ENVIRONMENTAL ENGINEERING SCIENCE Volume 25, Number 10, 2008 Mary Ann Liebert, Inc. DOI: 10.1089/ees.2007.

0218

Advanced Oxidation of Direct Red (DR 28) by Fenton Treatment

Filiz Ay, Ebru Cokay Catalkaya, Fikret Kargi*
Department of Environmental Engineering, Dokuz Eylul University, Buca, Izmir, Turkey. Received: August 13, 2007 Accepted in revised form: January 29, 2008

Abstract

Advanced oxidation of Direct Red 28 (DR 28) in aqueous solution by Fentons reagent using FeSO4 as source of Fe (II) was investigated. Effects of the dyestuff and the reagent concentrations (H2O2 and Fe (II)) on oxidation of the azo dye were investigated by using a Box-Behnken statistical experiment design and the surface response analysis. Degradation and mineralization (conversion to CO2 and H2O) of the azo dye by Fenton treatment was evaluated following total organic carbon (TOC) and color removal. Dyestuff removal increased with increasing H2O2 and Fe (II) concentrations up to a certain level. Fe (II) had a more profound effect on dyestuff removal as compared to H2O2. Complete color removal (100%) was achieved in 5 minutes. However, mineralization of the dyestuff took 15 minutes and required higher doses of H2O2. Percent color removal was always higher than TOC removal indicating formation of colorless organic intermediates. Optimal H2O2/Fe (II)/dyestuff ratio resulting in the maximum TOC (99.2%) and color (100%) removals was found to be 1450/78/235(mg L1). Key words: advanced oxidation; Box-Behnken design; Direct Red 28; Fenton treatment; reagent concentrations

Introduction

and dye industries are highly colored with significant amounts of auxiliary chemicals. Direct discharge of textile effluents introduces intensive color and toxicity to aquatic environments, causing serious environmental problems (Pierce, 1994). The azo dyes, characterized by having an azo group consisting of two nitrogen atoms (NN), are the largest class of dyes used in the textile industry. Different types of azo dyes were reported in literature such as direct, acidic, basic, reactive, disperse, metal complexed, mordant, and sulfur dyes (Yang and Xu, 1996). The azo dyes are usually the most problematic pollutants of textile effluents since more than 15% of the textile dyes end up in the effluents during dyeing operation (Park and Choi, 2003). Due to the complex aromatic structure and stability of these dyes, conventional biological treatment methods are not very effective for degradation (Dai et al., 1995). A number of physical, chemical, and biological methods and their combinations were reported in literature for the treatment of textile effluents (Kapdan and Kargi, 2002a,b; Kargi and Ozmihci, 2005, 2006). Among these methods, the advanced
FFLUENTS OF TEXTILE

*Corresponding author: Department of Environmental Engineering, Dokuz Eylul University, Buca, Izmir, Turkey. Phone: 90 2324127109; Fax: 90 2324531143; E-mail: fikret.kargi@deu.edu.tr

oxidation processes are more effective and capable of mineralizing a wide range of organic pollutants. Fenton reagent was used for degradation of refractory organic contaminants such as chlorophenols (Barbeni et al., 1987; Potter and Roth, 1993), chlorobenzene (Sedlak and Andren, 1991), nitrophenols (Kang et al., 1999), and dyestuffs (Kuo, 1992; Solozhenko et al., 1995). Fenton treatment was reported to completely decolorize the textile industry dyes in rather short reaction times (Meric et al., 2004; Neamtu et al., 2001). The oxidation power of Fenton reagent is due to the generation of hydroxyl radical (OH) during the iron catalyzed decomposition of hydrogen peroxide in acid medium. The hydroxyl radicals with high oxidation potential (2.8 V) completely destroys the pollutants in Fenton treatment. The degradation of pollutants can be considerably improved by using UV radiation due to the generation of additional hydroxyl radicals. The photo-Fenton treatment was also used for degradation of pollutants (Kang et al., 2000; Pignatello, 1992). For economic and effective color and TOC removals by the Fenton and photo-Fenton treatment the optimal doses of the reagents need to be determined. Most of the literature studies on Fenton ragent treatment of dyestuffs report decolorization efficiencies, but not TOC removal or mineralization. Therefore, the major objective of this study is to investigate the effects of reagent concentrations and to determine the optimal levels maximizing the color and TOC removals (mineralization) by the Fenton treatment of Direct Red 28 containing aqueous solution. The effects of initial

1455

1456 TABLE 1. CHARACTERISTICS

OF

AY ET AL. DIRECT RED (DR 28) AZO DYE Direct Red 28 Color index num. Synonyms Molecular Formula 22120 Kongo Red C32H24N6O6S2

Mol. Weight (g mol 696.671) max (nm) Purity (%)

497 85%

dyestuff, Fe (II) and H2O2 concentrations on oxidation of the dyestuff (DR 28) were investigated by using a Box-Behnken statistical experiment design and surface response methodology. Optimal values of the operating parameters maximizing TOC (mineralization) and color (degradation) removals were determined. Design of Experiments The classical approach of changing one variable at a time to study the effects of variables on the response is a timeconsuming method particularly for multivariable systems and also when more than one response is considered. Statistical design of experiments reduces the number of experiments to be performed, considers interactions among the variables, and can be used for optimization of the operating parameters in multivariable systems. Response surface methodology (RSM) is used when only several significant factors are involved in optimization. Different types of RSM designs include 3-level factorial design, central composite design (CCD) (Box and Wilson, 1951; Boza et al., 2000), BoxBehnken design (Singh et al., 1995), and D-optimal design (Sanchez-Lafuente et al., 2002). A modified central composite experimental design known as the Box-Behnken design is an independent, rotatable quadratic design with no embedded factorial or fractional factorial points where the variable combinations are at the midpoints of the edges of the variable space and at the center. Among all the RSM designs, the Box-Behnken design requires fewer runs than the others (e.g, 15 runs for a 3-factor experimental design). By careful design and analysis of experiments, the Box-Behnken design allows calculations of the response function at intermediate levels which were not experimentally studied and enables estimation of the system TABLE 2.

performance at any experimental point with different combinations of the variables (Hamed and Sakr, 2001). Materials and Methods Chemicals The azo dye (Direct red 28, DR 28) was used in the experimental studies since it is a widely used textile dyestuff in the Turkish textile industry and also is more resistant to degradation as compared to the other azo dyes. Direct Red 28 (Congo red) is the sodium salt of benzidinediazo-bis-1naphtylamine-4-sulfonic acid (formula: C32H22N6Na2O6S2; molecular weight: 696.66 g mol21) and is a secondary diazo dye. Congo red is water-soluble salt, yielding a red colloidal solution; its solubility is better in organic solvents such as ethanol. Characteristics of the DR 28 are presented in Table 1. Ferrous (FeSO4 7H2O), used as source of Fe (II), was analytical grade and purchased from Merck Co. (Germany). Hydrogen peroxide solution (30%, w w1) in stable form, H2SO4 (98%), and NaOH were all provided from Merck (Germany). Concentrated stock solution of Fe (II) (5000 mg L1) was prepared for further dilution to obtain solutions of desired concentrations. Fe (II) stock solution was stored in the dark to prevent oxidation of Fe (II). The pH of aqueous solutions was adjusted using either sodium hydroxide or sulfuric acid. All other chemicals were of analytical grade and used without any previous purification. Water for chemical solutions was purified using a Mili-Q system (milipore filtration). Experimental system A jar test apparatus consisting of four beakers of 2 liters each were used as the experimental system. The beakers

BOX-BEHNKEN STATISTICAL EXPERIMENT DESIGN VARIABLES Coded variable level Low Center 0 130 1050 50 High 1 250 2000 100

Variable Dye dose (mg L1) Hydrogen peroxide dose H2O2, (mg L1) Ferrous ion dose Fe (II), (mg L1)

Symbol X1 X2 X3

1 10 100 0

ADVANCED OXIDATION OF DIRECT RED BY FENTON TREATMENT TABLE 3. BOX-BEHNKEN EXPERIMENTAL RESULTS
AT

1457

PRE-DETERMINED EXPERIMENTAL POINTS Experimental percent removals Color 99.14 92.00 86.99 92.40 55.86 11.60 90.32 99.13 20.35 28.81 99.52 98.57 99.00 99.37 99.00 TOC 58.41 65.00 37.26 71.02 12.50 2.46 37.43 94.74 15.40 12.01 75.00 70.00 86.74 93.88 91.52

Actual and coded levels of variables Run No 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 X1 Dye, (mg L1) 1 1 1 1 1 1 1 1 0 0 0 0 0 0 0 (10) (250) (10) (250) (10) (250) (10) (250) (130) (130) (130) (130) (130) (130) (130) X2 H2O2, (mg L1) 1 1 1 1 0 0 0 0 1 1 1 1 0 0 0 (100) (100) (2000) (2000) (1050) (1050) (1050) (1050) (100) (2000) (100) (2000) (1050) (1050) (1050) X3 Fe (II), (mg L1) 0 0 0 0 1 1 1 1 1 1 1 1 0 0 0 (50) (50) (50) (50) (0) (0) (100) (100) (0) (0) (100) (100) (50) (50) (50)

were filled with 1 liter of the dyestuff solution and were mechanically mixed at 150 rpm using mixing motors and blades. The beakers were open to the atmosphere at room temperature (2325C). The Fe (II) and H2O2 solutions were added to the dyestuff solution at the beginning of the batch experiments in desired concentrations. Analytical methods Fentons reagent experiments were carried out at room temperature (2325C) using different dyestuff (DR 28), hydrogen peroxide, and ferrous ion doses at pH 3 which is the most suitable pH for Fenton treatment (Hsueh et al., 2005; Kim et al., 2004; Lin and Peng, 1995). Temperature changes during reactions were negligible. Predetermined amounts of oxidants (H2O2 and Fe (II)) were injected into the agitated reactors (150 rpm) containing dye solution at the beginning of each experiment. The iron salt was mixed well with aqueous dye solution before the addition of hydrogen peroxide solution. Samples withdrawn from the reactor at certain time intervals were analyzed immediately to avoid further reactions. Samples (10 ml) of raw and treated dyestuff solutions were analyzed for color and TOC contents after centrifugation at 8000 rpm. pH and conductivity levels were also recorded. A pH meter (WTW Scientific, Germany) was used to monitor pH. A spectrophotometer of Novaspec II (Pharmacia Biotech.) was used to measure the absorbance. Absorbance measurements were performed at 497 nm, the maximum of absorbance of DR 28. A DOHRMAN DC 190 TOC Analyzer (USA) was used to determine the total organic carbon (TOC) content of the samples. For the TOC measurements, potassium phthalate solution was used as calibration standards with the concentrations between 0 and 25 mg L1. Results and Discussion Box-Behnken statistical experiment design and the response surface methodology (RSM) (Charles and Kennneth,

1999) were used to investigate the effects of the three independent variables on the response function and to determine the optimal conditions maximizing the percent removals of dyestuff and TOC. The optimization procedure involves studying the response of the statistically designed combinations, estimating the coefficients by fitting the experimental data to the response functions, predicting the response of the fitted model, and checking the adequacy of the model. The independent variables were the dose of dyestuff (X1), hydrogen peroxide (X2), and ferrous ion (X3). The low, center, and high levels of each variable are designated as 1, 0, and 1, respectively, as shown in Table 2. Initial pH was kept constant at pH 3, which varied slightly between 3 and 3.5

TABLE 4. OBSERVED AND PREDICTED PERCENT REMOVALS FOR RESPONSE FUNCTIONS Predicted percent removals (%) Run No 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 Y1 Color 100.00 85.38 93.61 90.59 48.28 12.45 89.47 100.00 26.12 29.77 98.56 92.79 99.12 99.12 99.12 Y2 TOC 55.84 63.30 43.78 76.60 8.19 0.00 40.80 99.05 25.28 9.80 75.37 66.10 90.71 90.71 90.71 Observed percent removals (%) Y1 Color 99.14 92.00 86.99 92.40 55.86 11.60 90.32 99.13 20.35 28.81 99.52 98.57 99.00 99.37 99.00 Y2 TOC 58.41 65.00 37.26 71.02 12.50 2.46 37.43 94.74 15.40 12.01 75.00 70.00 86.74 93.88 91.52

1458 TABLE 5. Source Model X1 (Dye) X2 (H2O2) X3 (Fe (II)) X1X2 X1X3 X2X3 X12 X22 X32 Residual Lack of Fit Pure Error Total (corr) ANOVA TEST Sum of squares 14116.98 172.79 2.25 9174.71 39.38 704.11 22.14 15.33 73.21 3986.37 279.31 279.22 0.091 14396.29
FOR

AY ET AL. RESPONSE FUNCTION Y1 (% COLOR REMOVAL) Df 9 1 1 1 1 1 1 1 1 1 5 3 2 14 Mean Square 1568.55 172.79 2.25 9174.71 39.38 704.11 22.14 15.33 73.21 3986.37 55.86 93.07 0.046 F ratio 28.08 3.09 0.040 164.24 0.70 12.60 0.40 0.27 1.31 71.36 2039.58 P value 0.0009 0.1389 0.8489 0.0001 0.4394 0.0164 0.5567 0.6227 0.3041 0.0004 0.0005

R-squared 0.9806; R-squared (adjusted for df) 0.9457; standard error of estimate 7.47.

during the reaction period. Preliminary experiments at pH 3, 4, and 5 resulted in insignificant differences (13%) in percent dyestuff removal by the Fenton reagent. For this reason pH was not considered as a variable, but kept constant at pH 3 in all experiments since this was the recommended pH for Fenton reagent treatment (Hsueh et al., 2005; Kim et al., 2004; Lin and Peng, 1995). The dependent variables (or objective functions) were the percent color (Y1) and TOC (Y2) removals. The values of the independent variables and the experimental results at each experimental point are presented in Table 3. The center point (0, 0, 0) was repeated three times and nearly the same results were obtained, indicating the reproducibility of the data. Observed and predicted values of percent color and TOC removals are compared in Table 4. The regression model The application of RSM offers an empirical relationship between the response function and the independent variables. The mathematical relationship between the response

function (Y) and the independent variables (X) can be approximated by a quadratic polynomial equation, as follows: Y b0 b1X1 b2X2 b3X 3 b12X1X2 b13X1X3 b23 X2X3 b11X12 b22X22 b33X32 (1)

The coefficients of the response functions for different dependent variables were determined correlating the experimental data with the response functions by using a Stat-Ease regression program. Different response functions with the determined coefficients are presented by Equations (2) and (3). The results of analysis of variance (ANOVA) are also presented in Tables 5 and 6, indicating the fact that that the predictability of the model is at a 95% confidence interval. Response function predictions were in good agreement with the experimental data, with a coefficient of determination (R2) of larger than 0.97. Furthermore, the computed F value was much greater than that of the tabular F0.01 (14, 14) value of 3.70, suggesting that the treatment was highly significant. P values of less than 0.05 for any factor in the ANOVA test

TABLE 6. Source Model X1 (Dye) X2 (H2O2) X3 (Fe (II)) X1X2 X1X3 X2X3 X12 X22 X32 Total error Lack of Fit Pure Error Total (corr)

ANOVA TEST Sum of squares 15582.55 885.99 21.75 7302.36 184.55 1252.45 35.64 1174.53 825.84 4584.78 89.40 62.94 26.47 15671.95

FOR THE

RESPONSE FUNCTION Y2 (% TOC REMOVAL) Mean Square 1731.39 885.99 21.75 7302.36 184.55 1252.45 35.64 1174.53 825.84 4584.78 17.88 20.98 13.23 F ratio 96.83 49.55 1.22 408.39 10.32 70.04 1.99 65.69 46.19 256.41 1.59 P value 0.0001 0.009 0.3203 0.0001 0.0237 0.0004 0.2171 0.0005 0.0011 0.0001 0.4093

Df 9 1 1 1 1 1 1 1 1 1 5 3 2 14

R-squared 0.9943; R-squared (adjusted for df) 0.9840; standard error of estimate 4.23.

ADVANCED OXIDATION OF DIRECT RED BY FENTON TREATMENT indicated a significant effect of the corresponding variable on the response. Y1 45.72 0.14 X1 8.7 103 X2 1.75 X3 X2 X3 1.41 104 X12 4.93 106 X22 0.013 X32
Color Removal (%) 100 10 50 60 100 150 40 200 250 20 H2O2 1000 mg L1 Dye

1459

80

2.75 105 X1 X2 2.21 103 X1X3 4.95 105 (2)

Y2 0.486 0.2 X1 0.028 X2 1.70 X3 5.96 105 X1X2 2.95 103 X1X3 6.284 105 X2X3 1.238 103 X12 1.657 105 X22 0.014 X32 (3)

From the response function coefficients it can be said that the dyestuff concentration adversely affects percent color removal and Fe (II) concentration has more profound effect on color removal as compared to the H2O2 dose. TOC removal increases with dyestuff concentration and is also more profoundly affected from the Fe (II) doses as compared to H2O2. Color removal: Degradation of dyestuff Response functions with determined coefficients were used to estimate variations of response functions with the independent variables under different conditions. Figure 1 shows the effect of initial H2O2 concentration on percent color removal at different dyestuff concentrations after 5 minutes of reaction time when Fe (II) was 30 mg L1. Percent color (dyestuff) removal increased with increasing initial hydrogen peroxide concentration at all dyestuff concentrations. However, color removals decreased with increasing H2O2 concentrations above 1000 mg L1 at dyestuff concentrations below 200 mg L1 due to hydroxyl radical scavenging effect of high peroxide doses. Previous studies have reported that increases in H2O2 concentration improved the degradation of organic compounds in Fenton reactions up to a certain limit due to additional HO formation (Emilio et al., 2002; Nogueira and Guimaraes, 2000). However, adverse effects were also observed when excess concentrations of H2O2 were present (Ghaly et al., 2001; Torrades et al., 2003). The accepted explanation is the scavenging of HO by H2O2

0 0 20 40 60 80 Ferrous Ion Concentration (mg L1) 100

FIG. 2. Influence of Fe (II) concentration on DR 28 decolorization efficiency using different dye concentrations at constant peroxide dose of 1000 mg L1. and consequent formation of the less reactive radical HO2, as presented by the following equations: OH H2O2 H2O HO2 OH HO2 H2O O2 (4) (5)

90 50
Color Removal (%)

10 100 150 Dye

80

70

200 250

60

Fe () 30 mg L1

50 0 1000 1500 500 Hydrogen Peroxide Concentration (mg L1) 2000

FIG. 1. Influence of H2O2 concentration on DR 28 decolorization efficiency using different dye concentrations at constant Fe (II) dose of 30 mg L1.

At a dyestuff dose of 10 mg L1, the optimal H2O2/ Fe (II)/dyestuff ratio yielding the highest color removal (100%) was 545/50/10 mg L1, while at a high dyestuff dose of 250 mg L1 this ratio was 655/65/250 mg L1 yielding 100% color removal. Complete color (dyestuff) removal at high dyestuff concentrations requires high H2O2 and Fe (II) doses. Effects of Fe (II) and dyestuff concentrations on percent color removal by the Fenton treatments are depicted in Fig. 2 at a H2O2 concentration of 1000 mg L1. Percent color removal increased with increasing Fe (II) concentrations at all dyestuff concentrations up to 60 mg L1 and leveled off for Fe (II) concentrations between 60 and 100 mg L1. Further increases in Fe (II) concentrations above 60 mg L1 resulted in insignificant changes in percent color removal, especially for dyestuff doses below 100 mg L1, probably due to adverse effects of high Fe (II) doses. Optimal Fe (II) concentration was nearly 50 mg L1 for dyestuff concentrations below 100 mg L1 and 60 mg L1 for dyestuff doses above 100 mg L1. Percent color removals were 32.3, 99.0, and 100% with an initial dyestuff dose of 130 mg L1 and Fe (II) doses of 0, 50, and 100 mg L1, respectively, at a H2O2 dose of 1000 mg L1 indicating the fact that Fe (II) doses of above 50 mg L1 did not improve the extent of color removal under the specified conditions. From the comparison of Figs. 1 and 2, it can be said that Fe (II) doses had more profound effects on percent color removal as compared to H2O2. These results are in agreement with the literature reports, where a beneficial effect of increasing Fe (II) was observed in degradation of dyestuffs (Lodha and Chaudhari, 2007). However, high iron concentrations can also adversely affect dyestuff oxidation by scavenging OH. Strict pH control is required to avoid precipitation of iron hydroxides which hinders penetration of light and therefore reduces the rate of degradation (Nogueira and Guimaraes, 2000). Complete removal of color was accomplished at a hydrogen peroxide

1460 dose of 450 mg L1 and Fe (II) concentrations above 60 mg L1 after 5 minutes reaction time when the dyestuff dose was 250 mg L1. Fe (II) doses lower than 60 mg L1 did not result in complete dyestuff degradation at high dyestuff concentrations. Apparently the use of high oxidant (H2O2) and catalyst (Fe(II)) doses inhibited the removal of color for low dyestuff concentrations due to formation of hydroxyl radical scavengers. The ANOVA analysis indicated that all three variables dyestuff, H2O2 and Fe (II) doses and the interactions (X3, X1, X3, X3) were significant and played important roles in decolorization by the Fenton treatment. Total organic carbon (TOC) removal: Mineralization of dyestuff Decolorization of the dyestuff does not always result in complete mineralization to CO2 and H2O. In some cases, colorless reaction intermediates may be formed during the degradation of dyestuffs. The colorless reaction intermediates may be more toxic than the parent compounds. Therefore, it is important to know the degree of mineralization or total organic carbon (TOC) removal during decolorization of azo dyes by the Fenton treatment. In our study, complete mineralization of the dyestuff was achieved after 15 minutes of reaction time while decolorization was realized in 5 minutes. This difference indicated formation of some colorless intermediates during the oxidation reaction, which required 15 minutes for complete mineralization. The difference between percent color and TOC removals is a measure of formation of colorless organic intermediates which contribute to TOC, but not color measurements. The reaction scheme can be summarized as follows: Dyestuff H2O2 Fe (II) l colorless intermediates nitrate sulfate l CO2 H2O (6) The first reaction is for color removal and the second is for TOC removal or mineralization. In decolorization reactions, azo groups were removed from the dyestuff and some colorless organic intermediates were formed which were par100 150 80 TOC Removal (%) 200 Dye

AY ET AL.

100 50

60

10

40 250 20 H2O2 1000 mg L1

0 0 20 40 60 80 Ferrous Ion Concentration (mg L1) 100

FIG. 4. Influence of Fe (II) concentration on TOC removal efficiency using different dye concentrations at constant peroxide dose of 1000 mg L1.

100

150 Dye 100

200

250 80 50

60 Fe () 60 mg L1 40 0

10

1000 1500 500 Hydrogen Peroxide Concentration (mg L1)

2000

FIG. 3. Influence of H2O2 concentration on TOC removal efficiency using different dye concentrations at constant Fe (II) dose of 60 mg L1.

tially degraded further to CO2 and H2O for mineralization or TOC removal. Figure 3 depicts variation of percent TOC removal (mineralization) with H2O2 doses at different dyestuff concentrations (10250 mg L1) at a constant Fe (II) dose of 60 mg L1. Percent TOC removal increased with H2O2 doses up to 1000 mg L1, indicating limitations by H2O2 concentration at low peroxide doses. Further increases in H2O2 doses resulted in decreases in TOC removal due to hydroxyl radical scavenging effect of high H2O2 doses. Percent TOC removal or mineralization steadily increased with increasing dyestuff concentrations up to 200 mg L1. The reason for this is low levels of colorless intermediate formation at high dyestuff doses and high degree of mineralization at low intermediate (or high dyestuff) concentrations. Decrease in percent TOC removal for dyestuff concentrations above 200 mg L1 is due to limitations by the peroxide and Fe (II) doses which were probably below the required levels. The optimal H2O2/Fe/dystuff ratio yielding the highest TOC removal (99%) was 1000/60/200 mg L1. Initial dyestuff concentration was one of the most important parameters affecting the percent TOC removal by the Fenton treatment. Figure 4 depicts variations of percent TOC removal with Fe (II) concentration at different dyestuff doses and constant H2O2 dose of 1000 mg L1. TOC removal was profoundly affected by the Fe (II) concentration, as seen by the high coefficient of Fe (II) dose (X3) in Equation (3). Percent mineralization (TOC removal) increased with increasing Fe (II) doses up to nearly 60 mg L1 due to limitations by the Fe (II) ions at low doses and then decreased with further increases in Fe (II) due to radical scavenging effects of high Fe (II) doses. The optimal Fe (II) dose yielding the highest TOC removal was nearly 60 mg L1 under the specified experimental conditions. Percent TOC removal increased with increasing dyestuff concentrations up to 200 mg L1 and decreased with further increases in dyestuff doses. High TOC removals at high dyestuff doses is due to low levels of colorless intermediate formation yielding high mineralization efficiencies as described by Equation (6). When dyestuff concentration was 130 mg L1, percent TOC removals were

TOC Removal (%)

ADVANCED OXIDATION OF DIRECT RED BY FENTON TREATMENT TABLE 7. Response Color removal: Dye Degradation TOC removal: Mineralization OPTIMUM LEVELS
OF THE

1461 TOC REMOVALS

BY THE

VARIABLES MAXIMIZING Dyestuff (X1) mg L1 235 235

THE

COLOR

AND

FENTON TREATMENT Efficiency (Y) % 100.0 95.6

H2O2 (X2) mg L1 340 1720

Fe (II) (X3) mg L1 65 80

25.5, 95.4, and 85.9%, respectively, at Fe (II) doses of 0, 60, and 100 mg L1 at a hydrogen peroxide dose of 1000 mg L1, yielding optimal a Fe (II) dose of 60 mg L1 under the specified conditions. At a dyestuff dose of 10 mg L1, the optimal H2O2/Fe(II)/dyestuff ratio yielding the highest TOC removal (65%) was 740/60/10 mg L1, while at a high dyestuff dose of 250 mg L1 this ratio was 1125/85/250 mg L1, yielding 100% TOC removal. High H2O2 and Fe (II) doses should be used at high dyestuff concentrations for complete mineralization. The ANOVA analysis indicated that all three variables dyestuff, H2O2 and Fe (II) doses and independent variable interactions (X1, X3, X2X3, X12, X12, X32) played important roles for the mineralization of dye or TOC removal. In general, decolorization (dyestuff removal) took place faster (5 minutes) and required lower H2O2 and Fe (II) doses since functional groups on the dyestuff were removed more easily as compared to TOC removal (mineralization). Apparently, some colorless soluble organic intermediates were formed during Fenton treatment, which contributed to TOC content of the final solution. TOC removal or mineralization was realized when the colorless intermediates were degraded to CO2 and H2O, as described by the second reaction in Equation (6). Color removal at high dyestuff concentrations was low, yielding low colorless intermediate formations resulting in low mineralization efficiencies at low intermediate concentrations. The difference between the percent color and TOC removals is a measure of colorless intermediate formation. Unlike the Fe (II) dose, color removal was not affected from the H2O2 dose significantly. Decolorization does not take place by oxidation, but only by removal of azo groups. TOC removals were more profoundly affected by the oxidant (H2O2) and the catalyst (Fe (II)) doses since mineralization involves oxidation of the colorless intermediates. Low H2O2 doses may be satisfactory for decolorization, but not for complete mineralization. For an initial dyestuff concentration of 250 mg L1, only 450 mg L1 H2O2 is required for complete decolorization, whereas complete mineralization requires 1125 mg L1 H2O2 while Fe (II) dose requirement is 60 mg L1 for both cases. The optimal dye, H2O2 and Fe (II) doses resulting in the highest TOC and color removals were determined by using an optimization program and the results are presented in Table 7. Oxidant and catalyst requirements are different for maximum color and TOC removals since the reaction mechanisms are different. Maximum color removal (100%) and mineralization efficiency (98%) were obtained with a H2O2 /Fe (II)/dyestuff ratio of 1450/78/235 mg L1. Conclusions This study has demonstrated that the response surface methodology and the Box-Behnken statistical experiment de-

sign can provide statistically reliable results for advanced oxidation of dyestuffs by the Fenton treatment and also for determination of optimum conditions, maximizing the dyestuff removal. Predictions obtained from the response functions were in good agreement with the experimental results, indicating the reliability of the methodology used. The surface response methodology also provided a better understanding of the role of the Fe (II) and H2O2 concentration on the degradation of the dye for a large range of concentrations. Independent variables and their interactions were found to be effective in TOC and color removals by the Fenton treatment. High color and TOC removals indicated effective removal of azo groups from the dyestuff and mineralization. Percent color removals were higher than TOC removals, indicating formation of colorless intermediates. Functional groups imparting color were removed rather fast in 5 minutes, yielding colorless intermediates. Complete mineralization or oxidation of the intermediates to CO2 and H2O took nearly 15 minutes. At a constant dyestuff concentration percent, color removal increased with increasing H2O2 and Fe (II) concentrations up to a certain level above which color removal decreased due to scavenging effects of H2O2 and Fe (II) on hydroxyl radicals. Fe (II) doses affected percent dyestuff and TOC removals more profoundly as compared to the peroxide. Optimal peroxide and Fe (II) doses were determined for a given dyestuff concentration. Maximum color removal (100%) and mineralization efficiency (98%) were obtained with a H2O2/Fe (II)/dyestuff ratio of 1450/78/235 mg L1. The optimal concentrations determined for each response (mineralization and decolorization) were somewhat different since decolorization (removal of functional groups) and complete mineralization to CO2 and H2O had different reaction mechanisms. TOC removal required higher H2O2 and Fe (II) doses as compared to decolorization since complete mineralization required effective oxidation of the intermediates formed by the decolorization reaction. Author Disclosure Statement The authors declare that no competing financial interest exist. References
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