Titania-supported silver-based bimetallic nanoparticles as photocatalysts

Photocatalytic process has shown recently a great potential as an environmental friendly and clean remediation technology for organic pollutants in wastewater. This work described the synthesis of silver-based bimetallic nanoparticles using colloid chemistry and the subsequent immobilization onto titania to form composite photocatalytic materials (titania-supported Ag–Pt nanoparticles). The photocatalysts were characterized by X-ray diffraction, electron microscopy, and nitrogen physisorption. The catalytic activity of the photocatalysts was evaluated by photocatalytic degradation of phenol and 2-chlorophenol (2-CP) in synthetic wastewater solutions. The photocatalytic processes were conducted in a batch photoreactor containing appropriate solutions of phenol and 2-CP with UV irradiation of 450 W. UV-visible spectrophotometer was used for analyzing the concentration of phenol and 2-CP in solutions. Parameters affecting the photocatalytic process such as the solution pH, phenol and 2-CP concentrations, and catalyst concentration were investigated. The results obtained revealed that TiO₂-supported Ag/Pt nanoparticles showed a higher activity for UV-photocatalytic degradation of both phenol and 2-CP pollutants in the solution (as compared to the plain rutile TiO₂). The photodegradation processes were optimized by the 0.5-g/L catalyst with a pollutant concentration of 50 mg/L for all the samples. Complete degradation for both phenol and 2-CP was achieved after 120 min.     

Bioregeneration of powdered activated carbon in the treatment of alkyl-substituted phenolic compounds in simultaneous adsorption and biodegradation processes

The role of bioregeneration process in renewing the adsorbent surface for further adsorption of organics during simultaneous adsorption and biodegradation processes has been well recognized. The extent of bioregeneration of powdered activated carbon (PAC) as an adsorbent loaded with phenol, p-methylphenol, p-ethylphenol and p-isopropylphenol, respectively, in the simultaneous adsorption and biodegradation processes were quantitatively determined using oxygen uptake as a measure of substrate consumption. Bioregeneration phenomenon was also evaluated in the simultaneous adsorption and biodegradation processes under sequencing batch reactor (SBR) operation to treat synthetic wastewater containing 1200 mg l(-1) phenol and p-methylphenol, respectively. The SBR systems were operated with FILL, REACT, SETTLE, DRAW and IDLE periods in the ratio of 4:6:1:0.75:0.25 for a cycle time of 12 h. The results show that the percentage of desorption from loaded PAC decreased in the order phenol>p-methylphenol>p-ethylphenol>p-isopropylphenol. For the treatment of phenol and p-methylphenol in the SBR reactors, respectively, the simultaneous adsorption and biodegradation processes were able to produce a consistent effluent quality of COD < or = 100 mg l(-1) when the applied PAC dosage was 0.115 and 0.143 g PAC per cycle, respectively. When no further PAC was added, the treatment performance deteriorated to that of the case without PAC addition after 68 and 48 cycles of SBR operation, respectively, for phenol and p-methylphenol. This observation is consistent with the greater extent of bioregeneration for phenol-loaded PAC as compared to p-methylphenol-loaded PAC.     

Treatment of phenol-containing wastewater by photoelectro-Fenton method using supported nanoscale zero-valent iron

This study presents the degradation of phenol by the photoelectro-Fenton method using nano zero-valent iron (nZVI) immobilized in polyvinyl alcohol–alginate beads. The effect of nZVI loading, H₂O₂ concentration, pH, and initial phenol concentration on phenol degradation and chemical oxygen demand reduction was studied. The scanning electron microscope images of the nZVI beads were used to analyze their morphology, and their diameters were in the range of 500–600 μm. The concentration of nZVI in the beads was varied from 0.1 to 0.6 g/L. Fe²⁺ leakage of 1 and 3 % was observed with 0.5 and 0.6 g/L of nZVI, respectively, and the observed beads' fracture frequency was 2 %, which confirmed the stability of the beads. The optimum operating conditions that arrived for better degradation were 0.5 g/L of nZVI, pH 6.2, and 400 mg H₂O₂/L. The treatment of effluent by this method increased the biodegradability index of the effluent, and the degradation data were found to follow pseudo first-order kinetics.     

Kinetics of phenol and chlorophenol utilization by Acinetobacter species

Although microbial transformations via cometabolism have been widely observed, the few available kinetic models of cometabolism have not adequately addressed the case of inhibition from both the growth and nongrowth substrates. The present study investigated the degradation kinetics of self-inhibitory growth (phenol) and nongrowth (4-chlorophenol, 4-CP) substrates, present individually and in combination. Specifically, batch experiments were performed using an Acinetobacter isolate growing on phenol alone and with 4-CP present. In addition, batch experiments were also performed to evaluate the transformation of 4-CP by resting, phenol-induced Acinetobacter cultures. The Haldane kinetic model adequately predicted the biodegradation of phenol alone, although a slight discrepancy was noted in cases of higher initial phenol concentrations. Similarly, a Haldane model for substrate utilization was also able to describe the trends in 4-CP transformation by the resting cell cultures. The 4-CP transformation by the Acinetobacter species growing on phenol was modeled using a competitive kinetic model of cometabolism, which included growth and nongrowth substrate inhibition and cross-inhibition terms. Excellent agreement was obtained between the model predictions using experimentally estimated parameter values and the experimental data for the synchronous disappearance of phenol and 4-CP.     

Catalytic decomposition of hydrogen peroxide and 4-chlorophenol in the presence of modified activated carbons

The objective of this research was to examine the heterogeneous catalytic decomposition of H(2)O(2) and 4-chlorophenol (4-CP) in the presence of activated carbons modified with chemical pretreatments. The decomposition of H(2)O(2) was suppressed significantly by the change of surface properties including the decreased pH(pzc) modified with oxidizing agent and the reduced active sites occupied by the adsorption of 4-CP. The apparent reaction rate of H(2)O(2) decomposition was dominated by the intrinsic reaction rates on the surface of activated carbon rather than the mass transfer rate of H(2)O(2) to the solid surface. By the detection of chloride ion in suspension, the reduction of 4-CP was not only attributed to the advanced adsorption but also the degradation of 4-CP. The catalytic activity toward 4-CP for the activated carbon followed the inverse sequence of the activity toward H(2)O(2), suggesting that acidic surface functional group could retard the H(2)O(2) loss and reduce the effect of surface scavenging resulting in the increase of the 4-CP degradation efficiency. Few effective radicals were expected to react with 4-CP for the strong effect of surface scavenging, which could explain why the degradation rate of 4-CP observed in this study was so slow and the dechlorination efficiency was independent of the 4-CP concentration in aqueous phase. Results show that the combination of H(2)O(2) and granular activated carbon (GAC) did increase the total removal of 4-CP than that by single GAC adsorption.     

Enhanced in situ bioremediation of phenol in bioestimulated unsaturated and saturated sand-bed columns.

Biodegradation of phenol was observed in unsaturated sandbed columns, in which phenol concentration declined from 298 mg phenol/kg sand to less than 1 mg/kg after 21 days. In saturated sand-bed columns, phenol concentration declined from 230 mg phenol/kg to less than 1 mg/kg after 37 days. Pseudo-first-order phenol biodegradation rates were in the range 0.25 days(-1) (R2 = 0.9) to 0.66 days(-1) (R2 = 0.85) and 0.08 days(-1) (R2 = 0.68) to 0.14 days(-1) (R2 = 0.84) in the unsaturated and saturated sand-bed columns, respectively. Unsaturated columns presented a higher biomass density (21.5 mg/g) in the sand-bed and lower biomass concentration in the aqueous phase (3.5 NTU) compared with the saturated columns (6.4 mg/g and 14.0 NTU). A high concentration of phenol releases in the sand-bed columns resulted in an initial inhibition of microbial activity and destabilization of the attached biomass.     

Reductive transformation of 2,4-dichlorophenoxyacetic acid by nanoscale and microscale Fe3O4 particles

Reductive transformation of 2,4-dichlorophenoxyacetic acid (2,4-D) by nanoscale and microscale Fe₃O₄ was investigated and compared. Disappearance of the parent species and formation of reaction intermediates and products were kinetically analyzed. Results suggest that the transformation of 2,4-D followed a primary pathway of its complete reduction to phenol and a secondary pathway of sequential reductive hydrogenolysis to 2,4-dichlorophenol (2,4-DCP), chlorophenol (2-CP, 4-CP) and phenol. About 65% of 2,4-D with initial concentration of 50 μ M was transformed within 48 h in the presence of 300 mg L^?1 nanoscale Fe₃O₄, and the reaction rates increased with increasing dosage of nanoscale Fe₃O₄. The decomposition of 2,4-D proceeded rapidly at optimum pH 3.0. Chloride was identified as a reduction product for 2,4-D in the magnetite–water system. Reductive transformation of 2,4-D by microscale Fe₃O₄ was slower than that by nanoscale Fe₃O₄. The reactions apparently followed pseudo-first-order kinetics with respect to the 2,4-D transformation. The degradation rate of 2,4-D decreased with the increase of initial 2,4-D concentration. In addition, anions had a significant adverse impact on the degradation efficiency of 2,4-D.     

Experimental study on the thermal oxidation of 2-chlorophenol in air over the temperature range 450-900 degrees C

The thermal oxidation of 2-chlorophenol (2-CP) in air was investigated using a perfectly stirred reactor at 1 atm over the temperature range 450–900 °C. The relative concentration of 2-CP was 1000 ppmV (equivalence ratio Φ = 0.03). About fifty organic products were identified as trace species. The concentration profiles of 2-CP, carbon oxides as well as those of seventeen major organic intermediates and six non-to-lower chlorinated dioxins and furans were presented as a function of temperature for a residence time of 2 s. The most abundant intermediate products were carbon monoxide, 2 H-pyran-2-one, chlorobenzene, 4-cyclopenten-1,3-dione, phenol, benzofuran, 2-chlorohydroquinone and 2-indanone. These concentration profiles have revealed that temperatures of at least 900 °C were needed to completely oxidize 2-CP, CO and all other organic byproducts to carbon dioxide. Reaction pathways accounting for the formation of most observed products are proposed.     

Comparison of phenanthrene biodegradation by free and immobilized cell systems: formation of hydroxylated compounds

One of the foremost environmental issues having a key role in the feasibility study of polycyclic aromatic hydrocarbons (PAHs) biodegradation is the concern of the toxicity of the formed intermediate metabolites. In this study, biodegradability of phenanthrene (PHE) at initial concentrations of 100–500 ppm and its hydroxylated intermediate metabolites (IMs) in aqueous phase were investigated using free cells (FC) and immobilized cells (IC) in polyvinyl alcohol (PVA) cryogel beads. Results showed that both FC and IC systems were capable of complete PHE biodegradation at initial concentrations lower than 250 ppm after 7 days, though IC system showed a higher PHE removal rate. The maximum IM concentrations observed at initial PHE concentrations of 100 and 250 ppm were 20 and 49 ppm for FC system, whereas 7.4 and 19 ppm were obtained for IC system, respectively, and IMs were finally removed after 7 days. Similarly, at 500 ppm, IC system resulted in higher removal of PHE compared to FC system. However, during the 7-day period for FC system, IMs concentration rose up to 59 ppm, while for IC system, IMs concentration reaches a maximum at day 5 and thereafter it follows a negative rate. It was also shown that resorcinol as an indicator of hydroxylated aromatic metabolites at concentrations of 0–100 ppm can well be biodegraded by free and immobilized cell systems. No prohibition on PHE biodegradation could hence occur due to IMs formation. Additionally, stability of IC system was examined in repeated-batch cultures, showing the effective removal of PHE up to nine reuse cycles.     

超声波降解四环素类抗生素废水

采用超声波降解模拟废水中四环素类抗生素(TCs):土霉素(OTC)、四环素(TC)和金霉素(CTC),考查废水初始浓度、初始pH、超声波输入功率密度、曝气量和自由基清除剂(正丁醇)对降解效率的影响。结果表明,超声波可以快速高效地降解废水中的TCs,CTC最易被降解,TC和OTC次之;在OTC、TC和CTC初始浓度0.25 mg/L,初始pH=8.2,声功率密度1.2 W/mL,气水体积比30∶1的条件下,超声波辐照20 min后去除率分别达到76.8%、84.0%和94.4%。在实验研究条件下,TCs去除率均随初始浓度(0.25~2.00 mg/L)的增大而降低,但总去除浓度升高;碱性条件有利于TCs降解,去除率随初始pH(6~11)升高而升高;功率密度(0.24~1.96 W/mL)越高,TCs去除率也越高;曝气后TCs的去除率明显升高,随着气水比(10∶1~60∶1)的增大,去除率逐渐上升;正丁醇有效抑制TCs超声波降解,可推断TCs主要降解途径为自由基氧化。TCs超声波降解过程符合伪一级动力学反应特征。     

Photoelectrocatalytic degradation of 4-chlorophenol and oxalic acid on titanium dioxide electrodes

Photocatalytically active thin TiO(2) films were produced by spin-coating or dip-coating an alkoxy precursor onto a transparent conducting electrode substrate and by thermal oxidation of titanium metal. The thin films were used to study the photoelectrocatalytic or photoelectrochemical degradation of oxalic acid and 4-chlorophenol (4-CP) under near UV (monochromatic, 365 nm) light irradiation. Degradation was monitored by a variety of methods. In the course of oxalic acid degradation, CO(2) formation accounted for up to 100% of the total organic carbon degradation for medium starting concentrations; for the degradation of 4-CP, less CO(2) was detected due to the higher number of oxidation steps, i.e. intermediates. Incident-photon-to-current conversion efficiency, educt degradation and product formation as well as Faradaic efficiencies were calculated for the degradation experiments. Quantum yields and Faradaic efficiencies were found to be strongly dependent on concentration, with maximum values (quantum yield) around 1 for the highest concentrations of oxalic acid.     

Photoelectro-Fenton mineralization of phenol through optimization of ferrous regeneration

The degradation of phenol in acidic solution at pH 3 has been investigated under various photo- and electrochemical conditions. A laboratory-scale reactor on which were mounted net electrodes (RuO₂/IrO₂-coated Ti anodes (DSA) and stainless steel cathodes) and 254 nm UV lamps was established to effectively reduce ferric reagents. The experimental results of the photoelectron-chemical reaction suggested that the current efficiency of reducing ferric ion was improved by increasing the number of electrodes used, and the UV lamps were important to inducing the reduction of ferric carboxylates, which were the major intermediates that were formed upon a particular degree of phenol oxidation. Accordingly, the addition of an initial concentration of 400 ppm ferrous salt and 10,200 ppm hydrogen peroxide (in a continuous mode) resulted in the removal of over 92 % of TOC (initial phenol?=?2,000 ppm, TOC?=?1,532 ppm) by 4 h of the photoelectro-Fenton and the sequential 2 h of the photo-Fenton processes. HPLC was utilized to monitor the formation of aromatic and carboxylate byproducts, and revealed that the aid of photo irradiation eliminated most of the oxalate residue from the final solution, which would have contributed to the 25 % of the TOC that was inactive in the electrolytic system.     

Application of Klebsiella oxytoca immobilized cells on the treatment of cyanide wastewater

Klebsiella oxytoca, isolated from cyanide-containing industrial wastewater, has been shown to be able to biodegrade cyanide to non-toxic end products. The technology of immobilized cells can be applied in biological treatment to enhance the efficiency and effectiveness of biodegradation. In this study, potassium cyanide was used as the target compound and both alginate and cellulose triacetate techniques were applied for the preparation of immobilized cells. Results from this study show that KCN can be utilized as the sole nitrogen source by K. oxytoca. The free suspension systems reveal that the cell viability was highly affected by initial KCN concentration and pH. Results show that immobilized cell systems could tolerate a higher level of KCN concentration and wider ranges of pH. In the batch experiments, the maximum KCN removal efficiencies using alginate and cellulose triacetate immobilized beads were 0.108 and 0.101mM h(-1) at pH 7, respectively. Results also indicate that immobilized system can support a higher biomass concentration. Complete KCN degradation was observed after the operation of four consecutive degradation experiments with the same batch of immobilized cells. This suggests that the activity of immobilized cells can be maintained and KCN can be used as the nitrogen source throughout KCN degradation experiments. The maximum KCN removal rates using alginate and cellulose triacetate immobilized beads in continuous-column system were 0.224 and 0.192mMh(-1) with initial KCN concentration of 3mM, respectively. Results indicate that the immobilized cells of K. oxytoca would be applicable to the treatment of cyanide-containing wastewaters.     

四环素高效降解酵母菌Trichosporon mycotoxinivorans XPY-10降解特性

Trichosporon mycotoxinivorans XPY-10是一株分离自抗生素制药厂的高效四环素降解酵母菌。为了建立该菌株降解四环素的适宜条件,分别研究了碳源、有机氮源、金属离子等营养物质及初始底物浓度、接种量、pH、温度、装液量、摇床转速等理化因素对菌体生长及四环素降解效率的影响。结果表明,菌株XPY-10生长的最适碳源和氮源分别为蔗糖和蛋白胨。在含有0．05％FeSO4的培养基中,菌株XPY—10降解四环素的适宜条件为：接种量2％,pH8,温度3422,装液量100mL（250mL三角瓶）,摇床转速180r／min。在此条件下,菌株XPY—10在7d内对初始浓度为600mg／L的四环素降解率为83．63％。本菌株对养殖废水及制药废水中四环素的污染治理有一定的应用前景。     

Electrocatalytic hydrodechlorination of 4-chlorobiphenyl in aqueous solution using palladized nickel foam cathode

The electrocatalytic hydrodechlorination of 4-chlorobiphenyl on palladized nickel foam with high porous structure in an aqueous solution containing MeOH, bromide of hexadecyltrimethylammonium (CTAB), sodium acetate, and acetic acid were investigated in a membrane-separated flow-through cell. The Pd/Ni foam electrode was prepared by electroless deposition method, on which the Pd particles dispersed finely over Ni foam surface indicated by SEM-EDX analysis. The effects of current density, organic cosolvent, initial concentration, temperature, and flow rate on the hydrodechlorination of 4-chlorobiphenyl were examined. Methanol was among the best cosolvents and was used in preferential concentration of 50 vol%. Moderate current density (e.g., 2.23 mA cm(-2)), relatively high initial concentration, temperature, and flow rate were beneficial to improve the hydrodechlorination of 4-chlorobiphenyl. The current efficiencies for the conversion of 1mM 4-MCB decreased with increasing current density and range from 37.2% at 0.74 mA cm(-2) to 14.1% at 5.21 mA cm(-2) after 20 min electrolysis cut. Under the optimized conditions, 1mM of 4-MCB could be removed rapidly with the rate of 94.6% after 2h electrolysis, which gave current efficiencies and energy consumptions in range of 8.1-24.6% and 1.7-5.2 kW h kg(-1), respectively.     

Simultaneous Cr(VI) reduction and phenol degradation using Stenotrophomonas sp. isolated from tannery effluent contaminated soil

This study presents simultaneous hexavalent chromium (Cr(VI)) reduction and phenol degradation using Stenotrophomonas sp., isolated from tannery effluent contaminated soil. Phenol was used as the sole carbon and energy source for Cr(VI) reduction. The optimization of different operating parameters was done using Placket–Burman design (PBD) and Box–Behnken design (BBD). The significant operating variables identified by PBD were initial Cr(VI) and phenol concentration, pH, temperature, and reaction time. These variables were optimized by a three-level BBD and the optimum initial Cr(VI) concentration, initial phenol concentration, pH, temperature, and reaction time obtained were 16.59 mg/l, 200.05 mg/l, 7.38, 31.96 °C and 4.07 days, respectively. Under the optimum conditions, 81.27 % Cr(VI) reduction and 100 % phenol degradation were observed experimentally. The results concluded that the Stenotrophomonas sp. could be used to decontaminate the effluents containing Cr(VI) and phenol effectively.     

利用糖蜜废水生产微生物絮凝剂及条件优化和效果实验研究

用糖蜜废水取代葡萄糖作为发酵培养基中的碳源和能源培养微生物絮凝剂产生菌Pseudomonas alcaligenesPS-25。通过单因素试验和正交试验得到该菌株产絮凝剂的最佳培养条件:糖蜜废水COD浓度5 000 mg/L、培养基初始pH值6.5、接种量5%(体积比)、温度30℃、培养时间为72 h、摇床转速160 r/min,在此条件下,PS-25所产絮凝剂对高岭土悬浊液絮凝率达96.75%,并且对多种废水都有较好的净化效果,对废水中浊度和色度的去除率分别在90%和80%以上,COD去除率在73.60%～91.10%。研究表明,用糖蜜废水培养PS-25生产微生物絮凝剂处理废水是完全可行的,从而实现废物的资源化利用。     

Degradation of chlorophenols in aqueous media using UV XeBr excilamp in a flow-through reactor

2-Chlorophenol (2-CP), 4-chlorophenol (4-CP) and 2,4-dichlorophenol (2,4-DCP) at initial concentrations of 10, 20, 50 and 100mg l(-1) were degraded in aqueous media by direct UV photolysis using dielectric barrier discharge XeBr( *) excilamp (283nm) in a flow-through photoreactor. The pseudo-first order rate constants were highest and half-life times were lowest for 4-CP. The rates of photolysis under the experimental conditions increased in the order: 2-CP<2,4-DCP<4-CP. The intermediates of photolysis were identified by GC-MS and HPLC. The evolution of hydroquinone and p-benzoquinone as major intermediates of 4-CP photolysis was monitored.     

Adsorption of phenols by papermill sludges

In this paper we studied the sorption capacity of paper mill sludges for phenols. Phenol, 2-chlorophenol (2-CP), 3-chlorophenol 3-CP). 4-chlorophenol (4-CP), 2-nitrophenol (2-NP), 4-nitrophenol (4-NP), 2.4-dichlorophenol (2,4-DCP), 3,4-dichlorophenol (3,4-DCP) 3,5-dichlorophenol (3,5-DCP) and 2,4,5-trichlorophenol (2,4,5-TCP) were chosen for the sorption tests. Kinetic experiments showed that substituted-phenol sorption on papermill sludge was rapid (equilibrium was reached after 3 h); conversely, the time taken by the phenol to reach equilibrium conditions was 260 h. Experimental data showed that particle diffusion was involved in the sorption process but was not the only rate-limiting mechanism; several other mechanisms were involved. The adsorption isotherms showed the following order of retention capacity of papermill sludge: 2-NP = 4-NP < < 2-CP < phenol < 4-CP < or = 3-CP < 2,4 DCP<3,4 DCP=2,4,5 TCP<3,5 DCP. In all cases the experimental data showed a good fit with the Hill equation. which is mathemratically equivalent to the Langmuir-Freundlich model obtained by assuming that the surface is homogeneous, and that the adsorption is a cooperative process influenced by adsorbate-adsorbate interactions.     

好氧颗粒污泥降解苯酚

以人工配水启动SBR,逐步提高进水苯酚浓度,探究好氧颗粒污泥对苯酚的降解能力,同时分析苯酚对好氧颗粒污泥特性的影响。经过55 d的运行,进水苯酚浓度逐渐增到3 000 mg/L,苯酚、COD及NH+4-N去除率分别达到了98.33%、97.27%和57.58%,好氧颗粒污泥表现出对苯酚的良好的去除能力。扫描电镜照片显示投加苯酚后的颗粒污泥表面更加光滑,结构更为紧凑。胞外聚合物红外光谱分析表明投加苯酚前后好氧颗粒污泥EPS的主要组分没有明显改变。苯酚毒性刺激了颗粒污泥分泌更多胞外聚合物,胞外聚合物中多糖含量由初始的12.70 mg/g VSS增加到35.17 mg/g VSS,蛋白含量由4.93 mg/g VSS增加到8.01 mg/g VSS。投加苯酚后的污泥粒径明显增大,主要污泥粒径由0.5~2.0 mm增大到2.0 mm以上。