共价三嗪有机框架材料对水中氯酚类污染物的光催化脱氯降解

利用共价三嗪有机框架材料(CTF-1)对4-氯酚(4-CP)、2,4-二氯酚(2,4-DCP)、2,4,6-三氯酚(2,4,6-TCP)和五氯酚(PCP)等4种不同氯原子取代数目的氯酚类污染物进行光催化降解研究,探讨了底物结构对氯酚脱氯降解效率的影响及机制.结果表明,氯酚脱氯降解过程明显受苯环氯原子取代数目的影响,氯原子数目越多,脱氯降解效率越高,氯原子数目与表观速率常数呈显著正相关,氯酚降解及脱氯速率均为:PCP>2,4,6-TCP>2,4-DCP>4-CP.对CTF-1光催化降解氯酚机制研究表明,活性物种在反应中不起作用,体系反应机制为针对氯酚上取代氯位点进行水解脱氯过程.本研究结果为深入揭示氯酚脱氯降解机制提供了理论依据,也为光催化技术处理卤代酚类废水提供了技术参考.

亚硝酸盐对硫酸根自由基降解卤代酚的影响

系统研究了亚硝酸盐(NO_(2)^(-))对硫酸根自由基(SO_(4)^(•-))降解溴酚和氯酚的影响.结果表明,NO_(2)^(-)的加入明显促进了溴酚的降解,而氯酚的降解仅受到轻微促进;此外,两者都转化生成了有毒硝基产物.研究发现,卤代酚在SO_(4)^(•-)氧化过程中发生脱卤反应,脱下来的卤离子被SO_(4)^(•-)氧化为卤自由基和自由卤.其随后和中间产物甚至母体反应,生成卤代副产物,如卤仿和卤乙酸.若反应过程中存在NO_(2)^(-),首先,原位生成的活性卤物质能够被NO_(2)^(-)迅速捕获,生成强氧化性的硝酰卤.硝酰卤进攻卤代酚,导致其加速降解并生成硝基副产物.其次,NO_(2)^(-)被SO_(4)^(•-)氧化生成二氧化氮自由基(NO2•),其随后与卤代酚转化生成的酚氧自由基中间体结合,同样产生大量硝基卤代产物.数据显示,硝基溴酚的种类更多且产量更高.当加入200μmol/L NO_(2)^(-),溶液中硝基溴酚和硝基氯酚的总生成量最高分别可至9.2和5.7μmol/L.这是因为在SO_(4)^(•-)氧化过程中,溴酚较氯酚更容易发生脱卤反应,因此NO_(2)^(-)对溴酚转化行为的影响更显著.研究揭示了SO_(4)^(•-)氧化技术应用于地下环境中降解卤代污染物时的潜在风险,并对该过程中氮素和卤素的相互转化提供了新的见解.

酚类环境内分泌干扰物微生物降解研究进展

环境内分泌干扰物(EDCs)又名环境激素,具有类似激素的结构和效应,能够干扰生物体的内分泌系统,危害人类和动物健康。聚焦典型酚类EDCs,包括烷基酚(APs)、双酚类(BPs)和氯酚(CPs)的微生物降解研究。受污染的土壤、河流、沉积物或活性污泥中存在并可分离出能够有效降解酚类EDCs的细菌和真菌,这些降解菌在污染土壤或水体的生物原位修复,去除废水中酚类EDCs等方面具有良好的应用前景。系统综述了好氧和厌氧条件下酚类EDCs的降解功能菌及其降解途径,总结了酚类EDCs的降解功能酶和功能基因,包括参与羟化作用的单加氧酶和羟化酶、参与环裂解的双加氧酶和还原脱氯过程需要的还原脱卤酶等,旨在为推动高效削减酚类EDCs的微生物法技术创新提供科学依据。

皮革中19种含氯苯酚的快速测定方法研究

建立了高效液相色谱串联质谱(HPLC-MS/MS)法同时测定皮革中19种含氯苯酚。样品采用甲醇(10%乙酸铵)混合溶液超声萃取,经色谱柱ZORBAX RRHD StableBond C18(21 mm×100 mm,18μm)分离,HPLC-MS/MS测定。结果表明,19种含氯苯酚在1~50μg/L浓度范围内呈现线性(R2>099),3个不同添加水平的平均回收率在813%~1237%,精密度(n=7)为08%~97%。本方法简化了前处理过程,灵敏度高,重现性好,可用于皮革中19种含氯苯酚的快速检测。

Evidence against hydroxyl radical mechanism in photo-Fenton degradation of p-chlorophenol

This paper provides evidence for the degradation of organic pollutant by the photo-Fenton complex mechanism. Both the complex oxidation and HO. oxidation mechanisms were verified by p-chlorophenol degradation, UV/Vis spectra anaylsis, and quantum yield. The hydroxyl radical involved in the photo-Fenton process can also be generated from the decomposition of H2O2, photolysis of Fe^3＋ and degradation of hydrated Fe（Ⅵ）-complex, excepting the traditional Fenton reaction.

Studies on the Quantitative Structure-activity Relationship of Toxicity of Chlorophenol Serial Compounds in the ab initio Methods and Substitutive Position of Chlorine Atom (N_(PCS))

20 Quantum chemical parameters of chlorophenol compounds were fully optimized by using B3LYP method on both 6-31G^＊ and 6-311G^＊ basis sets. These structural parameters are taken as theoretical descriptors, and the experimental data of 20 compounds＇ aquatic photogen toxicity（-lgEC50） are used to perform stepwise regression in order to obtain two predicted -lgEC50 correlation models whose correlation coefficients R^2 are respectively 0.9186 and 0.9567. In addition, parameters of chlorine atom＇s substitutive positions and their correlations （NPCs） are taken as descriptors to obtain another predicted -lgEC50 model with the correlation coefficient R2 of 0.9444. Correlation degree of each independent variable in the three models is verified by using variance inflation factors （VIF） and t value. In the cross-validation method, cross-validation coefficients q^2 of 3 models are respectively 0.8748, 0.9119 and 0.8993, which indicates that the relativity and prediction ability of this model are superior to those of the model obtained by topological and BLYP methods.

Immobilization of microorganisms using carrageenan gels coated with chitosan and application to biodegradation of 4-chlorophenol

A new cell immobilization method based on the replacement of KCl by KCl+chitosan as the gelling agent was developed. The experimental results showed that through addition of chitosan into gelling agent, the mechanical strength and the thermal stability of the carrageenan gel were greatly improved. The new immobilization method was used to entrap a chlorophenol degrading microorganism. The immobilized microbial cells were applied for chlorophenol biodegradation. The experiments demonstrated that immobilized cells exhibit a higher bioactivity in the degradation of chlorophenol than free cells.

ADSORPTION CHARACTERISTICS OF CHLOROPHENOLS FROM AQUATIC SYSTEMS BY HYPERCROSSLINKED RESINS MODIFIED WITH BENZOYL GROUP

A hypercrosslinked polymeric adsorbent （ZH-03） for adsorbing and removing chlorophenolic compounds from their aqueous solutions was studied, including the static adsorption. The equilibrium adsorption data were fit to Freundlich adsorption isothermic models to evaluate the model parameters. Thermodynamic studies on the adsorption of chlorophenolic compounds on ZH-03 indicated that there were chemisorption transitions for 2,4,6-trichlorophenol and physical adsorption processes for 2-chlorophenol and 2,6-chlorophenol, and ZH-03 showed the homogeneous nature of the adsorbent surface. Column adsorption for chlorophenols wastewater shows the advantages of the ZH-03 adsorbent for adsorbing the following chlorophenolic compounds as 2-chlorophenol, 2,6-dichlorophenol and 2,4,6-trichlorophenol. Sodium hydroxide was used for desorpting chlorophenols from ZH-03 and showed excellent performance.

Microbial Removal of Phenol and P-Chlorophenol from Industrial Waste Water Using Rhodococcus sp.RSP8 and Its Growth Kinetic Modeling

A phenol-degrading microorganism, Rhodococcus sp.RSP8, was used to study the substrate interactions during cell growth on phenol and p-chlorophenol dual substrates. Both phenol and p-chlorophenol could be utilized by the bacteria as the sole carbon and energy sources. When cells grew on the mixture of phenol and p-chlorophenol, strong substrate interactions were observed. The p-chlorophenol inhibited the degradation of phenol, on the other hand, phenol also inhibited the utilization of p-chlorophenol. The overall cell growth rate depends on the co-actions of phenol and p-chlorophenol. In addition, the cell growth and substrate degradation kinetics of phenol, p-chlorophenol as single and mixed substrates for Rhodococcus sp.RSP8 in batch cultures were also investigated over a wide range of initial phenol concentrations (5-1600 mg.L–1) and initial p-chlorophenol concentrations (5 – 250 mg.L–1). The single-substrate kinetics was described well using the Haldane-type kinetic models, with model constants of μm1 = 0.15 h–1, KS1 = 2.22 mg.L–1 and Ki1 = 245.37 mg.L–1 for cell growth on phenol and of μm2 = 0.0782 h–1, KS2 = 1.30 mg.L–1 and Ki2 = 71.77 mg.L–1, K′i2 = 5480 (mg.L–1)2 for cell growth on p-chlorophenol. Proposed cell growth kinetic model was used to characterize the substrates interactions in the dual substrates system.

Reversed flow injection spectrophotometric determination of low residuals of chlorine dioxide in water using chlorophenol red

A novel, simple, rapid, sensitive and highly selective flow injection procedure for the spectrophotometric determination of chlorine dioxide in the presence of other chlorine species, viz,free chlorine, chlorite, chlorate and hypochlorite, is developed. The method is based on the discoloration reaction between chlorine dioxide and chlorophenol red and can overcome the shortcomings existed in direct spectrophotometric determination for chlorine dioxide owing to the serious interference of free and combined chlorine. The procedure gave a linear calibration graph over the range 0—0.71 mg/L of chlorine dioxide. With a detection limit of 0.024 mg/L and a sample throughput of 60 samples/h.

QSBR Study on the Anaerobic Biodegradation of Chlorophenols

18 Physicochemical and quantum chemical parameters of 12 kinds of chlorophenols are calculated in this paper. QSBR （quantitative structure-biodegradability relationship） study is performed using simca statistical software by PLS regression analysis method on anaerobic biodegradation data （logKb）, and the QSBR model is developed with favorable prediction. The model shows that the size and energy of the molecule are the dominant factors affecting the anaerobic biodegradation of chlorophenols. And the degradation rate constants （logKb） increase with the increase of core-core repulsion （CCR）, average molecular polarizability （α）, total surface area （TSA）, heat of formation （HOF） and total energy （TE）. while decrease with the increase of molecular connectivity index （^1X^V）, relative molecular mass （Mw） and electronic energy （EE）.

Efficient oxidative degradation of 2-chlorophenol and 4-chlorophenol over supported CuO-based catalysts

A series of metal oxide catalysts for catalytic oxidative degradation of 2-chlorophenol （2-CP） and 4-chlorophenol （4-CP） were prepared, and the supported CuO catalysts were studied particularly. The supported CuO catalysts were characterized by XRD and NH3-TPD techniques, in which CuO/γ-Al2O3 exhibited high degradation activity. The addition of Na2O or K2O into CuO/γ-Al2O3 improved the oxidative degradation of CPs remarkably, in which Na2O was more efficient than K2O. Over CuO/γ-Al2O3-Na2O, CPs were completely converted and the liberation of the inorganic chloride from 2-CP or 4-CP reached 97% or 100% respectively at 30 ？C for 2 h. The supported CuO catalysts with good dispersion of CuO particles and less acid sites were favorable for the efficient oxidative degradation of CPs. In addition, the initial pH of the reaction solution was found to be an important factor which influenced the catalytic oxidative degradation of CPs and the initial pH of 11.2 and 9.8 was preferred for the oxidative degradation of 2-CP and 4-CP respectively over CuO/γ-Al2O3 catalyst.

Phytotoxic Effects of 4-Chlorophenol and 2,4-Dichlorophenol in the Germination of Seeds of <i>Phaseolus vulgaris</i>and <i>Zea mayz</i>

Soil contaminated with pesticides may reduce plant development due to their toxicity. The aim of this study was to evaluate the influence on the germination of Zea mayz and Phaseolus vulgaris of the two main intermediates of the 2,4-D degradation, which are 4-chlorophenol (4-CP) and 2,4-dichlorophenol (2,4-DCP). Maize and bean seeds were treated with distilled water (control treatment) and increased concentrations of 4-CP and 2,4-DCP (0.006, 0.1, 1.0, 1.5 g·L-1). It was assessed seed germination and calculated various parameters. The parameter most affected by chlorophenols was the index of germination rate, being the P. vulgaris seeds most affected. 2,4-DCP was the compound most toxic for both plants. The germination index was dependent doses for both plant models tested. The results indicate that 4-CP and 2,4-DCP affected the index of germination rate but not influenced in other parameters of germination of Zea mayz and Phaseolus vulgaris. Maize was most tolerance to both chlorophenols in the assessed concentrations. 2,4-DCP was the most toxic of chlorophenols tested.

Electrochemical Removal of Chlorophenol Pollutants by Reactive Electrode Membranes: Scale-Up Strategy for Engineered Applications

Chlorophenols(CPs)are significant refractory pollutants that are highly toxic to humans and other organ-isms.Reactive electrode membranes(REMs)show considerable potential in the electrochemical removal of refractory pollutants by allowing flow-through operations with convection-enhanced mass transfer.However,relevant studies are commonly performed on the laboratory scale,and there is no straightfor-ward method that guarantees success in scaling up engineered REM reactors.In this study,we demon-strated that a tubular concentric electrode(TCE)configuration with a titanium suboxide ceramic anode and a stainless-steel cathode is suitable for large-scale CPs removal.Both theoretical and experi-mental results showed that the TCE configuration not only allows the electrode surface to be orthogonal to electric field lines everywhere,but also has an ohmic resistance that is inversely proportional to the length of the electrode.In addition,the TCE configuration can be operated in either the anode-to-cathode(AC)or the cathode-to-anode(CA)mode based on the flow direction,creating adjustable condi-tions for selective degradation of CPs.This was confirmed by 98%removal of 2,4-dichlorophenol(2,4-DCP)and 72.5%removal of chemical oxygen demand(COD)in the CA mode,in which the kinetic constant was one order of magnitude higher than that for the AC mode under flow-through single-pass operations.This can be explained by the lower activation energy and free energy in the CA mode,as revealed by the-oretical calculations and experimental measurements.The TCE configuration is also suitable for a numbering-up strategy to scale up the electrochemical reactor without increasing the ohmic resistance or decreasing the specific electrode area,achieving 99.4%removal of 2,4-DCP with an energy consump-tion of 1.5 kW·h·m^(-3) when three TCE modules were employed.This study presents a suitable electrode design configuration for the REM reactor,offering effective strategies to bridge the“Valley of Death”encountered when scaling up the electrochemical removal of CP pollutants.

Oxidative Degradation of 4-chlorophenol in Aqueous Induced by Plasma with Submersed Glow Discharge Electrolysis

The oxidative degradation of 4-chlorophenol （4-CP） in aqueous solution induced by plasma with submersed glow discharge has been investigated. The concentration of 4-CP and the reaction intermediates were determined by high performance liquid chromatography （HPLC）. Various influencing factors such as the initial pH, the concentration of 4-CP and the catalytic action of Fe^2＋ were examined. The results indicate that 4-CP is eventually degraded into inorganic ion, dioxide carbon and water. The attack of hydroxyl radicals on the benzene rings of 4-CP in the initial stage of oxidative reactions is presumed to be a key step. They also suggest that the reaction is of a pseudo-first order kinetic reaction and the proposed method is an efficient way for the 4-CP degradation,

Electrochemical treatment of wastewater containing chlorophenols using boron-doped diamond film electrodes

The electrochemical treatment of wastewater containing chlorophenols (2-monochlorophenol,4-monochlorophenol,2,4-dichlorophenol,2,4,6-trichlorophenol) was carried out experimentally with synthetic boron-doped diamond (BDD) thin film electrodes.Current vs time curves under different cell voltages were measured.Removal rate of COD,instant current efficiency (ICE) and energy consumption were investigated under different current densities.The influence of supporting media is reported,which plays an important role in determining the global oxidation rate.The oxidative chloride is stronger than peroxodisulphate.The electrochemical characteristics of boron-doped diamond electrodes were investigated in comparison with active coating Ti substrate anode (ACT).The experimental results show that BDD is markedly superior to ACT due to its different absorption properties.

Kinetics and Mechanism of Dechlorination of o-Chlorophenol by Nanoscale Pd/Fe

Nanoscale Pd/Fe bimetallic particles were synthesized with an efficient method to dechlorinate o-chlorophenol. The nanoscale Pd/Fe particles were determined by transmission electron microscopy and BET specific surface area analysis. Most of the particles are in the size range of 20—100 nm. The BET specific surface area of synthesized nanoscale Pd/Fe particles is 12.4 m 2/g. In contrast, a commercially available fine iron powder(<100 mesh) has a specific surface area of 0.49 m 2/g. Batch studies demonstrated that the nanoscale particles can effectively dechlorinate o-chlorophenol. The dechlorination reaction takes place on the surface of synthesized nanoscale Pd/Fe bimetallic particles in a pseudo-first order reaction. The surface-area-normalized rate coefficients(k_ SA) are comparable to those reported in the literature for chlorinated ethenes. The observed reaction rate constants(k_ obs) are dominated by the mass fraction of Pd and the mass concentration of the nanoscale Pd/Fe particles.

Effect of Sb dopant amount on the structure and electrocatalytic capability of Ti/Sb-SnO_2 electrodes in the oxidation of 4-chlorophenol

Ti/Sb-SnO2 anodes were prepared by thermal decomposition to examine the influence of the amount of Sb dopant on the structure and electrocatalytic capability of the electrodes in the oxidation of 4-chlorophenol. The physicochemical properties of the Sb-SnO2 coating were markedly influenced by different amounts of Sb dopant. The electrodes, which contained 5% Sb dopant in the coating, presented a much more homogenous surface and much smaller mud-cracks, compared with Ti/Sb-SnO2 electrodes containing 10% or 15% Sb dopant, which exibited larger mud cracks and pores on the surface. However, the main microstructure remained unchanged with the addition of the Sb dopant. No new crystal phase was observed by X-ray diffraction （XRD）. The electrochemical oxidation of 4-chlorophenol on the Ti/SnO2 electrode with 5% Sb dopant was inclined to electrochemical combustion; while for those containing more Sb dopant, intermediate species were accumulated. The electrodes with 5% Sb dopant showed the highest efficiency in the bulk electrolysis of 4-chlorophenol at a current density of 20 mA/cm^2 for 180 min; and the removal rates of 4-chlorophenol and COD were 51.0% and 48.9%, respectively.

Biodegradation of Phenol and 4-Chlorophenol by the Mutant Strain CTM 2

酚和 4-chlorophenol (4-cp ) 的 biodegradations 用 He-Ne 激光照耀在野类型的 Candida tropicalis 上获得的变异的紧张 CTM 2 被学习。结果证明到 biodegrade 4-cp 的 CTM 2 的能力被增加直到 400 mg 路 L ? 1 在 59.5 h 以内。在双底层的 biodegradation， 4-cp 与低集中的酚增加了降级的 CTM 2 的速度和能力。400 mg 路 L 的一个总数 ? 1 4-cp 完全面对 300 mg 路 L 在 50.5 h 以内被降级 ? 1 酚。最大的 4-cp biodegradation 能到达 440 mg 路 L ? 1 与 120 mg 路 L ? 1 酚。低集中的 4-cp 引起了 CTM 2 上的大抑制降级酚。另外，运动行为用在这个实验室建议的运动模型被描述。