Waste Management 30 (2010) 20962102

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Waste Management
journal homepage: www.elsevier.com/locate/wasman

Application of response surface methodology to the treatment landll leachate in a three-dimensional electrochemical reactor
Hui Zhang *, Yanli Li, Xiaogang Wu, Yanjun Zhang, Daobin Zhang
Department of Environmental Engineering, Wuhan University, P.O. Box C319, Luoyu Road 129#, Wuhan 430079, China

a r t i c l e

i n f o

a b s t r a c t
The inuence of different variables on the removal of ammonia nitrogen and COD from landll leachate was investigated in a three-dimensional electrochemical reactor. BoxBehnken statistical experiment design and the response surface methodology were used to investigate operating condition effects, such as current density, activated carbon to water ratio and the reaction time, on ammonia nitrogen removal efciency and COD removal efciency. The positive and negative effects of variables and the interaction between variables on ammonia nitrogen removal and COD removal were determined. The response surface methodology models were derived based on the results and the response surface plots were developed accordingly. 2010 Elsevier Ltd. All rights reserved.

Article history: Received 9 November 2009 Accepted 28 April 2010 Available online 21 May 2010

1. Introduction Landll leachate is one kind of highly contaminated wastewater generated from municipal sanitary landll. Organic contaminants (BOD5, COD and TOC) and ammonia nitrogen (NH3-N) are two principal chemical characteristics of environmental concern in landll leachate (Deng and Englehardt, 2007). The age of the landll has a signicant effect on the concentrations of the contaminants (Cabeza et al., 2007a; Renou et al., 2008). Renou et al. (2008) reported COD values could range from 70900 mg L1 in the leachate obtained from the Thessaloniki Greater Area (Greece) to 100 mg L1 from one more than 10-year old landll near Marseille (France). Meanwhile, values of ammonia nitrogen can range from 0.2 to 13,000 mg L1 (Renou et al., 2008). With a concentration of higher than 100 mg L1 of N, ammonia is highly toxic to aquatic organisms and may disrupt biological units for leachate treatment (Deng and Englehardt, 2007; Renou et al., 2008). Therefore, ammonia nitrogen has been identied as a major long-term pollutant in leachate (Deng and Englehardt, 2007; Renou et al., 2008). Although Fenton related processes have been successfully to degrade COD from landll leachate (Deng and Englehardt, 2006; Kurniawan et al., 2006; Zhang et al., 2006a,b, 2007; Fan et al., 2007; Altin, 2008; Atmaca, 2009; Hermosilla et al., 2009), they are ineffective for ammonia removal (Zhang et al., 2005; Cabeza et al., 2007a). Recently there are more and more reports about the treatment of landll leachate by electrochemical oxidation (Deng and Englehardt, 2007; Cabeza et al., 2007b; Anglada et al., 2009; Bashir et al., 2009). During the electrochemical oxidation of landll leachate, contaminants are primarily destroyed via indirect oxidation by
* Corresponding author. Tel.: +86 27 68775837; fax: +86 27 68778893. E-mail address: eeng@whu.edu.cn (H. Zhang). 0956-053X/$ - see front matter 2010 Elsevier Ltd. All rights reserved. doi:10.1016/j.wasman.2010.04.029

strong oxidants such as hypochlorite generated from anodic oxidation of chloride, which originally exists or is applied in the leachate (Chiang et al., 1995a),

2Cl ! Cl2 2e Cl2 H2 O ! HOCl H Cl HOCl ! H OCl

1 2 3

And ammonia nitrogen could be removed through the mechanism similar to breakpoint reactions (Chiang et al., 1995a),

HOCl NH ! NH2 Cl H2 O H 4 HOCl NH2 Cl ! NHCl2 H2 O NHCl2 H2 O ! NOH 2H 2Cl

4 5 6 7

NHCl2 NOH ! N2 HOCl H Cl

Although there were numerous reports on the removal of ammonia nitrogen from landll leachate by electrochemical oxidation (Chiang et al., 1995a,b; Cossu et al., 1998; Vlyssides et al., 2001; Moraes and Bertazzoli, 2005; Cabeza et al., 2007a,b; Feki et al., 2009), the treatment was carried out in a conventional two-dimensional electrode reactor (Rao et al., 2009). Compared with two-dimensional electrode, three-dimensional electrode could provide larger electrode surface and higher mass transfer (Wang et al., 2008). Therefore, the application of three-dimensional electrode to the electrochemical oxidation of pollutants in wastewater has acquired considerable interest recently (Kong et al., 2006; Wang et al., 2008; Wu et al., 2008; Xu et al., 2008). To our knowledge, only Rao et al. (2009) used a three-dimensional electrochemical reactor for the treatment of landll leachate. But the leachate from an industrial solid waste landll site instead of municipal solid waste landll leachate was treated in their study

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(Rao et al., 2009). Therefore, in this study, three-dimensional electrodes were employed for the removal of ammonia nitrogen from municipal landll leachate. Granular activated carbon was selected since they are the most commonly used particle electrodes (Wu et al., 2008). The effects of current density, activated carbon to water ratio and the reaction time on ammonia nitrogen removal as well as COD removal were investigated. The traditional one-factor-at-a-time approach has been widely used to study the effects of various factors on the objective. Experimental factors are varied one at a time, with the remaining factors being held at constant. This method estimates the effect of a single variable on a particular process while keeping all other variables at a xed condition (Catalkaya and Kargi, 2008; Ay et al., 2009; Islam et al., 2009; Zhang et al., 2009). But this classical approach is a time consuming method for multivariable systems and it cannot estimate the interactions among the variables (Catalkaya and Kargi, 2008; Ay et al., 2009; Islam et al., 2009; Zhang et al., 2009). Response surface methodology (RSM), a multivariate technique which mathematically ts the experimental domain studied in the theoretical design through a response function (Tavares et al., 2009), is then proposed to solve these problems (Catalkaya and Kargi, 2008; Ay et al., 2009; Islam et al., 2009; Zhang et al., 2009). The main types of RSM designs include three-level factorial design, central composite design (CCD), BoxBehnken design and D-optimal design (Catalkaya and Kargi, 2008, 2009; Ay et al., 2009). As one of the RSM designs, BoxBehnken design is known as a modied central composite experimental design (Catalkaya and Kargi, 2008, 2009; Ay et al., 2009). It is an independent, rotatable quadratic design with no embedded factorial or fractional factorial points in which the variable combinations are at the midpoints of the edges of the variable space and at the center (Catalkaya and Kargi, 2008, 2009; Ay et al., 2009). A comparison between BoxBehnken design and other RSM designs has demonstrated that BoxBehnken design is slightly more efcient than CCD, but much more efcient than the three-level full factorial designs (Ay et al., 2009). Moreover, it requires fewer experiments than other RSM designs with the same number of factors (Catalkaya and Kargi, 2008, 2009; Ay et al., 2009). For example, only 15 runs are needed for a three-factor experimental design. As a result, RSM with BoxBehnken design was used in this study to verify the various interactions of responsible factors for the removal of ammonia nitrogen as well as to investigate the effects of three variables on ammonia nitrogen removal. As COD would be removed to some extent in the electrochemical oxidation, COD removal efciency was also selected as a response factor in this study.

2 1

5
7 6 8

Fig. 1. Experimental set-up. 1, DC power supply; 2, electrochemical cell; 3, cathode; 4, anode; 5, carbon bed; 6, air diffuser; 7, ow meter; 8, pump.

down to room temperature, CAC was dipped in the leachate overnight for the establishment of adsorption equilibrium. Then it was transferred into the electrolytic reactor before each run in order to eliminate the contribution of adsorption to ammonia nitrogen and COD removal in the process of electrolysis. The experimental set-up is shown in Fig. 1. The commercial Ti/ RuO2IrO2 electrode was used as chlorine evolution anode (Trasatti, 2000), which was purchased from Baoji Xinyu GuangJiDian Limited Liability Company (China). Batch experiments were performed in a rectangular electrolytic reactor (prexy glass). One plate anode (15 cm 20 cm) and one plate cathode (stainless steel) of the same dimension were arranged parallel to each other at a distance of 4.8 cm. CAC with a diameter of 4 mm was packed between the cathode and anode to form a three-dimensional electrode. A perforated plate mounted above 3.5 cm from the reactor bottom was used to support the particle electrode. A total of 800 mL of the leachate was fed into the reactor prior to each run. No electrolyte was added and the pH value was not adjusted. After the air was sparged into the reactor, DC power supply (Model WYK-305, Yangzhou Jintong Source Co., Ltd., China) was switched on to initiate the reaction. Aliquots were taken from the reactor at pre-selected time intervals. Then the ammonia nitrogen and COD were determined, respectively. 3. Results and discussion BoxBehnken statistical experiment design and the response surface methodology were employed to investigate the effects of the three independent variables on the response functions. The independent variables were current density (X1), CAC to water ratio (X2) and reaction time (X3). The low, center and high levels of each variable are designated as 1, 0 and +1, respectively as illustrated in Table 1. The experimental levels for each variable were selected based on literature values, available resources and results from preliminary experiments. The maximum and minimum boundaries of current density were chosen from (according to) the report by Cabeza et al. (2007a) and taking into account the fact that no supporting electrolyte was added to the leachate prior to the experiments. The center value of CAC to water ratio was selected as 0.5 since it was usually employed in three-dimensional electrochemical reactors, and the 0.7 of CAC to water ratio was the maximum CAC loading which could be applied in the reactor. The dependent variables or objective functions were ammonia nitrogen removal efciency (Y1) and COD removal efciency (Y2).
Table 1 Experimental range and levels of the independent variables. Variables Current density (mA/cm2), A Carbon to water ratio, B Time (h), C Symbol X1 X2 X3 1 30 0.3:1 1 0 60 0.5:1 3 1 90 0.7:1 5

2. Materials and methods Fifty liter leachate samples were taken from a landll at Wuhan, China. Samples taken were preserved in a refrigerator at 4 C in accordance with the Standard Methods (APHA, AWWA, WPCF, 1998). Its characteristics were pH 8.4, COD 3782 mg/L, BOD5 560 mg/L, ammonia nitrogen 3143 mg/L and chloride 3702 mg/L. The pH value was measured with a Mettler-Toledo FE20/EL20 pH meter. COD was determined using closed reux titrimetric method based on the Standard Methods (APHA, AWWA, WPCF, 1998). BOD5 was measured by the respirometric method (WTW OxitopIS6, Germany). Ammonia nitrogen was analyzed using Nesslers reagent colorimetric method according to the National Standard of the Peoples Republic of China (GB 7479-87). Chloride was measured using argentometric method (APHA, AWWA, WPCF, 1998). Cylindrical activated carbon (CAC) was purchased from Gongyi City Yingli Filtration Materials Co., Ltd., China. It was rinsed 23 times with de-ionized water before dried around 100 C. After cool

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COD removal efficiency (%) NH3 -N removal efficiency (%)

BoxBehnken design requires an experiment number according to N = k2 + k + cp, where (k) is the factor number and (cp) is the replicate number of the central point (Tiwari et al., 2008; Tarangini et al., 2009). The total number of experiments in this study was 15 based on 3 levels and a 3 factor experimental design, with three replicates at the center of the design for estimation of a pure error sum of squares. Experimental data from the BoxBehnken design could be analyzed and tted to a second-order polynomial model using Design Expert 7.1.3 software,

100 90 80 70 60 50 40 30 20 30 20 10 0 -1

Y b0

bi X i

bii X 2 i

bij X i X j

where Y is predicted response for ammonia nitrogen removal (Y1) or COD removal (Y2), b0 is the intercept parameter and bi, bii and bij are parameters for linear, quadratic and interaction factor effects, respectively. The coded values of the process parameters in Eq. (1) could be determined by the following equation (Rajasimman et al., 2009; Yetilmezsoy et al., 2009),

Xi

xi x0 Dxi

COD removal efficiency (%) NH 3-N removal efficiency (%)

where Xi is dimensionless coded value of the ith independent variable, xi is the uncoded value of the ith independent variable, x0 is the uncoded ith independent variable at the center point and Dxi is the step change value between low level (1) and high level (+1). The coded values of the test variables and the experimental results of ammonia nitrogen and COD removal efciencies are presented in Table 2. Based on Table 2, the main effects plot and the interaction plots for ammonia nitrogen and COD removal efciencies were developed (Figs. 2 and 3). Fig. 2 illustrated the effects of three factors on the response variable. This type of representation shows the contribution to the response factor of changing one of the variables selected for electrochemical process. As can be seen, the effects of all three factors on ammonia nitrogen removal efciency are positive, i.e., the greater removal efciency could be achieved at high level (+1) of each factor than that at low level (1) of the factor. On the other hand, the effect of reaction time on COD removal efciency is positive, while that of current density or CAC to water ratio is negative. This means that high level (+1) of reaction time would lead to the greater COD removal, but the greater COD removal could be obtained at low level (1) of current density or CAC to water ratio. In Fig. 2, the slope of the plot is indicative of the importance of the variable on the response factor. It can be seen that the effect of CAC to water ratio on ammonia nitrogen removal is much less important than that of current density and reaction time. The Fishers F-test also indicated that the value of Prob > F for the factor of

-1

B 1

-1

C 1

Fig. 2. Main effects plot for ammonia nitrogen and COD removal efciencies ((A) current density; (B) carbon to water ratio; (C) reaction time; (D) ammonia; (d) COD).

100 90 80 70 60 50 40 30 20 30 20 10 0
B B
+ +

C B

C B
-

Table 2 Design matrix in coded units and the experimental responses. Run No. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 Current density (mA/cm2) 1 1 1 1 1 1 1 1 0 0 0 0 0 0 0 Carbon to water ratio 1 1 1 1 0 0 0 0 1 1 1 1 0 0 0 Time (h) 0 0 0 0 1 1 1 1 1 1 1 1 0 0 0 Ammonia nitrogen removal efciency (%) 36.1 93.9 50.5 98.8 23.3 36.4 36.2 99.6 42.0 24.6 73.1 98.1 69.9 67.0 72.1 COD removal efciency (%) 30.3 26.1 18.4 8.3 7.1 5.6 19.6 6.2 14.0 9.0 25.4 24.0 25.1 20.2 23.2

C C
-

-1 A +1

-1 A +1

-1 B +1

Fig. 3. Interaction plots for ammonia nitrogen and COD removal efciencies ((A) current density; (B) carbon to water ratio; (C) reaction time; (.r) ammonia; (N4) COD).

CAC to water ratio was higher than 0.1. Generally, the values of Prob > F less than 0.05 imply that the model terms are signicant, whereas the values greater than 0.1 indicate that the model terms are not signicant (Guven et al., 2008; Korbahti and Rauf, 2008; Arslan-Alaton et al., 2009). As a result, the factor of CAC to water ratio (X2) would be excluded from the RSM model for ammonia nitrogen removal. It should be noted that Fig. 2 just depicts the main effects plot for ammonia nitrogen or COD removal efciency. The dependence between the response variable (ammonia nitrogen or COD

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Y 1 69:76 22:82X 1 22:59X 3 12:57X 1 X 3 10:60X 2 X 3 15:59X 2 3 10

Predicted value

removal efciency) and all the design variables was not necessarily as linearly as depicted in Fig. 2. This will be revealed from the quadratic RSM model. Fig. 3 indicated interaction plots showing the existence or not of interaction among the factors. An interaction may occur if the change in the response variable from the low level to the high level of one design variable differs from the change in the response variable at the same two levels of a second design variable (Ormad et al., 2006). In other words, the effect of one design variable is dependent upon a second design variable (Ormad et al., 2006; Sleiman et al., 2007). The interaction effect on ammonia nitrogen removal between current density and CAC to water ratio is insignicant due to almost parallel plot as shown in Fig. 3 (Ormad et al., 2006). This was also conrmed the high probability value ((Prob > F) > 0.1) through analysis of variance (ANOVA) (Guven et al., 2008; Korbahti and Rauf, 2008; Arslan-Alaton et al., 2009) Therefore, the interaction effect between current density and CAC to water ratio (X1X2) will be removed from the RSM model for ammonia nitrogen removal. There may exist the interactions among other variables when ammonia removal is concerned since the plots are tending to cross (Ormad et al., 2006). Although the plot of the interaction effect on COD removal between current density and reaction time is crossed, the Fishers Ftest showed the value of Prob > F was higher than 0.1. This indicates that the interaction between current density and reaction time is insignicant (Guven et al., 2008; Korbahti and Rauf, 2008; Arslan-Alaton et al., 2009). Meanwhile, the interaction effects among other variables is also insignicant due to almost parallel plot illustrated in Fig. 3, which was veried by the high probability value ((Prob > F) > 0.1) through ANOVA analysis. Therefore, all the interaction items (X1X2, X1X3 and X2X3) would be dropped from the RSM model for COD removal (Guven et al., 2008; Korbahti and Rauf, 2008; Arslan-Alaton et al., 2009). After all the insignicant factors were removed according to the condence level selected ((Prob > F) > 0.1) (Guven et al., 2008; Korbahti and Rauf, 2008; Arslan-Alaton et al., 2009), the ultimate RSM models in terms of the coded factors were determined to calculate ammonia nitrogen removal efciency and COD removal efciency,

Table 4 ANOVA test for response function (COD removal efciency) Y 2 24:79 3:66X 1 4:51X 2 4:93X 3 5:47X 2 8:20X 2 (R2 = 0.8100). 1 3 Source Model X1 X2 X3 X2 1 X2 3 Residual Lack of t Pure error Cor. total Sum of squares 803.35 107.02 162.90 194.44 111.34 249.75 188.41 175.99 12.42 991.76 Degree of freedom 5 1 1 1 1 1 9 7 2 14 Mean square 160.67 107.02 162.90 194.44 111.34 249.75 20.93 25.14 6.21 F-ratio 7.68 5.11 7.78 9.29 5.32 11.93 4.05 P-value, Prob. > F 0.0046 0.0501 0.0211 0.0138 0.0465 0.0072 0.2123

conrmed by the coefcients of determination of the models (R2 = 0.9466 for ammonia nitrogen removal and R2 = 0.8100 for COD removal). This showed that only 5.34% (ammonia nitrogen removal) and 19.0% (COD removal) of the variability in the response were not explained by the models. The statistical signicance of the model was further evident from the fact that the values calculated with the predictive equations were very close to the experimental values (Fig. 4). This illustrated that the prediction of experimental data is quite satisfactory. The response surface plots were developed based on the RSM equations (10) and (11). As can be seen in Figs. 5 and 6, ammonia nitrogen removal efciencies were much higher than COD removal efciencies during the electrolysis. This is agreement with the reports by Chiang et al. (1995b) and Feki et al. (2009) when raw leachate and biological treated efuent of leachate were oxidized

a
100 80 60 40 20 0

R =0.9466

Y 2 24:79 3:66X 1 4:51X 2 4:93X 3

5:47X 2 1

8:20X 2 3

11

The adequacy of the models was justied by ANOVA analysis. The ANOVA for the quadratic models for ammonia nitrogen removal and COD removal were listed in Tables 3 and 4. Both computed values of F ratio are higher than those of the tabular, i.e., F0.05(5,9) value of 3.48 for both ammonia nitrogen removal and COD removal. The statistical signicance of the model was also

20

40

60

80

100

Actual value

b 30
R =0.8100
2

Predicted value

Table 3 ANOVA test for response function (ammonia nitrogen removal efciency) Y 1 69:76 22:82X 1 22:59X 3 12:57X 1 X 3 10:60X 2 X 3 15:59X 2 (R2 = 0.9466). 3 Source Model X1 X3 X1X3 X2X3 X2 3 Residual Lack of t Pure error Cor. total Sum of squares 10239.29 4167.84 4081.56 632.52 449.44 907.92 577.97 564.88 13.09 10817.26 Degree of freedom 5 1 1 1 1 1 9 7 2 14 Mean square 2047.86 4167.84 4081.56 632.52 449.44 907.92 64.22 80.70 6.54 F-ratio 31.89 64.90 63.56 9.85 7.00 14.14 12.33 P-value, Prob. > F <0.0001 <0.0001 <0.0001 0.0120 0.0267 0.0045 0.0770

25 20 15 10 5 0 0 5 10 15 20 25 30

Actual value
Fig. 4. Predicted values of ammonia nitrogen (a) and COD (b) efciencies versus experimental values.

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a
Ammonia nitrogen removal (%)
100 90 80 70 60 50 40

a
COD removal (%)

30 25 20 15 10 1

Carb

on t

0.5

ow

ater

-0.5

ratio

-1

-1

-0.5

(X2)

Cur

re

ens nt d

X 1) ity (

0.5

Carb 0.5 0 on t o w -0.5 -1 -1 ater ratio (X2)

-0.5

Cur

rent

) ty (X 1 ensi

0.5

b
Ammonia nitrogen removal (%)
120 100 80 60 40 20 0 -1 -0.5 0 Cu rre 0.5 nt de nsity (X ) 1

b
30

COD removal (%)

20

10

0 1

0.5
Tim

-1

0 -0.5 Time

0.5 (X 3)

e (X -0.5 3)

-1 -1

-0.5

0.5

Cur

de rent

nsity

(X 1)

Ammonia nitrogen removal (%)

100 80 60 40 20 1

COD removal (%)

40 30 20 10 0 1

0.5 Tim 0 e (X -0.5 3)

-1

-1

-0.5

0.5

Tim

e (X

-0.5

3)

-1

1 0.5 0 (X 2) atio -0.5 rr -1 wate n to arbo C

on Carb

to wa

) io (X 2 er rat

0.5

Fig. 5. Response surface showing ammonia nitrogen removal efciency as a function of two independent variables (other variables were held at their respective center levels). (a) current density (X1) and carbon to water ratio (X2); (b) current density (X1) and time (X3); (c) carbon to water ratio (X2) and time (X3).

Fig. 6. Response surface showing COD removal efciency as a function of two independent variables (other variables were held at their respective center levels). (a) current density (X1) and carbon to water ratio (X2); (b) current density (X1) and time (X3); (c) carbon to water ratio (X2) and time (X3).

in a two-dimensional electrode reactor, respectively. During the electrochemical oxidation of landll leachate, both ammonia nitrogen and COD would be removed simultaneously and there would be a competition between ammonia nitrogen removal and COD removal. According to the report by Deng and Englehardt (2007), the rule of competition between removal of ammonia nitrogen and COD seems to be that the removal of ammonia nitrogen is greater

than that of COD when indirect oxidation is prevalent, whereas COD removal takes priority under direct anodic oxidation. The greater ammonia nitrogen removal than COD removal indicated that indirect oxidation is dominant during electrochemical reaction (Feki et al., 2009). It is interesting to note that the dependence of COD removal on current density was not monotonous. In other words, COD removal efciency increased with the increasing current density, but further increase of current density would lead to the decrease of

H. Zhang et al. / Waste Management 30 (2010) 20962102

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COD removal efciency (Fig. 6a and b). At lower current densities, direct anodic oxidation of COD is favored against chlorine evolution at the anode (Anglada et al., 2009). Hence the increase in current density would lead to the increase of COD removal. But further increase of current density would enhance chlorine generation (Rao et al., 2009), and hence the direct anodic oxidation of COD would be depressed. In the meantime, the removal of ammonia nitrogen would be dominant in the competition between ammonia nitrogen removal and COD removal by the indirect oxidation (Chiang et al., 1995b). Consequently, COD removal efciency would decrease with current density after the highest COD removal was achieved. In order to compare the performance between a two-dimensional electrode reactor and a same-size three-dimensional electrochemical reactor, a separate experiment was carried out when the leachate characteristics were pH 8.4, COD 2091 mg/L, ammonia nitrogen 2531 mg/L and chloride 2660 mg/L. All the experiment variables were held at their respective center levels, i.e., 60 mA/ cm2 of current density was and 3 h of reaction time. The carbon to water ratio was 0.5:1 when three-dimensional electrochemical reaction was performed. The difference of COD removal between two-dimensional and three-dimensional electrochemical reaction was not signicant. In the two-dimensional electrode reactor, 20.2% COD removal efciency was obtained, while COD removal efciency increased to 26.5% in the three-dimensional electrochemical reactor. On the other hand, ammonia nitrogen removal efciency was as high as 81.1% in the three-dimensional electrochemical reaction compared with only 57.7% in the two-dimensional electrode reactor. This indicated that three-dimensional electrochemical reaction is superior to two-dimensional electrochemical reaction when ammonia removal was concerned. 4. Conclusions Ammonia nitrogen could be removed efciently from landll leachate in a three-dimensional electrochemical reactor. The effect of CAC to water ratio on ammonia nitrogen removal is much less important than that of current density and reaction time. The interaction effect on ammonia nitrogen removal between current density and CAC to water ratio is insignicant. COD removal was much lower than ammonia nitrogen removal due to the fact that the indirect oxidation of ammonia nitrogen oxidation was dominant in the competition with COD. The interaction effect between the variables on COD removal was negligible. The response surface methodology models were derived based on the ammonia nitrogen and COD removal efciency results and the models could t the data well. Acknowledgements This study was supported by SRF for ROCS, SEM, China (Grant No. [2001]498), China Hubei Provincial Science and Technology Department through The Gongguan Project (Grant No. 2003AA307B01), Wuhan Science and Technology Bureau through The Gongguan Project, China (Grant No. 201060723313) and the National High-Tech R&D Program (863 Program) of China (Grant No. 2008AA06Z332). We appreciate the valuable comments of the anonymous reviewers. References
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