ultrasound-based advanced oxidation process

Water pollution by pharmaceutically active compounds is an emerging issue. Toxicological studies reveal that pharmaceuticals are indeed toxic for living organisms. The lack of suitable treatment technology for the complete removal of pharmaceuticals is therefore a major challenge. Advanced oxidation processes are emerging removal techniques that have many advantages versus conventional technologies. Many studies indicate that advanced oxidation processes, either in single or in combination with other degradation techniques, can enhance the degradation of pharmaceuticals in aqueous solutions. Here, we review the degradation of pharmaceuticals by sonolysis, an oxidation processes using ultrasound. In this technique, hydroxyl radicals are generated by pyrolytic cleavage of water molecules. We review the influence of operational parameters, additives and hybrid techniques on the degradation of pharmaceuticals. The maximum degradation of organic compounds was observed in the frequency range of 100–1000 kHz, which is in the high-frequency medium-power ultrasound. Even though almost all the experiments presented more than 90 % removal and good biodegradability of the target compound, good mineralization and the toxicity removal were hardly achieved. The efficiency of the degradation varies with water matrixes and varying pH. Major pathways of degradation are hydroxylation, dehalogenation, demethylation, decarboxylation, deamination, etc. More hybrid techniques have to be developed to scale up the application of ultrasound.     

Removal of organic pollutants by peroxicoagulation

Peroxicoagulation is an electrochemical advanced oxidation processes in which both ferrous ions and hydrogen peroxide are generated in the cell. Organic pollutants are thus removed by degradation and coagulation. The peroxicoagulation process is a combination of electro-Fenton and electrocoagulation processes. The peroxicoagulation process is very efficient for the removal of aniline and herbicides from water and for the treatment of landfill leachate and textile wastewaters. Under acidic conditions, electro-Fenton is the predominant removal means, whereas electrocoagulation is the main removal means under neutral and alkaline conditions. As a consequence, pH regulation to acidic conditions is essential for the mineralization of organic pollutants.