Color Removal from Synthetic Textile Wastewater by Sono‐Fenton Process

In this study, the oxidative decolorization of C.I. reactive yellow 145 (RY 145) from synthetic textile wastewater including RY 145 and polyvinyl alcohol by Fenton and sono‐Fenton processes which are the combination of Fenton process with ultrasound has been carried out. The effects of some operating parameters which are the initial pH of the solution, the initial concentration of Fe²⁺, H₂O₂, and the dye, temperature, and agitation speed on the color and chemical oxygen demand (COD) removals have been investigated. The optimum conditions have been found as [Fe²⁺] = 20 mg/L, [H₂O₂] = 20 mg/L, pH 3 for Fenton process and [Fe²⁺] = 20 mg/L, [H₂O₂] = 15 mg/L, pH 3 for sono‐Fenton process by indirectly sonication at 35 kHz ultrasonic frequency and 80 W ultrasonic power. The color and COD removal efficiencies have been obtained as 91 and 47% by Fenton process, and 95 and 51% by sono‐Fenton processes, respectively. Kinetic studies have been performed for the decolorization of RY 145 under optimum conditions at room temperature. It has been determined that the decolorization has occurred rapidly by sono‐Fenton process, compared to Fenton process.     

Degradation of Phenol in Aqueous Solution by Fenton,Sono‐Fenton and Sono‐photo‐Fenton Methods

The present work focuses on the performance of Fenton, sono‐Fenton, and sono‐photo‐Fenton processes for the oxidation of phenol present in aqueous solution. The effects of H₂O₂ concentration, Fe²⁺ concentration, pH, and initial phenol concentration on the oxidation of phenol were studied. The optimum Fe²⁺ and H₂O₂ concentrations for the Fenton process were 45 and 800 mg/L, respectively. For the sono‐Fenton process, the optimum Fe²⁺ and H₂O₂ concentrations were 30 and 800 mg/L, respectively. The optimal conditions for the sono‐photo‐Fenton process were found to be 20 mg/L of Fe²⁺ and 700 mg/L of H₂O₂. The optimum pH was found to be 3 for the processes investigated in the present study. The analysis of results showed that the sono‐photo‐Fenton method reduced the Fe²⁺ concentration by 30–50% and the H₂O₂ concentration by 12.5%. It was found that the sono‐photo‐Fenton technique showed better performance than the Fenton and sono‐Fenton processes for the oxidation of phenol. A lumped kinetic model was used to predict the chemical oxygen demand reduction and the model was found to fit the data.     

Central Composite Design Optimization of Biological Dye Removal in the Presence of Macroalgae Chara sp.

Response surface methodology (RSM) was employed to investigate the effects of different operational parameters on the biological decolorization of a dye solution containing malachite green (MG) in the presence of macroalgae Chara sp. The investigated variables were the initial pH, initial dye concentration, algae amount, and reaction time. Central composite design (CCD) was used for the optimization of biological decolorization process. Predicted values were found to be in good agreement with experimental values (R² = 0.982 and Adj‐R² = 0.966), which indicated suitability of the employed model and the success of RSM. The results of optimization predicted by the model showed that maximum decolorization efficiency was achieved at the optimum condition of the initial pH 6.8, initial dye concentration 9.7 mg/L, algae amount 3.9 g, and reaction time 75 min. UV–VIS spectra and FT‐IR analysis showed degradation of MG.     

Electro‐Fenton Treatment of Photographic Processing Wastewater

In this work, the treatment of photographic processing wastewaters (PPW) by electro‐Fenton process has been investigated. The Influence of operating conditions on kinetics and efficiency of electro‐Fenton process has been evaluated using carbon felt cathode and platinium (Pt) or boron‐doped diamond (BDD) anode. The results of electro‐Fenton treatment of PPW have shown that nearly complete removal of total phenols was obtained for all combinations with pseudo‐first rate constants of 0.07, 0.012, and 0.018/min for carbon felt/Pt, carbon felt/BDD and Pt/BDD cathode/anode combinations, respectively. The combination of carbon felt cathode with BDD anode achieved the highest total organic carbon (TOC) removal of 90%, while it did not exeed 40% for carbon felt/Pt combination. Increasing current intensity and Fe²⁺ dose enhances the efficiency of electro‐Fenton process. However, increasing pH decreases TOC removal during the treatment of PPW by electro‐Fenton process. The highest efficiency of electro‐Fenton process using BDD anode can be explained by the contribution of direct and indirect oxidation routes in the degradation mechanism of organics including (i) oxidation via hydroxyl radicals generated from the catalytic decomposition of H₂O₂ and from water discharge on BDD anode, (ii) direct oxidation of certain organic compounds on BDD anode, and (iii) mediated oxidation with inorganic oxidants electrogenerated from anodic oxidation of supporting salts.     

Photocatalytic Decolorization Kinetics and Mineralization of Reactive Black 5 Aqueous Solution by UV/TiO2 Nanoparticles

The photocatalytic decolorization and mineralization of Reactive Black 5 (RB5) dye in presence of TiO₂ Degussa P25 has been studied using artificial light radiation in a shallow pond slurry reactor. The equilibrium adsorption of dye, influence of pH (3–11), catalyst load (0.5–3.0 g/L), and dye concentration (20–100 mg/L) on decolorization kinetics were studied. The effect of area to volume ratio of photoreactor on decolorization kinetics has been also studied. Mineralization studies were performed at optimized conditions of pH (3) and catalyst load (1.5 g/L). The maximum adsorption (26.5 mg/g) of dye was found to occur at pH 3. The apparent pseudo first order decolorization rate constant (k_app) value followed the order pH 3 > pH 11 > pH 9 > pH 7. As compared to available literature reduction in total organic carbon (TOC) was minimal by the time there was complete decolorization. Initial reduction in TOC was followed by subsequent increasing trend till complete decolorization. Final decreasing trend in TOC was observed only after complete decolorization. Twelve hours of treatment under experimental conditions reduced TOC content by 70% only. Discussion of results suggest that photocatalytic treatment of colored effluent under low UV intensity, and low A/V ratio may result in completely decolorized effluent but still having high COD.     

Removal of Copper,Nickel and Zinc Ions from Aqueous Solution by Chitosan‐8‐Hydroxyquinoline Beads

In this work, 8‐hydroxyquinoline is used as the active sites in cross‐linked chitosan beads with epichlorohydrin (CT‐8HQ). The CT‐8HQ material was shaped in bead form and used for heavy metal removal from aqueous solution. The study was carried out at pH 5.0 with both batch and column methods and the maximum adsorption capacity of metal ions by the CT‐8HQ was attained in 4 h in the batch experiment. The adsorption capacity order was: Cu²⁺ > Ni²⁺ > Zn²⁺ for both mono‐ and multi‐component systems with batch conditions. From breakthrough curves with column conditions, the adsorption capacity followed the order Cu²⁺ > Zn²⁺ > Ni²⁺ for both mono‐ and multi‐component systems. The CT‐8HQ beads maintained good metal adsorption capacity for all five cycles with absorbent restoration achieved with the use of 1.0 mol L^–1 HCl solution, with 90% regeneration.     

Adsorption of Two Taste and Odor Compounds IPMP and IBMP by Granular Activated Carbon in Water

Granular activated carbon (GAC) adsorption of two representative taste and odor (T & O) compounds, 2‐isopropyl‐3‐methoxy pyrazine (IPMP), and 2‐isobutyl‐3‐methoxy pyrazine (IBMP), in drinking water was investigated. Results show that the modified Freundlich equation best fit the experimental data during the adsorption isotherm tests, and the pseudo first‐order kinetics and intra‐particle diffusion kinetics well described the adsorption kinetics pattern. The calculated thermodynamic parameters (ΔH⁰, ΔS⁰, and ΔG⁰) indicated a spontaneous and endothermic adsorption process. Factors affecting the treatment efficiency were carefully evaluated. Acidic and alkaline conditions both favored GAC adsorption of IPMP and IBMP, especially the former. With the GAC dosage increasing, the first order adsorption rates increased, while the intra‐particle adsorption rates decreased. Within 12 h, 200 mg/L GAC could remove >90% of 150 µg/L IPMP and IBMP via adsorption at pH 3–11. Therefore, GAC is a promising treatment technology to control the T & O compounds associated water pollution.     

Decolorization of Textile Azo‐metal Complex Dyes by a Halophilic Bacterium Isolated from Çamaltı Saltern in Turkey

The decolorization of some of azo‐metal complex dyes used in textile industry was investigated in this study. The halophilic prokaryotes isolated from a solar sea‐saltern (Çamalt?) in Turkey were screened for resistance to five commercial azo and mixture of azo‐metal complex dyes. Only one bacterium was found to be resistant against two of dyes, namely Lanaset Navy R and Lanaset Brown B. The bacterium was identified as Halobacillus sp. C‐22 according to 16S rRNA gene sequence analyses. Decolorization experiments were carried out at 120 mg/L concentration of both dyes, at room temperature, and with an acidic pH of 4.5. Lanaset Brown B was decolorized at a high adsorbance ratio (96.12%) at the 78th hour. However, Lanaset Navy R was rapidly decolorized in 10 min (46.67%) and showed the highest adsorbance ratio (60.66%) at the third hour. Freundlich and Langmuir equilibrium isotherm models were used to evaluate the adsorption of dyes and Freundlich isoterm was more suitable for biosorpsiyon of both azo dyes. The functional groups on Halobacillus sp. C‐22 for decolorization were characterized by FT‐IR. This is the first study to reveal potential of Halobacillus sp. for decolorization of textile azo‐metal complex dyes.     

Solar Photocatalytic Decolorization and Detoxification of Industrial Batik Dye Wastewater Using P(3HB)‐TiO2 Nanocomposite Films

Solar photocatalytic decolorization and detoxification of batik dye wastewater using titanium dioxide (TiO₂) immobilized on poly‐3‐hydroxybutyrate (P(3HB)) film was studied. The effects of initial dye concentration, catalyst concentration, P(3HB) film thickness, and fabrication methods of the nanocomposite films were evaluated against methylene blue, a standard organic dye. It was observed that 0.4 g of P(3HB)‐40 wt% TiO₂ removed 96% of the color under solar irradiation. P(3HB) and TiO₂, mixed concurrently in chloroform followed by stirring for 24 h showed a more even distribution of the photocatalyst on the polymer surface and yielded almost 100% color removal. The photocatalytic films were able to completely decolorize real industrial batik dye wastewater in 3 h and induced a chemical oxygen demand (COD) reduction of 80%. Reusability of the 0.4 g P(3HB)‐40 wt% TiO₂ film in decolorizing the batik dye wastewater was also possible as it gave a high consistent value of decolorization percentage (>80%) even after the sixth repeated usage. Recovery step of the photocatalysts was also not required in this simple treatment system. The decolorized batik dye wastewater had less/no toxic effects on mosquito larvae, Aedes aegypti, and microalgae, Scenedesmus quadricauda indicating simultaneous detoxification process along with the decolorization process.     

Removal of Various Phenoxyalkanoic Acid Herbicides from Water by Organo‐clays

Dodecylammonium bentonite (DB) and dodecylammonium sepiolite (DS) were used as sorbents for phenoxyalkanoic acid herbicides 2,4‐D ((2,4‐dichlorophenoxy)acetic acid), 2,4‐DP ((RS)‐2‐(2,4‐dichlorophenoxy)propionic acid), 2,4‐DB (4‐(2,4‐dichlorophenoxy)butyric acid), 2,4,5‐T ((2,4,5‐trichlorophenoxy)acetic acid), and MCPA ((4‐chloro‐2‐methylphenoxy)acetic acid). Langmuir, Freundlich, and the linear Henry’s Law isotherm adsorption parameters were calculated from the adsorption isotherms. Langmuir equation showed poor fit for both adsorbents. According to the evaluation using the Freundlich equation, the DS sample showed much higher and stronger sorption capacity than DB. Similar behaviour was also observed in the case of the linear Henry’s Law isotherm. The adsorption of the herbicides on both DB and DS decreased in the order of 2,4‐DB > 2,4,5‐T > 2,4‐DP > 2,4‐D > MCPA.     

Treatment of a Trifluraline Effluent by Means of Oxidation‐Coagulation with Fe(VI) and Combined Fenton Processes

The amination water (AW) effluent stream from the industrial production of the trifluraline herbicide was submitted to an oxidation‐coagulation treatment with potassium ferrate, combined with advanced oxidation processes. The experimental results obtained by analysis of variance (ANOVA) for the oxidation‐coagulation‐Fenton process, evaluating the variables pH (A), Fe(VI) concentration (B), and H₂O₂ concentration (C), demonstrated that the regression equation resulting from the Response Surface Methodology (RSM) experimental design, for the quadratic model, was η_Abs (%) = 36.9– 21.58A + 8.37A² + 1.36B + 0.92B² + 1.08C + 1.52C² + 1.27AB – 1.34AC + 1.33BC. The maximum absorptiometric color reduction occurred at pH 3, with corresponding maximum amounts of iron and hydrogen peroxide. The absorptiometric color and COD reduction were 96% and 57%, respectively. For the oxidation‐coagulation‐photo‐Fenton process, the analyzed variables were pH (A), Fe(VI) concentration (B), H₂O₂ concentration (C), and temperature (D). The regression equation resulting from the quadratic model was η_Abs (%) = 38.3 – 20.2A + 8.12A² – 0.27B + 3.73B² + 0.3C + 3.6C² + 1.67D + 3.1D² + 1.72AB + 0.51AC – 1.82AD + 0.74BC – 1.11BD + 0.03CD. The ANOVA response showed that the highest absorptiometric color reduction occurred at pH 3, with respective maximum amounts of iron and hydrogen peroxide at 60°C. The maximum efficiencies achieved by the proposed treatment process for the trifluraline effluent stream were 95% and 85%, for absorptiometric color and COD reduction, respectively.     

Degradation of Monoazo Pigments Red 53:1 and Red 48:2 by Fenton,Photo‐Fenton and UV/Peroxide Reactions

The degradation reactions of two monoazo pigments, namely, Red 53:1 and Red 48:2, by Fenton, photo‐Fenton and UV/H₂O₂ systems have been studied. The efficiencies of the Fenton reactions increased with temperature, but the formation of solid agglomerates was observed when the reactions were carried out above 50°C indicating a coagulant action of Fe⁺² or Fe⁺³. Photo‐Fenton reactions irradiated by sunlight presented the best rate constants for cleavage of the azo bond and the naphthalene rings. The UV/H₂O₂ system exhibited the highest efficiency with respect to the consumption of H₂O₂. The presence of a carbonyl group in the ortho position of the naphthol ring hampered the oxidation of pigment Red 48:2 by hydroxyl radicals. This finding may be explained in terms of the acceptor character of the COOH group, and suggests the formation of a complex containing two six‐membered rings between Fe⁺³ and the pigment molecule.     

Optimization of a Photo‐assisted Fenton Oxidation Process: A Statistical Model for MDF Effluent Treatment

In the present study, the effects of initial COD (chemical oxygen demand), initial pH, Fe²⁺/H₂O₂ molar ratio and UV contact time on COD removal from medium density fiberboard (MDF) wastewater using photo‐assisted Fenton oxidation treatment were investigated. In order to optimize the removal efficiency, batch operations were carried out. The influence of the aforementioned parameters on COD removal efficiency was studied using response surface methodology (RSM). The optimal conditions for maximum COD removal efficiency from MDF wastewater under experimental conditions were obtained at initial COD of 4000 mg/L, Fe²⁺/H₂O₂ molar ratio of 0.11, initial solution pH of 6.5 and UV contact time of 70 min. The obtained results for maximum COD removal efficiency of 96% revealed that photo‐assisted Fenton oxidation is very effective for treating MDF wastewater.     

AMSR‐E algorithm for snowmelt onset detection in sub‐arctic heterogeneous terrain

The onset of snowmelt in the upper Yukon River basin, Canada, can be derived from brightness temperatures (T_b) obtained by the Advanced Microwave Scanning Radiometer for EOS (AMSR‐E) on NASA's Aqua satellite. This sensor, with a resolution of 14 × 8 km² for the 36·5 GHz frequency, and two to four observations per day, improves upon the twice‐daily coverage and 37 × 28 km² spatial resolution of the Special Sensor Microwave Imager (SSM/I). The onset of melt within a snowpack causes an increase in the average daily 36·5 GHz vertically polarized T_b as well as a shift to high diurnal amplitude variations (DAV) as the snow melts during the day and re‐freezes at night. The higher temporal and spatial resolution makes AMSR‐E more sensitive to sub‐daily T_b oscillations, resulting in DAV that often show a greater daily range compared to SSM/I. Therefore, thresholds of T_b > 246 K and DAV > ± 10 K developed for use with SSM/I have been adjusted for detecting the onset of snowmelt with AMSR‐E using ground‐based surface temperature and snowpack wetness relationships. Using newly developed thresholds of T_b > 252 K and DAV > ± 18 K, AMSR‐E derived snowmelt onset correlates well with SSM/I observations in the small subarctic Wheaton River basin through the 2004 and 2005 winter/spring transition. In addition, the onset of snowmelt derived from AMSR‐E data gridded at a higher resolution than the SSM/I data indicates that finer‐scale differences in elevation and land cover affect the onset of snowmelt and are detectable with the AMSR‐E sensor. On the basis of these observations, the enhanced resolution of AMSR‐E is more effective than SSM/I at delineating spatial and temporal snowmelt dynamics in the heterogeneous terrain of the upper Yukon River basin. Copyright © 2007 John Wiley & Sons, Ltd.     

Mineralization of Catechol by Fenton and Photo‐Fenton Processes

Catechol is one of the most abundant phenolic components of olive mill wastewaters. In this article, the mineralization of this compound in synthetic aqueous solutions by the Fenton and photo‐Fenton processes is studied. It has been found that for 1.44 mM catechol, the total organic carbon of solutions is reduced about 94.4% at best after 60 min of Fenton treatment at optimized conditions of pH 3.0, 0.2 mM Fe²⁺, 7.09 mM H₂O₂, and 25°C. A faster and overall mineralization is attained by applying photo‐Fenton with UVA irradiation. o‐Benzoquinone, 1,2,3‐trihydroxybenzene and 1,2,4‐trihydroxybenzene were identified by GC–MS as primary quinonic and polyhydroxylated derivatives. Small amounts of generated carboxylic acids like muconic, maleic, malonic, acetic, oxalic, and formic acids were detected by ion‐exclusion chromatography. The Fe(III) complexes of these acids persist in the medium under Fenton conditions, while their photolysis by UVA light and that of other by‐products account for by the faster degradation and total mineralization achieved in the photo‐Fenton process. A reaction sequence for catechol mineralization by Fenton and photo‐Fenton involving all intermediates detected is proposed.     

Effects of Fenton Pre‐Treatment on Waste Activated Sludge Properties

Fenton process was investigated for the purpose of biological sludge disintegration. The Box–Wilson experimental design was employed to evaluate the effects of major process variables (Fe(II) and H₂O₂ concentrations) on both disintegration and dewatering performance of sludge. Results showed that 4 g Fe(II)/kg total solids (TSs) and 60 g H₂O₂/kg TS are efficient for floc disintegration. Fenton pre‐treatment enhanced the biodegradability of sludge. For 4 g Fe(II)/kg TS and 60 g H₂O₂/kg TS, 19.4% higher methane production was achieved compared to raw sludge in biochemical methane potential assay. Fenton pre‐treatment resulted in the release of organic sludge components into the liquid phase. For 4 g Fe(II)/kg TS and 60 g H₂O₂/kg TS, dissolved organic carbon and total nitrogen in sludge's supernatant increased by 75.74 and 60.60%, respectively. Fenton pre‐treatment enhanced the filterability of sludge and it can be applied for conditioning purpose before mechanical dewatering units.     

Synthesis and Characterization of Poly(2‐hydroxyethylmethacrylate‐hydroxyapatite) a Novel Composite for the Removal of Lead(II) from Aqueous Solutions

In the present study, a novel adsorbent, poly (2‐hydroxyethylmethacrylate‐hydroxyapatite) [P(HEMA‐Hap)], was prepared and characterized. The synthesis was achieved by means of free‐radical polymerization and a number of structural characterization methods, including FT‐IR, XRD, TGA, SEM, BET‐porosity, and swelling tests. Pb²⁺ adsorption was performed using a series of pH, time, and temperature ranges. The reusability of the composite was also tested. The results obtained indicated that the novel adsorbent is able to bind Pb²⁺ ions with strong chemical affinity. The adsorption results were fitted to the classic Langmuir, Freundlich, and Dubinin–Radushkevich (D–R) sorption models. Thermodynamic parameters obtained demonstrated that the sorption process was spontaneous (ΔG < 0), endothermic (ΔH > 0), as expected. The process was also consistent with the pseudo‐second‐order model, and chemical adsorption was determined to be the rate‐controlling step. It was also shown that the composite could be used for five consecutive adsorption processes.     

Efficiency of Pleurotus florida Laccase on Decolorization and Detoxification of the Reactive Dye Remazol Brilliant Blue R (RBBR) under Optimized Conditions

Laccase from the white‐rot fungus Pleurotus florida, produced under solid‐state fermentation conditions, was used for the decolorization of reactive dye Remazol Brilliant Blue R (RBBR). RBBR was decolorized up to 46% by P. florida laccase alone in 10 min. In the presence of N‐hydroxybenzotriazole (HBT), the rate of decolorization was enhanced 1.56‐fold. Central composite design of response surface methodology with four variables namely, dye, enzyme, redox mediator concentrations, and time at five levels was applied to optimize the RBBR decolorization. The predicted optimum level of variables for maximum RBBR decolorization (87%) was found to be 52.90 mg L^?1 (RBBR), 1.87 U mL^?1 (laccase), 0.85 mM (HBT), and 7.17 min (time), respectively. The validation results showed that the experimental value of RBBR decolorization (82%) was close to the predicted one. The disappearance of C–N and C–X groups, and a small shift in N–H groups in Fourier‐transform infra red (FTIR) spectroscopy confirms the degradation of RBBR chromophore by laccase enzyme. The phytotoxicity of RBBR was considerably reduced after the treatment with laccase. RBBR decolorization kinetics; K_m and V_max were calculated to be 145.82 mg L^?1 and 24.86 mg L^?1 min, respectively.     

Treatability of Dye Solutions Containing Disperse Dyes by Fenton and Fenton‐Solar Light Oxidation Processes

This study attempts to explore the possibility of treating dye solutions containing Disperse Yellow 119 and Disperse Red 167 by Fenton and Fenton under solar‐light oxidation processes. Experiments were conducted to examine the effects of various operating conditions on the performance of the treatment systems. The Fenton results showed that 98.6% spectral absorption coefficient (SAC) and 90.8% chemical oxygen demand (COD) removals were proved at pH 3, 50 mg/L Fe²⁺, and 75 mg/L H₂O₂, 15 min oxidation time for Disperse Yellow 119. After 40 min solar irradiation time during Fenton process the SAC removal was 99.1%. COD reduction of about 98.3% was observed at the same time. It was also obtained as 97.8% SAC and 97.7% COD removal with pH 3, 75 mg/L Fe²⁺, 100 mg/L H₂O₂, and 25 min oxidation time for Disperse Red 167 at this optimum conditions. For Disperse Red 167 during Fenton under solar light process, after 40 min of solar irradiation time the SAC and COD reduction were obtained 99.3 and 98.4%, respectively.     

High‐frequency storm event isotope sampling reveals time‐variant transit time distributions and influence of diurnal cycles

High‐frequency sampling of stable water isotopes in precipitation and stream water during winter and summer storm events was carried out in a 2·3 km² lowland agricultural catchment. During peak flows of monitored events, the responses of δ²H and δ¹⁸O were comparable and inferred the dominance (ca 70%) of ‘old’ pre‐event water. Transit Time Distribution (TTD) inferred by a gamma function were fitted (Nash–Sutcliffe = 0·8) and were also similar for δ²H and δ¹⁸O. However, the shape (α) and scaling (β) parameters were markedly different for summer and winter events. Consequently, when antecedent wetness was high, mean transit times were in the order of days; when drier, they increased to months. Moreover, while the responses of δ²H and δ¹⁸O exhibited similar gradual recovery to pre‐event conditions during winter hydrograph recessions, they differed dramatically on summer recessions. Time series analysis showed that δ²H isotope content was correlated with the diurnal cycle of air temperature, suggesting an evaporative fractionation pattern which could be reproduced by a temperature‐based first‐order autoregressive model. The heavier δ¹⁸O isotope showed no evidence for such diurnal variability. The study highlights the utility of high‐frequency stable isotope sampling to explore the time‐variant nature of TTDs. Furthermore, it shows that the time of sampling in a diurnal cycle may have crucial significance for interpreting stream isotope signatures, particularly δ²H. Copyright © 2011 John Wiley & Sons, Ltd.