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PubMed2005

Modeling of chlorophenols competitive adsorption on soils by means of the ideal adsorbed solution theory.

The adsorption of 3-chlorophenol (3-CP) and 3,5-dichlorophenol (3,5-CP) on two Italian soils was studied at 20 degrees C. Experiments on the pure components showed that 3,5-CP was more strongly adsorbed than 3-CP, and that the adsorption capacity could be related to the organic carbon fraction of the soil. Competitive adsorption data were described by the fully predictive ideal adsorbed solution (IAS) theory. To this end, the Langmuir parameters determined from pure component adsorption data were used. Results showed that at low 3,5-CP concentration (up to 5-10 mM) the model describes satisfactorily the binary system behavior, whereas at higher concentrations predictions fail, suggesting that non ideality effects in the adsorbed phase should be accounted for.

Adsorption↗
PubMed2005

Degradation of 4-chlorophenol by a microwave assisted photocatalysis method.

In this work, the degradation of 4-chlorophenol (4CP) under simultaneous microwave assisted UV (electrodeless discharge lamp) photocatalysis technique (MW/UV/TiO2) was investigated. Several factors affecting the degradation of 4CP by MW/UV/TiO2 method, such as the dosage of photocatalysts, the initial pH value of the solutions, gas bubbling, light intensity and addition of H2O2 oxidant, were studied in detail. The synergistic effects between microwave irradiation and TiO2 photocatalysis were also studied. The major intermediates were found to be chlorobenzene, phenol, hydroquinone, benzoquinone and 4-chlorocatechol. Based on the results, a general reaction pathway for the degradation of 4CP was proposed.

Catalysis↗
PubMed2006

Adsorption of 4-chlorophenol from aqueous solutions by xad-4 resin: isotherm, kinetic, and thermodynamic analysis.

Removal of 4-chlorophenol (4-CP) from synthetic aqueous solutions through adsorption on Amberlite XAD-4 resin, a non-ionic macroreticular resins, under batch equilibrium experimental conditions at 298, 308 and 318K was investigated. It is necessary to propose a suitable model to a better understanding on the mechanism of 4-CP adsorption. For this purpose, Langmiur, Freundlich, Toth, and Redlich-Peterson (RP) isotherm models were compared. The two and three parameters in the adopted adsorption isotherm models were determined by the help of MATLAB package program. It was determined that best fitted adsorption isotherm models were obtained to be in the order: Redlich-Peterson>Langmuir>Toth>Freundlich isotherms. The pseudo-second-order kinetic model provided the best correlation to the experimental results. Results of the intra-particle diffusion model show that the pore diffusion is not the only rate limiting step. The lower correlation of the data to the Bangham's equation also represents that the diffusion of the adsorbate into pores of the sorbent is not the only rate-controlling step. The thermodynamic constants of adsorption phenomena; DeltaG degrees, DeltaH degrees, and DeltaS degrees were found as -4.17 (at 298K) kJ/mol, -42.01 kJ/mol, and -0.127 kJ/(mol K), respectively. The results showed that adsorption of 4-CP on Amberlite XAD-4, a nonionic polymeric resin was exothermic and spontaneous.

Adsorption↗
PubMed2006

Effect of biogenic substrate concentration on 4-chlorophenol degradation kinetics in sequencing batch reactors with instantaneous feed.

Two sequencing batch reactors (SBRs) instantaneously fed with 200 mg/l 4-chlorophenol (4-CP) were operated at different feed peptone concentrations to investigate the effect of biogenic substrate (peptone) concentrations on reactor performance, yield coefficient (Y) and 4-CP degradation kinetics. One of the reactors was operated at 10 days of sludge retention time (SRT) and the other was operated at 20 days of SRT. High chemical oxygen demand (COD) removal efficiencies (90-95%) and complete 4-CP removals (detection limit was 0.05 mg/l) were observed even in the absence of peptone. Accumulation of 5-chloro-2-hydroxymuconic semialdehyde (CHMS), meta cleavage product of 4-CP, was observed, which was completely removed at the end of the reactor cycle. It was concluded that decreasing peptone concentrations did not affect 4-CP degradation profiles and Haldane equation can be satisfactorily used to predict time course variation of 4-CP concentrations. It was assumed that specialists (competent biomass) are only responsible for 4-CP degradation and its concentration was constant although peptone concentration in the feed was varied, as competent biomass grows on 4-CP only. Model developed using this assumption well tracked the experimental data. The kinetic coefficients obtained for the reactor operated at 10 days of SRT were also valid for the reactor operated at 20 days of SRT although higher degradation rates were observed due to higher steady state biomass concentrations.

Bacteria↗
PubMed2006

Exploring the interparticle electron transfer process in the photocatalytic oxidation of 4-chlorophenol.

This work aimed to investigate the interparticle electron transfer (IPET) process within the coupled-photocatalyst systems on the basis of the degradation of 4-chlorophenol (4-CP). TiO(2), ZnO and SnO(2) are used as the model photocatalysts owing to their increasing energy levels which correspond to the IPET concept. In the single-photocatalyst tests, ZnO tests are associated with the highest degradation rate constants (0.347+/-0.083 h(-1) at pH 7 and 0.453+/-0.011 h(-1) at pH 11) and a better DOC reduction than in other single catalyst tests under given conditions. ZnO/SnO(2) coupled tests have constants of 0.612+/-0.068 and 0.948+/-0.069 h(-1) at pH 7 and 11, respectively. Additionally, the 4-CP prefers the breakdown of chloride group in TiO(2) system while proceeding hydroxylation reaction in ZnO systems. Meanwhile, a phenomenonlogical model coupled with the IPET effect was developed to explore the separation of photo-electrons and photo-holes within catalysts. Based on the model parameters, the recombination rate of photo-electrons and photo-holes in TiO(2)/SnO(2) and ZnO/SnO(2) systems is 20-45% lower than that obtained by a respective single catalyst. Thus, coupled-photocatalyst tests, TiO(2)/SnO(2) and ZnO/SnO(2) efficiently suppress the recombination, particularly for ZnO/SnO(2) tests at pH 11.

Catalysis↗
PubMed2006

Evaluation of the influences of solution path length and additives concentrations on the solar photo-Fenton degradation of 4-chlorophenol using multivariate analysis.

This study reports the photodegradation of 4-chlorophenol (4-CP) in aqueous solution by the photo-Fenton process using solar irradiation. The influence of solution path length, and Fe(NO(3))(3) and H(2)O(2) concentrations on the degradation of 4-CP is evaluated by response surface methodology. The degradation process was monitored by the removal of total organic carbon (TOC) and the release of chloride ion. The results showed a very important role of iron concentration either for TOC removal or dechlorination. On the other hand, a negative effect of increasing solution path length on mineralization was observed, which can be compensated by increasing the iron concentration. This permits an adjustment of the iron concentration according to the irradiation exposure area and path length (depth of a tank reactor). Under optimum conditions of 1.5 mM Fe(NO(3))(3), 20.0 mM H(2)O(2) and 4.5 cm solution path length, 17 min irradiation under solar light were sufficient to reduce a 72 mg CL(-1) solution of 4-CP by 91%.

Chlorine↗
PubMed2006

Reaction paths and efficiency of photocatalysis on TiO2 and of H2O2 photolysis in the degradation of 2-chlorophenol.

The kinetics of 2-chlorophenol (2-CP) degradation and mineralization in the aqueous phase was investigated under irradiation at 254 nm, employing either photocatalysis in the presence of titanium dioxide, or hydrogen peroxide photolysis, to compare the efficiency of these photoinduced advanced oxidation techniques. Photocatalysis under 315-400 nm wavelength irradiation was also investigated. The concentration versus time profiles of the degradation intermediates catechol, chloro- and hydroxy-hydroquinone allowed the identification of the reaction paths prevailing under the different experimental conditions. Efficient CCl bond cleavage occurred as a consequence of direct light absorption by 2-CP, while hydroxyl radicals, photogenerated at the water-photocatalyst interface or during H(2)O(2) photolysis, were the main oxidation agents, able to attack both 2-CP and its degradation intermediates. Highest degradation and mineralization efficiencies were achieved under H(2)O(2) photolysis at 254 nm.

Catalysis↗
PubMed2006

The formation and influence of hydrogen peroxide during ozonation of para-chlorophenol.

Hydrogen peroxide was detected during the ozonation of para-chlorophenol (4-CP) in aqueous solutions. Its formation and influence on the reaction mechanism were examined. Semi-batch experiments showed that hydrogen peroxide was formed during the direct reaction between molecular ozone and 4-CP. The detected hydrogen peroxide could reach 12.3% of the initial mole concentration of 4-CP. Hydrogen peroxide reacts with ozone in neutral pH and leads to the appearance of the powerful oxidant, OH* radicals. An O(3)/OH* probe compound, succinate was then developed, and also included in the 4-CP solution matrix. The disappearance of succinate with time shows the amount of OH radicals. With enough tert-butanol inhibiting the OH* radical oxidation, results showed that 4-CP was transformed to para-quinone by ozone, and subsequently destroyed to formic acid and oxalic acid. Without scavengers of inactivation the OH* radicals, 4-CP was destroyed to low molecular weight acid.

Chlorophenols↗
PubMed2006

Performance of a hybrid-loop bioreactor system in biological treatment of 2,4,6-tri-chlorophenol containing synthetic wastewater: effects of hydraulic residence time.

A hybrid-loop bioreactor system consisting of a packed column biofilm and an aerated tank bioreactor with effluent recycle was used for biological treatment of 2,4,6-tri-chlorophenol (TCP) containing synthetic wastewater. Effects of hydraulic residence time (HRT) on COD, TCP and toxicity removal performance of the reactor were investigated for the HRT values between 5 and 30 h, while the feed COD (2700+/-100 mgl(-1)), TCP (300+/-10 mgl(-1)) and the solids retention time (sludge age, SRT, 20 d) were constant. Percent TCP, COD and toxicity removals increased with increasing HRT resulting in more than 90% COD, TCP and toxicity removals at HRT values above 25 h. Biomass concentrations in the packed column and in the aeration tank increased with increasing HRT resulting in low reactor TCP concentrations and therefore high TCP, COD and toxicity removals at high HRT values. Volumetric and specific rates of TCP and COD removals decreased with increasing HRT due to increased biomass and decreased flow rates at high HRT levels. Volumetric and specific removal rates of COD and TCP were maximum at an HRT of 5 h.

Bioreactors↗
PubMed2006

Improvement in sonochemical degradation of 4-chlorophenol by combined use of Fenton-like reagents.

Studies on the sonolysis of a wide range of organic compounds have demonstrated that ultrasonic irradiation has potential for decomposition of organic pollutants in hazardous wastewater. However, the ultrasonic irradiation alone cannot provide high enough rate of decomposition to be used practically. One of the solutions to increase the degradation efficiency is to combine the ultrasound application with other advanced chemical oxidation processes (AOPs). In this study, in order to increase the efficiency of ultrasonically assisted degradation of organic pollutants in water, we examined effects of three kinds of solid Fe-containing catalysts, namely iron powder, basic oxygen furnace (BOF) slag and mill scale on the degradation rate of 4-CP (4-chlorophenol) in aqueous solutions containing hydrogen peroxide. In the experiments, 4-CP was considered as a model organic compound. All three Fe-containing matters when react with hydrogen peroxide are involved in the Fenton-like reaction system, which is one of the promising AOPs. The results showed that both the iron powder and mill scale additions can accelerate the degradation of 4-CP, although the effect is dependent on the solution pH. All 4-CP could be decomposed for 2 min at pH=3 and for 1h at pH=5.6. On the other hand, the BOF slag had no catalysis effect on the 4-CP degradation because of higher concentration of calcium and lower concentration of iron.

Chlorophenols↗
PubMed2005

Catalytic wet oxidation of o-chlorophenol at mild temperatures under alkaline conditions.

Wet oxidation of a 100 ppm aqueous solution of o-chlorophenol (o-CP) was performed in a lab-scale batch reactor using 3% Ru/TiO(2) catalyst at 373 and 413 K, and a partial oxygen pressure of 0.1 MPa. The experiments were conducted by varying the initial pH values of o-CP solution from pH 6.3 to 9.8 and 11.8. From the results, it was revealed that the catalytic decomposition of o-CP occurred most effectively at 413 K and at the initial pH of 9.8. Complete decomposition and dechlorination of o-CP were almost achieved within 1h, and about 85% of TOC was removed in 3.0 h. On the other hand, the catalytic wet oxidation of o-CP at a higher pH value of 11.8 was not effective in the removal of TOC. The incomplete removal of TOC at the initial pH of 11.8 is likely attributed to a low pK(a) of carboxylic acids formed during the wet oxidation of o-CP.

Carbon↗
PubMedDate not supplied

Rose bengal-sensitized photooxidation of 2-chlorophenol in water using solar simulated light.

The decomposition of 2-chlorophenol (2CP) in an aqueous solution by means of photosensitized oxidation using rose bengal has been studied. The influence of initial 2CP concentration, pH of reaction mixture and oxygen content on reaction rate has been observed. The reaction of 2CP with singlet oxygen (type II of photooxidation) appeared the most important pathway of degradation. The rate constants of singlet oxygen quenching and reaction with 2CP were determined and the rate constant of excited rose bengal quenching by 2CP was also estimated. An attempt was made to identify the main photooxidation products.

Chlorophenols↗
PubMed2005

Evaluation of two control strategies for a sequencing batch reactor degrading high concentration peaks of 4-chlorophenol.

The operation of a sequencing batch reactor (SBR) exposed to high concentration peaks (shock loads) of a toxic compound (4-chlorophenol, 4CP) was evaluated. Two control strategies based on on-line measurements of the dissolved oxygen concentration were tested. The first strategy, called variable timing control (VTC), detects the end of the reaction period to stop it. In the second control strategy, called observer-based time optimal control (OB-TOC), the automated system tries to maintain the critical specific growth rate by controlling the feed rate, i.e. the maximum growth rate when the substrate is toxic. The system operating under the VTC strategy presented a stable and efficient operation when the acclimated microorganisms (to an initial concentration of 350 mg 4CP/L) were exposed to punctual concentration peaks of 700 mg 4CP/L. A 4CP concentration peak higher than or equal to 1050 mg/L disturbed the system (1 month to recover). A 1400 mg/L peak caused strong inhibition that shut down the metabolic activity of the microorganisms, leading to reactor failure. With the OB-TOC strategy, the system was stable and worked efficiently when punctual concentration peaks of 700, 1050 and 1400 mg 4CP/L were fed. The system controlled by the OB-TOC strategy treated 1400 mg 4CP/L in less than 8h without affecting the operation of the reactor. The conclusion is that the OB-TOC strategy is more efficient than the VTC strategy to control a bioreactor when there are variations of concentrations of toxic organic compounds.

Biodegradation, Environmental↗
PubMed2000

Cloud point preconcentration of rather polar compounds: application to the high-performance liquid chromatographic determination of priority pollutant chlorophenols.

The potential of the cloud point methodology for the preconcentration of relatively polar compounds was studied using the non-ionic surfactant Triton X-114 and five EPA chlorophenols as test analytes. Analyte determination was performed using reversed-phase gradient LC with electrochemical and spectrophotometric detection. The amount of surfactant used is a critical variable in the preconcentration factor because it determines the extraction yield and the volume of surfactant-rich phase obtained. These values were determined as a function of the Triton X-114 concentration, together with the phase ratio, which allows prediction of the maximum preconcentration factor under given conditions.

Calibration↗
PubMed2001

New polymeric sorbent for the solid-phase extraction of chlorophenols from water samples followed by gas chromatography-electron-capture detection.

A polymeric material, polyaniline, was employed as a new sorbent for solid-phase extraction (SPE) of some environmental pollutants from water samples. Chlorophenols were extracted from aqueous samples by SPE using 120 mg polyaniline and determined by gas chromatography with electron-capture detection. The acetate esters of these phenols were formed by the direct addition of acetic anhydride to the organic extractant in the presence of K2CO3. Different conditions were applied to obtain higher retaining capacity and breakthrough volumes. The results compared with those obtained by other groups. The RSD for a river water sample spiked at sub-ppb level was lower than 10% (n = 3) and detection limits were between 3 and 110 ng(-1).

Chlorophenols↗
PubMed2002

Determination of chlorophenols by solid-phase microextraction and liquid chromatography with electrochemical detection.

A solid-phase microextraction method has been developed for the determination of 19 chlorophenols (CPs) in environmental samples. The analytical procedure involves direct sampling of CPs from water using solid-phase microextraction (SPME) and determination by liquid chromatography with electrochemical detection (LC-ED). Three kinds of fibre [50 microm carbowax-templated resin (CW-TPR), 60 microm polydimethylsiloxane-divinylbenzene (PDMS-DVB) and 85 microm polyacrylate (PA)] were evaluated for the analysis of CPs. Of these fibres, CW-TPR is the most suitable for the determination of CPs in water. Optimal conditions for both desorption and absorption SPME processes, such as composition of the desorption solvent (water-acetonitrile-methanol, 20:30:50) and desorption time (5 min), extraction time (50 min) and temperature (40 degrees C) as well as pH (3.5) and ionic strength (6 g NaCl) were established. The precision of the SPME-LC-ED method gave relative standard deviations (RSDs) of between 4 and 11%. The method was linear over three to four orders of magnitude and the detection limits, from 3 to 8 ng l(-1), were lower than the European Community legislation limits for drinking water. The method was applied to the analysis of CPs in drinking water and wood samples.

Chlorophenols↗
PubMed1983

High-performance liquid chromatographic analysis of chlorophenols in cardboard food containers and related materials.

A technique has been developed for the extraction of a clean concentrate of chlorophenols from cardboard food containers and adhesives of the type used in their manufacture. A simple, reversed-phase, isocratic high-performance liquid chromatographic (HPLC) system employing an optimised mobile phase permitted the separation of nineteen different phenols. The use of a carefully selected internal standard permitted the estimation of (sub) parts per million levels of pentachlorophenol, 2,3,4,6-tetrachlorophenol and 2,4,6-trichlorophenol in several samples of adhesives and various sections of cardboard food containers. Pentachlorophenol (50 ng) and 2,4,6-trichlorophenol (20 ng) gave significant HPLC peaks, readily permitting their detection in parts per billion from 100-g samples.

Adhesives↗
PubMed2003

Conductive polymers as new media for solid-phase extraction: isolation of chlorophenols from water sample.

Three different conductive polymers, poly-N-methylaniline (PNMA), polyaniline and polydiphenylamine were synthesised and used as sorbents for the solid-phase extraction of some phenolic compounds from water. The separation and determination was, subsequently, performed by gas chromatography-electron-capture and flame ionization detection. Among these easy-made polymers, PNMA gave better recovery for the extraction of the studied analytes. The capability of the PNMA to extract other non-polar compounds such as chloro- and methylbenzene, decane, decanol, cyclohexane and cyclohexanol was also studied. The polymer showed some sort of selectivity towards aromatic compounds than aliphatic. Preconcentration of sample volumes up to 1 l at pH 2 using 120 mg of PNMA led to acceptable recoveries for phenolic compounds, except for phenol. Recovery of phenol for 100 ml of water was 72%. Limits of detection for chlorophenols when 250 ml river water was preconcentrated were between 1 and 40 ng l(-1), analyzed by GC-electron-capture detection.

Chlorophenols↗