Desalination 277 (2011) 74–82

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Desalination
j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / d e s a l

Optimization of coagulation and dissolved air flotation (DAF) treatment of

semi-aerobic landfill leachate using response surface methodology (RSM)
Mohd Nordin Adlan ⁎, Puganeshwary Palaniandy, Hamidi Abdul Aziz
School of Civil Engineering Campus, Universiti Sains Malaysia, 14300 Nibong Tebal, Pulau Pinang, Malaysia

a r t i c l e i n f o a b s t r a c t

Article history: FeCl3 coagulation and dissolved air flotation (DAF) were combined to assess the success of these techniques
Received 14 December 2010 for the treatment of semiaerobic landfill leachate. Treatment parameters (i.e.; flow rate, coagulant dosage, pH
Received in revised form 30 March 2011 and injection time) were optimized via response surface methodology (RSM) using central composite design
Accepted 1 April 2011
(CCD) to yield the maximum removal of turbidity, chemical oxygen demand (COD), color and ammonia
Available online 4 May 2011
nitrogen (NH3-N). Model-determined optimum conditions were tested to confirm the predicted results.
Keywords:
Initial concentrations of turbidity (259 FAU), COD (2010 mg/L), color (4000 PtCo) and NH3-N (1975 mg/L)
Dissolved air flotation were reduced by 50%, 75%, 93% and 41%, respectively. These experimental results were consistent with those
Coagulation predicted by the model. The optimum operating conditions for coagulation and DAF were 599.22 mg/L of
Ferric chloride FeCl3 at pH 4.76 followed with saturator pressure of 600 kPa, flow rate 6 L/min and injection time of 101 s.
Landfill leachate © 2011 Elsevier B.V. All rights reserved.
Response surface methodology

1. Introduction In addition to the successful removal of contaminants and

Landfill dumping is one of the most abundant methods in developing
countries for municipal solid waste disposal; however, this method is
considerably hazardous to humans and the environment due to the
leaching of gasses and contaminated wastewater. The latter is
concentrated with organic and inorganic contaminants that can be
either biodegradable or refractory in the environment, including humic
substances, ammonia nitrogen, heavy metals, and chlorinated organic
and inorganic salts [1–4]. These compounds are the main contributors to
high COD, nitrogen, turbidity and color pollution [5].
Landfill leachate requires a series of biological, chemical, and
physical treatments that are complicated and expensive [6–9].
Biological treatments involving aerobic and acetogenic degradation
are effective for removing relatively young, recently produced leachate,
such as volatile fatty acids [10]. Older leachate contains more
biorefractory contaminants and additional pollutants (i.e. ammonia)
that are produced during acetogenic and methanogenic phases of
degradation. In order to cope with the changing chemical composition
of the leachate, treatment processes combining additional chemical and
physical mechanisms have been applied [3,5,11,12]. For example, the
dissolved air flotation (DAF) treatment method which relies on the
collision of air bubbles with the suspended particles could float the latter
to the surface of the flotation tank and thus help to reduce leachate
contamination [13,14].
production of thick sludge, DAF provides further benefits for wastewater
treatment, including increases in dissolved oxygen and decreases in
color, algae, turbidity, and oil and grease [15,16]. DAF treatment also
offers low capital investment, low operational cost and high separation
efficiency [17,18].
To successfully perform DAF, a coagulation process must be
introduced to facilitate the destabilization of colloidal particles or
emulsions. This is generally accomplished using four different mecha-
nisms, including double layer compression, charge neutralization,
entrapment in a precipitate and inter-particle bridging [19].
The charge of the particle and bubble is the most important factor
for inducing flotation and removing pollutants, [20].
Previously, DAF treatment has successfully removed 60% of humic
acids (which contribute to COD and color concentrations in leachate)
from synthetic landfill leachate [21]. The aim of this study was to
optimize the combination of coagulation and DAF processes for actual
landfill leachate treatment using RSM. This study examined the
individual and interactive influences of coagulation and flotation factors
(i.e., pressure, flow rate, coagulant dose, pH, and bubble injection time)
on the removal of turbidity, color, COD, and NH3-N from landfill leachate.
2. Methods and materials
2.1. Sampling and characterization

Raw leachate was collected from Pulau Burung sanitary landfill,

located within the Byram Forest Reserve in Penang, Malaysia (5° 24′ N,
⁎ Corresponding author. Tel.:+60 4 599 6252; fax: +60 4 594 1009. 100° 24′E). The landfill was developed in 1980's by Seberang Prai
E-mail address: cenordin@eng.usm.my (M.N. Adlan). Municipal Council. The pollutant composition of the waste stream at

0011-9164/$ – see front matter © 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.desal.2011.04.006
 M.N. Adlan et al. / Desalination 277 (2011) 74–82 75

Table 1 and was converted into a semiaerobic Level 2 sanitary landfill by

Mean waste composition of municipal solid waste in Pulau Burung Sanitary Landfill, establishing a controlled tipping technique in 1991 [1]. In 2001 this
[22].
landfill was further upgraded to Level 3 by establishing controlled
Waste Composition Waste Composition tipping with leachate recirculation. The piping system collects leachate
components components at the bottom of the landfill and channels it into a collection pond [23].
(% weight) (% weight)
The capacity of the collection and retention ponds are 200 m3 and
Food waste 40.08 Textile 5.08
Paper 12.89 Yard 9.23 11400 m3, respectively. Raw leachate used in this study was sampled
Plastics 24.04 Glass 3.28 from the collection pond; the characteristics of the leachate are shown
Wood 1.54 Ferrous 0.47 in Table 2.
Rubber 1.29 Aluminum 2.10 Leachate samples were collected in 2 week intervals from April
2008 to September 2008. The sampling method was based on the
Standard Methods for the Examination of the Water and Wastewater,
Table 2
[24]. The pH and dissolved oxygen (DO) of leachate samples were
Characterization of Pulau Burung landfill leachate.
analyzed on site, while COD, color, turbidity, NH3-N, alkalinity, and
Parameter Maxa Mina Averageb suspended solid (SS) measurements were performed immediately
pH 8.24 7.84 8.13 upon return to the laboratory [24].
COD (mg/L) 3041 2370 2610
Color (PtCo Unit) 4932 3625 4000
Turbidity (FAU) 386 207 259
Alkalinity (mg/L as CaCO3) 11,000 8117 10,416
2.2. Materials and chemicals
Suspended solids (mg/L) 317 177 218
Dissolved oxygen (mg/L) 4.10 0.09 0.58 The bench scale DAF unit used for this study was designed to
Ammoniacal nitrogen (mg/L) 2117 1797 1975 perform coagulation and DAF in the same cell. It consists of an
a
The values are the average of 3 replicates. Replicate analyses varied by less than 1%. unpacked saturator, a flotation cell, a compressor, a water tank and a
high pressure pump. The air injection nozzle in the flotation cell (USM
b
An average of 10 samples were collected at 2 week intervals from April 2008 to
September 2008.
nozzle) was developed by Adlan and co-workers [25]. The sampling
point is located 7.5 cm above the floor of the flotation cell and a scour
valve was installed at the bottom of the flotation cell (Fig. 1).
Pulau Burung Sanitary Landfill is presented in Table 1 [22]. The relative Ferric chloride (FeCl3; supplied by R&M Chemicals, UK) was
humidity in this area ranges between 70 and 90% and the annual chosen to induce coagulation. Sodium hydroxide (NaOH) and sulfuric
average rainfall is 2670 mm. The landfill area is approximately 23.7 ha acid (H2SO4) were used to adjust pH during the coagulation process.

Fig. 1. Schematic diagram of the DAF batch study.

76 M.N. Adlan et al. / Desalination 277 (2011) 74–82
2.3. Experimental set-up and procedure
The coagulation and DAF processes were performed as follows:
(i) the pH of the leachate (4 L) was adjusted according to the experiment
and the sample was added to the flotation cell, (ii) FeCl3 was added to the
cell according to the design of experiment (iii) the leachate and FeCl3
were rapidly mixed (470 rpm for 5 min), (iv) water saturated with air
was injected from the saturator into the flotation cell for 2 min, and
(v) flotation was allowed to occur for 20 min and samples were collected
from the sampling point. Treated leachate samples were analyzed using
the standard method [24]. COD was measured according to Method
5220D [24], (closed reflux, colorimetric method). Colors were reported
as true color (filtered using 0.45 μm filter paper) and were determined
using a DR 2010 HACH spectrophotometer, as in Method 2120C [24].
Turbidity was determined using a DR2010 HACH spectrophotometer.
NH3-N was measured according to the Nessler method and using a DR
2010 HACH spectrophotometer as in Method 4500C. Alkalinities were
measured using 2320B titration methods [24] and are reported as mg/L
of calcium carbonate. SS were determined using a DR 2010 HACH
spectrophotometer, similar to Method 2540D [24]. The pH and DO were
measured using a W-100 Witeg pH meter and WTW multi-parameter
340i, respectively.
2.4. Calculations
The removal of the studied parameters from leachate was
calculated based on the following formula:
 
Co −Ci
Removal Percentage = × 100
Co
where Co and Ci are the initial and final concentrations of the studied
parameters. Here the concentration was based on absolute contents in
the flotation cell (including the dilution effect of the tap water
introduced for the flotation) [9].
2.5. Experimental design, analysis and optimization
The design, mathematical modeling and optimization of this study
were performed using Design Expert 6.0.7 software. Central composite
design (CCD) was used to model the RSM in this design. The former is the
most widely used experimental design for fitting a second-order response
surface [26]. The independent variables (factors) used in this experimen-
tal study were pressure, flow rate, dosage of coagulant, pH and injection
time, and are coded as A, B, C, D, and E respectively (Table 3). The
independent variables were varied over three levels, between −1, 0 and
+1, and the range was determined based on preliminary studies and
literature review. In the preliminary study, the responses became
constant after the dosage concentration was increased up to 1500 mg/L.
For the pH, FeCl3 worked well in the acidic range, this was also found by
Aziz et al. [7]. Mixing intensity at 470 rpm (5 min) and flotation time
(20 min) were kept constant for each experiment; these factors appeared
to be insignificant for coagulation and flotation as determined in the
Table 3
Actual and coded values for the independent variables of the CCD design.
Factor (symbol) Coded value
−1 0 +1
Actual value
A. Pressure (kPa) 400 500
B. Flow rate (B) 4 5
C. Coagulant dose (mg/L) 125 812.5
D. pH 4 5
E. Injection Time (s) 30 75
preliminary experiments [27]. Another factor that was concern in this
study is the injection time. The maximum value for the injection time was
set at 120 s in order to reduce the dilution effect in the batch study. The
injection times were varied from 30 up to 120 s. However, increasing of
injection time will also increase the number of bubbles in the flotation
cell, which simultaneously promotes more bubble particle attachment
and thus more particles will be floated. The values of pressure and flow
rate were set based on the research work conducted by Edzwald et al. [28]
in order to produce microbubbles in the flotation cell. This has been
proved by Al-Shamrani et al. [14] in her study on treating oily wastewater.
Four main parameters were chosen to evaluate the effectiveness of
the coagulation/DAF process, including turbidity (Y1), COD (Y2), color
(Y3) and NH3-N (Y4).
Generally, the CCD consists of a 2k factorial with nF factorial runs
(points with all possible combination of the minimum and maximum
values of the control parameters), 2k axial or star runs (one of the
parameters has the minimum or maximum value and all other
parameters have their nominal value), and nC center runs (all control
parameters are set to their nominal values). In this study, a total of 50
experiments were performed to assess the five experimental factors,
according to the equation CCD = 2k + 2 k + 8, where k is the number
of factors. Forty-two experiments were improved with eight replica-
tions at the design center to evaluate the pure error, [26]. Eq. (2)
shows the quadratic model used to estimate the optimal point:
k k k k
2
Y = β0 + ∑ βi :Xi + ∑ βii :Xi + ∑ ∑ βij :Xi :Xj + … + e ð2Þ
i=1 i=1 ii≤j j
ð1Þ
where Y is the response; Xi and Xj are the variables; β0 is a constant
coefficient; βi, βii, and βij are the interaction coefficients of linear, quadratic
and second-order terms, respectively; k is the number of studied factors;
and e is the random error.
The coefficient of determination (R2) was used to identify the
quality of the fit of polynomial model and the P-value associated with
the 95% confidence level was used to evaluate the variables and the
interactions between them. The significance and adequacy of the
model was assessed according to the calculated F-value (Fisher
variation ratio), probability value (ProbNF), and Adequate Precision.
Finally, the values of response variables (flow rates, pressures,
dosages, injection times and pH) were compared in an overlay plot
to identify the optimum region of leachate treatment.
3. Results and discussion
The leachate used in this study, exhibited low BOD5/COD ratio
(0.03–0.06), high alkalinity and high NH3-N, which can be classified as
“stabilized leachate” and resistant to biodegradation, [29].
Leachate contains high concentration of bacteria, organic substances
and suspended particles. Generally, particles carry a negative charge on
the surface of the liquid in which the pH ranges from 5 to 9, with a typical
size range of 0.01–1 μm [30–32]. Coagulation increases the size and
alters the surface characteristics of the particles. In a leachate solution
adjusted to be slightly acidic (pH 4 to 6), ferric chloride disassociates into
Fe3+, Fe(OH)+ 2 and FeOH
2+
ions. In this phase, charged particles are
neutralized by the coagulant. This results in the formation of flocs, which
lead to more bubble-particle attachment during the DAF process. The
bubble-particle attachment involves three mechanisms; (i) precipitation
or collisions, (ii) bubbles trapped in a floc structure as the bubbles rise
through the liquid media and (iii) bubbles adsorbed in a floc structure as
the floc is formed, [21]
600 In this experiment, a total of 50 CCD batch runs were conducted
6 (Table 4). Using these treatments, the highest percentage removal for
1500 turbidity was 54% (Table 4). However, high dosages of FeCl3 increased
6 turbidity due to the formation of heavy sludge that did not float to the
120
surface of the flotation cell; this observation is consistent with
 M.N. Adlan et al. / Desalination 277 (2011) 74–82 77

Table 4
Results of the central composite design.

Run Process variable Responses

A B C D E Actual Model predicted

1 2 3 4 1 2 3 4

1 500 5 812.5 5 75 43.2 71.6 91.7 37.5 2.74 32.37 50.21 10.88
2 600 4 125 4 30 − 4.8 36.5 54.9 9.5 2.74 36.70 55.62 10.88
3 500 5 812.5 5 120 54.0 74.6 95.1 39.3 2.74 30.20 50.21 10.88
4 600 4 125 6 30 − 6.4 28.7 34.9 3.0 2.74 34.53 55.62 10.88
5 600 4 1500 6 30 −80.8 50.5 78.5 6.7 − 31.38 53.44 65.84 19.43
6 400 4 125 4 30 −12.1 32.3 51.6 8.0 − 31.38 57.77 71.26 19.43
7 400 6 125 4 30 − 4.0 30.7 51.9 11.9 − 31.38 55.61 65.84 19.43
8 400 5 812.5 5 75 29.9 68.8 93.8 33.5 − 31.38 59.94 71.26 19.43
9 500 6 812.5 5 75 7.8 70.8 90.8 38.1 − 24.21 26.46 35.65 10.88
10 600 6 125 6 30 − 0.3 32.0 37.8 2.8 − 24.21 30.79 41.07 10.88
11 600 4 1500 4 120 −37.2 74.3 89.6 49.5 − 24.21 24.29 35.65 10.88
12 600 4 125 6 120 26.7 57.9 60.8 40.0 − 24.21 28.62 41.07 10.88
13 500 5 812.5 5 30 46.7 64.4 94.1 9.3 − 58.33 47.52 71.25 19.43
14 600 6 125 4 30 0.4 33.4 53.6 16.6 − 58.33 51.85 76.66 19.43
15 500 5 812.5 5 75 45.2 72.3 95.7 27.1 − 58.33 49.69 71.25 19.43
16 600 5 812.5 5 75 16.6 77.5 93.8 41.5 − 58.33 54.02 76.66 19.43
17 500 5 1500 5 75 15.5 71.0 89.4 38.3 32.63 55.89 64.98 40.54
18 600 4 125 4 120 30.1 59.4 74.6 48.6 32.63 60.22 70.40 40.54
19 400 6 1500 6 30 −48.5 54.4 80.6 18.2 32.63 53.72 64.98 40.54
20 500 5 125 5 75 15.8 46.9 56.5 29.7 32.63 58.05 70.40 40.54
21 500 5 812.5 5 75 44.9 72.6 91.8 34.6 − 1.48 67.97 80.62 49.08
22 600 6 1500 6 30 − 104.6 53.5 80.1 30.6 − 1.48 72.30 86.03 49.08
23 500 5 812.5 6 75 − 48.3 53.3 70.0 36.1 − 1.48 70.14 80.62 49.08
24 500 5 812.5 5 75 46.5 72.8 94.9 31.0 − 1.48 74.47 86.03 49.08
25 400 4 1500 6 120 − 63.1 63.8 79.4 47.9 5.68 49.98 50.43 40.54
26 400 4 125 6 30 − 20.6 27.7 55.6 12.2 5.68 54.31 55.84 40.54
27 500 4 812.5 5 75 48.8 72.2 89.0 36.9 5.68 47.81 50.43 40.54
28 500 5 812.5 4 75 − 11.5 65.5 80.9 39.2 5.68 52.14 55.84 40.54
29 400 6 125 4 120 26.4 54.3 64.8 42.6 − 28.44 62.06 86.03 49.08
30 400 4 1500 4 30 − 52.8 57.7 53.4 28.1 − 28.44 66.39 91.44 49.08
31 400 6 125 6 30 − 12.5 22.9 19.6 11.9 − 28.44 64.23 86.03 49.08
32 400 4 125 6 120 19.1 51.2 54.4 41.2 − 28.44 68.56 91.44 49.08
33 600 6 125 6 120 39.3 53.7 48.7 49.8 35.85 68.94 88.21 35.53
34 400 4 125 4 120 30.2 54.2 64.0 42.8 35.85 73.27 93.63 35.53
35 400 6 1500 4 120 −11.7 69.7 78.9 41.4 35.85 71.11 90.92 35.53
36 400 6 125 6 120 −41.2 49.2 59.8 41.5 35.85 71.11 90.92 35.53
37 600 4 1500 4 30 8.7 59.6 82.1 23.2 52.91 51.76 64.33 31.26
38 500 5 812.5 5 75 35.3 70.5 86.6 43.2 18.79 70.51 89.95 39.80
39 600 6 1500 6 120 43.6 73.5 93.2 50.8 0.63 64.56 81.90 35.53
40 400 4 1500 6 30 −80.4 41.8 66.3 13.9 − 26.32 58.64 77.33 35.53
41 400 4 1500 4 120 − 4.2 68.9 81.3 55.0 20.90 61.60 83.53 15.16
42 600 6 125 4 120 30.8 56.8 69.4 34.6 50.79 80.62 98.31 44.81
43 600 4 1500 6 120 − 21.2 61.2 89.7 46.6 35.85 71.11 90.92 35.53
44 500 5 812.5 5 75 50.3 71.8 89.6 33.9 35.85 71.11 90.92 35.53
45 600 6 1500 4 30 − 27.3 54.9 66.5 29.8 35.85 71.11 90.92 35.53
46 400 6 1500 6 120 − 48.5 61.8 84.9 42.4 35.85 71.11 90.92 35.53
47 500 5 812.5 5 75 25.2 70.9 86.5 30.6 35.85 71.11 90.92 35.53
48 500 5 812.5 5 75 48.0 69.2 88.0 37.5 35.85 71.11 90.92 35.53
49 400 6 1500 4 30 6.8 55.0 65.1 22.0 35.85 71.11 90.92 35.53
50 600 6 1500 4 120 42.8 74.7 89.3 47.8 35.85 71.11 90.92 35.53

A, B, C, D, and E = pressure, flow rate, dosage, pH and injection time.

1, 2, 3, and 4 = turbidity, COD, color and ammonia nitrogen.

previous reports [14]. COD was reduced by 22.9 to 77.5%, color by 19.6
to 95.7%, and NH3-N by 2.8 to 55% (Table 4). COD was reduced by a
maximum of 78%, from an initial concentration of 2610 mg/L, using
the following treatment conditions: pressure, 600 kPa; flow rate, 5 L/
min; FeCl3 dose, 812.5 mg/L; pH 5; and injection time, 75 s. Using a
coagulation/flocculation treatment, Tatsi and co-workers [33] dem-
onstrated a reduction in COD by 80% with a FeCl3 dosage of 1500 mg/L
and flotation time of 20–30 min [7]. The coagulation/DAF treatment
used in the current study required only 5–10 min and also reduced
the amount of sludge produced after treatment.
Reduction in color was considerably high, with the highest removal of
96%, from an initial measurement of 4000 PtCo units. This was achieved
using 812.5 mg/L FeCl3 with pH 5, at 500 kPa, 5 L/min flow rate and 75 s
injection time. The maximum removal of NH3-N (55%), from an initial
concentration of 1975 mg/L, was achieved at pH 4, 400 kPa, 4 L/min flow
rate, and 120 s injection time, and FeCl3 dose of 1500 mg/L.
3.1. Regression model equation and analysis of variance (ANOVA)
Based on the sequential model sum of squares, the models for
turbidity, COD, color and NH3-N percentages removal were selected based
on the highest order polynomials where the additional terms were
significant and the models were not aliased. The models were coded as Y1,
Y2, Y3 and Y4 for turbidity, COD, color and NH3-N, respectively.
The quadratic model for all four terms, Y1, Y2, Y3 and Y4, were selected
as suggested by the software and are shown in Eqs. (3)–(6). The
independent variables in the models were pressure, flow rate, dosage, pH
and injection time and were coded as A, B, C, D, and E respectively. The
78 M.N. Adlan et al. / Desalination 277 (2011) 74–82

final empirical models used to generate coded factors for each variable determination (R2) for each empirical equation from Eq. (3)–Eq. (6),
are as follows: were 0.65, 0.97, 0.89 and 0.86 respectively. Three out of four models
(Y2, Y3 and Y4) show a good agreement between the experimental and
2
Y1 = 35:85−17:06 C−13:48D + 14:95E−48:70D ð3Þ model-predicted values. The standard deviations for the models were
24.58, 2.89, 6.50, and 5.44 for Y1, Y2, Y3 and Y4 respectively. Here, for
2 2 turbidity removal, the coefficient of determination was considerably
Y2 = 71:11 + 2:16A + 9:37C−2:96D + 9:51E–9:97C –9:51D ð4Þ
low and the standard deviation model was fairly high compared to
+ 1:09BC–2:25CE
other models. As shown in Table 5, 65%, 97%, 89% and 86% of the total
2 2
variability in turbidity, COD, color and NH3-N removal percentages
Y3 = 90:92 + 2:71A + 12:81C−2:29D + 7:39E−13:78C −11:31D ð5Þ were accredited to the empirical model, respectively. The ANOVA
+ 4:99CD (Table 5) revealed that all independent variables were significant
(p b 0.05) for determining turbidity, COD, color, and NH3-N.
2
Y4 = 35:53 + 4:27 C + 14:83E–5:55E : ð6Þ
3.2. Effect of factors on turbidity, COD, color, and NH3-N removal
The quality of the model was evaluated based on the coefficient of
determination in addition to the ANOVA statistical analysis. The Perturbation plots were analyzed in order to further identify the
ANOVA results for the quadratic model for turbidity, COD, color and most sensitive factors for leachate treatment (Fig. 2). Coagulant dose,
NH3-N percentage removal are shown in Table 5. The coefficients of pH, and injection time appeared to be the most influential for
reducing turbidity (Fig. 2a). COD and color removals were affected by
Table 5
pressure, flow rate, coagulant dosage, pH, and injection time (Fig. 2b
ANOVA of quadratic model for turbidity (Y1), COD (Y2), color (Y3) and NH-N3 (Y4) and c). However, only injection time and coagulation dose were
percentage removal with the operating parameters. (pressure (A), flow rate (B), dosage important for NH3-N removal (Fig. 2d).
of coagulant (C), pH (D) and injection time (E)). Coagulant dosage is the only factor that exhibited a significant
Source/operating Sum of Degree of Mean F Value Prob N F effect for all parameters. For example, turbidity is removed with
parameters squares freedom square increasing FeCl3 concentration up to a threshold level (above 813 g/L
Model (Y1) 49461.46 4 12365.37 20.47 b0.0001 based on Table 4), after which higher dosages produced bigger and
C 9893.44 1 9893.44 16.38 0.0002 heavier flocs. This result was likely due to high concentrations of
D 6174.92 1 6174.92 10.22 0.0025 humic acids in the leachate [34], which are able to react with the
E 7594.30 1 7594.30 12.57 0.0009 metal coagulant and form complex substances that produce sludge
2
D 25798.81 1 25798.81 42.70 b0.0001
Residual 27187.12 45 604.16
[35]. This sludge cannot be removed by DAF, thus increasing turbidity
Lack of Fit 26714.91 38 703.02 10.42 0.0017 and impeding leachate treatment [14]. COD and color exhibited a
Pure error 472.20 7 67.46 similar response to coagulant dosage (Fig. 2b and c). These results
Std. Dev. = 24.58 PRESS = 34,356.53 C.V. = 898.97 R-squared = 0.6453 suggest that similar components of the leachate contribute to both
Adj R-squared = 0.6138 Adeq precision = 14.311
COD and color [3,36]. Color was steadily removed with increasing
Model (Y2) 10469.67 8 1308.71 156.92 b0.0001 FeCl3 dose until it reached a maximum removal percentage (~96%;
A 159.37 1 159.37 19.11 b0.0001 Fig. 2c). The color of the treated leachate then increased with higher
C 2986.03 1 2986.03 358.03 b0.0001 coagulant dosage due to the excess ferric chloride in the treated
D 297.54 1 297.54 35.68 b0.0001 sample. NH3-N was also removed with increasing coagulant dosage
E 3077.06 1 3077.06 368.94 b0.0001
C2 361.33 1 361.33 43.32 b0.0001
(Fig. 2d). According to Dempsey [37], charged NH3-N particles are
D2 328.42 1 328.42 39.38 b0.0001 neutralized during coagulation and subsequently adsorbed onto floc
BC 37.69 1 37.69 4.52 0.0396 surfaces. The sludge that is generated is then removed by DAF.
CE 161.69 1 161.69 19.39 b0.0001 As shown in Fig. 2(a), (b) and (c), pH strongly influenced turbidity,
Residual 341.95 41 8.34
COD and color removals. Coagulation induced by FeCl3 was most
Lack of Fit 331.49 34 9.75 6.52 0.0076
Pure Error 10.46 7 1.49 effective under acidic conditions. This finding is consistent with
Std. Dev. = 2.89 PRESS = 543.48 C.V. = 4.99 R-squared = 0.9684 previous leachate treatment studies that used coagulation/flocculation
Adj R-squared = 0.9622 Adeq precision = 45.980 strategies [6,10,33]. This is likely due to the adsorption of negatively
charged organic matter [21] onto the positively charged coagulant ions
Model (Y3) 14882.44 7 2126.06 50.37 b0.0001
A 249.43 1 249.43 5.91 0.0194
(e.g., Fe3+, Fe(OH)+2 , and Fe(OH)
2+
) under acid conditions [38]. The
C 5577.22 1 5577.2 132.14 b0.0001 ideal pH for leachate treatment thus lies in the slightly acidic region
D 177.80 1 177.80 4.21 0.0464 (pH = 4.76). On the other hand, pH did not appear to influence NH3-N
E 1856.22 1 1856.22 43.98 b0.0001 removal (Fig. 2d). At pH 4 to 7, the majority of ions will exist as NH+4
2
C 689.87 1 689.87 16.34 0.0002
[39], thus the pH range (4 to 6) considered for this study did not alter
D2 464.33 1 464.33 11.00 0.0019
CD 797.30 1 797.30 18.89 b0.0001 conditions enough to affect NH3-N adsorption.
Residual 1772.73 42 42.21 Injection time also influenced turbidity, COD, color and NH3-N
Lack of Fit 1684.84 35 48.14 3.83 0.0350 reduction, as all variables were significantly reduced with increasing
Pure Error 87.89 7 12.56 injection time (Fig. 2(a), (b), (c) and (d)). This may be due to the
Std. Dev. = 6.50 PRESS = 2627.93 C.V. = 8.80 R-squared = 0.8936
Adj R-squared = 0.8758 Adeq precision = 24.112
dilution effect resulting from the sustained injection of the air-
saturated water.
Model (Y4) 8429.14 3 2809.71 94.90 b0.0001 Overall, pressure and flow rate did not appear to be as important as
C 620.60 1 620.60 20.96 b0.0001 other factors. Fig. 2b and c indicate that slight increases in these
E 7473.73 1 7473.73 252.44 b0.0001
parameters resulted in slightly enhanced removal of COD and color.
E2 334.81 1 334.81 11.31 0.0016
Residual 1361.89 46 29.61 However, saturator pressure and flow rate are very important in order
Lack of Fit 1185.24 39 30.39 1.20 0.4314 to obtain higher saturator efficiency and bubble volume concentration
Pure error 176.66 7 25.24 as well as smaller bubble size [16]. These features are important for
Std. Dev. = 5.44 PRESS = 1617.29 C.V. = 17.13 R-squared = 0.8609 designing and operating of DAF as a solid–liquid separation process
Adj R-squared = 0.8518 Adeq precision = 24.819
[18].
 M.N. Adlan et al. / Desalination 277 (2011) 74–82
Fig. 2. Perturbation plot for (a) turbidity, (b) color, (c) COD, and (d) NH3-N removal. Coded values are shown for each factor and refer to actual values listed in Table 3 (Note: A =
pressure, B = flow rate, C = dosage, D = pH and E = injection time).
In order to study the interactive relationship between independent
variable and responses, 3D surface response and counter plots of the
quadratic model were drawn using Design Expert software. Fig. 3(a),
(b), (c) and (d), show the 3D surface response and counter plots, where
two variables were varied within the experimental range while others
were kept constant. The constant variables were chosen based on the
level of sensitivity of the variables toward the responses, (based on
Fig. 2).
Fig. 3(a), shows the pH and dosages of coagulant were varied. Other
factors pressure, flow rate and injection time were kept constant at the
maximum values. This is because, based on the perturbation plots, only
three factors (pH, coagulant dosage and injection time) had contributed
significant effect toward the percentage removal of turbidity. As
mentioned above, highest injection time, flow rate and pressure offer
a favorable condition. Due to that, these three conditions were kept
constant at highest value (120 s, 6 L/min and 600 kPa respectively).
Based on Fig. 3(a), the optimum condition was at pH 5, with coagulant
dosage 125 mg/L, and the removal of turbidity was 70%. Fig. 3(a) also
79
shows that at constant pH 5, the turbidity removal has reduced with an
increase in coagulant dosage.
Based on Fig. 3(b), the COD removal was optimum at higher dosage
of 812.5 to 1156.25 mg/L FeCl3, with pH between 4.5 and 5.5. At this
condition, the percentage removal of COD was 73%. In this figure, the
dosage and the pH values were varied, while other factors (pressure,
flow rate and injection time) were kept constant at higher values due to
the same reason as for the turbidity removal as shown in Fig. 3(b).
However, for COD removal pressure and flow rate were observed given
less significant effect compared to Fig. 2(a).
As for color removal, Fig. 3(c) indicated that the maximum removal
was at coagulant dosage of 812.5 mg/L with pH value between 4.5 and 5.
Again in this 3D response surface, the coagulant dosage and pH were
varied. This is because, the perturbation plot in Fig. 2(c), suggested that
coagulant dosage and pH had significant effect toward the color removal.
In terms of ammonia nitrogen removal Fig. 3(d) indicates that, the
dosage and the injection time were varied based on the significance in
the perturbation plot (Fig. 2(d)). Other factors (pressure, flow rate
80 M.N. Adlan et al. / Desalination 277 (2011) 74–82

Fig. 3. 3D response surface for (a) turbidity, (b) COD, (c) color and (d) ammonia nitrogen removal.

Fig. 4. Overlay defining optimal treatment conditions.

 M.N. Adlan et al. / Desalination 277 (2011) 74–82
and pH) were kept constant. The highest removal was obtained at the
highest dosage with highest injection time. At this condition, the
ammonia nitrogen removal was 49%.
3.3. Optimization of experimental conditions
Graphical optimization was used to determine the optimum process
parameters for maximum removal of turbidity, COD, color, and NH3-N
from leachate using the combined coagulant-DAF process (Fig. 4). The
contour line for response surfaces were superimposed in an overlay plot.
By defining the value of the responses, the shaded portion of the overlay
plot as shown in Fig. 4, defines the permissible values of the dependent
values. The optimum region was identified by considering the highest
turbidity, COD, color, and NH3-N removals. Three independent variables,
pressure, flow rate and injection time were kept constant while dosage
and pH, were used in x and y-axes to construct the graph. These two
independent variables were varied because; coagulant dosage and pH
were highly influenced the dependent variables.
Using this overlay plot few points were selected in the optimum
region to obtain optimum value for the responses as well as value for the
varied independent variables (coagulant dosage and pH). Based on
Fig. 4, the optimum region as shown by point A, occurred at pressure
(600 kPa), FeCl3 dosage (547.66 mg/L), pH (4.88), flow rate (6 L/min)
and injection time (98 s). The removal percentages of turbidity, COD,
color and NH3-N predicted by the model using Eq. (1)–Eq. (4) (i.e., 51%,
73%, 91%, and 40%, respectively) were in good agreement with empirical
results using these optimum conditions (Table 6).
However, the values of the factors particularly coagulant dosage
and injection time could influence the studied responses (run 3,
Table 4). This was due to higher coagulant dosage and injection time
where the latter may contribute to the dilution effect of the response
variables. Thus the optimization process in this study successfully
reduced the coagulant dosage and injection time which consequently
result in lower sludge production and less dilution effect [9].
4. Conclusions
Leachate treatment using batch coagulation/DAF techniques was
optimized using RSM. The influence of five decisive factors (i.e., pressure,
flow rate, coagulant dose, pH and injection time) were modeled and
optimized to increase the removal of four response variables. The
optimum conditions suggested from the model for pressure, flow rate,
coagulant dosage, pH and injection time were 600 kPa, FeCl3 dosage of
547.66 mg/L, pH 4.88, flow rate 6 L/min and injection time 98 s
respectively. Under these conditions, results from laboratory tests showed
that removals of turbidity, COD, color and NH3-N were 53%, 72%, 94% and
43% respectively. Overall, pressure and flow rate were less significant for
pollutant removal; however, these two factors are fundamental for
maximizing the performance of the DAF system. These findings are
directly applicable to the commercial use of DAF for the treatment of
landfill leachate.
Table 6
Removal of leachate pollutants using model-predicted optimum values of pressure
(600 kPa), FeCl3 dosage (547.66 mg/L), pH (4.88), flow rate (6 L/min) and injection
time (98 s).
Responses
Turbidity COD Color NH3-N
Experimental value 53% 72% 94% 43%
Model response 51% 73% 91% 40%
Error 2 1 3 3
Standard deviation 1.41 0.71 2.12 2.12
81
Acknowledgments
This study was funded by the Ministry of Science, Technology
and Environment of Malaysia (Grant no. 6013309) and Universiti
Sains Malaysia USM-RU-PGRS (Grant no. 1001/PAWAM/8042021).
The author also wishes to acknowledge cooperation provided by the
Majlis Perbandaran Seberang Perai, Penang and the contractor Idaman
Bersih Sdn. Bhd., Penang
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