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Electrocatalysis offers great promise for water purification but is limited by low active area and high uncontrollability of electrocatalysts. To overcome these constraints, we propose hybrid bulk electrodes by synthesizing and binding a Pd nanocatalyst (nano-Pd) to the electrodes via amyloid fibrils (AFs). The AFs template is effective for controlling the nucleation, growth, and assembly of nano-Pd on the electrode. In addition, the three-dimensional hierarchically porous nanostructure of AFs is beneficial for loading high-density nano-Pd with a large active area. The novel hybrid cathodes exhibit superior electroreduction performance for the detoxification of hexavalent chromium (Cr 6+ ), 4-chlorophenol, and trichloroacetic acid in wastewater and drinking water. This study provides a proof-of-concept design of an AFs-templated nano-Pd-based hybrid electrode, which constitutes a paradigm shift in electrocatalytic water purification, and broadens the horizon of its potential engineered applications., (© 2022 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

The biocomposites of polypyrrole (PPY), polyaniline (PANI) and sodium alginate (NaAlg) with cellulosic biomass barley husk (BH) were prepared and employed for the removal of 2,4-dichlorophenol (2,4-DCP) form aqueous media. The sorption of 2,4-DCP was studied using native and biocomposites (PPY/BH, PANI/BH and NaAlg/BH) as function of various process variables. The maximum sorption (q e , 7.55-24.57 mg/g) of 2,4-DCP was achieved in the range of 7-10 pH, 0.05 g composite dose, 25 mg/L initial concentration of 2,4-DCP and 120 min contact time at 30 °C. The FTIR analysis revealed the involvement of amino, hydroxyl and carboxylic groups for the binding of 2,4-DCP on the surface of biocomposites. The Freundlich and pseudo second order kinetics models best explained the 2,4-DCP adsorption on to the biocomposites. The ∆G, ∆H and ∆S parameters were also computed, which revealed the favorable and exothermic adsorption nature of 2,4-DCP. Presence of salts affected the 2,4-DCP adsorption negatively. HCl found to be efficient desorbing agent for 2,4-DCP from composites and up to 65.12% was eluted using 0.5 N solution. In view of promising efficiency, the biocomposites have potential to remove 2,4-DCP form industrial effluents., (Copyright © 2020 Elsevier B.V. All rights reserved.)

Laccases were studied for their ability to remove two compounds, 2-chlorophenol and sulfamethoxazole, in batch studies, both in buffered solutions and in wastewater samples from different points in a municipal water resource recovery facility. Two enzymes with and without a mediator (acetosyringone) were investigated: a commercial product derived from Myceliphthora thermophile and a laboratory-generated enzyme mix derived from Tramates versicolor. The chlorophenol was removed rapidly by the commercial enzyme in the presence of acetosyringone, but the primary products were coupling complexes of the reactants. Excellent removal was achieved without acetosyringone by the natural enzyme mix. Sulfamethoxazole was poorly removed in all laboratory-generated chemically buffered solutions, but was very well removed, without the addition of mediators, in secondary effluent suspensions from a municipal water resource recovery facility. Mechanistic studies are still required, but the results suggest that treatment via direct addition of enzymes is feasible to remove recalcitrant compounds in municipal wastewater., (© 2018 Water Environment Federation.)

In this work, a novel core-shell structured magnetic polyimide@layered double oxides (LDO) composites coating a porous polyimide (PI)-coated Fe 3 O 4 magnetic core and layered double hydroxide (LDH) has been successfully synthesized by solve-thermal synthesis and co-precipitation process. The magnetic PI@LDO composites were characterized by scanning and transmission electron microscopy (SEM and TEM), X-ray diffraction (XRD), thermogravimetry analysis (TGA) and magnetic properties analysis. The composite materials displayed core-shell structure with flower-like morphology. The magnetic PI@LDO composites were applied to remove tetracycline (TC), 2,4-dichlorophenol (2,4-DCP) and glyphosate (GP) from aqueous solution. The action pH value was ranged from 5 to 9 for TC and GP and 3 to 7 for 2,4-DCP, respectively. Cl - showed a weak competitive adsorption effect to TC, 2, 4-DCP and GP. In addition, the presence of humic acid (HA) could slightly reduce the adsorption capacity of magnetic PI@LDO composites. The adsorption process could be well described by pseudo-second-order model for TC and GP, while pseudo-first-order model for 2,4-DCP. The experimental data of TC and 2,4-DCP could be fitted better with Freundlich model, while that of GP were fitted better with Langmuir model. The adsorptions of TC, 2,4-DCP and GP were both spontaneous and endothermic. The adsorption capacity decreased slightly after adsorption-desorption cycles repeated five times. This study demonstrated that magnetic PI@LDO exhibited great potential to be a mild and cost-effective adsorbent for the removal of various organic contaminants from wastewater., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

Chlorinated phenols are a class of contaminants found in water and have been regarded as a great potential risk to environment and human health. It is thus urgent to develop effective techniques to remove chlorinated phenols in wastewater. For this purpose, we employed dielectric barrier discharge (DBD) in this work and studied the efficiency of DBD for the degradation of 2,4-dichlorophenol (2,4-DCP), one of the most typical chlorophenols in the environment. The effects of pH value, applied voltage and plasma-working gases on the dichlorophenol-removal efficiency were investigated. The results demonstrate that DBD plasma could successfully degrade 2,4-DCP, achieving efficiency of 98.16% (k = 1.09 min -1 ) in the Ar-DBD system, and 77.60% (k = 0.48 min -1 ) in the N 2 -DBD system, with the process following the first-order kinetics. The removal efficiency was reduced in the presence of radical scavengers, confirming that hydroxyl radicals played a key role in the degradation process, while other active substances were also found such as nitrogen radicals in the N 2 -DBD system, which was found to have also contribution to the degradation of 2,4-DCP. The intermediates and final products generated in the degradation process were analyzed using gas chromatography-mass spectrometry (GC-MS). Based on the identification of intermediates, the degradation pathways and mechanism were proposed and discussed. Besides, the toxicity of the DBD treated 2,4-DCP solution was also assessed using GFP-expressing recombinant Escherichia coli (E. coli) as the testing organism, showing that plasma treatment could substantially reduce the toxic effect of 2,4-DCP., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

In order to remediate organic contaminants in natural waters and soils, a novel zero-valent iron [Fe(0)]-included biochar was synthesized via slow pyrolysis. 2,4-Dinitrotoluene (DNT) and 2,4-dichlorophenol (DCP) were removed in water via sorption to the Fe(0)-included biochar. Compared to sorption control without Fe(0), the sorbed DNT and DCP were further transformed to reduction products by Fe(0)-included biochar. Compared to the reduction control with Fe(0), the presence of biochar promoted the reductive transformation of DNT and DCP. Increasing the pyrolysis temperature resulted in enhancing the removal of DNT and DCP, suggesting that the aromaticity of biochar may be responsible for the removal. The yields of the reduction products also indicated that unlike the direct reduction by Fe(0), different reduction pathways existed in the reduction of DNT and DCP with Fe(0)-included biochar. The results suggest that Fe(0)-included biochar is a viable option to immobilize and transform redox-sensitive organic contaminants in natural environments., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

A photosensitizer tetra-α-(2,4-di-tert-butylphenoxy)-phthalocyaninato zinc [ZnPc(OAr)4] was successfully encapsulated in SiO2 nanoparticle by the microemulsion method. The photosensitized composite nanoparticle was able to degrade 2,4,6-trichlorophenol (TCP) in aqueous solution. Under visible light irradiation, the nanoparticles efficiently generated reactive oxygen species; 95.4% of TCP was degraded after 270 min of reaction. Some aromatic compounds and aliphatic carboxylic acids were detected by mass spectrometry as the reaction intermediates. The results were different from those of previously reported photocatalytic reactions, in which valence band holes or hydroxyl radicals functioned as the main oxidants. The photosensitizing composite nanoparticle is potentially applicable to the oxidation of phenol.

A photosensitized BiOCl catalyst was found to be effective for photocatalytic water purification and air remediation under visible light irradiation (λ > 420 nm). Prepared by a solvothermal method, the BiOCl crystals possessed a 3D hierarchical spherical structure with the highly active facets exposed. When sensitized by Rhodamine B (RhB), the photocatalyst system was more active than N-doped TiO2 for breaking down 4-chlorophenol (4-CP, 200 ppm) and nitric monoxide (NO, 500 ppb). The high activity could be attributed to the hierarchical structure (supplying feasible reaction tunnels for adsorption and transition of reactants or products) and the efficient exposure of the {001} facets. The former provides an enriched oxygen atom density that promotes adsorption of cationic dye RhB, and creates an oxygen vacancy state. The HO˙ and ˙O2(-) radicals produced from the injected electrons from the excited dye molecule (RhB*) into the conduction band of BiOCl were responsible for the excellent photocatalytic performance of the RhB-BiOCl system.

A greener method based on cloud point extraction was developed for removing phenol species including 2,4-dichlorophenol (2,4-DCP), 2,4,6-trichlorophenol (2,4,6-TCP) and 4-nitrophenol (4-NP) in water samples by using the UV-Vis spectrophotometric method. The non-ionic surfactant DC193C was chosen as an extraction solvent due to its low water content in a surfactant rich phase and it is well-known as an environmentally-friendly solvent. The parameters affecting the extraction efficiency such as pH, temperature and incubation time, concentration of surfactant and salt, amount of surfactant and water content were evaluated and optimized. The proposed method was successfully applied for removing phenol species in real water samples., (Copyright © 2013 Elsevier B.V. All rights reserved.)

Multiwalled carbon nanotubes were synthesised by the nebulised spray pyrolysis method and purified to remove amorphous carbon and fullerenes. The purified multiwalled carbon nanotubes were oxidised using a 3:1 H2SO4/HNO3 mixture to introduce carboxylic groups and to a smaller extent hydroxyl groups on the walls of the carbon nanotubes. Subsequently, the oxidised carbon nanotubes were chlorinated using oxalyl chloride to generate acyl chloride groups through which phosphorylation took place. 4-Aminophenyl methylphosphonate was attached to the multiwalled carbon nanotubes via an amidation reaction. FT-IR and XPS confirmed the presence of PO, PO and PCP functional groups in the phosphorylated carbon nanotubes. Polymerisation of the phosphorylated carbon nanotubes with cyclodextrins was achieved using hexamethylene diisocyanate as a bifunctional linker. Surface morphology of the polymer was investigated by SEM while FT-IR was used to confirm the polymerisation reaction. Moreover, the thermal stability of the polymer was probed using TGA while BET was employed to determine the surface area and pore volume of the polymer. Furthermore, the polymer was tested for the removal of cobalt and 4-chlorophenol from synthetic aqueous solutions of the pollutants. The polymer displayed potential as an adsorbent for both cobalt and 4-chlorophenol., (Copyright © 2013 Elsevier Ltd. All rights reserved.)

Palladium/Iron (Pd/Fe) nanoparticles were prepared by using ultrasound strengthened liquid phase reductive method to enhance dispersion and avoid agglomeration. The dechlorination of 2,4-dichlorophenol (2,4-DCP) by Pd/Fe nanoparticles was investigated to understand its feasibility for an in situ remediation of contaminated groundwater. Results showed that 2,4-DCP was first adsorbed by Pd/Fe nanoparticles, then quickly reduced to o-chlorophenol (o-CP), p-chlorophenol (p-CP), and finally to phenol (P). The induction of ultrasound during the preparation of Pd/Fe nanoparticles further enhanced the removal efficiency of 2,4-DCP, as a result, the phenol production rates increased from 65% (in the absence of ultrasonic irradiation) to 91% (in the presence of ultrasonic irradiation) within 2h. Our data suggested that the dechlorination rate was dependent on various factors including Pd loading percentage over Fe(0), Pd/Fe nanoparticles availability, temperature, mechanical stirring speed, and initial pH values. Up to 99.2% of 2,4-DCP was removed after 300min reaction with these conditions: Pd loading percentage over Fe(0) 0.3wt.%, initial 2,4-DCP concentration 20mgL(-1), Pd/Fe dosage 3gL(-1), initial pH value 3.0, and reaction temperature 25°C. The degradation of 2,4-DCP followed pseudo-first-order kinetics reaction and the apparent pseudo-first-order kinetics constant was 0.0468min(-1)., (Copyright © 2012 Elsevier B.V. All rights reserved.)

Cork manufacturing is a traditional industry in Southern Europe, being the main application of this natural product in wine stoppers and insulation. Cork processing begins at boiling the raw material. As a consequence, great volumes of dark wastewaters, with elevated concentrations of chlorophenols, are generated, which must be depurated through costly physicochemical procedures before discarding them into public water courses. This work explores the potential of bacteria, isolated from cork-boiling waters storage ponds, in bioremediation of the same effluent. The bacterial population present in cork-processing wastewaters was analysed by DGGE; low bacterial biodiversity was found. Aerobic bacteria were isolated and investigated for their tolerance against phenol and two chlorophenols. The most tolerant strains were identified by sequencing 16S rDNA. The phenol-degrading capacity was investigated by determining enzyme activities of the phenol-degrading pathway. Moreover, the capacity to form biofilms was analysed in a microtitre plate assay. Finally, the capacity to form biofilms onto the surface of residual small cork particles was evaluated by acridine staining followed by epifluorescence microscopy and by SEM. A low-cost bioremediation system, using phenol-degrading bacteria immobilised onto residual cork particles (a by-product of the industry) is proposed for the remediation of this industrial effluent (self-bioremediation)., (Copyright © 2011 Elsevier Ltd. All rights reserved.)

Pd/TiO2 catalysts were prepared by the deposition-precipitation and impregnation methods, and were further characterized by TEM, XRD and ICP-AES. The liquid catalytic hydrodechlorination of 2,4-dichlorophenol over the catalysts was investigated. It is demonstrated that despite catalyst prepared by deposition-precipitation method exhibits higher activity than that synthesized from impregnation method, both catalysts show good performance in hydrodechlorination process. When initial concentration of the reactant was 3.11 mmol x L(-1), pH was 12 and amount of catalyst used was 50 mg, hydrodechlorination of 2,4-dichlorophenol was completed within 45 min. Acidic condition facilitates hydrodechlorination process. The initial activity was not significantly influenced when the amount of catalyst used varied between 15-80 mg, which proves that mass transport limitation exerts little impact on hydrodechlorination reaction. Finally, the initial activity sharply enhanced with the increase of initial concentration of 2,4-dichlorophenol when the concentration was in the range of 0.62-3.11 mmo x L(-1) while it almost remained constant with further increasing the initial concentration. Therefore, the catalytic hydrodechlorination of 2,4-dichlorophenol over Pd/TiO2-DP follows the Langumuir-Hinshelwood model, indicating that the catalytic hydrodechlorination is controlled by 2,4-dichlorophenol adsorption.

To evaluate the effect of pH on the degradation of 2,4-DCP by zero-valent iron nanoparticles (with the particle size of 30-40 nm in diameter) samples were taken for TEM, SEM-EDX, and ICP-OES analysis and investigated on the particle morphology changes and 2,4-DCP removal under different pH conditions. It is shown that iron nanoparticles agglomerate from individual particles and tiny clusters into massive aggregate assemblies with their surfaces oxidized and coated by the needle-like rotten iron oxide products (FeOOH) in the degradation process, which will block up a further reaction of 2,4-DCP dechlorination, while the low pH value condition in acidic system can effectively suppress particles aggregation and the surface oxidation, although iron loss in the solid phase is somehow inevitable. Large quantity of Fe2+ ions soaked out from iron nanoparticles significantly promote 2,4-DCP removal by reduction, and the solution pH tends to go up in the reaction process. Acidic conditions facilitate 2,4-DCP dechlorination, and the removal efficiency became higher with the pH reduced, in which 90% of 2,4-DCP removal is reached in 24 h under the pH value of 3.

The chitosan/fly-ash-cenospheres/γ-Fe(2)O(3) (CTS/γ-Fe(2)O(3)/FACs) magnetic composites were prepared by microemulsion process. The resulting composites were characterized by XRD, FT-IR, SEM, TGA, DTG and VSM, and the results indicated that CTS/γ-Fe(2)O(3)/FACs exhibited magnetic property (M(s)=6.553 emu g(-1)) and thermal stability, and composed of chitosan wrapping magnetic γ-Fe(2)O(3) and fly-ash-cenospheres (thickness of the cross-linked chitosan was about 5.2 μm). Then the CTS/γ-Fe(2)O(3)/FACs were employed as adsorbents for the fast removal of bisphenol A (BPA) and 2,4,6-trichlorophenol (TCP) from aqueous solutions. The adsorption performances of CTS/γ-Fe(2)O(3)/FACs were investigated by batch mode experiments with respect to pH, temperature, initial concentration, contact time and binary solution system. The Langmuir isotherm model was fitted to the equilibrium data better than the Freundlich model, and the kinetic properties were well described by the pseudo-second-order equation. The effects of binary solution systems also demonstrated that BPA adsorption onto CTS/γ-Fe(2)O(3)/FACs was more affected by the simultaneous presence of competitive phenolic compound than that of TCP. In addition, the resulting composite reusability without obviously deterioration in performance was demonstrated by at least three repeated cycles., (Copyright © 2011 Elsevier B.V. All rights reserved.)

Para-chlorophenol (4-chlorophenol, 4-CP) containing synthetic wastewater was treated using a rotating perforated tubes biofilm reactor (RTBR). Box-Wilson statistical experiment design and response surface methodology (RSM) were used to investigate the effects of the feed COD, 4-CP contents and the A/Q (biofilm surface/flow rate) ratio on percent COD, 4-CP and toxicity removals. Increases in A/Q ratio and the feed COD contents improved COD, 4-CP and toxicity removals. High feed 4-CP contents adversely affected the system performance due to toxic effects of 4-CP on microorganisms. High A/Q ratio and feed COD contents were required for effective 4-CP and toxicity removals at high feed 4-CP contents. More than 95% 4-CP and toxicity removals were obtained with an A/Q ratio of 186 m(2) d m(-3), and feed COD of 6000 mg L(-1) with the feed 4-CP content of 1000 mg L(-1). The RTBR was proven to be more efficient than the RBBR used for the same purpose in our previous studies., (2010 Elsevier Ltd. All rights reserved.)

We investigated biological, photocatalytic, and combination of biological and photocatalytic treatments in order to remove a mixture of 2-chlorophenol, 2,4-dichlorophenol, 2,4,5-trichlorophenol, and pentachlorophenol in tap water (total: 100 mg L(-1), each: 25 mg L(-1)). The removal of chlorinated phenols was conducted with a flow biological treatment and a circulative flow photocatalytic treatment under black light and sunlight irradiations integrated with titanium dioxide separation and reuse. The combined biological-photocatalytic treatment significantly shortened the degradation and mineralization time of both the biological treatment and the photocatalytic treatment. The removed chlorophenols per hour by the combined biological-photocatalytic treatment was 25.8 mg h(-1), whereas by the combined photocatalytic-biological treatment was 10.5 mg h(-1). After a large portion of biodegradable 2-chlorophenol and 2,4-dichlorophenol, and around half amount of slightly biodegradable 2,4,5-trichlorophenol were removed by the biological treatment, the remained three chlorophenols, biorecalcitrant pentachlorophenol, and biodegradation products were completely removed by the subsequent photocatalytic treatment. Since titanium dioxide particles in tap water spontaneously sedimented on standing after the photocatalytic treatment, the combined treatment can be operated by integrating with the titanium dioxide separation and reuse. The TiO(2) particles were recovered and reused at least three times without significantly decreasing the removal efficiency., (Copyright © 2010 Elsevier B.V. All rights reserved.)

Catalysts based on pillared clays with Pd-Al were synthesized from a commercial bentonite and tested for catalytic hydrodechlorination (HDC) using 4-chlorophenol (4-CPhOH) as target compound and formic acid as hydrogen source. Stable Pd-Al pillared clays, with a strong fixation of the active phase to the solid support were obtained since no Pd was detected in the reaction media. The incorporation of Pd to the pillared clay structure yielded catalysts with high activity in the reaction studied reaching a complete removal of the 4-CPhOH under mild conditions of temperature (50-70 degrees C). Phenol was not the only reaction product formed, since a more hydrogenated product such as cyclohexanone was detected in the effluent, which indicates additional hydrogenation of phenol. The influence of the method of introduction of Pd in the pillared clay (ion-exchange or impregnation) and Pd concentration in the catalytic activity were studied as well as other important operating variables such as reaction temperature, catalyst concentration, 4-CPhOH initial concentration and formic acid to 4-CPhOH molar ratio. The catalysts prepared suffered deactivation after three consecutive runs, probably due to carboneous deposits formation since no appreciable Pd leaching was observed.

Molecularly imprinted polymer (MIP) for selective recognition and removal of chlorophenols from contaminated water was prepared by reversible addition-fragmentation chain transfer (RAFT) polymerization using RAFT agent functionalized silica gel as the chain transfer agent. The prepared MIP nano-film hybrid silica gel (silica-MIP) was characterized using Fourier transform infrared spectrometer (FT-IR), scanning electron microscopy (SEM), thermogravimetric analysis (TGA), and BET adsorption isotherm analysis. The proper adsorption and selective recognition ability of the silica-MIP were studied by an equilibrium-adsorption method. The resulting silica-MIP showed outstanding affinity towards 2,4-dichlorophenol (2,4-DCP) in aqueous solution. The silica-MIP bind the original template 2,4-DCP with an appreciable selectivity over structurally related compounds, and the molecular recognition of 2,4-DCP was analyzed in detail.

A novel biodenitrification process, termed as "solid-phase denitrification", was used to remove nitrate and 4-chlorophenol (4-CP) from water. The experimental results indicate that nitrate can be effectively removed using biodegradable meal box (BMB) as carbon source and biofilm carrier of denitrifying microorganisms. Volumetric denitrification rate was 24.0 mg/(L x h) with the 50 mg/L of initial NO3(-)-N concentration under the batch experiments. Denitrification was facilitated with 4-CP concentration which was less than 30 mg/L, and was repressed with over 40 mg/L of 4-CP. When the initial concentration of 4-CP was 5 mg/L and 30 mg/L, the removal efficiency of 4-CP was 90% and 71% within 8 h under denitrifying condition, respectively. 4-CP removal was due to both the absorption onto BMB and degradation by microorganisms attached to BMB.

The removal of phenol (Ph) and 2-chlorophenol (2-CPh) from aqueous solution by native and heat inactivated fungus Funalia trogii pellets were investigated. The effects of contact time, solid/liquid ratio, optimum pH and temperature on the phenols removal capacity by the pellets were established. The removal efficiency of phenols increased significantly with increasing biomass dose. The optimum pH was detected to be 8.0. The second-order equations are described and evaluated on the basis of a comparative estimation of the corresponding coefficients. The phenol removal equilibrium isotherm was modeled by the Langmuir equations. The enthalpy change values were obtained between -7.62 and -10.64 kJ/mol. This indicated that the uptake of phenols either on native or heat inactivated fungal pellets was based on a physical adsorption process.

Adsorption equilibrium of 2,4,6-trichlorophenol (TCP) on multi-walled carbon nanotubes (MWCNTs) was investigated to explore the possibility of using MWCNTs for concentration, detection and removal of TCP from contaminated water. The adsorption of TCP on MWCNTs at pH 4 was nonlinear, reversible and best fit by a Polanyi-Manes model. Oxidation treatment increased surface area and introduced hydrophilic carboxylic groups to the defect sites of MWCNTs, hence increased the sorption of TCP and Cu(II) individually. Cu(II) suppressed the sorption of TCP on oxidized MWCNTs15A, but had little effect on as-grown MWCNTs15. TCP had no influence on Cu(II) sorption to either. The mechanisms of Cu(II) suppression effect on TCP adsorption are ascribed to the formation of surface complexes of Cu(II), which was verified by X-ray absorption spectroscopy. Cu(II) exerts a cross-linking effect of functional groups on adjacent tubes, creating a more tightly knit bundle and suppressing the condensation of TCP in the pore spaces between the tubes. The large hydration sphere around surface complexes of Cu(II) may also intrude or shield hydrophilic sites, leading to the "crowding out" of TCP around the Cu(II)-complexed sites.

Synthetic wastewater containing 2,4-dichlorophenol (DCP) was biologically treated using a hybrid-loop bioreactor system consisting of a packed column biofilm reactor (PCBR) and an aerated tank with effluent recycle. Effects of the feed DCP concentration on COD, DCP and toxicity removals were investigated. Biomass concentration in the packed column and in the aeration tank decreased with increasing feed DCP content due to toxic effects of DCP on the microorganisms. Low biomass concentrations at high DCP contents resulted in low COD, DCP and toxicity removals. Therefore, percent DCP, COD and toxicity removals decreased with increasing feed DCP content. Nearly 70% COD removal was achieved with a feed DCP content of 380 mg L(-1). The system should be operated with the feed DCP lower than 100 mg L(-1) in order to obtain DCP, COD and toxicity removals above 90%.

This study investigated the adsorption potential of oil palm shell-based activated carbon to remove 2,4,6-trichlorophenol from aqueous solution using fixed-bed adsorption column. The effects of 2,4,6-trichlorophenol inlet concentration, feed flow rate and activated carbon bed height on the breakthrough characteristics of the adsorption system were determined. The regeneration efficiency of the oil palm shell-based activated carbon was evaluated using ethanol desorption technique. Through ethanol desorption, 96.25% of the adsorption sites could be recovered from the regenerated activated carbon.

This work presents the design and practical implementation of a control strategy for the operation of a sequencing batch reactor with a submerged membrane. The bioreactor is used for treating wastewater that is inhibitory for sufficiently high concentrations. The strategy combines the use of a robust feeding strategy to ensure biodegradation near an optimal unknown concentration value, using only the dissolved oxygen concentration as feedback signal, and a strategy to minimize membrane fouling based on flux and transmembrane pressure measurements during filtration. The strategy was tested on a 10 L laboratory bioreactor treating synthetic wastewater containing 4-chlorophenol as inhibitory model compound and sole source of carbon. Experimental results show the applicability of the proposed strategy.

The effect of carbon sources and shock loadings have been studied using two sets of sequential upflow anaerobic sludge blanket (UASB) and rotating biological contactor (RBC) reactors viz., UASB-I followed by RBC-I and UASB-II followed by RBC-II for the removal of two different priority pollutants, 2-CP and 2,4-DCP present in simulated wastewaters. Sodium formate, sodium propionate, glucose and methanol were used separately as four different carbon sources in the feed as co-substrate. Methanol was found to be the best carbon source for UASB reactors showing 95% 2-CP and 81.1% 2,4-DCP removals. The carbon sources formate and propionate were not found suitable in UASB reactors as only 22.6-46.8% 2-CP and 41.9-42.8% 2,4-DCP removals were observed. With glucose as carbon source 93.7% 2-CP and 79.6% 2,4-DCP removals were observed in UASB reactors. For all the four carbon sources more than 97.6% 2-CP and 99.7% 2,4-DCP removals were observed in sequential reactors. Although all the four carbon sources could not serve as good carbon source for UASB reactor alone but could be successfully used by the sequential reactors for the removal of chlorophenols. The Performance of sequential reactors was also evaluated at five different chlorophenolic shock loadings. During shock loading study the concentration of chlorophenols in the wastewaters was increased to 45, 60, 75, 90 and 105 mg/l as compared to the normal feed containing 30 mg/l 2-CP or 2,4-DCP. During shock loading study complete removal of 2-CP and more than 99.6% removal of 2,4-DCP was observed in sequential reactors. Sequential reactors successfully withstood all the shock loadings and produced high quality effluents.

The adsorption equilibrium isotherms of five phenolic compounds from aqueous solutions onto granular activated carbon (GAC) were studied and modeled. Phenol (Ph), 2-chlorophenol (2-CP), 4-chlorophenol (4-CP), 2,4-dichlorophenol (DCP), and 2,4,6-trichlorophenol (TCP) were chosen for the adsorption tests. To predict the adsorption isotherms and to determine the characteristic parameters for process design, seven isotherm models: Langmuir (five linear forms), Freundlich, Elovich, Temkin, Fowler-Guggenheim, Kiselev, and Hill-de Boer models were applied to experimental data. The results reveal that the adsorption isotherm models fitted the data in the order: Fowler-Guggenheim>Hill-de Boer>Temkin>Freundlich>Kiselev>Langmuir isotherms. Adsorption isotherms modeling shows that the interaction of phenolic compounds with activated carbon surface is localized monolayer adsorption, that is adsorbed molecules are adsorbed at definite, localized sites. Each site can accommodate only one molecule. The interaction among adsorbed molecules is repulsive and there is no association between them, adsorption is carried out on energetically different sites and is an exothermic process. Uptake of phenols increases in the order Ph<2-CP<4-CP

The removal of 3-chlorophenol (CP) from water by carbon derived from burning of rice straw was evaluated in this study. Rice straw was burned at 300 degrees C in the air to obtain rice carbon (RC). Scanning electron micrographs showed a highly porous structure of RC. NMR and FTIR spectroscopy suggested an enhanced aromaticity of RC and the presence of oxygen-containing functional groups. Adsorption of CP by RC was characterized by L-shaped nonlinear isotherms, suggesting surface adsorption rather than partitioning. The adsorption occurred most strongly when CP existed as a neutral species. The adsorption decreased with increasing pH due to increased deprotonation of surface functional groups of RC and dissociation of CP. The adsorption capacity determined by data-fitting to the Langmuir model was 14.2, 12.9, 11.4 and 4.9 mg g(-1) at pH 4, 6, 8 and 10, respectively. These results suggest that rice-straw-based carbon may be effectively used as a low-cost substitute for activated carbon for removal of chlorophenols from water.

Reactive Green HE 4BD carrying polyamide hollow fibers were investigated as dye-affinity adsorbents for removal of chlorophenols (i.e., phenol, o-chlorophenol, p-chlorophenol and 2,4,6-trichlorophenol). Adsorption rates of chlorophenols were very high. Equilibrium was achieved in about 30 min. The applicability of two kinetic models including pseudo-first order and pseudo-second order model was estimated on the basis of comparative analysis of the corresponding rate parameters, equilibrium capacity and correlation coefficients. Results suggest that chemisorption process could be the rate-limiting step in the adsorption process. The maximum adsorption values of chlorophenols onto the Reactive Green HE 4BD carrying hollow fibers were 145.9 micromol/g for phenol, 179.2 micromol/g for 2,4,6-trichlorophenol, 194.5 micromol/g for p-chlorophenol and 202.8 micromol/g for o-chlorophenol. The affinity order was as follows: o-chlorophenol>p-chlorophenol>2,4,6-trichlorophenol>phenol. The adsorption capacity of chlorophenols decreased with increasing pH. Desorption of chlorophenols was achieved using methanol solution (30%, v/v). The Reactive Green HE 4BD-carrying hollow fibers are suitable for repeated use for more than 10 cycles without noticeable loss of adsorption capacity.

The sorption potential of chemically and thermally treated rice husk (RHT) for the removal of 2,4-dichlorophenol (DCP) from aqueous solutions has been investigated. Sorption of DCP by rice husk was observed over a wide pH range of 1-10. The effect of contact time between liquid and solid phases, sorbent dose, pH, concentration of sorbate and temperature on the sorption of DCP onto rice husk has been studied. The pore area and average pore diameter of RHT by BET method are calculated to be 17+/-0.6 m2g-1 and 51.3+/-1.5 nm, respectively. Maximum sorption (98+/-1.2%) was achieved for RHT from 6.1x10(-5) moldm(-3) of sorbate solution using 0.1g of rice husk for 10 min agitation time at pH 6 and 303K, which is comparable to activated carbon commercial (ACC) 96.6+/-1.2%, but significantly higher than chemically treated rice husk (RHCT) 65+/-1.6% and rice husk untreated (RHUT) 41+/-2.3%. The sorption data obtained at optimized conditions was subjected to Freundlich, Langmuir and Dubinin-Radushkevich (D-R) isotherms. Sorption intensity 1/n (0.31+/-0.01) and sorption capacity multilayer C(m) (12.0+/-1.6 mmolg(-1)) have been evaluated using Freundlich sorption isotherm, whereas the values of sorption capacity monolayer Q (0.96+/-0.03 mmolg(-1)) and binding energy, b, (4.5+/-1.0)x10(4)dm(3)mol(-1) have been estimated by Langmuir isotherm. The Langmuir constant, b, was also used to calculate the dimensionless factor, R(L), in the concentration range (0.6-6.1)x10(-4) moldm(-3), suggesting greater sorption at low concentration. D-R sorption isotherm was employed to calculate sorption capacity X(m) (2.5+/-0.07 mmolg(-1)) and sorption energy E (14.7+/-0.13 kJmol(-1)). Lagergren and Morris-Weber equations were employed to study kinetics of sorption process using 0.2g of RHT, 25 cm(3) of 0.61x10(-4)moldm(-3) sorbate concentration at pH 6, giving values of first-order rate constant, k, and rate constant of intraparticle transport, R(id), (0.48+/-0.04 min(-1) and 6.8+/-0.8 nmolg(-1)min(-1/2), respectively) at 0.61x10(-4)moldm(-3) solution concentration of DCP, 0.1g RHT, pH 6 and 2-10min of agitation time. For thermodynamic studies, sorption potential was examined over temperature range 283-323 K by employing 6.1x10(-4)moldm(-3) solution concentration of DCP, 0.1g RHT at pH 6 and 10 min of agitation time and values of DeltaH (-25+/-1 kJmol(-1)), DeltaS (-61+/-4 Jmol(-1)K(-1)) and DeltaG(303K) (-7.1+/-0.09 kJmol(-1)) were computed. The negative values of enthalpy, entropy, and free energy suggest that the sorption is exothermic, stable, and spontaneous in nature.

The augmentation of activated sludge with two strains of Pseudomonas putida, CP1 and A(a) was investigated. Both strains of bacteria degraded 1.56 mM 4-chlorophenol. P. putida CP1 degraded the chemical using a modified ortho-cleavage pathway while P. putida A(a) used the meta-cleavage pathway. When activated sludge incapable of 4-chlorophenol degradation was augmented with either strain, substrate degradation occurred and followed the same biochemical pathways as when the bacteria were grown in pure culture. Insertion, in tandem, of the genes for gentamycin resistance and green fluorescent protein into the chromosomes of the two strains, enabled the survival and spatial location of the bacteria in the mixed microbial population to be monitored. Labelling the bacteria did not alter their degradative capabilities. P. putida CP1::Tn7-gfp survived in higher numbers than P. putida A(a)::Tn7-gfp following addition to the activated sludge. This was attributed to the ability of this strain to flocculate and become integrated in the activated sludge floc. Addition of P. putida CP1::Tn7-gfp or A(a)::Tn7-gfp to activated sludge resulted in smaller decreases in total cell numbers indicating a protective effect of the introduced P. putida strains on the overall microbial population from the harmful effects of 4-chlorophenol. The non-flocculant strain A(a) did not survive as well as CP1 in the activated sludge system and required a higher inoculum size to effect substrate degradation.

Phenolic compounds have become a cause for worldwide concern due to their persistence, toxicity and health risks. This paper reports a three-step approach to remove 2-chlorophenol from dilute aqueous solution and compares each technique. The first step utilizes Horse Radish Peroxidase (HRP) in presence of hydrogen peroxide to oxidize this organic pollutant (enzyme treatment). For a more efficient removal of 2-chlorophenol, it is necessary to add the enzyme solution gradually to the contents of the reactor instead of rapid addition. The second step, involving ultrasonic waves eliminated 2-chlorophenol through hydroxyl radical generated by the cavitation process (sono-degradation). In the third step, a combination of ultrasonic waves and enzyme was used (sono-enzyme degradation). It should be mentioned that, the enzyme can be active in the presence of ultrasonic waves under the proper sonication. The degradation has been studied at different temperatures, intensities of irradiation, and concentrations of enzyme. The rate of degradation exhibited pseudo-first order behavior and the combination method was more effective than sonolysis and enzyme treatment individually.

Chlorophenols are typical priority pollutants listed by USEPA (U.S. Environmental Protection Agency). The removal of chlorophenol could be carried out by a combination of electrochemical reduction and oxidation method. Results showed that it was feasible to degrade contaminants containing chlorine atoms by electrochemical reduction to form phenol, which was further degraded on the anode by electrochemical oxidation. Chlorophenol removal rate was more than 90% by the combined electrochemical reduction and oxidation at current of 6 mA and pH 6. The hydrogen atom is a powerful reducing agent that reductively dechlorinates chlorophenols. The instantaneous current efficiency was calculated and the results indicated that cathodic reduction was the main contributor to the degradation of chlorophenol.

Catalytic wet air oxidation (CWAO) of o-chlorophenol in wastewater was studied in a stainless steel autoclave using four different Fe catalysts in the temperature range of 100-200 degrees C. Experimental results showed that high rate of o-chlorophenol and COD(Cr) (Chemical Oxygen Demand, mg/L) removal by CWAO was obtained at relatively low temperature and pressure. The catalysts Fe2(SO4)3, FeSO4, Fe2O3 and FeCl3 all exhibited high catalytic activity. More than 93.7% of the initial COD(Cr) and nearly 100% of o-chlorophenol were removed at 150 degrees C after 150 min with FeSO4 as catalyst. The CWAO of o-chlorophenol was found to be pseudo-first order reaction with respect to o-chlorophenol, with activation energy of 75.56 kJ/mol in the temperature range of 100-175 degrees C.

This study evaluates the application of Wet Peroxide Oxidation (WPO) for the treatment of solutions containing 4-chlorophenol (4-CP) and 2,4-dichlorophenol (2,4-DCP). These compounds are of special interest due to their high toxicity and low biodegradability. WPO is included in the Advanced Oxidation Processes, which are technologies based on an initial formation of hydroxyl radicals that further oxidize the organic matter. The influence of some operating conditions such as temperature, dosage of hydrogen peroxide and initial concentration of the chlorophenols was studied in absence of a catalyst. The results of this study prove that 4-CP and 2,4-DCP can be completely removed from wastewaters by means of WPO. Total Organic Carbon (TOC) and 4-CP removals of 72.3% and 100%, respectively, were achieved working at 100 degrees C with 2.5 mL of H(2)O(2) and an initial concentration of 500 ppm of 4-CP after 90 min of reaction. Under the same conditions but with an initial concentration of 500 ppm of 2,4-DCP a TOC removal of 59% and a complete removal of the target compound were achieved.

In this study the sorption of phenol and 4-chlorophenol on pumice modified with the cationic surfactants hexadecyltrimethyl ammonium bromide (HDTMA) and benzyldimethyl tetradecylammonium chloride (BDTDA) was investigated. Experimental studies indicate that HDTMA-pumice and BDTDA-pumice have the capability to remove phenol and 4-chlorophenol from aqueous solution. The influence of initial concentration and adsorbent dosage was studied. The adsorption of phenol and 4-chlorophenol increased with increasing initial concentration and decreased with increasing amount of adsorbent used. The Freundlich adsorption isotherm was found to describe well the equilibrium adsorption data. The parameters of the Freundlich model have been determined using the adsorption data.

The physical and biochemical characteristics of the biomass in three lab-scale sequencing batch reactors (SBR) treating a synthetic wastewater at a 20-day target solids retention time (SRT) were investigated. The synthetic wastewater feed contained biogenic compounds and 22 organic priming compounds, chosen to represent a wide variety of chemical structures with different N, P and S functional groups. At a two-day hydraulic retention time (HRT), the oxidation-reduction potential (ORP) cycled between -100 (anoxic) and 100 mV (aerobic) in the anoxic/aerobic SBR, while it remained in a range of 126+/-18 and 249+/-18 mV in the aerobic sequencing batch biofilm reactor (SBBR) and the aerobic SBR reactor, respectively. A granular activated sludge with excellent settleability (SVI=98+/-31 L mg(-1)) developed only in the anoxic/aerobic SBR, compared to a bulky sludge with poor settling characteristics in the aerobic SBR and SBBR. While all reactors had very good COD removal (>90%) and displayed nitrification, substantial nitrogen removal (74%) was only achieved in the anoxic/aerobic SBR. During the entire operational period, benzoate, theophylline and 4-chlorophenol were completely removed in all reactors. In contrast, effluent 3-nitrobenzoate was recorded when its influent concentration was increased to 5 mg L(-1) and dropped only to below 1 mg L(-1) after 300 days of operation. The competent (active) biomass fractions for these compounds were between 0.04% and 5.52% of the total biomass inferred from substrate-specific microbial enumerations. The measured competent biomass fractions for 4-chlorophenol and 3-nitrobenzoate degradation were significantly lower than the influent COD fractions of these compounds. Correspondent to the highest competent biomass fraction for benzoate degradation among the test SOCs, benzoate oxidation could be quantified with an extant respirometric technique, with the highest specific oxygen uptake rate (SOUR(benzoate), 0.026 g O2 h(-1) g(-1) XCOD) in the anoxic/aerobic SBR. These combined results suggest that operating SBRs with alternative anoxic/aerobic cycles might facilitate the formation of granular sludge with good settleability, and retain comparable removal of nitrogen and synthetic organic compounds. Hence, the practice of anoxic/aerobic cycling should be considered in wastewater treatment systems whenever possible.

In this study, the potential use of the fungus Pleurotus sajor caju to remove phenols (i.e., phenol, o-chlorophenol, p-chlorophenol and 2,4,6-trichlorophenol) from aqueous solutions was evaluated. Biosorption of phenol or chlorophenols reached equilibrium in 4 h. The maximum adsorptions of phenol and chlorophenols onto the Pleurotus sajor caju were 0.95 mmol/g for phenol, 1.24 mmol/g for o-chlorophenol, 1.47 mmol/g for p-chlorophenol and 1.89 mmol/g for 2,4,6-trichlorophenol. The affinity order was as follows: 2,4,6-trichlorophenol> p-chlorophenol> o-chlorophenol>phenol. Phenol and chlorophenols bindings onto Pleurotus sajor caju were clearly pH dependent. The adsorption of phenol and chlorophenols increased with increasing pH. Desorption was achieved using methanol solution (30%, v/v). Pleurotus sajor caju biomass is suitable for reuse for more than five cycles without noticeable loss of adsorption capacity.

Removal of 2-chlorophenol by ultrasonic waves (sonolysis), inorganic catalyst, and a combination of the two processes was tested and compared with each technique. In sonolysis, 2-chlorophenol mostly degraded indirectly in the bulk of solution by the radicals produced in the cavitation process. In catalyst treatment, the removal was performed in the presence of Al2O3, TiO2 and CuO. The highest removal was achieved in the presence of TiO2 for this pollutant. In the combined method an enhancement was observed for the removal of 2-chlorophenol. This could be attributed primarily to the continuous cleaning and chemical activation of the catalyst by acoustic cavitation. The mass transfer between the liquid phase and the catalyst and also the surface area of the catalyst are accelerated by the ultrasonic waves. The removal of 2-chlorophenol was performed under different intensities of irradiation, temperatures and quantities of catalyst. Some experiments were conducted in the presence of a Fenton reagent. In kinetic point of view, the removal of pollutant showed a pseudo-first order behavior. The combined method had a higher rate coefficient than sonolysis and catalyst treatment individually. Under some conditions, the presence of ultrasound has increased the rate coefficient of removal to about 10 times that in the absence of ultrasound.

A Mexican clinoptilolite-rich tuff was modified with the hexadecyltrimethyl ammonium (HDTMA) and used for the sorption of phenol and 4-chlorophenol. Whereas the zeolitic tuff had no affinity for phenol and 4-chlorophenol, the modified zeolite removed these organic compounds. The sorption behavior from aqueous solutions was studied by means of batch type and column experiments and isotherms were determined. It was found that the uptake was higher for 4-chlorophenol than for phenol.

Batch mode studies were conducted to study the removal of phenol, 2,4,6-Trichlorophenol (TCP) and Pentachlorophenol (PCP) from aqueous solution on coir pith carbon by adsorption process under varying experimental conditions such as agitation time, adsorbent dose, pH and temperature. Kinetics of adsorption obeyed second order rate equation and the rate constant was found to be in the range 0.0098-0.0672, 0.0949-0.8801 and 0.172-0.305 g/mg/min for phenol, TCP and PCP respectively. Equilibrium adsorption data follow Langmuir isotherm for phenol and PCP and the adsorption capacities were found to be 48.3 mg and 3.7 mg/g, respectively. For TCP, adsorption followed Freundlich isotherm only. Acidic pH was favorable for the adsorption of all the chlorophenols. Studies on pH effect and desorption show that chemisorption seems to play a major rule in the adsorption process. The positive values of H0 24.99, 18.69, and 8.907 kJ/mol for phenol, TCP and PCP respectively, confirm the endothermic nature of adsorption.

A novel in-situ electrochemical oxidation method was applied to the degradation of wastewater containing chlorophenol. Under oxygen sparging, the strong oxidant, hydrogen dioxide, could be in-situ generated through the reduction of oxygen on the surface of the cathode. The removal rate of chlorophenol could be increased 149% when oxygen was induced in the electrochemical cell. The promotion factor was estimated to be about 82.63% according to the pseudo-first-order reaction rate constant (min(-1)). Important operating parameters such as current density, sparged oxygen rate investigated. Higher sparged oxygen rate could improve the degradation of chlorophenol. To make full use of oxygen, however, sparged oxygen rate of 0.05 m(3)/h was adopted in this work. Oxidation-reduction potential could remarkably affect the generation of hydrogen peroxide. It was found that the removal rate of chlorophenol was not in direct proportion to the applied current density. The optimum current density was 3.5 mA/cm(2) when initial chlorophenol concentration was 100 mg/L and sparged oxygen rate was 0.05 m(3)/h.

The photocatalytic removal rates r of dichloroacetic acid (DCAA), 4-chlorobenzoic acid (4-CBA) and 4-chlorophenol (4-CP) in water were compared for TiO2 samples used either as a powder or as a coating on a fiber glass tissue, SiO2 being the binder. From SEM-EDX measurements it was deduced that SiO2 prevails over TiO2 in the coating top layers and 18O2-Ti16O2 isotopic exchange showed that the accessibility of O2 to TiO2 was markedly reduced when TiO2 was thus coated. The unfavorable effect of the restricted TiO2 accessibility on r was drastic for DCAA, much less pronounced for 4-CBA, and still smaller for 4-CP. It is inferred that DCAA can be attacked only when it directly interacts with TiO2, whereas 4-CP can also react within the near-TiO2 surface water layers. The 4-CBA intermediate behavior is in line with the structural similarities of 4-CBA with DCAA and 4-CP.

Transformation of chlorophenols by nanoscale bimetallic particles represents one of the latest innovative technologies for environmental remediation. Nanoscale Pd/Fe bimetallic particles were synthesized in the laboratory for treatment of o-chlorophenol. Most of the nanoscale particles are in the size range of 20-100 nm. BET specific surface area of the nanoscale Pd/Fe particles is 12.4 m2/g. In comparison, a commercially available Fe powder( < 100 mesh) has a specific surface area of just 0.49 m2/g. Batch experiments demonstrated that the nanoscale Pd/Fe bimetallic particles can effectively dechlorinate o-chlorophenol. Dechlorination efficiency is affected by the mass fraction of Pd in the bimetal, nanoscale Pd/Fe mass concentration and mixing intensity.

The effect of the photo-Fenton process on biodegradability enhancement of 100 mg x L(-1) aqueous 2,4-dichlorophenol (2,4-DCP) solution has been investigated. An initial concentration of 65 mg x L(-1) H2O2 and 10 mg x L(-1) Fe (II) during 35 minutes of irradiation time was sufficient for total 2,4-DCP removal. At these working conditions, biodegradability, measured as BODS/COD ratio, was increased from 0 for the original solution up to 0.15. Biological oxidation of photo-Fenton pre-treated solutions was performed in a sequencing batch reactor (SBR). After 32 days of start-up, the reactor was fed with different pre-treated solutions and cycle duration was reduced progressively. TOC removal efficiencies in the SBR went from 30 up to 70%.

The effect of combining the photocatalytic processes using TiO2 and the photo-Fenton reaction with Fe3+ or ferrioxalate as a source of Fe2+ was investigated in the degradation of 4-chlorophenol (4CP) and dichloroacetic acid (DCA) using solar irradiation. Multivariate analysis was used to evaluate the role of three variables: iron, H2O2 and TiO2 concentrations. The results show that TiO2 plays a minor role when compared to iron and H2O2 in the solar degradation of 4CP and DCA in the studied conditions. However, its presence can improve TOC removal when H2O2 is totally consumed. Iron and peroxide play major roles, especially when Fe(NO3)3 is used in the degradation of 4CP. No significant synergistic effect was observed by the addition of TiO2 in this process. On the other hand, synergistic effects were observed between FeOx and TiO2 and between H2O2 and TiO2 in the degradation of DCA.

The photodegradation of p-cholorophenol in a hydrogen peroxide-aided photolysis process was investigated. The reaction was influenced by the original concentration of p-chlorophenol and H2O2 addition and carrier gas. With the aid of dioxygen, the removal of phenol and CODCr were reached about 96% and 50% respectively if the original concentration of H2O2 added was only half of stoichiometric calculation. A pseudo-first order kinetic model was adopted to represent the reaction.

Use of additives, such as polyethylene glycol (PEG), selected surfactants, chitosan gel, or activated carbon, has been shown to enhance enzymatic treatment of water polluted with organic compounds. In this study, additives were used to facilitate the removal of 2,4-dichlorophenol (2,4-DCP) from water using minced horseradish (Armoracia rusticana P. Gaertn. et al.) as a carrier of peroxidase activity. The specific objectives of the study were to (i) enhance the pollutant removal activity of minced horseradish by the addition of PEG and other additives (e.g., Tween 20, Triton X-100, and rhamnolipid); (ii) eliminate colored reaction products by the addition of chitosan; and (iii) eliminate color by amending treated water with activated carbon. The disappearance of 2,4-DCP in horseradish-treated water samples amended with PEG or various surfactants (75-90%) was greatly increased over that observed in nonamended samples (29%). The effect of PEG depended on its average molecular weight. As indicated by visible spectrophotometry, enclosing horseradish pieces between two sealed chitosan films completely eliminated colored reaction products; however, the decolorization was accompanied by a reduction in 2,4-DCP removal (from 95 to 60%). On the other hand, commercially available activated carbon completely removed colored reaction products from the treated water without reducing the removal efficiency. Based on the results obtained, it can be concluded that the use of additives may considerably improve the quality of wastewater treated by plant materials.

Effect of pH on the sorption and desorption of the chlorinated phenols (2-chlorophenol and 2,4-dichlorophenol) in HDTMA-montmorillonite organoclays was investigated using sequential batch experiments. 2,4-dichlorophenol exhibited higher affinity in both sorption and desorption than 2-chlorophenol at pH 4.85 and 9.15. For both chlorophenols, the protonated speciation (at pH 4.85) exhibited a higher affinity in both sorption and desorption than the predominant deprotonated speciation (about 80% and 95% of 2-chlorophenate and 2,4-dichlophenate anions at pH 9.15, respectively). Desorption of chlorinated phenols was strongly dependent on the current pH regardless of their speciation during the previous sorption stage. No appreciable desorption resistance of the chlorinated phenols was observed in organoclays after sequential desorptions. Affinity of both chlorophenols in bisolute competitive sorption and desorption was reduced compared to that in a single-solute system due to the competition between solutes. The ideal adsorbed solution theory coupled with the single-solute Freundlich model successfully predicted the bisolute competitive sorption and desorption equilibria.

The combination of high voltage pulse discharge and ozonation as an advanced oxidation technology was used to investigate the degradation of 4-chlorophenol (4-CP) in water. The factors that affect the rate of degradation were discussed. The 1.95 x 10(-3) mol/L solutions of 4-CP were almost completely (96%) degraded after the discharge treatment of 30 min. The degradation of 4-CP was investigated as a function of the ozone concentration, radical scavenger and electrode distance. The rate of 4-CP degradation increases with an increase in ozone concentration and a decrease in the electrode distance from 20 mm to 10 mm. The presence of radical scavenger decreased the rate of 4-CP degradation.