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C, shaking rate of 150 rpm and contact time of 2 hours. The adsorption kinetics was found to follow pseudo-
second-order kinetic model. The experimental data fitted well with the Langmuir model with a monolayer adsorption capacity
of 188.7mg/g. It was also found that prepared and spent PH/CFO-Ac adsorbents have a homogenous particle size distribution.
In addition, the surface morphology of the spent PH/CFO-Ac adsorbents had more compact structures with small granular
particles attached on the surface.
Keywords: Colour removal, Synthetic Dye Wastewater, Psyllium Husk
1. INTRODUCTION
Due to the increase in the world population and
development of industrial applications, environmental
pollution problem became very important, especially
wastewater pollution problem. Communities produce
both liquid and solid wastes. The liquid waste, i.e.
wastewater, is essentially the water supply of the
community after it has been used in a variety of
applications. Wastewater handling, disposal &
treatment are serious worldwide problem. Many
industrial and agricultural activities use water in an
excessive way. However, it is now well known that
the fresh water resources are limited and fragile, so
they must be protected. Discharge of sanitary
wastewater, industrial effluent and agricultural fields
runoff can be the main source of freshwater pollution.
This causes many diseases for human, and it is known
that 70-80% of illness in developing countries is
related to water contamination, particularly for
children and women (WHO/UNICEF, 2000).
Textile industries consume large volumes of water
and chemicals for wet processing of textiles. The
chemical reagents used are very diverse in chemical
composition, ranging from inorganic compound to
polymers and organic compound (Correia et al.,
1994). The color is an evident indicator of water
pollution by the dyes. Industrial dye effluents are
visible even at concentrations lower than 1 mg/l.
Moreover, some dyes and their degradation products
are carcinogenic (Ahn et al., 1999). Also, some dyes
are harmful to aquatic life in rivers where they are
discharged. Since, dye can reduce light penetration
into the water thereby decreasing the efficiency of
photosynthesis in aquatic plants and hence having
adverse impact on their growth (Che Ani, 2004).
Textile wastewater is generally high in both color
and organic content. Effluents discharged from dyeing
industries are highly colored and they can be toxic to
aquatic life in receiving waters (Lee et al., 1999,
Kadirvelu et al., 2003). Color removal from textile
effluents has been given much attention in the last few
years, not only because of its potential toxicity, but
mainly due to its visibility problems (Morais et al.,
1999). The total dye consumption of the textile
industry worldwide is in excess of 10
7
kg/year, and an
estimated 90% of this ends up on fabrics.
Consequently, 1000 tonnes/year or more of dyes are
discharged into waste streams by the textile industry
worldwide (Ahmad et al., 2007).
Development of the appropriate techniques for
treatment of dye wastewater is important for the
protection of natural water. To eliminate dyes from
aqueous colored effluents and reduce their ecological
consequences, several biological and chemical
techniques have been proposed: anaerobic/aerobic
degradation (Ahmed et al., 2007),
coagulation/flocculation (Papi et al., 2000) and also
oxidative/reductive chemical and photochemical
processes (Lucas and Peres, 2006). Due to relatively
high operating costs and low removal efficiencies
using the above-mentioned processes, textile, pulp and
Dahlan and Tayeh
Removal of Colour from Synthetic Dye Wastewater Using Adsorbent Prepared from Psyllium Husk
16
paper industries seldom apply these to treat their
effluents.
Among several chemical and physical methods, the
adsorption has been found to be superior to other
techniques in water reuse methodology because of its
capability for adsorbing a broad range of different
types of adsorbates efficiently, and simplicity of
design. Many researchers researched for cheaper
substitutes, which are relatively inexpensive, and are
at the same time endowed with reasonable adsorptive
capacity. These studies include the use of coal, fly
ash, activated clay, palm-fruit bunch, Bagasse pith,
cellulose-based waste, peat, bentonite, slag and fly
ash, rice husk, activated sludge, etc (Ahmad et al.,
2007).
Psyllium husk has not been investigated as
adsorbent for color removal from dye solutions. This
research studied the adsorption for color removal from
synthetic dye wastewater using an adsorbent prepared
from an inexpensive and readily available material,
i.e. psyllium husk. Also, the study aims to achieve the
following measureable objectives:
1- To prepare and characterize adsorbent from
psyllium husk using quaternized and magnetic
methods.
2- To investigate the ability of the best psyllium
husk adsorbent for removal of color from synthetic
dye under various operating conditions (initial dye
concentration, amount of sorbent, shaking rate,
contact time, pH, and temperature).
3- To determine the kinetic behavior and
isotherms for the adsorption process of color onto
psyllium husk adsorbent.
2. MATERIALS AND METHODS
2.1. Materials
The raw psyllium husk (Fig. 1) was obtained directly
from a store in Parit Buntar, Penang, and used in the
preparation of the adsorbent for this study. Direct blue
dye (DB71) was provided by Sigma Aldrich, Co.,
and used without further purification. The dye was
used as the adsorbate in the batch experimental study.
The chemicals used in this study are Na
2
CO
3
and
Ferric nitrate [Fe(NO
3
)
3
9H
2
O] which is provided by
Bendosen Laboratory Chemicals, whereas NaOH,
H
2
SO
4
and Cobalt nitrate [Co(NO
3
)
2
6H
2
O] are
provided by Qrc, Bright Chem. Sdn Bhd. In addition,
N-(3-chloro-2-hydroxy-propyl)-trimethylammonium
chloride was provided by Aldrich Chemistry. All
chemicals were used without any purification process.
Fig. 1: Raw psyllium husk (PH).
2.2. Preparation of Adsorbent
2.2.1. Preparation of raw psyllium husk
The raw psyllium husk was dried in the oven at 100
o
C
for 24 hours, and then ground by using domestic
blender to pass through a 1mm-sieve (Laboratory Test
Sieve). The husk obtained was kept in a closed plastic
and labeled as raw psyllium husk (RPH).
2.2.2. Preparation of Quaternized Adsorbent
About 20g of the raw psyllium husk was treated with
250 ml of 1% w/v Na
2
CO
3
solution (Fig. 2a). The
mixture was shaken for 45 min at room temperature
(Fig. 2b). It was subsequently rinsed several times
with distilled water (Fig. 2c) and dried at 60C (Fig.
2d). The husk obtained was labeled as natural
psyllium husk (NPH). A portion of NPH was
quaternized according to the method reported by Low
and Lee (1997). The natural psyllium husk (10g) in
12.5 ml of 5 M NaOH solution was left at room
temperature for 30 min (Fig. 2e). At the end of
incubation period 10 ml of 4 M N - (3-chloro-2-
hydroxy-propyl) - trimethylammonium chloride was
added to the mixture (Fig. 2f). It was thoroughly left
in the oven at 60-70C for 4 hours (Fig. 2g) with
intermittent stirring. The reaction mixture was then
rinsed several times with water and finally with
Wastewater Engineering: Advanced Wastewater Treatment Systems
Chapter 2: Wastewater Treatment by Physical-Chemical Technologies
17
distilled water (Fig. 2h). The product after drying was
labeled as quaternized psyllium husk (QPH).
2.2.3. Preparation of psyllium husk/CoFe
2
O
4
adsorbent (PH/CFO)
Psyllium husk/CoFe
2
O
4
adsorbent was synthesized by
a facile refluxing route in alkaline solution as reported
by Ai et al., (2010) with some modifications. In a
typical procedure, 8g of raw psyllium husk was added
into a 150mL alkaline solution containing 3.4g NaOH,
and stirred at room temperature for 30 minutes (Fig.
3a) to get the psyllium husk suspension. The
suspension was then maintained at 100C to keep
boiling state (Fig. 3b). A 50mL metal nitrate aqueous
solution was prepared by dissolving Fe(NO
3
)
3
9H2O
(5.4944 g) and Co(NO
3
)
2
6H2O (1.9790 g) in distilled
water (Fig. 3c). The solution was poured as quickly as
possible into the above boiling suspension (Fig. 3d).
The mixture solution was then refluxed at 100C for 2
h (Fig. 3e). By a simple magnetic procedure, the
resulting product was separated from water, dried at
80C for 12 h (Fig. 3f), and the product was labeled as
PH/CFO-Al. This preparation method was repeated
twice, the second time was by replacing the 150 mL
alkaline solution NaOH by 150ml acidic solution
H
2
SO
4
(2N
) to obtain PH/CFO-Ac.
Table 1: Summary of batch studies
Preliminary Batch study Main Batch study
Using four types of adsorbent prepared from
psyllium husk, to select the best adsorbent with the
highest efficiency to be used in the main study, the
effect of two parameters were studied:
a- Effect of adsorbent amount (using 1g
and 3g adsorbent)
b- Effect of initial dye concentration (using
5mg/ L, 15mg/L)
Main experiments for synthetic wastewater
a. Effect of contact time using 1hr, 2hr, 3hr, 4hr and 5hr
b. Effect of adsorbent amount using 0.1g, 0.3g, 0.6g, 1g
and 1.5g
c. Effect of shaking rate using 100rpm, 150rpm,
200rpm, 250rpm and 350rpm.
d. Effect of initial dye concentration using 15, 30, 60,
100 and 200mg/L
e. Effect of pH using pH 3, 4.5, 6, 7.5, 9 and10.5
f. Effect of temperature using 30, 40, 50 and 60
o
C
2.4. Isotherm and Kinetic studies
For the isotherm and kinetic studies, one batch
experiment was conducted using 1000ml of synthetic
wastewater with initial dye concentration of 200mg/L
and pH 9. About 1.0g of adsorbent was added to the
sample, it was agitated at the agitation rate of 150
rpm. Samples were taken at different time intervals (0
60 min), and the final concentration of the dye was
measured at each time t. At time t = 0 and
equilibrium, the dye concentration was measured and
the amount of adsorption at equilibrium, q
e
(mg/g)
was calculated using Equation
where C
o
and C
e
(mg/L) are the liquid-phase
concentrations of sample at initial and equilibrium,
respectively. W (g) is the mass of sorbent used and V
(L) is the volume of the solution. The removal
efficiency of dye can be calculated from Equation 2
where C
t
is the dye concentration at time t.
Adsorption isotherm is fundamentally essential to
explain how solutes interact with sorbents, and is
critical in optimizing the use of sorbents. In the
present study, the equilibrium isotherms were
analyzed using the Langmuir and Freundlich,
isotherms. The linear form of Langmuir isotherm is
given in Equation 3 (Keleolu, 2007) and Freundlich
isotherm is given in Equation 4 (Schwarzenbach et
al., 2003),
where the constant Q
o
signifies the adsorption
capacity (mg/g) and b is related with the energy of the
adsorption (L/mg), K
F
and n are Freundlich constants.
To investigate the adsorption mechanism, pseudo-
rst-order and pseudo-second-order kinetic models
were tested to nd the best tted model for the
experimental data. The pseudo-rst-order equation is
given by Equation 5.
where k
1
is the pseudo-rst-order rate constant
(min
1
), q
e
and q
t
are the amounts of dye adsorbed
(mg/g ) at equilibrium and at time t (min). The
pseudo-second-order model can be expressed in
Equation 6 (Ho and McKay, 1998):
Dahlan and Tayeh
Removal of Colour from Synthetic Dye Wastewater Using Adsorbent Prepared from Psyllium Husk
18
where k
2
(g mg
1
min
1
) is the rate constant of the
pseudo-second-order adsorption.
2.5. Analysis and Characterization
The initial concentration of dye (direct blue 71 dye
solution) and samples after sorption treatment were
measured using DR 2800 spectrophotometer
according to the Platinum Cobalt Standard Method
(Adopted from Standard Methods for the Examination
of Water and wastewater and NCASI, Technical
Bulletin No. 253, Dec. 1971). All the concentrations
of sample analysis were conducted in triplicate to
increase the precision of the results, and only the
average value was reported throughout this analysis.
Selected magnetic sorbents, before and after the
adsorption process, were characterized using
Mastersizer 2000 in order to study the particle size
distribution for the adsorbent. To obtain the surface
morphologies of the selected adsorbent, before and
after the adsorption process, the scanning electron
microscopy (SEM) examinations were performed with
5 kV of accelerating voltage using Leo Supra 35VP-
24-58 microscope.
3. RESULTS AND DISCUSSIONS
3.1. Preliminary Batch Study
As described before, four types of adsorbents were
prepared to select the best adsorbent for the main
batch experimental studies. Figure 4(a) shows the
results for the adsorbent selection based on dye
concentration, and Figure 4(b) shows the results for
the adsorbent selection based on adsorbent amount. It
was noticed from Figure 4(a) that the PH/CFO-Ac
which is the magnetic adsorbent prepared from
psyllium husk treated with acidic solution (H
2
SO
4
) has
the best removal efficiency with 79% color removal
from the 5mg/L initial DB71 dye concentration, and
88% color removal from the 15mg/L initial dye
concentration, while the other kinds of adsorbent
(PH/CFO-Al, QPH and NPH), gave negative
efficiency due to the color of dye became more
darker.
It was noticed also from Figure 4 (b) that the
PH/CFO-Ac, has the best removal efficiency, with
88.6%% color removal when 1g adsorbent was used
and 73% color removal when 3g adsorbent was used,
while the other three kinds of adsorbent gave negative
efficiency due to the color of dye became more
darker. Based on the results of the preliminary study,
PH/CFO-Ac was selected to be used for the main
study.
3.2. Batch Experiments for Synthetic Wastewater
3.2.1. Effect of contact time
One of the most important parameters affecting the
adsorption process is the contact time. It is supposed
that the color removal efficiency will increase by the
increasing of the contact time, until reaching a time at
which no significant amount of dye is removed; this
time is called the equilibrium time. Figure 5 shows the
effect of contact time on the adsorption of DB71 using
PH/CFO-Ac adsorbent
It was shown in Figure 5 that the removal
efficiency of PH/CFO-Ac increased rapidly from
90.8% to 94.03 % when the contact time was
increased from 1 to 2 hours. After that, no significant
increase was noticed in the removal efficiency with
increasing the contact time. This is probably due to
larger surface area of the PH/CFO-Ac adsorbent being
available at the beginning of the adsorption process,
so the adsorption rate was fast. As the surface
adsorption sites become exhausted, the uptake rate is
controlled by the rate at which the adsorbate is
transported from the exterior to the interior sites of the
adsorbent particles (Ai et al., 2010, Kumar et al.,
2010).
Wastewater Engineering: Advanced Wastewater Treatment Systems
Chapter 2: Wastewater Treatment by Physical-Chemical Technologies
19
Fig. 2: Preparation of quaternized adsorbent
Dahlan and Tayeh
Removal of Colour from Synthetic Dye Wastewater Using Adsorbent Prepared from Psyllium Husk
20
Fig. 3: Preparation of psyllium husk/CoFe
2
O
4
adsorbent (PH/CFO)
Wastewater Engineering: Advanced Wastewater Treatment Systems
Chapter 2: Wastewater Treatment by Physical-Chemical Technologies
21
Fig. 4: (a) Adorbent selection based on dye concentration, and (b) adsorbent selection based on adsorbent amount.
Fig. 5: Effect of contact time on the adsorption of DB71 from synthetic wastewater
3.2.2. Effect of adsorbent amount
Figure 6 shows the plot of amount of PH/CFO-Ac
adsorbent against percentage removal efficiency of
DB71. It was observed that the removal efficiency is
varied with varying amount of adsorbent and it
decreased with increasing the amount of adsorbent.
The removal efficiency decreased from 94.78% to
81.1% for an increase in adsorbent amount from
0.1g/100ml to 1.5g/100ml. The decrease in removal
efficiency with increasing adsorbent amount may be
due to the concentration gradient between solute
concentration in the solution and the solute
concentration in the surface of the adsorbent. Thus
Dahlan and Tayeh
Removal of Colour from Synthetic Dye Wastewater Using Adsorbent Prepared from Psyllium Husk
22
with increasing adsorbent amount, the amount of dye
adsorbed onto unit weight of adsorbent gets reduced,
thus causing a decrease in adsorption capacity and
removal efficiency with increasing adsorbent amount
(Vadivelan and Kumar, 2005).
Fig. 6: Effect of adsorbent amount on the adsorption of DB71 from synthetic wastewater
3.2.3. Effect of shaking rate
Figure 7 shows the effect of shaking rate on the
adsorption of DB71. The removal efficiency of DB71
was 98.74% at low shaking rate (100 rpm) and rose to
99.36% as the shaking rate was increased to 150 rpm.
This effect can be attributed to the decrease in
boundary layer thickness around the adsorbent
particles being a result of increasing the degree of
mixing (Gupta et al., 2011). The removal efficiency
decreased again when the shaking rate was increased
to 350 rpm. This might be due to higher boundary
layer resistance to mass transfer in the bulk (Dahlan
and Razali, 2011).
Fig. 7: Effect of shaking rate on the adsorption of DB71 from synthetic wastewater
3.2.4. Effect of initial dye concentration
The effect of initial dye concentration in the range of
15 to 200 mg/l on adsorption was investigated and the
results are shown in Figure 8. It is evident from figure
that the percentage dye removal increased with the
increasing in initial concentration of dye. The increase
in initial dye concentration enhances the reaction
between dye and PH/CFO-Ac. The percentage dye
removal was found to be 95.11% for 15 mg/l of initial
concentration, and it increased to 99.54% when the
initial dye concentration was increased to 200mg/l.
Wastewater Engineering: Advanced Wastewater Treatment Systems
Chapter 2: Wastewater Treatment by Physical-Chemical Technologies
23
Fig. 8: Effect of initial dye concentration on the adsorption of DB71 from synthetic wastewater
3.2.5. Effect of pH
The pH of the solution plays an important role in the
whole adsorption process. To determine the optimum
pH for the adsorption of DB71 using PH/CFO-Ac, the
effect of solution pH was investigated in the range of
310.5 and the results are shown in Figure 9. The
removal efficiency of DB71 at pH less than 7 is
relatively lower than at pH more than 7. It increased
up from 87.8% to 91.5% when pH was increased from
3 to 9. Solution pH may affect both aqueous chemistry
and surface binding-sites of the adsorbent. The
decrease of adsorption at pH less than 7 can be
explained by the fact that at this acidic pH, H
+
may
compete with dye ions for the adsorption sites of
adsorbent, thereby inhibiting the adsorption of dye
(Hameed and El-Khaiary, 2008).
Fig. 9: Effect of pH on the adsorption of DB71 from synthetic wastewater
3.2.6. Effect of temperature
The effect of temperature on the adsorption process
was investigated by carrying out the adsorption
experiments using PROTECH Shaker Incubator with
different degrees of temperature ranging from 30 -
60
o
C. Figure 10 shows that the highest removal
efficiency (92.04%) was obtained at temperature
30
o
C, and decreased slowly until temperature 50
o
C,
after that it decreased rapidly to 76.36% when the
temperature was increased to 60
o
C. Similar results
were obtained by various authors for the adsorption of
dyes on various adsorbents (Ho and McKay, 1998;
Chern and Wu, 2001; Chiou and Li, 2002; Hamdaoui,
2006). This can be explained by the exothermic
spontaneity of the adsorption process and by the
weakening of bonds between dye molecules and
active sites of adsorbents at high temperatures (Amin,
2009).
Dahlan and Tayeh
Removal of Colour from Synthetic Dye Wastewater Using Adsorbent Prepared from Psyllium Husk
24
Fig. 10: Effect of temperature on the adsorption of DB71 from synthetic wastewater
3.3. Adsorption kinetics
Figure 11 shows that the adsorption capacity of
PH/CFO-Ac increased rapidly in the initial stages of
the experiment and it reached equilibrium at 40
minutes although the data were measured for 2 hours.
The results indicate that, at the beginning the dye ions
were adsorbed by the exterior surface of PH/CFO-Ac,
so the adsorption rate was fast. When the adsorptions
of the exterior surface reached saturation, the dye
exerted onto the pores and was adsorbed by the
interior surface of the adsorbent. The time profile of
dye uptake is a single, smooth and continuous curve
leading to saturation, suggesting also the possible
monolayer coverage of dye on the surface of the
PH/CFO-Ac A similar phenomenon was observed
from previous study for the adsorption of direct blue
71 dye on palm ash adsorbent and the equilibrium
time was 1 hour (Sengil, 2003).
Fig. 11: The variation of adsorption capacity of DB71 onto PH/CFO-Ac with adsorption time, 1L solution, 1g adsorbent,
200mg/L dye concentrations, pH 9, at 30 C
To investigate the adsorption kinetic of DB71 on
the surface of PH/CFO-Ac, pseudo-rst-order and
pseudo-second-order kinetic models were tested. The
plots of pseudo-rst-order and pseudo-second-order
kinetic models are shown in Figure 12 and Figure 13,
respectively. Kinetic constants obtained by linear
regression for the two models are listed in Table 2.
The correlation coefficient for the pseudo-rst-order
model is relatively good (R
2
= 0.85), however, the
calculated q
e
(q
e
,
cal
) obtained from this equation does
not give reasonable value (Table 2), which is much
lower compared with q
e
obtained from the
experimental data (q
e,exp
).
Wastewater Engineering: Advanced Wastewater Treatment Systems
Chapter 2: Wastewater Treatment by Physical-Chemical Technologies
25
Fig.12: Pseudo-first-order kinetic plot for adsorption of DB71 onto PH/CFO-Ac (C
0
= 200mg/L, pH 9)
Fig. 13: Pseudo-second-order kinetic plot for adsorption of DB71 onto PH/CFO-Ac (C
0
= 200mg/L, pH 9)
Table 2: Kinetic parameters for adsorption of DB71 onto PH/CFO-Ac
q
e,exp
(mg g
-1
)
Pseudo-rst-order Pseudo-second-order
K
1
(min
-1
) q
e,cal
(mg g
-1
)
R
2
K
2
(g mg
-1
min
-1
)
q
e,cal
(mg g
-1
)
R
2
196.48 0.032 3.0 0.85 0.031 196 0.997
This result suggests that the adsorption process
does not follow the pseudo-rst-order kinetic model,
which is similar to the result reported for adsorption
of direct blue 71 onto palm ash adsorbent (Ahmad et
al., 2007). In many cases the pseudo-rst-order
equation of Lagergren does not t well to the whole
range of contact time and is generally applicable over
the initial stage of the adsorption processes (Ho and
McKay, 1999, Hameed and Hakimi, 2008). For the
pseudo-second-order kinetic model, the R
2
value is
0.997 and the (q
e,cal
=196mg/g) agrees very well with
the (q
e,exp
=196.48mg/g) value, which indicates that
the adsorption of DB71 onto PH/CFO-Ac follows a
pseudo-second-order kinetic model.
3.4. Adsorption isotherm
The adsorption isotherm is the most important
information which indicates how the adsorbate
molecules distribute between the liquid phase and the
Y= -0.013X + 0.545
R
2
= 0.85
Y = 0.00509 X + 0.00083
R
2
= 0.997
Dahlan and Tayeh
Removal of Colour from Synthetic Dye Wastewater Using Adsorbent Prepared from Psyllium Husk
26
solid phase when the adsorption process reaches an
equilibrium state. To optimize the design of an
adsorption system for the adsorption of adsorbates, it
is important to establish the most appropriate
correlation for the equilibrium curves. In this study,
the equilibrium isotherms were examined using the
Langmuir and Freundlich isotherms.
In the linear form of Langmuir isotherm, a plot of
C
e
/q
e
versus C
e
(Fig. 14) yields a straight line with
slope 1/Q
0
and intercepts 1/Q
0
b. The essential
characteristics of the Langmuir isotherm can be
expressed in terms of dimensionless constant
separation factor R
L
given by (Mahmoodi et al., 2011)
(7)
where b is the Langmuir constant and C
o
is the
highest initial dye concentration (mg/L). According to
the value of RL the isotherm shape may be interpreted
as shown in Table 3.
Fig. 14: Linearized Langmuir isotherm
Table 3: Adsorption Types based on R
L
value (Mahmoodi et al., 2011)
Value of R
L
Type of adsorption
R
L
> 1.0
R
L
= 1.0
0 < R
L
< 1.0
R
L
= 0
Unfavourable
Linear
Favourable
Irreversible
The value of R
L
calculated (0.00066) was in the
range between 0 and 1 which indicate that the
adsorption is favorable at operation conditions
studied. Table 4 summarizes Langmuir constants and
computed maximum adsorption capacity Q
0
of DB71
onto the PH/CFO-Ac.
Table 4: Langmuir and Freundlich isotherm model constants and correlation coefficients for adsorption of DB71 onto
PH/CFO-Ac
Langmuir
isotherm
b (L/mg) Q
o
(mg/g) R
L
R
2
7.57 188.7 0.00066 0.997
Freundlich isotherm K
F
Q
o
(mg/g) n
R
2
203 177.7 40 0.991
In addition, the Freundlich isotherm is an empirical
equation based on a heterogeneous surface. A plot of
ln q
e
versus ln C
e
(Fig. 15) enables the constant K
F
and exponent n to be determined. K
F
can be defined as
adsorption of distribution coefficient and represents
the quantity of dye adsorbed onto adsorbent for an
equilibrium concentration. The slope 1/n is a measure
of adsorption intensity or surface heterogeneity. These
values together with the correlation coefficient are
presented in Table 3.3. Based on the values of
correlation coefficients (R
2
) and Q
o
shown in Table
3.3, the adsorption isotherm with PH/CFO-Ac can be
described by Langmuir equation. The Langmuir
equation yields a better fit of the experimental data
than Freundlich equation.
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Chapter 2: Wastewater Treatment by Physical-Chemical Technologies
27
Fig. 15: Linearized Freundlich isotherm
3.5. Characterization of magnetic PH/CFO-Ac
adsorbent
3.5.1. Particle Size Distribution analysis
Figure 16 shows the particle size distribution of
prepared adsorbent, spent adsorbent with high
removal efficiency and spent adsorbent with low
removal efficiency, respectively. The maximum
volume percentage corresponds to the particle size of
approximately 1000m, 900m and 600m for
prepared adsorbent, spent adsorbent with low removal
and spent adsorbent with high removal, respectively.
The average volume of the particle size distribution
range of spent PH/CFO-Ac adsorbents is higher than
the prepared PH/CFO-Ac adsorbent, which means that
higher particle size distributions range are formed
after DB71 adsorption onto PH/CFO-Ac adsorbent. It
was also found that the specific surface area of the
prepared adsorbent was much higher (0.034 m
2
/g)
than that of the spent adsorbent with low removal and
spent adsorbent with high removal (0.0158 and 0.0112
m
2
/g, respectively). The lower specific surface area of
spent PH/CFO-Ac adsorbents could be due to the
agglomerating of smaller particles (which is most
probably the dye particles that cover the surface of the
adsorbent) during the adsorption process. It was also
shown from the figure that prepared and spent
PH/CFO-Ac adsorbents have a unimodal particle size
distribution, which indicates a homogeneous particle
size for the prepared and the spent adsorbents.
Dahlan and Tayeh
Removal of Colour from Synthetic Dye Wastewater Using Adsorbent Prepared from Psyllium Husk
28
Fig. 16: Particle size distribution of prepared PH/CFO-Ac adsorbent, spent adsorbent with high removal efficiency, and spent
adsorbent with low removal efficiency.
3.6.2. Surface morphology analysis (SEM)
The morphology of the raw psyllium husk, prepared
and spent PH/CFO-Ac adsorbent is shown in Figure
17. Surface analysis indicated that the surface
morphology of the raw psyllium husk (Figure 17a)
consists of lumps of uneven shapes particles. After the
preparation of PH/CFO-Ac adsorbent, it can be
observed from Figure 17b that the prepared adsorbent
consists of irregular rough particles that were
unevenly scattered together which might be due to the
CoFe
2
O
4
particles deposited on the surface of raw
psyllium husk. After the adsorption of DB71, the
surface of the PH/CFO-Ac adsorbents was found to
have more compact structures with small granular
particles attached on the surface (Figure 17c) which is
most probably the dye particles that covered the
external surface of PH/CFO-Ac adsorbents.
4. CONCLUSIONS
This study showed that PH/CFO-Ac adsorbent was
successfully synthesized by a facile one-step refluxing
route could be used as an effective adsorbent for the
removal of direct blue dye (DB71) from synthetic
wastewater. All experimental parameters such as
contact time, adsorbent amount, shaking rate, initial
dye concentration, pH and temperature affected the
adsorption of dye from synthetic wastewater. The
equilibrium of adsorption of dye onto PH/CFO-Ac
adsorbent was suitably described by the Langmuir
models. The process of adsorption was relatively rapid
and was best described by the pseudo-second-order
kinetic model. The results obtained in this study
shows that PH/CFO-Ac adsorbent could be used as an
effective adsorbent for the removal of direct blue dye
from synthetic wastewater and this has never been
reported in the literature.
Wastewater Engineering: Advanced Wastewater Treatment Systems
Chapter 2: Wastewater Treatment by Physical-Chemical Technologies
29
Fig. 17: SEM micrographs of (a) raw psyllium husk, (b) prepared PH/CFO-Ac adsorbent and (c) spent PH/CFO-Ac adsorbent
ACKNOWLEDGMENT
The authors wish to acknowledge the financial
support from the Universiti Sains Malaysia (Short
Term Grant A/C. 60310014 and Incentive Grant).
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Dahlan I, Razali MHM (2011). Waste-Derived
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Hameed B, El-Khaiary M (2008). Malachite green
adsorption by rattan sawdust: Isotherm, kinetic
and mechanism modeling. Journal of
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Hameed B, Hakimi H (2008). Utilization of durian
(Durio zibethinus Murray) peel as low cost
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Kadirvelu K, Kavipriya M, Karthika C, Radhika M,
Vennilamani N, Pattabhi S (2003). Utilization
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sorbent for reactive dyes. Bioresource
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Wastewater Engineering: Advanced Wastewater Treatment Systems
Available online at http://www.ijsrpub.com/books
2014 IJ SRPUB
31
COD and BOD Removal from Textile Wastewater Using Naturally Prepared
Adsorbents and Their Activation Forms Using Sulphuric Acid
Himanshu Patel*, R.T. Vashi
Department of Chemistry, Navyug Science College, Rander Road, Surat 395009, Gujarat, INDIA
*Corresponding Author: hjpatel123@yahoo.co.in
Abstract. Comparative adsorption studies of naturally prepared adsorbents (Neem leaf powder, Gauva leaf powder and
Tamarind seed powder) and their activation forms using sulphuric acid were conducted for removal COD and BOD from
textile wastewater. Process parameters like adsorbent dose, conduct duration, temperature and pH were examined in this study.
The adsorption data were analyzed using Freundlich, Langmuir, Dubinin-Raduskevich, Flory-Huggins, Redlich-Peterson, Sips,
Toth and Khan model to understand adsorption mechanism. Activated Neem leaf powder was most suitable than investigated
adsorbents. The maximum adsorption capacities were found to be 87.58, 85.65 and 81.25 mg/g for NLPs, GLPs and TSPs
respectively for COD and 84.51, 81.45 and 75.54 mg/g for NLPs, GLPs and TSPs respectively for BOD.
Keywords: Textile wastewater, Naturally prepared adsorbents and their activated form, Process Parameters, Adsorption
equilibrium isotherms
1. INTRODUCTION
Increasing public pressure and administrative concern
to arrest further deterioration of the environment may
result in more stringent standards. The objective of
wastewater treatment has expanded considerably from
simple nuisance control to include public health,
environmental, aesthetic and ecological
considerations. The day is not far off when industries
will have to acquire a nonpolluting or zero polluting
status to meet future environmental regulations. The
problem is more severe for the textile industry
because of its dynamic nature. Constantly changing
process lines result in diverse and complex wastes that
are ever changing in constitution and color (Venkata
Mohan et al., 1999). The textile industry is very
chemical-intensive; wastewater from textile-
processing contains huge residues from different
textile dyeing and finishing operations. Of particular
concern are dyestuffs, which are often major sources
of heavy metals, salt, adsorbable organic halogens and
color in dyehouse effluent, sizing agents, which have
high BOD and COD levels; and anionic/non-ionic
surfactants, most of which are still of poorly
biodegradable nature (Alaton et al., 2006).
There are many methods for the removal of
contaminations from wastewater, such as membrane
process, ion exchange, biological degradation and
adsorption using various kinds of adsorbent.
Adsorption process is proven to be an effective
process for the removal of various pollutants from its
aqueous solutions because adsorption process can
remove pollutant in wide range of concentrations
(Budyanto et al., 2008). The adsorption process has
not been used extensively in wastewater treatment, but
demands for a better quality of treated wastewater
effluent, including toxicity reduction, have led to an
intensive examination and use of the process of
adsorption. The relative advantages of adsorption over
other conventional advanced treatment methods are:
(1) it can remove both organic as well as inorganic
constituents even at very low concentrations, (2) it is
relatively easy and safe to operate, (3) both batch and
continuous equipment can be used, (4) no sludge
formation, and (5) the adsorbent can be regenerated
and used again. Moreover the process is economical
because it requires low capital cost and there are
abundant low-cost materials available which can be
used as adsorbents (Mohanty, et al., 2006). Low cost
adsorbents especially made from natural sources like
plant root, leaf, seed, peel, etc are being investigated.
Ulmus leaves and their ash, rubber (Hevea
brasiliensis) seed shell, Platanus orientalis leaves,
Rich husk, Sunflower stalks and Neem leaf powder
have been used for wastewater treatment and
adsorption has emerged as a cost-effective and
efficient alternative for the removal of hazardous
contaminations including dyes from low strength
wastewaters. Also, some acids were also utilized for
activation of adsorbents (Patel and Vashi, 2011).
Previously we had utilized activated neem leaf
powder (Patel and Vashi, 2012), activated guava leaf
powder (Patel and Vashi, 2011) and tamarind seed
powder (Patel and Vashi, 2010) for removal of dyes
from its aqueous solution and provided outstanding
results. There are very few research literatures
available for removal of COD and BOD from real
wastewater as per authors best knowledge. Present
investigation involved the preparation of naturally
prepared adsorbents (and its activation form) and
treatment of textile wastewater using these adsorbents
for removal of COD and BOD. Effect of adsorbent
dose, contact duration, temperature and pH were
studied. Freundlich, Langmuir, Dubinin-Raduskevich,
Flory-Huggins, Redlich-Peterson, Sips, Toth and
Khan models were tested for their applicability.
Patel and Vashi
COD and BOD Removal from Textile Wastewater Using Naturally Prepared Adsorbents and Their Activation Forms
Using Sulphuric Acid
32
2. METHODS AND MATERIALS
2.1. Adsorbent
The Neem (scientific name: Azadirachta indica)
belongs to the meliaceae family and is native to Indian
sub-continent. The Guava (Psidium Guajava; Family:
Myrtaceae) tree are easily available in Indian region.
The mature leaves of plant (Neem and Guava) used in
the present investigation are collected from the
available trees near Navyug Science College, Gujarat.
The mature leaves of plant washed thrice with water
to remove dust and water soluble impurities and were
dried until the leaves become crisp. The dried leaves
were crushed and powdered and further washed with
distilled water till the washings were free from color
and turbidity. Then this powder was dried in an oven
at 60 2 C and placed in desiccator for the
adsorption studies, thus natural adsorbent prepared.
The Tamarind (Tamarindus indica), a family of
Fabaceae, has used for preparation of medicines for
internal and external applications and as condiment in
many dishes. Tamarind fruit seed, collected from
nearby Navyug Science College, Gujarat, a waste
product of tamarind pulp, are washed, dried and
pulverized. This powder was washed with distilled
water till the washings were free from color and
turbidity and thereafter, dried in the oven at 60 C. For
activation of adsorbent, each adsorbent was stirred
with excess amount of 0.1 N sulphuric acid.
Thereafter, it washed with de-ionized water to remove
untreated acid dried in an oven at 60 2 C.
2.2. Experimental Details
The textile wastewater samples were withdrawn from
Pandesara, GIDC, Gujarat, India. Combine
wastewater samples were collected bimonthly for
three times in sampling bottles and placed in ice box
to preserve the characteristics of wastewater and were
analyzed as per standard method (APHA, 1992). For
removal of COD and BOD, batch experiments of
textile wastewater were carried out as per table 1.
Briefly, each adsorbent i.e. NLP and a-NLP (NLPs),
GLP and a-GLP (GLPs) and TSP and a-TSP (a-TSP)
was added to wastewater samples and the mixture was
stirred at 400 rpm. Each adsorbent was kept in contact
till equilibrium state was attained. The required pH of
system was maintained by using 0.1 N HCl or 0.1 N
NaOH during experiment. All chemicals used were of
analytical reagent grade and purchased from
Qualigens, India. The important physico-chemical
characteristics i.e. COD and BOD were determined
before and after treatment using standard methods.
Table 1: Experimental Details for treatment of wastewater using adsorbents
Effect of System Adsorption Dose (g/l) Temperature (K) Contact Duration (min) pH
Effect of adsorption dose
1, 2, 4, 6, 8, 10, 12, 14,
16, 18 and 20
300 180 7
Effect of contact duration 5.0 300
30, 60, 90, 120, 150,
180, 210 and 240
7
Effect of temperature 5.0
298, 303, 308, 313, 318,
323 and 328
180 7
Effect of pH 5.0 300 180 3, 5, 7, 9 and 11
2.3. Batch adsorption model
The equilibrium sorption isotherm is fundamentally
important in the design of sorption systems.
Equilibrium studies in sorption give the capacity of
the sorbent. It is described by sorption isotherm
characterized by certain constants whose values
express the surface properties and affinity of the
sorbent. (samsun clone). Different equilibrium models
were available to predict the sorption behavior. The
most commonly available models are Freundlich,
Langmuir, Dubinin-Raduskevich, Flory-Huggins,
Redlich-Peterson, Sips, Toth and Khan models.
2.3.1. Freundlich Isotherm
The Freundlich expression is an empirical equation
based on sorption on a heterogeneous surface and
effectively on multilayer and is expressed by the
following equation.
q
e
= K
F
C
e
1/n
or log q
e
= log K
F
+ 1/n log C
e
Where, q
e
and C
e
is the amount of adsorbed
adsorbate per unit weight of adsorbent and
unadsorbed adsorbate concentration in solution at
equilibrium, respectively and K
F
(L/mg) and n are
Freundlich constant characteristics of the system,
which are determined from the log q
e
vs. log C
e
. If the
value of exponent n was greater than 1 (n >1) then the
adsorption represent favorable adsorption
2.3.2. Langmuir Isotherm
This monolayer adsorption isotherm is very useful for
predicting adsorption capacities and also interpreting
into mass transfer relationship. The isotherm can be
written as follows:
Wastewater Engineering: Advanced Wastewater Treatment Systems
Chapter 2: Wastewater Treatment by Physical-Chemical Technologies
33
q
e
= k
L
C
e
/ (1 + a
L
C
e
) or (C
e
/q
e
) = (1/ K
L
) + (a
L
/K
L
)
C
e
The constant K
L
(L/g) is the Langmuir equilibrium
constant and the K
L
/a
L
gives the theoretical monolayer
saturation capacity, Q
max
(mg/g). These Langmuir
parameters were obtained from the linear correlations
between the values of C
e
/q
e
and C
e
. Generally, the
Langmuir equation, applies to the cases of adsorption
on completely homogeneous surfaces where
interactions between adsorbed molecules are
negligible (Ozacar and Sengil, 2005).
2.3.3. Dubinin-Raduskevich Isotherm
This isotherm can be used to describe adsorption on
both homogenous and heterogeneous surfaces. The
DubininRadushkevich equation has the following
form:
q
e
= q
m
e
-2
or In q
e
= In q
m
-
2
Where q
m
(mg/g) is the DubininRadushkevich
monolayer capacity a constant related to sorption
energy, and is the Polanyi potential which is related
to the equilibrium concentration as follows:
= RT In (1 + 1/C
e
)
Where R is the gas constant (8.314 J/mol K) and T
is the absolute temperature. The constant gives the
mean free energy, E, of adsorption per molecule of the
adsorbate when it is transferred to the surface of the
solid from infinity in the solution and can be
computed using the relationship.
E = 1/ (2)
The magnitude of E is useful for estimating the
mechanism of the adsorption reaction. In the case of E
< 8 kJ/mol, physical forces may affect the adsorption.
If E is in the range of 816 kJ/mol, adsorption is
governed by ion exchange mechanism, while for the
values of E > 16 kJ/mol, adsorption may be dominated
by particle diffusion.
2.3.4. Flory-Huggins Isotherm
The Flory-Huggins model accounts for the degree of
surface coverage characteristics of adsorbate on the
adsorbent and the linear form of the Flory-Huggins
equation is expressed as:
ln (q/C
e
) = ln(K
FH
) + a
FH
ln(1- q
e
)
Where q is the surface coverage of the adsorbent
by adsorbate. K
FH
(mg/g) and a
FH
are the Flory-
Huggins constants. These constants can be obtained
from the plot of log (q/C
e
) versus log (I-q
e
)
Furthermore the equilibrium constant K
FH
,
obtained from the Flory-Huggins isotherm model is
used to compute the Gibbs free energy for the
adsorption process. The Gibbs free energy is related to
equilibrium constant as follows:
G
0
= - RT/ In K
FH
Where R is universal gas constant 8.314 J/K/mol,
T is absolute temperature (K) and K
FH
is equilibrium
constant from Flory-Huggins isotherm equation
(Israel et al., 2010).
2.3.5. Redlich-Peterson Isotherm
The Redlich-Peterson isotherm model is widely used
as a compromise between the Langmuir and
Freundlich systems, since it combines elements from
both the Langmuir and Freundlich equations, where
the mechanism of adsorption is a hybrid one and does
not follow ideal monolayer adsorption. The Redlich-
Peterson isotherm has a linear dependence on
concentration in the numerator and an exponential
function in the denominator. It approaches the
Freundlich model at high concentration and is in
accordance with the low concentration limit of the
Langmuir equation. It can be applied either in
homogenous or heterogeneous systems due to the high
versatility of the equation. This model incorporates
three parameters into an empirical isotherm. It can be
described as follows,
ln[(K
RP
C
e
/q
e
) 1] =
RP
ln(C
e
) + ln(a
RP
)
Where, q
e
(mg/g), is the solid-phase adsorbate
concentration at equilibrium, C
e
(mg/l) is the liquid-
phase adsorbate concentration at equilibrium, K
RP
(1/mg) and a
RP
(L
mg
s
ln(C
e
) = - ln(K
s
/q
e
) + ln(a
s
)
Where K
s
is the total number of binding sites
(mg/g), as the median association constant (L/mg) and
1/n is the heterogeneity factor. If the value for
s
is
Patel and Vashi
COD and BOD Removal from Textile Wastewater Using Naturally Prepared Adsorbents and Their Activation Forms
Using Sulphuric Acid
34
less than one, it indicates that it is heterogeneous
adsorbents, while values closer to or even one
indicates that the adsorbent has relatively more
homogeneous binding sites.
2.3.7. Toth Isotherm
Toth isotherm model, is another empirical equation
developed to improve Langmuir isotherm fittings
(experimental data), and useful in describing
heterogeneous adsorption systems, which satisfying
both low and high-end boundary of the concentration.
Its correlation presupposes an asymmetrical quasi-
Gaussian energy distribution, with most of its sites has
adsorption energy lower than the peak (maximum) or
means value
q
e
= (q
m
b
T
C
e
) / [1 + (b
T
C
e
)
1/nT
]
nT
Where, q
m
(mg/g) is the Khan adsorption capacity,
and b
T
(1/mg) is the Toth model constant and n
T
the
Toth model exponent (Foo and Hameed, 2010).
3. RESULTS AND DISCUSSION
3.1. Characterization of Textile Wastewater
It was reported that water requirement vary from 61 to
646 liters per kg of cloth processed with an average
value of 235 liters per kg. These values correspond to
12 - 130 liter per meter of cloth with an average value
of 47 liters per kg. The pH of the investigated textile
mill effluent ranges from 9.24 to 7.64 having average
value of 8.2. The color of the wastewater is brownish
yellow having color unit 291.3 Hazen. The average
value of COD, BOD, Total Dissolved Solid (TDS),
Hardness, Alkalinity, Fluoride, Chloride and Sulphate
were 1556.2, 924.1, 6845.3, 1086.7, 670.7, 874.3,
475.3 and 877.1 ppm respectively. Also, average
value of Electrical Conductivity and Sulphate were
found to be 7417.0 s/cm. High value of
contaminations are presented due to usage of
chemicals such as starches, dextrin, gums, glucose,
waxes, pectin, alcohol, fatty acids, acetic acid, soap,
detergents, sodium hydroxide, carbonates, sulfides,
sulfites, chlorides, dyes, pigments, carboxymethyl
cellulose, gelatin, peroxides, silicones, flourcarbons,
resins, etc. in wet processes of textile mill. Same types
of contaminations were found, while investigating
textile wastewater (Fanchiang et al., 2006, Pathe et al.,
2005, Martins et al., 2006).
3.2. Effect of Adsorbent Dose
Figure 1, 2 and 3 shows the effect of different doses
(Ceq vs. Adsorbent dose) of naturally prepared
adsorbents i.e. NLPs, GLPs and TSPs respectively
maintaining temperature of 300 K, contact duration of
180 and pH 7. It can be seen that there is a large
reduction in the COD content when NLPs was used,
from an initial value of 1625.8 ppm to zero and 110.2
ppm at a dosage of 20 g/L of a-NLP and NLP
respectively. BOD had an initial value of 1002.4 to
11.2 and 51.5 ppm by 20 g/L of a-NLP and NLP
respectively. It can be also seen that there is a large
reduction in the COD content when GLPs is used,
from an initial value of 1625.8 to 258.4 and 411.2
ppm at a dosage of 20 g/L of a-GLP and GLP
respectively. BOD had an initial value of 1002.4 to
201.2 and 212.2 ppm when 20 g/L of a-GLP and GLP
was used respectively. It can be seen that there is a
large reduction in the COD content using TSPs, from
an initial value of 1625.8 to 411.2 and 312.2 ppm at a
dosage of 20 g/L of TSP and a-TSP respectively.
BOD had an initial value of 1002.4 to 280.5 and 251.2
ppm by 20 g/L of TSP and a-TSP respectively.
Fig. 1: Effect of adsorbent dose for percentage COD and BOD removal using NLPs
Wastewater Engineering: Advanced Wastewater Treatment Systems
Chapter 2: Wastewater Treatment by Physical-Chemical Technologies
35
Fig. 2: Effect of adsorbent dose for percentage COD and BOD removal using GLPs
Fig. 3: Effect of adsorbent dose for percentage COD and BOD removal using TSPs
From all the adsorbents, a-NLP was found to be
more effective than all investigated adsorbents for
removal of COD and BOD. Also, it was easily
appeared that value of Ceq was continuously
decreasing with increasing adsorbent dose upto 18.0
g/L. The increase in adsorption with increase in
adsorbent may be attributed due to the reason of
increased adsorbent surface and availability of more
adsorption sites. The reason behind the phenomenon
may be speculated to be due to the interference
between binding sites at higher concentrations in
solution with respect to available binding sites. Then
after straight line indicated the equilibrium was
attained at dose of 18.0 g/l for all adsorbents
investigated. It can explain that further increase in the
dose of adsorbent did not affect the uptake capacity
because of the unavailability of adsorbate sites due to
saturation (Li et al., 2008).
3.3. Effect of Contact Duration
Table 2 reveals effect of different contact durations
(30 to 240 minutes) on the COD, BOD and color
removal using 5.0 g/L dosage of NLPs, GLPs and
TSPs at constant temperature (300 K), pH (7) and
agitator speed (400 rpm). Percentage removal of COD
was found to be 30.3 to 63.6, 19.6 to 63.4 and 9.5 to
41.5 using a-NLP, a-GLP and a-TSP respectively.
Also, percentage removal of COD was found to be
20.1 to 57.2, 11.2 to 47.5 and 13.4 to 56.2 using NLP,
GLP and TSP respectively. Percentage removal of
BOD was found to be 26.1 to 57.4, 14.6 to 49.7 and
5.2 to 32.1 using a-NLP, a-GLP and a-TSP
respectively. Also, percentage removal of BOD was
found to be 15.2 to 46.2, 9.2 to 42.1 and 10.1 to 40.1
using NLP, GLP and TSP respectively. These
removals were found at contact duration of 30 to 240
min respectively.
In adsorption process, a knowledge regarding the
contact time required to achieve the equilibrium is
highly important. Table 2 clearly indicates a rapid
increase in the amount of adsorption with increase in
time initially, gradually leading to equilibrium.
Although at higher contact time, the rate of adsorption
decreased and a saturation stage was attained due to
the accumulation of the adsorption sites. This decline
is due to decrease in total adsorbent surface area and
increased diffusion pathway. It can also elucidate that
Patel and Vashi
COD and BOD Removal from Textile Wastewater Using Naturally Prepared Adsorbents and Their Activation Forms
Using Sulphuric Acid
36
mechanism of solute transfer to the solid includes
diffusion through the fluid film around the adsorbent
particle and diffusion through the pores to the internal
adsorption sites. Initially the concentration gradient
between the film and the solid surface is large, and
hence the transfer of solute onto the solid surface is
faster. That is why it takes lesser time to attain
percentage removal of COD and BOD. As time
increases, intraparticle diffusion becomes
predominant. Hence solute takes more time to transfer
from solid surface to internal adsorption sites through
the pores (Hameed et al., 2008, Gulipalli et al., 2011).
Table 2: Effect of contact duration for percentage COD and BOD removal using naturally prepared adsorbents
Adsorbent % Removal
Contact Duration (min)
30 60 90 120 150 180 210 240
a-NLP
COD 30.3 39.9 50.4 54.1 57.2 60.1 63.6 63.6
BOD 26.1 31.2 39.0 49.5 53.6 55.7 57.4 57.4
NLP
COD 20.1 30.2 41.2 45.2 51.0 55.2 57.2 57.2
BOD 15.2 20.5 28.5 40.5 44.2 45.5 46.2 46.2
a-GLP
COD 19.6 32.3 44.3 48.9 56.5 58.5 63.4 63.4
BOD 14.6 28.6 34.5 40.1 45.1 48.1 49.7 49.7
GLP
COD 11.2 20.2 30.2 35.5 41.2 45.5 47.4 47.4
BOD 9.2 15.4 20.4 30.2 34.5 40.1 42.1 42.1
a-TSP
COD 9.5 14.5 19.5 28.9 33.3 39.5 41.5 41.5
BOD 5.2 10.2 16.5 20.5 27.5 30.2 32.1 32.1
TSP
COD 13.4 20.9 30.5 39.7 50.4 53.1 56.2 56.2
BOD 10.1 18.8 24.7 31.2 36.7 38.0 40.1 40.1
3.4. Effect of Temperature
The effect of variation in temperature i.e. 298, 303,
308, 313, 318, 323 and 328 K on the adsorption by a-
NLP, a-GLP and TSP at constant contact duration,
with respect to COD, BOD and color of wastewater is
depicted in Table 3. It can be seen that the increase in
temperature leads to linear decrease in percent
removal in three cases. Also, straight line after
temperature of 323 K indicating equilibrium
accomplished at temperature of 323 K. The values of
percent removal of COD were seen to increase from
39.1 to 75.6 % by a-NLP, 20.15 to 65.6 by NLP
whereas from 30.3 to 72.3 % by a-GLP, 20.1 to 61.2
% using GLP and from 15.2 to 47.7 % by a-TSP and
also, 24.3 and 63.0 % by TSP at temperature of 298 to
328 K respectively. The values of percent removal of
BOD were seen to increase from 34.7 to 63.2 % by a-
NLP, 20.25 to 55.5 by NLP whereas from 29.0 to 68.0
% by a-GLP, 18.2 to 60.0 % using GLP and from 7.2
to 47.7 % by a-TSP and also, 18.7 and 58.1 % by TSP
at temperature of 298 to 328 K respectively. The
adsorption capacity increases with the increasing
temperature, indicating that the adsorption is an
endothermic process. This may be a result of an
increase in the mobility of chemicals (contributing
COD and BOD) with increasing temperature. An
increasing number of molecules may also acquire
sufficient energy to undergo an interaction with active
sites at the surface. Furthermore, the increasing
temperature may produce a swelling effect within the
internal structure of adsorbents (NLPs, GLPs and
TSPs), enabling to penetrate further (Malkoc et al.,
2007).
3.5. Effect of pH
The effect of pH (3 to 11) is represented in Table 4
using NLPs, GLPs and TSPs (dose: 5.0 g/L) for
removal of COD, BOD and color from textile
wastewater at constant contact duration of 180 min,
temperature of 300 K and agitator speed of 400 rpm.
The percentage removal was increasing, as pH of
system increases. The highest percentage removal of
COD was found to be 64.8, 55.5, 57.4, 47.5, 50.2 and
56.5 by a-NLP, NLP, a-GLP, GLP, a-TSP and TSP
respectively at pH 11. The highest percentage removal
of BOD was found to be 60.0, 54.2, 48.7, 40.2, 41.2
and 44.7 by a-NLP, NLP, a-GLP, GLP, a-TSP and
TSP respectively at pH 11. Though, the factor pH is
an important parameter in adsorption studies, but due
to presence of various elements in dyeing mill
wastewater such as starches, dextrin, gums, glucose,
waxes, pectin, alcohol, fatty acids, acetic acid, soap,
detergents, sodium hydroxide, carbonates, sulfides,
sulfites, chlorides, dyes, pigments, carboxymethyl
cellulose, gelatin, peroxides, silicones, flourcarbons,
resins; the moderate removal of COD, BOD and color
was found with change of factor, pH (ONeill et al.,
1999).
Wastewater Engineering: Advanced Wastewater Treatment Systems
Chapter 2: Wastewater Treatment by Physical-Chemical Technologies
37
Table 3: Effect of temperature for percentage COD and BOD removal using naturally prepared adsorbents
Adsorbent
% Removal
Temperature (K)
298 303 308 313 318 328 328
a-NLP
COD 39.1 48.6 56.0 62.2 70.1 75.6 76.0
BOD 34.7 41.4 48.0 52.6 60.1 63.0 63.2
NLP
COD 20.1 32.2 45.5 50.5 61.2 65.6 65.6
BOD 20.2 32.2 35.6 42.5 51.2 55.5 55.5
a-GLP
COD 30.3 39.1 54.6 62.2 68.3 72.3 73.0
BOD 29.0 35.0 45.4 52.1 61.6 67.6 68.0
GLP
COD 20.0 28.5 44.2 52.1 57.2 61.2 61.2
BOD 18.2 25.5 34.4 41.1 54.2 60.0 60.0
a-TSP
COD 15.2 20.2 26.5 37.3 44.5 47.5 47.5
BOD 7.8 12.5 25.5 35.8 43.6 47.7 47.7
TSP
COD 24.3 37.9 44.9 52.2 56.5 62.5 63.0
BOD 18.7 25.9 38.6 45.9 51.6 58.1 58.1
Table 4: Effect of temperature for percentage COD and BOD removal using naturally prepared adsorbents
Adsorbent % Removal
pH
3 5 7 9 11
a-NLP
COD 14.8 23.6 39.0 56.5 64.8
BOD 9.7 17.6 32.1 50.1 60.0
NLP
COD 10.0 15.5 27.4 45.5 55.5
BOD 5.2 10.5 20.5 41.4 54.2
a-GLP
COD 7.5 14.8 26.5 42.1 57.4
BOD 3.2 10.2 20.2 34.7 48.7
GLP
COD 5.5 10.2 15.5 30.2 47.5
BOD 1.2 5.5 11.1 25.5 40.2
a-TSP
COD 4.5 12.5 24.5 41.5 50.2
BOD 3.5 15.2 20.5 31.5 41.4
TSP
COD 8.0 24.2 34.8 50.4 56.5
BOD 5.7 21.7 31.7 40.0 44.7
3.6. Adsorption Model
Table 5 described Freundlich and Langmuir
parameters for COD and BOD removal using
naturally prepared adsorbents i.e. NLPs, GLPs and
TSPs. Freundlich adsorption capacity, K
F
was found
to be 79.39 and 41.64 L/mg using a-NLP and 45.12
and 40.25 L/mg using NLP for COD and BOD
respectively. Freundlich adsorption capacity was
found to be 28.69 and 12.13 L/mg using a-GLP and
20.45 and 15.18 L/mg using GLP for COD and BOD
respectively. Freundlich adsorption capacity was
found to be 20.45 and 15.18 L/mg using a-TSP and
23.07 and 11.71 L/mg using TSP for COD and BOD
respectively. Langmuir adsorption capacity, Q
max
for
COD and BOD was obtained 87.58 and 84.51 mg/g
respectively using a-NLP and 80.45 and 79.58 mg/g
respectively using NLP. Langmuir adsorption capacity
for COD and BOD was obtained 85.65 and 81.45
mg/g respectively using a-GLP and 82.41 and 78.57
mg/g respectively using GLP. Langmuir adsorption
capacity for COD and BOD was obtained 75.14 and
70.45 mg/g respectively using a-TSP and 81.25 and
75.54 mg/g respectively using TSP. Freundlich and
Langmuir adsorption capacities indicate the good
sorbing capacity of the naturally prepared adsorbents.
Also, it shows that a-NLP is more preferable
adsorbent then other investigated adsorbents.
Activation of Neem Leaf Powder and Guava Leaf
Powder using sulphuric acid were found more
proficient than regular NLP and GLP. Regular
Tamarind Seed Powder (TSP) was found to be more
efficient than activated TSP using sulphuric acid. This
shows that H
2
SO
4
is effective in creating well-
developed pores on the surface of NLP and GLP with
large surface area and porous structure. But in the case
of TSP, there was no change in surface of TSP while
activation using sulphuric acid. Further, value of
exponent n was greater than 1 (n > 1), so, the
adsorption represents favorable adsorption.
DubininRadushkevich and FloryHuggins
parameters for COD and BOD removal using
naturally prepared adsorbents were depicted in Table
6. Maximum DubininRadushkevich monolayer
capacity, q
m
was found to be 18.45, 15.27 and 10.65
mg/g for NLPs, GLPs and TSPs respectively for COD
and 13.27, 12.17 and 8.54 mg/g for NLPs, GLPs and
TSPs respectively for BOD. All these value are close
to that obtained from the Langmuir isotherm model.
The calculate energy was found to be in the range of
1.2412 - 0.5258 KJ/mol, which confirm physical
adsorption reaction. Physisorption processes have
adsorption energies less than 8 KJ/mol and the energy
in the range of 1.2412 - 0.5258 KJ/mol for removal of
Patel and Vashi
COD and BOD Removal from Textile Wastewater Using Naturally Prepared Adsorbents and Their Activation Forms
Using Sulphuric Acid
38
COD and BOD using naturally prepared adsorbents
indicates that the sorption process is physisorption and
the positive value of energy (E), of sorption indicates
that the sorption process is endothermic and that
higher solution temperature will favor the sorption
process. The FloryHuggins adsorption capacity, k
FM
was calculated and found to be 0.0555, 0.0450 and
0.0252 mg/g for NLPs, GLPs and TSPs respectively
for COD and 0.0452, 0.0402 and 0.0301 mg/g for
NLPs, GLPs and TSPs respectively for BOD. The
G
0
for this study was computed in the range of -
9.1909 to -13.8271 kJ/mol. The negative value of G
0
indicates that the sorption process is spontaneous in
nature.
Table 5: Freundlich and Langmuir parameters for COD and BOD removal using naturally prepared adsorbents
Adsorbent Removal
Freundlich Parameters Langmuir Parameters
K
F
(L/mg) n Q
max
(mg/g) K
L
(L/mg)
a-NLP
COD 79.39 0.1377 87.58 0.049
BOD 41.64 0.2262 84.51 0.037
NLP
COD 45.12 0.1379 80.45 0.045
BOD 40.25 0.1919 79.58 0.012
a-GLP
COD 28.69 0.4065 85.65 0.12
BOD 12.13 0.1447 81.45 0.14
GLP
COD 20.45 0.3175 82.41 0.21
BOD 15.18 0.2809 78.57 0.54
a-TSP
COD 17.4 0.2353 75.14 0.14
BOD 7.45 0.1212 70.45 0.024
TSP
COD 23.07 0.1570 81.25 0.17
BOD 11.71 0.1350 75.54 0.016
Table 6: DubininRadushkevich and Flory-Huggins parameters for COD and BOD removal using naturally prepared
adsorbents
Adsorbent Particular
Dubinin-Radushkevich Parameters Flory-Huggins Parameters
q
m
(mg/g) (mmol
2
/J
2
)
E (kJ/mol) n
FH
k
FH
(mg/g) G
0
(kJ/mol)
a-NLP
COD 18.45 4.613 1.2412 -0.699 0.0552 -6.9707
BOD 13.27 10.332 0.9574 -0.657 0.0452 -7.2395
NLP
COD 15.21 15.485 0.8747 -0.547 0.0212 -6.1091
BOD 8.27 22.258 0.8547 -0.512 0.0392 -6.7909
a-GLP
COD 15.27 0.3547 0.8258 -0.431 0.0450 -10.2111
BOD 12.17 0.3948 0.6847 -0.379 0.0402 -11.2551
GLP
COD 12.41 0.5158 0.5258 -0.3954 0.0166 -9.1909
BOD 7.55 0.7414 0.6868 -0.354 0.0305 -10.7929
a-TSP
COD 8.65 0.3470 0.7265 -0.407 0.0185 -9.4405
BOD 5.87 0.5081 0.8584 -0.317 0.0205 -12.6157
TSP
COD 10.65 0.6587 0.7457 -0.375 0.0252 -10.2332
BOD 8.54 0.8714 0.6585 -0.298 0.0301 -13.8271
Table 7 depicted Redlish-Peterson and Sips
parameters for COD and BOD removal using
naturally prepared adsorbents, in which an exponent
of Redlish-Peterson,
RP
not far from 1, indicate that
the Langmuir isotherm best-fits the isotherm data for
removal of COD and BOD using naturally prepared
adsorbents. The Sips adsorption capacity, q
m
was
calculated and found to be 19.7, 17.9 and 15.5 mg/g
for NLPs, GLPs and TSPs respectively for COD and
18.5, 17.9 and 10.0 mg/g for NLPs, GLPs and TSPs
respectively for BOD. Similar to the RedlichPeterson
model constants, the same trends were observed for
the Sips model constants. The exponent, n values were
close to unity. This means that sorption data obtained
in this study is more suited to Langmuir form than
Freundlich.
Table 8 described the Toth and Khan Isotherm
parameters for COD and BOD removal using
naturally prepared adsorbents. Maximum Toth
adsorption capacity, q
m
was found to be 14.25, 10.47
and 6.58 mg/g for NLPs, GLPs and TSPs respectively
for COD and 7.87, 5.84 and 4.58 mg/g for NLPs,
GLPs and TSPs respectively for BOD. Further, It is
obvious that for Toth model exponent, n
T
= 1, this
isotherm reduces to the Langmuir sorption isotherm
equation. Maximum Khan adsorption capacity, q
m
was
found to be 17.34, 11.44 and 11.14 mg/g for NLPs,
GLPs and TSPs respectively for COD and 15.82,
10.78 and 10.47 mg/g for NLPs, GLPs and TSPs
respectively for BOD.
Wastewater Engineering: Advanced Wastewater Treatment Systems
Chapter 2: Wastewater Treatment by Physical-Chemical Technologies
39
Table 7: Redlish-Peterson and Sips parameters for COD and BOD removal using naturally prepared adsorbents
Adsorbent Particular
Redlish-Peterson Parameters Sips Parameters
KRP
(1/mg)
aRP (Lmg) RP qm (mg/g) Ks (L/mg) n
a-NLP
COD 2.40 0.234 0.874 19.7 1030.2 0.734
BOD 3.18 7.489 0.907 18.5 9217.4 0.847
NLP
COD 1.25 45.12 0.915 14.4 9845.5 0.745
BOD 1.02 0.245 0.995 10.8 5545.5 0.824
a-GLP
COD 1.23 61.67 0.940 17.9 8462.5 0.885
BOD 0.31 0.032 1.007 15.2 1251.4 0.755
GLP
COD 0.915 75.45 0.954 10.5 4578.5 0.705
BOD 0.29 0.025 0.54 7.4 1020.2 0.821
a-TSP
COD 0.83 149.8 0.991 12.1 1656.5 0.927
BOD 0.24 0.004 0.96 7.2 768.5 0.835
TSP
COD 0.71 158.5 0.542 15.5 754.5 0.812
BOD 0.12 0.0011 0.547 10.0 625.5 0.714
Table 8: Toth and Khan parameters for COD and BOD removal using naturally prepared adsorbents
Adsorbent Particular
Toth Isotherm Khan Isotherm
q
m
(mg/g) b
T
(1/mg) n
T
q
m
(mg/g) b
K
(L/mg) a
K
a-NLP
COD 14.25 0.025 0.854 17.34 0.245 0.057
BOD 7.87 0.058 0.754 15.82 0.547 0.047
NLP
COD 11.24 0.047 0.687 14.14 0.657 0.068
BOD 4.58 0.052 0.847 10.25 0.847 0.084
a-GLP
COD 10.47 0.047 0.856 11.44 0.574 0.064
BOD 5.84 0.065 0.884 10.78 0.632 0.057
GLP
COD 8.66 0.043 0.785 7.45 0.478 0.068
BOD 4.58 0.045 0.847 15.45 0.558 0.062
a-TSP
COD 5.58 0.042 0.748 8.45 0.874 0.041
BOD 3.85 0.028 0.789 7.45 0.658 0.038
TSP
COD 6.58 0.045 0.840 11.14 0.782 0.057
BOD 4.58 0.036 0.705 10.47 0.687 0.047
4. CONCLUSION
This study provides characterization of textile
wastewater and, simple and effective adsorption
process for COD and BOD removal using naturally
prepared adsorbents (NLP, GLP and TSP) and their
activation forms using sulfuric acid. It is observed
from the present investigation that the textile
wastewater contains various types of pollutants, which
are not easily removed. Batch adsorptive treatment
was carried out using various parameters like
adsorbent dose, conduct duration, temperature and
pH, in whixch activation of Neem Leaf Powder and
Guava Leaf Powder using sulphuric acid was found
more proficient than investigated regular NLPs and
GLPs. Regular Tamarind Seed Powder (TSP) was
found to be more efficient than activated TSP using
sulphuric acid. The adsorption equilibrium isotherms,
viz. Freundlich, Langmuir, Dubinin-Raduskevich,
Flory-Huggins, Redlich-Peterson, Sips, Toth and
Khan isotherm ware analyzed, in which maximum
adsorption capacities of linear equation Langmuir
isotherm was calculated and found to be 87.58, 85.65
and 81.25 mg/g for NLPs, GLPs and TSPs
respectively for COD and 84.51, 81.45 and 75.54
mg/g for NLPs, GLPs and TSPs respectively for
BOD. Also, Langmuir isotherm best-fits the isotherm
data for removal of COD and BOD using naturally
prepared adsorbents. This sorption process is
physisorption and endothermic and that higher
solution temperature will favor the sorption process,
derived from calculated free energy, E. The negative
value of G0 indicates that the sorption process is
spontaneous in nature.
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Using Sulphuric Acid
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Wastewater Engineering: Advanced Wastewater Treatment Systems
Available online at http://www.ijsrpub.com/books
2014 IJ SRPUB
41
Fenton Oxidation for the Treatment of Liquid Waste with High COD and
Anionic/Non-ionic Surfactants
M.C. Collivignarelli
1
, S. Sorlini
2*
, A. Abb
1
, M. Sordi
1
1
Department of Civil Engineering and Architecture, University of Pavia, via Ferrata 1, 27100, Pavia, Italy
2
Department of Civil Engineering, Architecture, Land, Environment and Mathematics, University of Brescia, via Branze 43,
25123, Brescia, Italy
*Corresponding Author: Email: sabrina.sorlini@ing.unibs.it
Abstract. In the present work, liquid wastes from different kinds of industrial plants, characterized by high COD (up to
100,000 mg/L) and surfactants (up to 16,000 and 3,800 mg/L for non-ionic and anionic respectively) concentrations were
treated by means of Fenton oxidation. During the experimental research 28 tests at laboratory scale were performed. Each test
was characterized by specific dosage of reagents (Fe
2+
e H
2
O
2
) and contact time. In particular, Fe
2+
/H
2
O
2
ratio varied from 0.25
to 0.50, H
2
O
2
/COD ratio from 0.72 to 1.5 while the contact time increased from 30 to 120 minutes. The main objective of this
work was to define the dosage of reagents and the reaction contact time able to optimize the process performance in terms of
removal yields of COD and surfactants. The results showed that the optimal treatment conditions could be obtained with a
Fe
2+
/H
2
O
2
ratio equal to 0.25, a H
2
O
2
/COD ratio of 1 and a reaction time of 30 minutes. An average removal yield of 70% for
AS (non-ionic surfactants) and COD and 95% for MBAS (anionic surfactants) respectively was obtained.
Keywords: Surfactants, Fenton Oxidation, High COD
1. INTRODUCTION
Surfactants are a group of compounds used daily in
huge amounts mainly in household applications and as
industrial cleaning agents (Gonzalez et al., 2007;
Hosseinnia et al., 2006). As is known, the surfactants
can be classified in different groups depending on the
electrostatic charge of its hydrophilic groups: anionic
(MBAS), non-ionic (TAS), cationic and amphoteric
surfactants (the last compounds behave as acids or
bases, depending on the solution acidity). The first
two groups are the most common and account for over
80% of the total usage in detergents. Cationic
surfactants are used mainly in fabric conditioners to
give a pleasant soft feel to the product while
amphoteric surfactants are used mainly for their skin
mildness properties (AISE, 2012). The new European
Detergent Regulation (Regulation 648/2004, that
entered in force on 2005) requires that the surfactants
used in household detergents must be biodegradable,
while derogation may be accepted for surfactants in
detergents used in special industrial or institutional
sectors. In Western Europe each year over 2.5 million
tonnes of surfactants are produced (45% anionic, 43%
non-ionic, 8% cationic, 4% amphoteric) (CESIO,
2012).
In the past, some types of surfactants (non-ionic)
resulted to be dangerous for the humans and the
environment also after biological treatment. In fact,
although they were easily removable in well operating
treatment plants with removal yields of about 90-95%,
the last oxidation step was much slower due to the
formation of by-products that are toxic and refractory
to biological treatment (Gonzalez et al., 2007). The
main methods for the treatment of sewage and liquid
wastes containing surfactants involve chemical and
physical processes such as coagulation, foaming,
advanced chemical oxidation, adsorption on different
types of active carbon and polyelectrolytes (Kowalska
et al., 2006). Liquid wastes produced in personal care
product manufacturing are primarily treated by
aerobic activated sludge systems coupled with
physico-chemical methods, although biological
methods are generally favoured because they produce
more tractable solids residuals (Ahammad et al.,
2013). Anaerobic biological processes typically are
not used for high color waster because of the presence
of compounds that inhibit anaerobic microorganisms
(Ahammad et al., 2013). Often liquid wastes
containing surfactants (such as those arising from
industries for the production of personal care
products) are characterized by high COD
concentrations and by poorly biodegradable
compounds that may be toxic (Dias de Melo et al.,
2013). Also liquid waste from tannery industries
belong to the same typology, so conventional
treatments produce effluents still do not meet the
required limits, at least for some parameters such as
COD, salinity, ammonia and surfactants (Kurt et al.,
2007). Hence chemical oxidation systems appear to be
more suitable in treating liquid wastes characterized
by poorly biodegradable and toxic compounds and
high concentrations contents in COD and surfactants.
In the present study Fenton oxidation was
experimented at laboratory scale in order to evaluate
the treatment of colored liquid wastes with high
concentrations of COD and surfactants.
Collivignarelli et al.
Fenton Oxidation for the Treatment of Liquid Waste with High COD and Anionic/Non-ionic Surfactants
42
2. MATERIALS AND METHODS
2.1. Equipment used for Fenton oxidation
Fenton experimental tests were carried out at lab scale
with a 2 liter-glass beaker placed over a magnetic
stirrer (Figure 1 a). A probe for the measurement of
pH was placed inside the beaker (Figure 1 b).
Each experimental test was carried out according
to the following procedure:
(1) Addition of 1 L- volume of liquid waste into
the beaker;
(2) pH adjustment of the liquid waste through the
gradual addition of 1 N sulfuric acid until the desired
pH test;
(3) Dosage of reagents (hydrogen peroxide 40%
w/v solution and FeSO
4
7H
2
O ferrous salt in solid
form) and start of the reaction; both the two reagents
were dosed gradually inside the beaker in order to
allow a better distribution within the mixture;
(4) Monitoring of the reaction, at regular intervals,
maintaining the sample in stirring conditions: H
2
O
2
and Fe
2+
concentrations, temperature and pH were
measured;
(5) pH increasing up to 8.5-9 by gradual dosage of
lime milk (Ca(OH)
2
) in solution at 5%;
(6) settling of the mixture for 2 hours by means of
an Imhoff cone in order to observe the sedimentation
characteristics of the treated liquid waste (Figure 1c);
the level of the solid/liquid interface was recorded
every 30 minutes;
(7) Samples extraction by 0.45 m (paper filter)
filtration of the supernatant obtained from step 6.
Fig. 1: Equipment used for Fenton oxidation tests 1 a - pH measurement 1 b - settling of the mixture 1 c
2.2. Characteristics of liquid wastes
Table 1 shows the qualitative characteristics of the
liquid wastes (LW) treated during the experimental
tests: raw LW II - III - IV and LW I, previously
mixed with an acid liquid waste (characterized by
COD concentration of 30000 mg/L and pH < 1.5) that
allowed to reach the optimal pH without the addition
of sulfuric acid (LW I - mix 1 and mix 2 contained
83% and 17% of LW I respectively).
Table 1: Qualitative characteristics of the liquid wastes
PARAMETER U.M. LW I LW II LW III LW IV
COD mg/L 17800 56680 50450 101900
TAS mg/L 24.7 1033 845 16000
MBAS mg/L 102 1490 13100 3870
BOD
5
mg/L 8000 6000 - -
BOD
20
mg/L - - - -
TN mg/L 307 < 0.5 - -
N-NH
4
+
mg/L 37.4 < 0.5 8.8 65
N-NO
3
-
mg/L 17.3 < 0.5 - -
N-NO
2
-
mg/L 0.2 < 0.1 - -
TP mg/L 393 < 0.5 - -
pH - 6.7 5.8 5.5 8.6
color/appearance - green/limpid white/mushy gray/mushy brown/limpid
Wastewater Engineering: Advanced Wastewater Treatment Systems
Chapter 2: Wastewater Treatment by Physical-Chemical Technologies
43
2.3. Experimental tests
The tests were carried out with different dosages of
reagents (expressed as H
2
O
2
/COD and Fe
2+
/H
2
O
2
),
reaction time and temperature in order to determine
the optimal process conditions. The detailed
experimental conditions are reported in Table 2.
Table 2: Experimental conditions applied during Fenton oxidation
Tests Liquid Waste (LW)
Operative conditions
Contact time [minutes] (H
2
O
2
/COD)
0
Fe
2+
/H
2
O
2
F 1
I
(mix 1)
30 0.36 1/2
F 2 30 0.36 1/5
F 3 30 0.72 1/4
F 4 60 1 1/2
F 5 60 0.72 1/2
F 6
I
(mix 2)
60 0.72 1/2
F 7 60 1.17 1/2
F 8 60 2 1/4
F 11
II
60 0.72 1/4
F 12 60 1 1/4
F 13 60 0.72 1/2
F 14 30 0.72 1/4
F 15 60 1.5 1/4
F 16 120 0.72 1/4
F 17
III
60 0.72 1/4
F 18 60 1 1/4
F 19 60 1.5 1/4
F 20 30 0.72 1/4
F 21 60 1 1/2
F 22 120 1 1/4
F 23
IV
60 0.72 1/4
F 24 60 1 1/4
F 25 60 1.5 1/4
F 26 30 0.72 1/4
F 27 60 1 1/2
F 28 120 1 1/4
2.4. Analytical methods
The physical-chemical parameters such as COD, N-
NH
4
+
, N-NO
2
-
, N-NO
3
-
, TN (total nitrogen), MBAS
(anionic surfactants), TAS (non-ionic surfactants), pH
were measured according to the standard methods for
water and wastewater (APHA et al., 2001). TP (total
phosphorus) was analyzed by ICP-MS. BOD
5
was
determined at 20 C by inoculation of active biomass
collected from an activated sludge wastewater
treatment plant (WWTP).
3. RESULTS AND DISCUSSIONS
3.1. Effect of the Fe
2+
dosage
In order to assess the optimal dosage of iron, each
liquid waste was tested with two ratios of Fe
2+
/H
2
O
2
:
0.25 and 0.5 respectively. The removal yields of COD
and surfactants (MBAS and TAS) versus Fe
2+
/H
2
O
2
and with different contact time and H
2
O
2
/COD ratio
are reported in Figures 2 and 3 respectively. As
concerns COD the optimal dosage of iron seems to be
Fe
2+
/H
2
O = 0.25, for which most of the processed LW
showed better removal yields for reaction times of 30
and 60 minutes and for H
2
O
2
/COD ratio equal to 0.36,
0.72 and 1 (LW I - mix1, LW II, LW III). The tests
performed on the LW II and LW IV show a decrease
of COD removal yields with increasing the iron
dosage. The best removal yields were achieved in the
treatment of liquid waste LW III with values slightly
below 90%.
Collivignarelli et al.
Fenton Oxidation for the Treatment of Liquid Waste with High COD and Anionic/Non-ionic Surfactants
44
Fig. 2: Effect of the iron dosage on COD removal
The removal yields of surfactants as a function of
the iron dosage are shown in Figure 3. In this case
doubling the iron dosage a reduction in the removal
yields of surfactants occurred (LW - mix 2, LW II,
LW IV), in particular for TAS that showed a higher
reduction than MBAS (LW I - mix 2, LW II).
Doubling Fe
2+
/H
2
O
2
ratio an improvement of
surfactant removal yields was observed only for LW I
- mix 1 and LW III. Moreover, the anionic surfactants
are the most easily removed, as shown by the average
yield obtained for all the tests equal to about 90%and
60% respectively for anionic and non-ionic
surfactants.
Fig. 3: Effect of the iron dosage on TAS and MBAS removal
3.2. Effect of the H
2
O
2
dosage
After determining optimal dosages of iron, different
laboratory tests were carried out on the same liquid
wastes in order to evaluate the optimal dosage of
hydrogen peroxide. The H
2
O
2
/COD ratios were 0.72,
1, 1.5 and only for LWI - mix 2 the 1.17 ratio was
added. Figure 4 shows the removal yields of COD
obtained during these tests. All liquid wastes showed
an increase of COD removal yields with increasing
the dosage of hydrogen peroxide with the exception of
the LW III for which the removal yield was constantly
about 85%.
Wastewater Engineering: Advanced Wastewater Treatment Systems
Chapter 2: Wastewater Treatment by Physical-Chemical Technologies
45
Fig. 4: Effect of the hydrogen peroxide dosage on COD removal
The anionic surfactants showed a similar behavior
to COD. Instead, for the non-ionic surfactants (TAS)
the yield of removal (Figure 5) significantly increased
with increasing the dosage of hydrogen peroxide with
respect to the initial COD from 0.72 to 1. A further
increase of the dosage of hydrogen peroxide (from 1
to 1.5 H
2
O
2
/COD ratio), does not lead to any
improvement in TAS removal yields (as concerns LW
II, LW III LW IV).
Fig. 5: Effect of the hydrogen peroxide dosage on TAS and MBAS removal
3.3. Effect of contact time
Finally, the effect of the contact time on the removal
of COD (Figure 6) and surfactants (Figure 7) was
evaluated. The results obtained showed that the
optimal contact time was equal to 30 minutes for each
liquid waste. Indeed, the low increase of removal
yields is observed for COD increasing the contact
time from 30 to 60 minutes may be partially caused by
an increase of the dosage of hydrogen peroxide (LW
III, LW IV) or iron (LW I - mix 2).
Collivignarelli et al.
Fenton Oxidation for the Treatment of Liquid Waste with High COD and Anionic/Non-ionic Surfactants
46
Fig. 6: Effect of reaction time on COD removal
The effect of contact time on surfactants removal is
shown in Figure 7. The optimal contact time for
anionic surfactants for all the tested liquid wastes is 30
minutes. Going into detail, for LW II a removal yield
of 90% was obtained after a 30 minutes contact time;
moreover, the slight increase of the removal efficiency
observed for the LW I - mix 2 at 60 minutes may be
due to the use of a higher dosage of iron. Regarding
TAS, as observed for COD, all tested liquid wastes
(LW - mix 2, LW III, LW IV) show the best removal
condition at 30 minute contact time, with the
exception of LW II for which the removal yield
increased from 40% to 60% and 80% with increasing
the test duration from 30 minutes to 60 and 120
minutes respectively.
Fig. 7: Effect of reaction time on TAS and MBAS removal
4. CONCLUSION
The results showed that the optimal treatment
conditions for surfactant removal from liquid wastes
can be obtained with a Fe
2+
/H
2
O
2
ratio equal to 0.25
and a H
2
O
2
/COD ratio of 1 and a reaction duration of
30 minutes. These process conditions allow obtaining
an average removal yield of 70% for TAS and COD
95% for MBAS. In fact, the experimental data
obtained show that higher dosages of Fe
2 +
produce for
almost all tested liquid wastes a lower removal yield
of both the surfactants. Instead, regarding H
2
O
2
the
Wastewater Engineering: Advanced Wastewater Treatment Systems
Chapter 2: Wastewater Treatment by Physical-Chemical Technologies
47
used of dosages lower than the optimal one reduces
the removal yields of both TAS and MBAS, while
higher dosages do not significantly improve the
process efficiency). Finally, an increase of contact
time over 30 minutes does not generally improve the
removal of surfactants.
ACKNOWLEDGEMENT
The authors would like to give a special thanks to the
company ASMortara spa for the financial support to
the experimental research; moreover we want to thank
l'Eng. Chiara Clemente for the assistance in carrying
out the tests.
REFERENCES
Ahammad SZ, Zealand A, Dolfing J, Mota C,
Armstrong DV, Graham DW (2013). Low-
energy treatment of colourant wastes using
sponge biofilters for the personal care product
industry. Bioresource Technology, 129: 634
638
AISE (2012). The new detergents regulation: fact
sheet on aerobic biodegradation of surfactants.
http://www.aise.eu/downloads/05_Fact%20shee
t%20biodegradability-
updated%2027082012.pdf
APHA, AWWA, WEF (2001). Standard methods for
the examination of water and wastewater, 21
st
edition. American Public Health Association,
Washington DC, USA.
CESIO - European Committee of Organic Surfactants
and their Intermediates (2012). CESIO
surfactants statistics for Western Europe.
http://www.cefic.org/Documents/About-
Us/Industry%20sectors/CESIO/CESIO-
Statistics-2012.pdf
Dias de Melo E, Mounteer A H, Henrique de Souza
Leo L, Cibele Barros Bahia R, Ferreira
Campos IM (2013). Toxicity identification
evaluation of cosmetics industry wastewater.
Journal of Hazardous Materials, 244245: 329
334.
European Commission (2004). Regulation (EC) No
648/2004 of the European Parliament and of the
Council of 31 March 2004 on detergents.
Official Journal of the European Union.
http://eur-
lex.europa.eu/LexUriServ/LexUriServ.do?uri=
OJ:L:2004:104:0001:0035:en:PDF
Gonzalez S, Petrovic M, Barcelo D (2007). Removal
of a broad range of surfactants from municipal
wastewater Comparison between membrane
bioreactor and conventional activated sludge
treatment. Chemosphere, 67: 335 343.
Hosseinnia A, Hashtroudi M S, Pazouki M,
Banifatemi M (2006). Removal of surfactants
from wastewater by Rice Husk. Iranian Journal
of Chemical Engineering, 3(3).
Kowalska I, Majewska-Nowak K, Kabsch-
Korbutowicz M (2006). Ultrafiltration
treatment of detergent solutions. Desalination
200: 274276.
Kurt U, Apaydin O, Gonullu MT, (2007). Reduction
of COD in wastewater from an organized
tannery industrial region by electro-fenton
process. Journal of Hazardous Materials, 143:
3340.
Wastewater Engineering: Advanced Wastewater Treatment Systems
Available online at http://www.ijsrpub.com/books
2014 IJ SRPUB
48
Ultrasound Irradiation on the Treatment of Aromatic Compounds in Wastewater
Wong Lai Peng, Guo Xinxin, Mohammed J. K. Bashir
*
Department of Environmental Engineering, Faculty of Engineering and Green Technology, Universiti Tunku Abdul Rahman,
31900 Kampar, Perak, Malaysia
*Corresponding Author: jkbashir@utar.edu.my; Tel: 605-4688888 ext: 4559; Fax: 605-4667449
Abstract. The presence of aromatic compounds such as, chlorinated aromatic compounds, phenolic compounds and dyes can
contaminate aquatic environment. Owing to the toxic, mutagenic and carcinogenic properties of some of aromatic pollutants,
their levels need to be controlled strictly in treated wastewater. Nevertheless, most of the conventional treatments methods are
not able to remove the toxicity of these pollutants completely. Ultrasonication treatment has been employed for the treatment
of hazardous materials in wastewater. Thus, the aim of this study is to investigate the characteristics, influencing factors and
applications of ultrasonic irradiation method. Also, review the current situation of applying cavitation process individually and
combined with other AOPs treatment methods for treatment of aromatic pollutants. In addition, the possible degradation
mechanism of aromatic compound is discussed and the configuration of ultrasonic equipment is suggested.
Keywords: Ultrasound Irradiation, Wastewater, Aromatic Compounds
1. INTRODUCTION
Recalcitrant aromatic compounds have been
extensively used in many industrial processes like
textile industry for dying leather, silk wool and paper.
Consequently, these industrial wastewater streams
always contain high concentration of aromatic
compounds which is harmful to human due to their
carcinogenicity and genotoxicity by accumulating in
fat tissue (Berberidou et al., 2007; Gogate and Pandit,
2004a; Gregory, 2009; Ju et al., 2008). Therefore it is
necessary and important to remove aromatic
compounds from wastewater before discharge and
keep the concentration of chemicals in the effluent
stream at a certain minimum level (Gogate and Pandit,
2004a; Zhou et al., 2012). Due to the stringent
environmental laws and regulations against hazardous
pollutants, the technologies for wastewater treatment
have been extensively developed in the last decades
(Pera-Titus et al, 2004). However, aromatic
compounds are resistant to conventional biological
wastewater treatment process due to high toxicity and
carcinogenicity of the pollutants. So, it is necessary to
develop novel and efficient methods degrade
biorefractory aromatic compounds into smaller
molecules, which can be complete minimized by
conventional biological or photochemical
technologies.
Researchers have tested various methods with
advanced oxidation processes (AOPs) for the
degradation of biorefractory aromatic compounds,
such as ozone oxidation, hydrogen peroxide oxidation,
Fenton with UV light or catalysts and cavitation
generated by ultrasonic irradiation (Ai et al., 2010;
Berberidou et al.,2007; Guinea et al., 2009; Meric et
al., 2005; Zhang and Zheng, 2009). Cavitation have
been found to be the most attractive and suitable
system in degradation or decolorization of recalcitrant
organic pollutants and also used as pretreatment to
convert pollutants into shorter chain compounds that
can be treated by conventional or biological methods
(Anjaneyulu et al., 2005; Gogate and Pandit, 2004a;
Gogate and Pandit, 2004b). This method is based on
the producing of highly reactive hydroxyl radicals
(OH) with high oxidation potential compared to the
conventional oxidants like potassium permanganate
and hydrogen peroxide (Gogate and Pandit, 2004a).
The combination of different AOPs has been found to
be more efficient for the treatment of aromatic
compounds as compared to individual oxidation
process due to the high energy efficiency and
production of higher amount of free radicals
(Chakinala et al., 2008; Ioan et al., 2007; Namkung et
al., 2008; Papadaki et al., 2004; Sun et al., 2007).
The aim of this study is to consider the principles,
characteristics, influencing factors and applications of
ultrasonic irradiation method and takes an overview of
the current situation on applying cavitation process
individually and combined with other AOPs treatment
methods for treatment of aromatic pollutants including
chlorinated aromatic pollutants, phenolic pollutants,
dyes etc. In addition, the possible degradation
mechanism of aromatic compound is discussed and
the configuration of ultrasonic equipment is
suggested.
2. BASIC PRINCIPLES OF ULTRAONIC
CAVITATION AND SONOCHEMISTRY
Ultrasound is the term given to sound waves above 20
kHz which is the frequency above the range audible to
human being. Depending on the application and
frequency, ultrasonication is broadly divided into
three areas: i) low frequency or conventional power
ultrasound (20-100 kHz), (ii) medium frequency or
sonochemical effects ultrasound (300-1000 kHz) and
Peng et al.
Ultrasound Irradiation on the Treatment of Aromatic Compounds in Wastewater
49
iii) high frequency or diagnostic ultrasound (2-10
MHz) (Mason and Lorimer, 1988; Show and Wong,
2012). The effect of ultrasound in liquid medium was
first recognized by Alfred L. Loonis in 1927, however
the major developments in sonochemistry took place
in 1980s after the arrival of inexpensive high-intensity
ultrasound generators (Suslick, 1989). Recently, the
majority utilization of ultrasound in chemical reaction
included synthesis (organic, organometallic and
inorganic), polymer chemistry (degradation, initiation,
and copolymerization) and nanomaterial preparation
and some aspects of catalysis (Mason and Lorimer,
1988). In addition, ultrasound show great potential in
environmental engineering and protection, thus since
1990 there has been an increased interest in the use of
ultrasound to destroy organic contaminants present in
water and/or wastewater (Hao et al., 2003;
Chowdhury and Viraraghavan, 2009; Eden, 2012).
Environmental sonochemistry is a rapidly growing
area, and cavitation is an effective tool for degrading
different organic pollutants, including aromatic
compound (Hamdaoui et al., 2008; Minero et al.,
2008; Sonawane et al., 2009; Suslick, 1990).
Ultrasonic irradiation is generated by directly
introducing the source, i.e. a probe in the reactor or
immersing the reactor in an ultrasonic bath (Hong et
al., 1999; Vinodgopal and Peller; 2003). Ultrasonic
bath is the most widely used and cheapest source of
ultrasound however it does not produce better
sonochemical effects compare to the probe-type
ultrasonic irradiation (Goel et al., 2004).
2.1. Cavitation
The diffuse energy of sound is enhanced through
cavitation (Suslick, 1990). The process is principally
based on the phenomenon of acoustic cavitation,
which includes the formation, growth, and implosive
collapse of micro-bubbles in a liquid. When a liquid is
sonicated, positive and negative pressures are exerted
on a liquid by compression and expansion cycles
respectively of ultrasound waves (Suslick, 1989). The
dissolved gas molecules are entrapped by micro-
bubbles that grow and expand upon rarefaction of the
acoustic cycle; when a sufficiently large negative
pressure is applied to the liquid, the average distance
between the molecules would exceed the critical
molecular distance necessary to hold the liquid intact,
and the liquid will break down and voids or cavities
will be created; cavitation bubbles will then be formed
(Mason and Lorimer, 1988). These cavities, voids or
bubbles may grow in size until the maximum of the
negative pressure then extreme temperature release
upon adiabatic collapse (Mason and Lorimer, 1988;
Lin et al., 2008; Wang et al., 2007).
There are three possible reaction sites in
ultrasonically irradiated homogeneous liquids: i) the
gaseous interiors of collapsing cavities; ii) the
interfacial liquid region between cavitation bubbles
and the bulk solution, where high temperature and
high temperature gradients exist; and, iii) the bulk
solution at ambient temperature, where small amounts
of hydroxyl radicals (
H) and
hydroxyl radicals (
H +
OH (1)
OH +
H H
2
O (2)
H + O
2
HO
2
(3)
2
OH H
2
O
2
(4)
2
HO
2
H
2
O
2
+ O
2
(5)
Violent and fast collapse of the bubbles
compresses adiabatically gas and entrapped vapour,
which conducts to short and local hot spots (Crum,
1995). At the final step of the collapse, temperature
inside the residual bubble is thought to be above 2000
K. Under these conditions, entrapped molecules of
dissolved gases, vaporised water and solutes can be
brought to an excited state and dissociate. The local
concentration of
OH radical
formation were enhanced with high frequency
ultrasonication (Petrier et al., 1994; Hung and
Hoffmann, 1999).
Reaction temperature also influences sonochemical
reactions as it is directly related to solvent vapor
pressure. Higher temperature lowers the threshold
intensity required to produce cavitation. This could be
due to rising of vapour pressure or lowering of
viscosity or surface tension. The maximum
sonochemical benefit is achieved at as low
temperature as is feasible (Mason and Lorimer, 1988).
Cavitation is favored by the liquid of high vapor
pressure and low density. This was supported by the
results of Petrier et al. (1998) for sonochemical
degradation of chlorobenzene and 4-chlorophenol.
Chlorobenzene degradation was much faster than 4-
chlorophenol because of its higher vapor pressure.
Again solvents with higher viscosity, surface tension
Peng et al.
Ultrasound Irradiation on the Treatment of Aromatic Compounds in Wastewater
51
and density showed poor cavitation efficiency
(Adewuyi, 2001). The lower the vapour pressure for a
given external pressure, the larger the acoustic
pressure, thus the type of solvent in the systems plays
an important factor.
In general, it is assumed that the bubbles collapse
is an adiabatic process. A higher temperature and
pressure are expected with gases of higher heat
capacity ratio () values. Lower thermal conductivity
and higher solubility provides better cavitation in the
system (Price, 1992).
Cavitation threshold is the minimum amount of
energy required to intitiate cavitation. Only the energy
applied above the threshold will contribute to the
formation of cavitation bubbles. The higher the
intensity level, the higher the acoustic amplitude and
the collapse pressure. Thus, the collapse is faster and
more violent. However, at frequencies greater than 1
MHz, the acoustic wave impacts on the liquid and
creates micro-currents together with stable and
oscillating gas bubbles which will not collapse but
occasionally rise to the surface of the water body
(Neis et al., 2000).
4.1. Sonochemical Degradation of Aromatic
Pollutants
A large variety of aromatic contaminants detected in
water bodies which included chlorinated aromatic
compounds, phenolic compounds and dyes. The
presence of these compounds even in low
concentration can contaminate aquatic environment.
Besides, due to the toxic, mutagenic and carcinogenic
properties of some of these pollutants, their
concentrations need to be controlled strictly in treated
wastewater. Some of these compounds are listed as
US-EPA and EU priority pollutants (Adewuyi, 2001,
2005). However, as consequences of the
characteristics of the aromatic compounds, most of the
conventional treatments methods are not able to
remove the toxicity of these pollutants completely.
Ultrasonication treatment have been proposed and
employed for the treatment of hazardous materials in
wastewater. Table 1 presented some studies conducted
of aromatic pollutant degradation by ultrasound
treatment.
4.2. Degradation of Chlorinated Aromatic
Pollutants
The application of high intensity ultrasound to a liquid
system may lead to physical and chemical reactions
that can significantly modify the structure and
materials present in the system. Ultrasonic
degradation of chlorobenzene (ClBz) takes place
predominantly within both the bubbles where it
undergoes pyrolysis and within the liquid gas
interface of bubble. Jiang et al. (2002) concluded that
during ClBz degradation by ultrasonication, more than
90% of the chlorine was recovered as chloride ions
along with carbon monoxide (CO), acetylene (C
2
H
2
),
methane (CH
4
) and carbon dioxide (CO
2
) as gaseous
products. Some hydroxylated intermediates, namely
4-chlorophenol, hydroquinone and 4-chlorocatechol
were also detected in a low yield (less than 2 M),
however these compounds disappeared on extended
ultrasonic irradiation.
Petrier et al. (1998) examined preferential thermal
degradation of chlorobenzene inside the cavitation
bubble. In this study, the degradation rate increased at
a higher frequency which may be due to a lower
resonance radius of the cavitation bubble.
Peller et al. (2001) investigated high frequency
sonolysis of 2,4-dichlorophenoxyacetic acid (2,4-D)
in oxygen and argon saturated aqueous medium. The
study shown that the degradation rate was faster in
argon medium compared to oxygen medium due to
argon has a higher heat capacity ratio () value than
oxygen.
4.3. Degradation of Phenolic Pollutants
Petrier et al. (1994) observed that ultrasonic
degradation of phenol was favored at a higher
frequency. At 20 kHz, only 2% of carbon was
recovered in gaseous phase after 300 min, however at
487 kHz, 15% of the carbon was recovered. Besides,
they found that the resonant radius of cavitation
bubble (6.6 m) as well as the life of the bubble
(4.110
7
s) was lower in the case of 487 kHz
frequency. These factors enhanced the release of
OH
radical at a high frequency. Entezari et al. (2003)
reported only 20% degradation of phenol under
sonolysis (C
0
=60 mg/L; time=150 min). This study is
similar to the study conducted by Maleki et al. (2005)
who reported only 13% degradation of phenol under
sonolysis (C
0
= 100 mg/L; time=300 min) and by
Mahamuni and Pandit (2005) who reported 17%
degradation (C
0
=85 mg/L; time=60 min). Phenol is
hydrophilic moderately soluble compound with a
relatively low vapor pressure. These characteristics
prevent the diffusion of phenol molecule into
cavitation bubble, so it remains in the bulk of the
solution during cavitation.
Wastewater Engineering: Advanced Wastewater Treatment Systems
Chapter 2: Wastewater Treatment by Physical-Chemical Technologies
52
Table 1: Sonochemical degradation of aromatic compounds
No. Aromatic compounds Sonochemical conditions Results Reference
1 Chlorobenzene (ClBz)
Ulrasonic power: 9.4 W
Ultrasonic frequency: 520 kHz
Undatim reactor
At concentration above 1000 M,
pyrolysis was the dominant mechanisms,
at concentration 1-5M, radical
mechanisms played a crucial role.
Dewulf et al., 2001
2
2,4-
dichlorophenoacetic
acid
Ultrasonic power: 50 W
Ultrasonic frequency: 640 kHz
Product: Oxalic acid,
Intermediate: 2,4-dichlorophenol,
hydroquinone, catechol were detected
OH and H
2
O
2
)
during ultrasonic degradation. They found the radical
formation rate was 20-25 folds higher in plate type
system compare to probe type system at same acoustic
power. Tauber et al. (2005) reported that ultrasound
treatment successfully degraded six azobenzene dyes
(Acid Orange 5, Acid Orange 52, Direct Blue 71,
Reactive Black 5, Reactive Orange 16, Reactive
Orange 107) whereas enzyme treatment was unable to
degrade. In another study, Byun and Kwak (2005)
achieved the multi bubble sonoluminescence (MBSL)
condition by adjusting the ultrasound intensity, liquid
temperature and the distance between horn tip and the
bottom of the cell. At MBSL condition the
degradation efficiency of methylene blue was much
better than conventional photolytic degradation (TiO2
dispersion/UV). pH is interior optimization factor for
ultrasonic dye degradation. Acidic pH accelerates the
dye degradation by protonation of negatively charged
SO
-
3
sites, thus providing hydrophobic enrichment of
the molecules (Behnajady et al., 2008). Acidic
conditions enhance the probability of the dyes
approaching to the negatively charged cavity bubbles
where
OH
radicals ejected into the solution bulk cause oxidative
dye destruction, whereas hydrophobic and volatile
species degrade thermally to the gas phase or gas-
liquid interface (Ince and Tezcanli- Gyer, 2004;
Vajnhandl and Le Marechal, 2007). However, for
hydrophilic compounds with high concentration, an
additional degradation mechanism occurs quickly via
reactions with
OH
formation whereas ClBz degradation was basically a
thermal degradation inside the cavitation bubble. In
the similar study by Stavarache et al. (2002) showed
the decomposition of ClBz took place inside
cavitation bubbles forming phenyl (C
6
H
5
) and
chlorine (Cl
OH radicals. However,
the second reaction scheme was recognized as a minor
Wastewater Engineering: Advanced Wastewater Treatment Systems
Chapter 2: Wastewater Treatment by Physical-Chemical Technologies
54
pathway as the hydroxylated intermediate production
was too low.
The degradation of phenol compound can be
proved by the formation of hydroxylated
intermediates (hydroquinone, catechol and resorcinol).
According to Petrier et al. (1994), phenol degradation
in terms of free radical reaction was following two
possible reactions as presented in Eqs 6-7:
OH +
OH H
2
O
2
(6)
C
6
H
5
-OH +
OH C
6
H
5
(OH)
2
(7)
However, the degradation of phenol by ultrasound
was comparable low due to the hydrophilic nature of
phenol which made it unavailable for free radical
reaction with
OH radical or lack of
dissipated power. Therefore, to overcome these
disadvantages in the sonochemical process, ultrasound
has been widely used as an auxiliary process with
other treatment techniques mostly biochemical,
electrochemical, ozonation, photolysis, photocatalysis
and Fenton processes.
Studies of the combined process involving
ultrasound and ozone had shown faster degradation
rates for a range of chemical contaminants than either
method applied alone (Mason and Petrier, 2004). As
the mass transfer rate of ozone in the solution was the
limiting parameter, thus the combined operation of
sonolysis and ozonation renders synergistic effected in
degradation and accelerateed the mass transfer of
ozone in the solution due to ultrasonic effects. When a
liquid was sonicated in the presence of ozone (O
3
), the
thermal decomposition of ozone in the cavitation
bubbles enhanced
OH and H
2
O
2
yields. Xu et al.
(2005) studied on synergetic effect of ozonation with
ultrasonic treatment for p-nitrophenol degradation. In
O
3
/ultrasonic system produced more
OH and H
2
O
2
than the sonolysis system alone. This combined
sonolysis/ozonolysis process showed 116%
enhancement in removal rate for p-nitrophenol.
Gultekin and Ince (2006) investigated the
degradation of aryl-azo-naphthol dyes with
ultrasound, ozone and combination of the two
processes at optimized condition. The US/O
3
combination was the best option for the degradation of
these dyes. The synergetic effect incorporated three
main factors, i) increased mass transfer of ozone, ii)
Peng et al.
Ultrasound Irradiation on the Treatment of Aromatic Compounds in Wastewater
55
excess hydroxyl radical generation, and iii)formation
of secondary oxidation species (
O
2
-
and
O
2
H). The
major part of the dissolved ozone was therefore
efficiently decomposed by ultrasonic irradiation
because of the additional pathways involving the
production of these secondary oxidation species. The
combination of these two processes provided three
sources of
OH
which could be readily used for dye degradation. The
pseudo first-order rate constant of dye by sono-Fenton
oxidation was three fold greater than that of its
sonolysis alone in the presence of Fe (II) in the
concentration range of 0.1 mM to 0.5 mM. The
increment was due to the formation of more
OH
radical via Fenton reaction (Joseph et al. (2000). In
ultrasonic assisted Fenton process, the highest
decolorization efficiency of dye is achieved at pH 3
(Song et al., 2009). This process was pH dependent
when pH was below 3, hydrogen radicals could be
consumed by the scavenging effects of H
+
and
hydrogen peroxide would formed ozonium ion which
could enhanced the stability and reduced the reactivity
between hydrogen peroxide and ferrous ions (Sun et
al., 2007; Wang et al., 2008a). Another similar study
by Zhang et al. (2009) evaluated the decolorization of
C.I. Acid Orange 7 with the combination of
ultrasound and advanced Fenton process. The
decolorization fit the modified pseudo-first order
kinetic model where the decolorization rate increased
with hydrogen peroxide concentration and power
density but decreased with the increased of initial pH
value.
Wastewater Engineering: Advanced Wastewater Treatment Systems
Chapter 2: Wastewater Treatment by Physical-Chemical Technologies
56
From the studies can concluded that the
combination of ultrasound with relevant treatment
were more economically attractive than the use of
ultrasound alone for aromatic pollutants treatment.
7. CONFIGURATION OF ULTRASONIC
EQUIPMENT
In sonochemical treatment the electrical energy was
basically converted to vibration via a transducer
(Price, 1992). Depending upon the application or the
reaction to be achieved, one can choose different
generators and design appropriate transducers as
required (Ashokkumar and Grieser, 1999).
In general there were four types of laboratory
ultrasonic equipments that were widely used namely,
i) whistle, ii) bath, iii) probe (horn) and iv) cup-horn
system (Mason and Lorimer, 1988). The whistle
reactors were primarily applicable for emulsification,
polymerization and phase transfer reactions.
Ultrasonic bath system was the low intensity load
system with a power density of 12 W/cm2 (Mason
and Lorimer, 1988). The main advantages of bath
system were simplicity and economy. While the
disadvantages were the limitation in temperature
control and ultrasonic intensity control. The ultrasonic
probe system was a high intensity system with better
temperature control. However, horn configuration
became a major limiting factor when dealing with
high amplitudes. Sometimes there were some
chemical interference issues due to the cavitational
erosion of the horn tip metal. The horn design could
essentially limit its ability to achieve greater
cavitation levels and power output. The cup-horn
system was a combination of bath and horn (probe)
system with a better temperature control device. It
allows much higher intensity without any
contamination by the horn tip material (Price, 1992).
Most of the studies describing the degradation of
organic dyes (Rehorek et al., 2004; Vajnhandl and
LeMarechal, 2007 , phenolic compounds (Petrier et
al., 1994; Nagata et al., 2000; Maleki et al., 2005; Xu
et al., 2005) and chlorinated organic compounds
(Drijvers et al., 1998; Gaddam and Cheung, 2001)
used probe (horn) type systems because of its high
power output and optimum performance at different
amplitudes. In the case of a low intensity irradiation a
batch reactor with a submersible transducer was
shown to be the best option (Mason and Tiehm,
2001). Gogate and co-researches (2004) suggested a
few important points on large scale sonochemical
reactors:
(i) multiple frequencies gave higher intensities of
cavitation compared to a single frequency operation.
(ii) Hexagonal geometry was more efficient in
terms of better distribution of cavitational activity.
Bhirud et al. (2004) used ultrasonic bath having
longitudinally vibrating transducer for formic acid
degradation. The longitudinally vibrating reactor
provided 45 times more cavitational yield than
multiple frequency flow cells. The design of the
reactor and the reactor performance also greatly
affected by the ultrasonic poser and free volumetric
flow rate (Gondrexon et al. (1999). According to
Asakura et al. (2008) the sonochemical reactor
volume for pilot scale and industrial scale should be
more than 100 L and 1000 L, respectively. The
observed sonochemical efficiency of the large reactor
was comparable with the laboratory scale reactors. It
was found that the sonochemical efficiency was
dependent on frequency and liquid height in the
frequency range of 45490 kHz.
8. CONCLUSION
Ultrasound technologies have been widely used for
the degradation of aromatic compounds at laboratory
scale and the combination of ultrasound with other
relevant treatments can prove to achieve complete
mineralization and be more economically attractive
than the use of individual techniques due to the
generation of higher quantum of free radicals and high
degree of energy efficiency. It has been observed that
the efficacy of sonochemical reactions in cavitation
process is influenced by many important operating
parameters such as resonance frequency of bubbles,
reaction temperature and energy intensity. An
optimised reactor configuration should be able to
maximize the expected output. Thus, the
configurations of the sono-reactor may significantly
affect the efficacy of ultrasonic system for
sonochemical degradation.
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Wastewater Engineering: Advanced Wastewater Treatment Systems
Available online at http://www.ijsrpub.com/books
2014 IJ SRPUB
62
Wastewater Engineering: Advanced Wastewater
Treatment Systems
Chapter 3: Wastewater Treatment by Biological
Methods
Wastewater Engineering: Advanced Wastewater Treatment Systems
Available online at http://www.ijsrpub.com/books
2014 IJ SRPUB
63
Wastewater Treatment by Biological Methods
Dadrasnia A.
1,*
, Shahsavari N.
2
, Emenike C.U.
1
1
Institute of Biological Sciences, Faculty of Science, University of Malaya, 50603 Kuala Lumpur, Malaysia
2
Science and Research Branch, Islamic Azad University, Sirjan, Iran
*Corresponding Author: are.dadrasnia@gmail.com
Abstract. Wastewater generation is just inevitable but discharging it into the environment in a sustainable way is the subject of
concern. Hence, treatments adopted have the common goal of conforming to water quality standards to ensure environmental
protection. Different sources that range from industrial productions to domestic use of water has continued to generate
wastewater and various treatment methods are employed, which includes biological methods. For effective treatment,
considerations are paid to wastewater characteristics, requirement of treated wastewater quality, treatment alternatives and
associated sampling techniques with analysis. Most biological treatments often take care of the removal of biochemical oxygen
demand, chemical oxygen demand, suspended solids, ammonia and even other inorganic compounds that includes heavy
metals. This chapter evaluated the use of oxidation, anaerobic, aerobic ponds, and activated sludge process as biological
treatment methods for wastewater. Common to the options is the utilization of microorganisms to degrade pollutants of
interest, but varied on certain conditions that border on design and oxygen utilization and limitation. Biological treatments can
be achieved under reduced cost when compared to physical and chemical methods, yet time consumption appear to be its
drawback.
Keywords: Wastewater, Treatment, Biological Methods
1. INTRODUCTION
Wastewater emanates from many sources which
includes industrial production and domestic use of
water. Hence, wastewater characteristics are highly
dependent on the source, and when it is not properly
treated before discharge, it can significantly pollute
watercourses. Regardless of the treatment option
adopted for any form of wastewater, the end
expectation is to relate to discharge/effluent standards
and quality. With high level of varied forms of
production and changing lifestyle, chemical
composition and loading of most wastewater are of
significant interest world over, excess organic
Chemical pollution from heavy metals, dyes,
solvents and pesticides is one of the major threats to
water quality. Chemicals enter the aquatic
environment through different ways, among which are
via wastewater treatment plants (WWTP) that do not
fulfill their obligations (Oller et al., 2011), and direct
discharge of industrial effluents. Similarly, indirect
chemical pollution of water arises from the use of
plant health products, such as biocides and, fertilizers
in agriculture (Oller et al., 2011). Considering the fact
that water soluble substances can be distributed and
transported more easily in the water cycle, treatment
of wastewater by discharge becomes paramount.
Wastewater treatment refers to the process of
removing pollutants from water, especially those
associated with agricultural, industrial and municipal
activities. This process is designed to achieve the
expectation and/or standard level in the quality of the
wastewater. Current methods used for removing
pollutants present in the wastewater can be divided
into chemical, physical, biological and energetic
methods.
The aim of applying various treatment processes
are to reduce:
(a) Biodegradable organic parts [chemical oxygen
demand (COD) and Biochemical oxygen demand
(BOD)] serve as food for bacteria. Microorganisms
combine oxygen with organic part of the wastewater
to yield the energy they need to multiply and thrive; in
addition, fish and other organisms in the river need
this oxygen as well. Heavy organic pollution of the
environment may result in dead zones and simply
imply that no fish is found; sudden releases of heavy
organic may result in dramatic Fishkill.
(b) Suspended solid part (including those particles
that can block channels or rivers)
(c) Pathogenic bacteria/disease organisms. These
are most appropriate where the water is necessary for
drinking, or where people would otherwise have close
contact by using it; and
(d) Nutrients, which includes nitrates as well as
phosphates. These nutrients can bring about excessive
levels of algal distribution, which can significantly
contribute to higher loading of biodegradable organic
matter. Treatment techniques could also remove or
neutralize industrial wastes and dangerous chemicals.
Such remedy goal should be practiced in-situ
industrial plant, before final effluent discharge,
especially to watercourses.
1.1. Levels of wastewater treatment
In order to be able to bring about effective treatment
of the effluent, it is necessary to know more about:
Dadrasnia et al.
Wastewater Treatment by Biological Methods
64
(a) Characteristics of wastewater to be treated
(b) Requirement of treated wastewater quality
(c) Types of treatment alternatives available
(d) Techniques of wastewater sampling and analysis
These are the additions to the preventive and
corrective maintenance of the treatment machinery,
knowledge of repairs to and replacement of various
parts of equipment, record keeping, report
preparation, and aspects of safety in treatment plants.
The characterization involves determination of
biological, physical and chemical characteristics of
the samples of wastewater using laboratory techniques
such as gravimetry, colorimetry and titrimetry.
Knowledge of the characteristics helps the plant
operators to provide the information on:
(a) The strength of the raw and treated wastewater
(b) The efficiency of the plant operation as a whole
and each of the treatment processes
(c) The nature of treatment required in the case of the
given wastewater to meet the quality standard.
1.1.1. Primary treatment (mechanical)
Primary treatment (mechanical) is a preliminary
treatment used to protect and facilitate other
equipment in the treatment processes. It is designed to
cut up or remove the large suspended, gross and
floating solids, and heavy organic solids or amount of
oil from raw sewage. However, this stage is called
mechanical treatment, while chemical substances
can be used to increase the actual sedimentation
procedure. It includes screening or sieving to trap and
remove sediments and solid parts based on principle
of gravity. By this way, the BOD of the incoming
wastewater can be reduced by 20-30% alongside 50-
60% of total suspended solids. Primary treatment is
usually done at the initial period of wastewater
treatment. Many devices are employed for preliminary
treatment, including screens bar, rack, pre-aeration
tanks, as well as grit chambers. These devices require
careful operation and design. Several advanced
wastewater treatment facilities in industrialized places
started with primary treatment, and have after that
included other treatment phases as wastewater load
has grown, and there is requirement for
comprehensive treatment.
1.1.2. Secondary treatment
Secondary treatment method eliminates the dissolved
organic matter which escapes preceding treatment
method. This is realized by microbes consuming the
organic matter as meal, and converting it to CO
2
,
water, and energy for their own reproduction and
growth. The biological method is then followed by
inclusion more sedimentation tanks to adequately
remove remaining suspended solids. In relation to
removal of 85% of the suspended solids, BOD may be
taken off by a well designed plant with secondary
treatment part. Secondary treatment method
technologies are classified as the necessary stimulated
sludge procedure, the variants of pond and constructed
wetland systems, trickling filtration and other forms of
treatment method designed to use biological activity
in order to break down organic matter.
1.1.3. Tertiary treatment
Tertiary treatment is simply an added treatment option
that is more advanced than the secondary treatment.
Tertiary treatment can certainly take away
approximately 99% of all the impurities from sewage,
producing great effluent associated with practically
drinking-water top quality. This associated technology
are often very expensive, requiring a high level of
technical know-how as well as expert plant operators,
a steady energy supply, chemicals and specific
products which in turn may not be easily obtainable.
An example of a typical tertiary treatment action will
be the change of a secondary treatment method to take
out more phosphorus as well as nitrogen.
Disinfection, usually together with chlorine, could
possibly be the last move ahead before discharge of
the effluent. Even so, a few environmental authorities
are concerned which chlorine residuals in the effluent
can be a problem. Disinfection is often that are part of
treatment plant design, although not properly used, as
a result of the higher price of chlorine, as well as
decreased efficiency of ultraviolet radiation where the
normal water is not completely clear, and without any
contaminants.
2. BASICS OF BIOLOGICAL TREATMENTS
2.1. BOD, COD and suspended solids
Biochemical oxygen demand (BOD) is similar in
function to chemical oxygen demand (COD), Organic
waste and natural organic detritus from wastewater
treatment plants, failing septic methods, and farm and
downtown runoff, functions as a food source for
water-borne microorganisms. Bacteria decompose
these natural components employing dissolved
oxygen, thus reducing the DO present for fish or even
marine organisms. Biochemical oxygen demand
(BOD) is usually a way of measuring how much
oxygen bacteria utilize while decomposing organic
matter under aerobic conditions. Biochemical oxygen
need is dependent upon incubating a sealed sample of
water for several times and also measuring the loss of
oxygen from the beginning to the end of the test.
Samples must be diluted prior to incubation; else the
Wastewater Engineering: Advanced Wastewater Treatment Systems
Chapter 3: Wastewater Treatment by Biological Methods
65
bacteria will drastically reduce the available oxygen
inside the container prior to end of the test. The main
focus of all wastewater treatment facilities is to reduce
the BOD in the effluent discharged to natural waters.
Wastewater treatment plants are created to function as
bacteria farms, where bacteria are usually given
oxygen and organic waste. The excess bacteria grown
in the system are usually taken away as sludge, and
disposed of on land as solid waste.
Chemical oxygen demand (COD) does not
basically differentiate between organic matter that is
biologically available and the inert one. However, it is
a measure of the total amount of oxygen required to
oxidization of all organic materials to carbon dioxide
and water. When values are compared, BOD is often
less than COD, though COD measurements can be
produced in some hours though BOD measurements
take five days (BOD
5
).
3. BIOLOGICAL WASTEWATER TREATMENT
3.1. Oxidation Ponds
Before the discharge of wastewater into an aquatic
ecosystem, oxidation ponds are often used for
effective reduction of BOD considering its relatively
low cost and simple technology. It is involves ring
channel that is equipped with mechanical ventilation
apparatuses. Monitored wastewater penetrating the
pool is ventilated by mechanical apparatuses which
circulate at about 0.250.35 m/s. Oxidation pools
normally operate in an expanded aeration mode with
long confinement and solids retention times (Sperling,
et al., 2005). Kotsou et al (2004) had studied an
aerobic biological method by utilizing an Aspergillus
niger strain in a bubble column bio-reactor that was
combined with chemical oxidation treatment of
process wastewater from table olive. Authors reported
that a relatively significant decline of chemical
oxygen require (COD) was found 2 days after
biological treatment, just as the simple and total
phenolic complexes were also reduced by 41 and
85%, respectively. The stage of chemical oxidation
principally influenced the clearance of constant
phenolic complexes during the biological treatment of
total phenolic compounds. Furthermore, coagulation
support from CaO considerably enhanced the
treatment efficiency.
3.2. Anaerobic Ponds
Anaerobic ponds (Figure 1) are planned in a manner
that such will enable effective pretreatment of high
resistance wastewaters. This is applied to the aerobic
treatment and is regularly very efficient and cost-
effective for eliminating BOD and COD high
concentrations (Dewil et al., 2006). These ponds have
more organic loading in comparison to the oxygen
content entering the pond for sustaining the anaerobic
state of the pond surface. Anaerobic bacteria which
occur naturally degrade the organic components in the
wastewater, releasing carbon dioxide and methane.
The ensuing sludge will settle at the bottom while a
crust may aggregate at the surface (Doorn et al.,
2006). Fu et al. (2011) demonstrated textiles
wastewater treatment with the application anoxic filter
bed (AFB) and (BWB-BAF). The study showed that
the AFB effluent COD content reduction upon
addition of new carriers and the average efficiency for
the COD removal was 20.2%.
Leal et al. (2010) studied the occurrence of
xenobiotics in gray water and the associated removal
via three different biological treatment systems. In this
study, 18-selected xenobiotics related to chemicals
from personal care and household products were
estimated in gray water from different houses (32) and
in effluents of three different biological treatment
systems (aerobic, anaerobic, and anaerobic-aerobic).
The authors pointed out that the degree of removal
was optimal was highest at aerobic condition than
when anaerobic situation was used.
3.3. Aerobic Ponds
Aerobic ponds contain suspensions, typically bacteria
and algae that sustain aerobic conditions throughout
their depth. Two types of aerobic wetlands namely,
aerated and shallow ponds are often used
(Vijayaraghavan, 2007). Souza et al., (2011)
investigated the treatment of refinery wastewater by
AOPs along with biological activated carbon (BAC)
with the objective to produce water intended for reuse.
BAC filtration were being observed to be effective,
attaining average efficiencies up to 65% in a
sufficiently long period (84 days), while granular
activated carbon filters were saturated after twenty-
eight days. Cao et al. (2011) suggested internal
electrolysis biological contact oxidation process for
the treatment wastewater containing linear
alkylbenzene sulfonate.
Dadrasnia et al.
Wastewater Treatment by Biological Methods
66
Figure 1- Anaerobic pond
4. MODELING THE BIOLOGICAL
PROCEEDING
Biology aims to understand the mechanisms by which
organisms survive, grow, and reproduce. It collects
remarks, identifies returning phenomena, and using
existing knowledge attempts to explain these
phenomena, Like other scientific fields. However, this
attempt is a compound one, and biologists would
advantage from computational tools to support them
in construct and evaluate their models.
The achievement of apparatus learning and data
extraction in business areas has led to enhanced
interest in using comparable methods to find out
information in biology and other scientific
arrangements (Fayyad et al., 1996). However, in the
absence of background knowledge, the best-developed
techniques are designed to operate on large data sets.
Regardless the contrary of rhetoric, biology stay puts
a data-sparse field, but it has significant knowledge
available to limit the study for models.
The construction descriptive models are another
disadvantage of standard induction methods. These
can construct precise forecasts on new assessment
cases, which may be adequate for commercial uses,
but biologists naturally desire descriptive models of
behavior. A reason of some occurrence is cast in terms
of other knowledge, such as constructions or courses
that are well-known to field specialists.
Finally, customary instruction techniques create
models that are articulated in documents designed by
computer scientists, few of which biologists discover
intelligible. Even effort on inducing causal models,
which often have an instructive taste, spotlights on
summary formalisms that compose little contact with
implications from biomedical science. Information
that supports the integration of area impressions more
directly would most probably be easier to recognize
and make available additional controls on model
mechanism (Langley et al., 2006).
Biologists require computational methods for data
analysis and organization, with the increasing volume
of genomic data available. We first require a
knowledge model that can indicate biological systems,
to develop computer applications that aid in this task.
Such a model should demonstrate the advanced
physiological processes and attach them to molecular-
level applications. The appearance of structural
reforms, such as the Gene Ontology (The Gene
Ontology Consortium, 2000) is an important first step
in making the communications requisite for a
biological knowledge model (Peleg et al., 2001).
A model of biological process can (1) constantly
indicate the dynamic knowledge about advanced
biological processes, in the framework of their part
molecular-level sub-processes, and (2) be agreeable to
deduction, validation of dynamic (control-flow)
characteristics, and qualitative simulation.
There are a set of desirable requirements for a
model of biological process. First, the model has to
show the following three cases of a biological system.
(1) The Static-structural outlook of bio-molecular
compounds, chemical, and biopolymers that
contribute in the system, their characteristics, and the
relationships between them;
(2) The Dynamic view that indicates how methods
are arranged over time (control flow) and how a
course is recursively decomposed to component
processes and reactions (atomic processes). The
dynamic model have to carry parallel, consecutive,
restrictive and iterative processes; and
(3) The practical view that demonstrates the
performers (e.g., enzyme) that carries out each
purpose, the substrates (input) of each function, and
the results of the function (outputs). The cellular
position of the substrates and products has to be
particular (Peleg et al., 2001).
Wastewater Engineering: Advanced Wastewater Treatment Systems
Chapter 3: Wastewater Treatment by Biological Methods
67
Second, the model has to comprise a biological
ontology that will characterize biological thoughts and
organize them in classification hierarchies. Ontologies
make available constant definitions and explanations
of biological concepts, and make possible software
applications to share and reprocess the knowledge
constantly (Gruber, 1995). Ontologies can be used to
make logical conclusion over the set of impressions to
provide for simplification and clarification facilities
(Schulze- Kremer, 1998).
Third, the demonstration should be sensitive.
Biologists have to find it easy to make and realize a
system that is demonstrated using the model.
Fourth, the model has to be hierarchical to handle the
density of the represented system.
Fifth, the model has to be mathematically based to
permit verification of characteristics that are
advantageous in biological systems, and simulation of
system activities. For example, we were able to
validate that there is no toxic aggregation of
metabolites in pathways (boundedness property).
For a high-level biological process consisting of
lower-level processes, could validate that all the
component processes can contribute (liveness
property). We are able to also investigate to processes
that are constantly in use (violate the fairness
property) and may consequently be good objectives
for affecting system manners. A formal model have to
also make possible us to ensure whether we are able to
move from one system state (e.g., parasite inside host
liver cell) to another status (e.g., parasite cleared).
And sixth, the model should permit important
deduction abilities. For example, proposing the
consequences of knockout experiments substrates
that may accumulate, other reactions that might
procedure these substrates, etc. Other examples
contain recognizing processes that are operated in
response to environmental effects (e.g., heat shock),
or discovery procedures that are active during a
determined developmental stage. The argument
mechanism should apply the biological concept model
to structure abstract concepts (e.g., tight-junction
formation is a kind of adhesion process) (Peleg et al.,
2001).
4.1. TAMBIS model
Clear Access to numerous Biological Information
resources (TAMBIS) (Baker et al., 1999) is ontology
for a description of data to be fined from
bioinformatics resources. TAMBIS goes beyond
taxonomic models. It demonstrates biological
concepts and appearances a semantic template of
concept relations that can be used to create deductions
from biological data. TAMBIS is defined as a logic-
based knowledge representation formalism using
explanation Logic (Bordiga, 1995) that defines
concepts using argument to sort the concepts based on
those descriptions in terms of their properties.
4.2. The Workflow model of the Workflow
Management Coalition
The Workflow Management Coalition is defined as a
Workflow model for business procedures (Workgroup
Management Coalition, 1999). Definition of the
Workflow model is a representation of a business
(high-level biological) process in an automated
manipulation form. The process definition presents a
functional and dynamic model that includes of a
network of activities (logical steps in the process) and
their relationships, criteria to demonstrate the start and
ending of the process, and information about the
participants of individual activities.
4.3. Petri Nets model
A Petri Net (Peterson, 1981) which is used to model
concurrent systems defined a formal model. A Petri
Net is represented by a directed, bipartite graph in
which nodes are either locations or transmissions,
where locations indicate conditions (e.g., parasite in
blood stream) and transitions demonstrate activities
(e.g., invasion of host erythrocytes).
5. ACTIVATED SLUDGE PROCESS
The activated-sludge process (ASP) is one of the
forms of wastewater treatment via biological method.
It is principally based on the utilization of different
but mixed community of microbes within an aerobic
aquatic environment. The carbonaceous organic
matter in the aerated wastewater serve as the source of
energy for the microbes which they use for generation
of new cells via biosynthesis, while undergoing
respiration simultaneously by giving out energy when
the organic matter is converted into compounds of
lower energy, especially carbon dioxide and water.
Similarly, some of the microbes in this system
generate energy through nitrification process;
ammonia nitrogen is converted to nitrate nitrogen.
Therefore, activated sludge refers to the consortium of
microbes with the associated biological component of
the process.
5.1. Principles of Activated Sludge Process (ASP)
Dadrasnia et al.
Wastewater Treatment by Biological Methods
68
Storage of the wastewater in aeration tank
Bacteria growth is enhanced by supplying
oxygen, food (BOD), time and optimal temperature.
The consortium of BOD substrate enhances bacteria
growth and increased population.
Secondary clarifiers receive the treated
wastewater, and the bacteria cells that settle are
collected from the clarifiers as sludge.
A portion of the sludge is returned back to the
activated sludge tank (partial recycling) to ensure that
certain bacteria population is maintained in the
system.
Remaining sludge is totally removed as waste.
-ASP 1
The ASP comprised of interrelated equipment (5) and
components. Aeration tanks(s) are the first
components which serve as an aerobic environment
when air or oxygen is injected/supplied to the system.
Such environment basically satisfies the requirement
of the biological community and thoroughly ensures
proper mixing of the activated sludge (Figure 2).
Fig. 2: Schematic presentation of aeration reactors in Activated Sludge Process
-ASP 2
An aeration source is the second vital component
which supplies sufficient oxygen to the tanks and
ensures adequate mixing within the system. The
oxygen supply can be in form of mechanical aeration
or introduction of pure compressed oxygen.
Equipment for the supply of oxygen to this system can
vary in design and operation due to the number and
modifications in shape of aeration tanks used.
-ASP 3
Third in the line of ASP equipment are the secondary
clarifiers. Here, separation of activated sludge solids
from water occurs. This is based on the principle of
flocculation (aggregation of large particles or flocs
due to adherence of floc-forming organisms to
filamentous organisms) and gravity sedimentation,
where flocs settle at the base of the clarifier sluggish
environment. Subsequently, a secondary effluent
(wastewater characterized of low-level activated-
sludge solids that are in suspension) is formed from
the separation at the upper segment of the clarifier.
However, at the base of the clarifier is a thickened
sludge characterized of flocs and referred to as return
activated sludge (RAS).
-ASP 4
The RAS generated must be removed from the
clarifiers and reintroduced into the aeration tank(s)
before depletion of the dissolved oxygen present. By
so doing, there is replenishment of the biological
Wastewater Engineering: Advanced Wastewater Treatment Systems
Chapter 3: Wastewater Treatment by Biological Methods
69
community required to metabolize influent organic or
inorganic matter in the wastewater stream.
-ASP 5
Here, the activated sludge which is characterized of
high microbial load must be removed or discarded
(referred to as waste activated sludge or WAS) from
the treatment process. It is done using pumps and
carried out in parts so as to regulate the food-to-
microorganism ratio (F:M) inside the aeration tank.
5.2. ASP Process Requirements
A standard activated sludge process will require the
following for effective operation;
(a) Formation of flocs as it ensures effective
separation of the microbial biomass.
(b) The mean cell residence time (MCRT) should
be increased alongside adequate aeration in order to
enhance settling ability of the microbial biomass.
(c) Oxygen level needs to be properly regulated.
(d) Microorganisms constitute the biological
component of activated sludge system. The microbes
can contain about 70 90% organic matter. In fact,
the wastewater composition and the specific
characteristics of microbes in the biological
community determine the cell makeup.
(e) Most commonly found organisms within the
biological component of activated sludge are bacteria,
fungi, protozoa and rotifiers. In some cases, nematode
worms which are from metazoan can be present.
However, the growth of higher microbes can be
impaired by the constant agitation in the aeration
tanks in addition to recirculation connected with
sludge.
In 1990s when ASP was developed, it was
characterized of fill and draw reactors (batch process).
The continuous flow reactors were developed in order
to tackle the problem of regulating a number of batch
reactors that always have varied influent flow rate.
Interestingly, over the years, sequential batch reactor
(SBR) has replaced the old system and aeration
process is the significant energy consumption
operation of the system, whereas operations on RAS
and clarifiers are insignificant. Yet, the major
expenses can arise from the sludge processing and
disposal.
6. CONCLUSION
Previously, water was regarded as the most abundant
natural resource based on its global distribution, and
as such less caution was taken to on securing its
natural quality. Unfortunately, it has turned out to be
the scarcest resource now and no thanks to some
socio-economic developments that do not take into
account environmental impact assessment. Therefore,
wastewater treatment has been adopted as a mitigation
agent that will prevent aquatic pollution. Hence many
treatment options abound; physical, chemical and
biological. Adoption of biological method ahead of
others is being canvassed for due to its greener nature
and relatively reduced cost. Yet, the time consumed
when using biological methods of wastewater
treatment is a recurring factor that is a drawback, and
the broad spectrum of pathogens in wastewater often
rise concerns on the use of microbes in treatments.
Acknowledgement
We wish to express our deepest gratitude to all the
researchers whose valuable data as reported in their
respective publications and cited in this chapter have
been of considerable significance in adding substance.
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Wastewater Engineering: Advanced Wastewater Treatment Systems
Available online at http://www.ijsrpub.com/books
2014 IJ SRPUB
72
Biological Treatment of Recycled Paper Mill Wastewater Using Modified Anaerobic
Inclining-Baffled Bioreactor (MAIB-R)
Haider M. Zwain
1
, Irvan Dahlan
2*
1
School of Civil Engineering, Universiti Sains Malaysia, Engineering Campus, Seri Ampangan, 14300 Nibong Tebal,
Pulau Pinang, Malaysia.
2
School of Chemical Engineering, Universiti Sains Malaysia, Engineering Campus, Seri Ampangan, 14300 Nibong Tebal,
Pulau Pinang, Malaysia.
*Corresponding Author: chirvan@eng.usm.my
Abstract. Industrial wastewater treatment has gained importance due to the insistence of the environmental groups,
environmental regulation and public awareness. Wastewater from pulp and paper industry is among the most harmful
wastewater that needs to be treated since it contains high organic substances. Although the raw materials of this kind of
industry has been replaced by recycled materials in order to reduce wastes, however effluent from this recycled paper mill is
still highly polluted that need to be treated. In this study, the start-up performance of treating recycled paper mill wastewater
using a modified anaerobic inclining-baffled bioreactor (MAIB-R) has been studied. The MAIB-R was started with a hydraulic
retention time (HRT) of 5 days at 37C. The start-up process took 14 days before it reached steady state on day 15. The MAIB-
R, after successful start-up, can achieve relatively high average COD removal of 92% with pH level of effluent relatively
stable at 6.63. In addition, the biogas production reached 0.77L/d with methane content up to 57% on day 15. The result shows
that during the start-up period, MAIB-R was successfully operated in treating recycled paper mill wastewater.
Keywords: Anaerobic Inclining-Baffled, Biological Treatment, Paper Mill Wastewater
1. INTRODUCTION
1.1. Recycled Paper Mills
Paper and pulp industry together with recycled paper
mill ranked among the largest industries in the world.
There are mills found in more than 100 countries in
every region of the world. The major pulp and paper
producing nations include the United States, China,
Japan, Canada, Germany, Brazil, Sweden, Finland and
France. In Malaysia, recycled paper and boards are
important sources for pulp and paper industry. Of 20
paper mills in the country, only Sabah Forest
Industries Sdn. Bhd. is an integrated pulp and paper
mill. All of the 19 others utilize 95% waste papers as
their main raw material except for Kimberly Clark
(M) Sdn. Bhd. which uses 80% imported virgin pulp.
Table 1 shows the existing pulp and paper companies
in Malaysia (Roda and Rathi, 2006).
Table 1: Pulp and Paper Industry in Malaysia.
Company Total Capacity Per Annum (mt)
Cita Peuchoon 30,000
Johmewah 35,000
Genting Sanyen 300,000
Muda Paper (Kajang) 170,000
Muda Paper (S. Prai) 130,000
Malaysia Newsprint 250,000
Nibong Tebal 60,000
Pascorp Paper 140,000
Pembuatan Kertas (Perak) 3,000
Sabah Forest 165,000
See Hua Paper 12,000
Taiping Paper 2,400
Theen Seng Paper 15,000
Trio Paper 30,000
Union Paper 12,400
United Paper Board 80,000
Yeong Chaur S 3,600
1.2. Recycled Paper Mill Wastewater and Its
Environmental Hazards
Recycled paper mills (RPM) are using recovered
paper as their feedstock, unlike paper and pulp mills
which are using wood pulp, mixture of cellulose fibers
and water as the basis of all paper products. The
recovered paper is used to produce new paper
products. This is an effort emphasize on the present
green awareness which can help to reduce the cutting
of trees. However, RPM is one of the industries that
have caused concerns about hazardous water
pollutants being continuously discharged into streams
and other water bodies without clean-up treatment.
Zwain and Dahlan
Biological Treatment of Recycled Paper Mill Wastewater Using Modified Anaerobic Inclining-Baffled (MAIB)
Bioreactor
73
The RPM wastewater characteristics is shown in
Table 2 (arkovi et al., 2011). Furthermore, the RPM
wastewater contain heavy metal is given in Table 3
(Hassan et al., 2014).
Table 2: Typical Physico-chemical characterization of RPM wastewater
Parameter (in mg/L, except pH value) Range Mean S.D.
pH 7.0-7.7 7.30.22
Chemical oxygen demand, COD 3770-9330 5539412
Biochemical oxygen demand, BOD 816-2495 1372108
Ammonia, as NH4 1.4-3.8 2.360.8
Total solids, TS 2051-11161 4654276
Total dissolved solids, TDS 200-892 59550
Total suspended solids, TSS 603-8495 3993216
Settleable solids, SS 40-850 48058
Table 3: Heavy metals present in RPM wastewater
Heavy metals Concentration (mg/L) Standard B*(DOE, 2009)
As 1.06 0.1
Be 0.01
Ca 398.78
Cd 0.39 0.02
Co 0.64
Cr 0.51 0.05
Cu 1.10 1.00
Fe 2.39 1.00
Li 0.65
Mg 12.19
Mn 0.85 0.20
Mo 0.92
Ni 0.72 0.20
Pb 1.11 0.50
Sb 1.47
Se 1.63
Ti 0.99
Tl 0.82
V 0.86
Zn 1.39 1.00
*Acceptable conditions for discharge of industrial effluent or mixed effluent of standards B.
Untreated recycled paper mill effluent (RPME) can
cause disastrous environmental consequences,
including the destruction of fisheries and the
contamination of drinking and irrigation water.
Studies have showed that pulp and paper industry is
considered as the third largest polluter in the United
States (Sinclair, 1991). The effluent generated by pulp
and paper industry contains a considerable amount of
pollutants characterized by biochemical oxygen
demand (BOD), chemical oxygen demand (COD),
suspended solids (SS), toxicity, and colour when
untreated or poorly treated effluents are discharged to
receiving waters (Pokhrel and Viraraghavan, 2004).
Black liquor, an aqueous solution of lignin
residues, hemicelluloses and inorganic chemicals used
in the paper manufacturing process is by-product of
many paper pulp mill and recycled paper industries. It
comprises 15% solids by weight of which 10% are
inorganic and 5% are organic. Black liquor released
by paper mills constitutes only 10-15% of total
wastewater, but contributes approximately 95% of the
total pollution load of pulp and paper mill effluents
(Grover et al., 1999). The black liquor has
characteristically contained high biochemical oxygen
demand (BOD), chemical oxygen demand (COD), and
total solids (TS) along with slowly degradable lignin
compounds, which make it significantly toxic to the
environment. Thus pulp and paper mill effluent
treatment has to be taken seriously as it can cause
serious environmental pollution and threat to human
health.
1.3. Biological Treatment
Many new wastewater treatment methods are being
developed and designed from recent research findings
to create more efficient and cost effective wastewater
treatment systems. Wastewater is treated by removing
or reducing certain harmful constituents found in
wastewater. These constituents are removed by
physical, chemical and biological methods. Table 4
listed the processes involve for each method (United
Nations, 2003).
Almost all wastewater contains biodegradable
constituents, therefore it can be treated biologically
with proper analysis and understanding of biological
treatment processes. Biological unit operations shown
in Table 1.4 are used to transform (i.e. oxidize)
Wastewater Engineering: Advanced Wastewater Treatment Systems
Chapter 3: Wastewater Treatment by Biological Methods
74
dissolved and particulate biodegradable constituents
into desired end products (i.e. biogas and cell tissues).
Besides that, these unit operations are used to remove
or reduce the concentration of organic content which
measured as BOD, TOC or COD and nutrient content
(mainly nitrogen and phosphorus) that are relatively
high and above allowable limit in regulations.
Physical and chemical methods, although quite
effective in reducing the constituents of wastewater
which are harmful, are unattractive for industrial
applications because of the high costs involved.
However, biological methods of effluent treatment
have the advantage of being cost-effective and they
can also reduce both the biological oxygen demand
(BOD) and chemical oxygen demand (COD) of the
wastewater. Biological treatment can be divided to
aerobic process, anaerobic process, and anoxic
process.
Table 4: Wastewater treatment unit operations and processes
Methods Unit operations
Physical unit operation Screening
Comminution
Flow equalization
Sedimentation
Floatation
Granular-medium filtration
Chemical unit operation Chemical precipitation
Adsorption
Disinfection
Dechlorination
Other chemical applications
Biological unit operation Activated sludge process
Aerated lagoon
Trickling filters
Rotating biological contractors
Pond stabilization
Anaerobic digestion
Biological nutrient removal
1.4. Anaerobic Process
Since the early 1980s, anaerobic process for
wastewater treatment has attracted a lot of attention.
This process has advantages as design simplicity, use
of non-sophisticated equipment, high treatment
efficiency, low excess sludge production and low
operating and capital cost (Saktaywin et al., 2005).
There are three basic steps are involved in the overall
anaerobic oxidation of a waste: (1) hydrolysis, (2)
fermentation (also referred to as acidogenesis) and (3)
methanogenesis. The first step for most fermentation
processes, in which particulate material is converted
to soluble compounds that can then be hydrolyzed
further to simple monomers that are used by bacteria
that perform fermentation, is termed hydrolysis.
The second step is fermentation (also referred to as
acidogenesis). In the fermentation process, amino
acids, sugars, and some fatty acids are degraded
further. Organic substrates serve as both the electron
donors and acceptors. The principal products of
fermentation are acetate, hydrogen, CO
2
, and
propionate and butyrate. The propionate and butyrate
are fermented further to produce hydrogen, CO
2
, and
acetate. Thus, the final products of fermentation
(acetate, hydrogen, and CO
2
) are the precursors of
methane formation (methanogenesis) (Wang, 2012).
The third step, methanogenesis, is carried out by a
group of organisms known collectively as
methanogens. Two groups of methanogenic organisms
are involved in methane production. One group,
termed aceticlastic methanogens, split acetate into
methane and carbon dioxide. The second group,
termed hydrogen-utilizing methanogens, uses
hydrogen as the electron donor and CO
2
as the
electron acceptor to produce methane. Bacteria within
anaerobic processes, termed acetogens, are also able
to use CO
2
to oxidize hydrogen and form acetic acid.
However, the acetic acid will be converted to
methane, so the impact of this reaction is minor
(Wang, 2012).
1.5. Methane Gas Production
The microorganisms responsible for methane
production, classified as archaea, are strict obligate
anaerobes. Many of the methanogenic organisms
identified in anaerobic digesters are similar to those
found in the stomachs of ruminant animals and in
organic sediment taken from lakes and rivers. In
methanogenesis, methanogens consume the acids
produced by the acidogens, generating biogas
(methane gas) as byproduct. Instead of oxygen
accounting for the change in COD, the COD loss in
Zwain and Dahlan
Biological Treatment of Recycled Paper Mill Wastewater Using Modified Anaerobic Inclining-Baffled (MAIB)
Bioreactor
75
the anaerobic reactor is accounted for by the methane
production (Ngre and Jonsson, 2010). By
stoichiometry the COD equivalent of methane can be
determined as shown in equation 1.1.
(1.1)
1.6. Anaerobic Baffled Reactor
Nowadays, many researchers have focused on
anaerobic reactors for the treatment of wastewater. As
one of the high-rate anaerobic reactors, ABR was
extensively used in treating wastewater (Liu et al.,
2010). The reactor design has been developed since
the early 1980s. ABR comprises a series of vertical
baffles to force the wastewater to flow under and over
them and therefore, the wastewater comes into contact
with a large active biological mass (Grover et al.,
1999). Bacteria within the reactor gently rise and
settle due to flow characteristics and gas production,
but move down the reactor at a slow rate. Figure 1
shows a schematic diagram of anaerobic baffled
reactor (Zwain et al., 2013).
Fig. 1: Schematic diagram of anaerobic baffled reactor.
Each gas chamber was separated permitting the
measurement of gas composition and production from
each compartment. The separation of the gas can also
enhance the reactor stability by shielding syntrophic
bacteria from the elevated levels of hydrogen which
are found in the front compartments of the baffled
reactor (Barber and Stuckey, 1999).
The performance of the ABR in treating a variety
of wastewaters, in particular, low and high strength
wastewater and other refractory wastewaters has been
well reviewed in the literature (Liu et al., 2010).
Table 5 shows low strength wastewater treated by
ABR. Dilute wastewaters inherently provide a low
mass transfer driving force between biomass and
substrate, and subsequently biomass activities will be
greatly reduced according to Monod kinetic. Thus,
ABR is effective in treating low strength wastewater
with no substantial change occurred in the population
of acid producing bacteria down the length of the
reactor. Lower gas production rates can help to
overcome the problem of sludge washout with low
HRTs (6-2 days) in which can increase hydraulic
turbulence, which can lower apparent K
S
values, thus
enhance treatment efficiency. When treating dilute
wastewater, baffled reactors should be started-up with
higher biomass concentrations in order to obtain a
sufficiently high sludge blanket (and better mixing) in
as short time as possible to counteract the problem of
low sludge blankets caused after long periods of
biomass settling (Kato et al., 1997).
In addition, ABR is also applied for the treatment
of high strength wastewaters. A brief summary of the
literatures on high strength treatment is shown in
Table 6. In high strength wastewater treatment, longer
retention times are necessary due to the high gas
mixing caused by improved mass transfer between the
biomass and substrate. Longer retention time
enhances biomass settling ability. According to
kinetic consideration, high substrate concentrations
will encourage to increase the rate of bacteria growth
and gas production.
Wastewater Engineering: Advanced Wastewater Treatment Systems
Chapter 3: Wastewater Treatment by Biological Methods
76
Table 5: Selected low strength performance data (Liu et al., 2010).
Wastewater HRT
(h)
Influent COD
(mg/L)
COD Removal
(%)
OLR
(kg/m
3
d)
Gas Produced
(LCH
4
/g COD d)
Reference
Synthetic
wastewater
10 501 90.7 1.2 0.36 (Gopala Krishna and
Kumar, 2007)
Domestic
wastewater
1
48 305.1836.22 745 - - (Feng et al., 2008)
Municipal
wastewater
6 350 86 2.62 0.34 (Bodkhe, 2009)
Complex
wastewater
8 500 88 2 0.31 (Gopala Krishna et al.,
2008)
Diluted wastewater 10 500 95 0.13 0.3 (Langenhoff and
Stuckey, 2000)
Domestic
wastewater
2
22 71654.4 723 - - (Foxon et al., 2004)
Low strength
wastewater
12 550 89 1.69 - (Shen Y.L., 2004)
Low strength
wastewater
3 850 90 6.9 - (Shen Y.L., 2004)
1= at 281C; 2= on pilot scale; others carried out on laboratory scale.
Table 6: Selected high strength performance data (Liu et al., 2010)
Wastewater HRT
(h)
Influent COD
(mg/L)
COD Removal
(%)
OLR
(kg/m
3
d)
Gas Produced (LCH
4
/g
COD d)
Reference
Palm oil mill wastewater
72 16000 77.3 5.33 0.33 (Faisal and Unno,
2001)
Whisky distillery
wastewater
96 9500 96.1 2.38 - (Akunna and Clark,
2000)
Brewery wastewater
19.23 10720 93 13.38 - (Baloch et al.,
2007)
Soybean protein processing
wastewater
39.5 1000 97 6.0 - (Zhu et al., 2008)
ABR shows a promise for industrial wastewater
treatment due to its ability to withstand severe
hydraulic and organic shock loads, intermittent
feeding, temperature changes, and tolerant certain
toxic materials. The successful application of
anaerobic technology in the treatment of industrial
wastewater critically dependent on the development
and use of high rate anaerobic bioreactors (Barber and
Stuckey, 1999). Table 7 shows the recommendations
based on literature findings on anaerobic baffled
reactor.
1.7. Advantages of Anaerobic Baffled Bioreactor
The most significant advantage of the ABR is its
ability to separate acidogenesis and methanogenesis
longitudinally down the reactor, allowing the reactor
to behave as a two-phase system without the
associated control problems and high costs (Hassan et
al., 2013). Barber and Stuckey (1999) study showed
that ABR is capable of treating a variety of
wastewaters of varying strength, over a large range of
loading rates, and with high solids concentrations.
Table 8 shows the advantages associated with
anaerobic baffled reactor.
2. CASE STUDY
The development of effective and simple methods for
treatment recycled paper mills (RPM) wastewater is a
challenging task to environmental engineers and
scientists. Therefore, in this study, a novel modified
anaerobic inclining-baffled bioreactor (MAIB-R) was
developed and tested for RPM wastewater treatment.
The aims of this study are to characterize the RPM
wastewater and to perform the start-up of MAIB-R.
Zwain and Dahlan
Biological Treatment of Recycled Paper Mill Wastewater Using Modified Anaerobic Inclining-Baffled (MAIB)
Bioreactor
77
Table 7: Recommendations based on literature findings (Barber and Stuckey, 1999)
Recommendations
Start-up
Low initial loading rates will encourage granule/ floc growth.
Pulses of methane precursors (e.g. acetate) have been successfully used to encourage
methanogenic growth and dampen the effects of increases in loading rate.
Start-up with long retention times reduces solids loss due to low liquid upflow
velocities and promotes higher methanogenic populations in every compartment.
Recycle
Recycle is beneficial with respect to diluting toxicants in feed stream, increasing front
pH and reducing production of foam and SMPs.
Low strength wastewater Low retention time enables better mass transport due to improved hydraulic mixing
and reduces biomass starvation in latter Compartments.
methane production will originate from scavenging bacteria (Methanosaeta).
High strength wastewater
Long retention times reduce solids washout caused by high gas production, otherwise
the reactor may be modified (by adding packing) to decrease biomass loss.
Methane production will be mainly due to Methanosarcina, and hydrogen scavenging
methanogens.
High solids wastewater
A larger front compartment has proved to be effective in treating wastewater with high
solids content.
Temperature Reducing temperature to 25C from 35C has no effect on easily degradable waste,
further decreases in temperature are detrimental on reactor performance, this may be
due to potential toxicity, nutrient bioavailability and slower kinetic rates.
Reactors started-up and kept at lower temperatures perform consistently well
2.1. Reactor Design and Fabrication
MAIB-R used in this study was rectangular, consisted
of five compartments and constructed by using plexi-
glass with a dimension of 80cm long, 15cm wide and
30cm in height, having a total effective volume of 35
L as shown in Figure 2. Each compartment composed
of upflow and downflow sections by using modified
inclining baffles in series in which this bioreactor is
called as modified anaerobic inclining-baffled
bioreactor (MAIB-R). It was a modification from
ABR. Feed tank was equipped with a mixer to mix the
RPM wastewater well before it was pumped into
MAIB-R. Peristaltic pump was used to adjust the flow
rate of incoming RPM wastewater into the MAIB-R.
The biogas generated from each compartment was
collected by using biogas bag. The volume of the
biogas was measured according to the volume of
biogas bag. Each compartment was equipped with
liquid sampling ports for the convenient of grabbing
liquid sample to be analyzed for its characteristic. The
MAIB-R was maintained at 37 C in a water bath. The
treated RPM wastewater was collected in effluent
collection tank to be analyzed for its characteristic.
2.2. Seeding and Acclimatization
The inoculum for seeding the MAIB-R was
anaerobically digested sludge taken from Palm Oil
Mill Effluent (POME) (Malpom Palm Industries Bhd,
Penang, Malaysia). While the RPM wastewater
samples were taken from Muda Paper Mill Penang,
Malaysia. The sludge and RPM wastewater samples
were kept in refrigerator at 4C before they were used
for seeding process to avoid biological contamination
at different temperature.
Initially, the MAIB-R was inoculated with mixture
of POME sludge (about 10% of total volume of
MAIB-R) and fresh RPM wastewater taken from
Muda Paper Mills Penang (about 10% of total sludge
mixture). Then, the MAIB-R was sealed tightly so that
no air could enter the MAIB-R. Besides that, the
MAIB-R was flushed with nitrogen gas to displace
any air inside the bioreactor and purge out to remove
oxygen content before feeding with RPM wastewater.
Then, the MAIB-R was daily batch-fed with fresh
RPM wastewater which was diluted to 1000 mg
COD/L as much as 10% of total volume of bioreactor
(3.5 liter) every day until the MAIB-R reach its
capacity. Then, continuous phase was started. The
acclimatization of sludge with RPM wastewater
during start-up period was monitored by daily
measurement of physico-chemical parameters (pH,
temperature, COD and biogas production) until steady
state is achieved.
Wastewater Engineering: Advanced Wastewater Treatment Systems
Chapter 3: Wastewater Treatment by Biological Methods
78
Table 8: Advantage associated with the anaerobic baffled reactor (Barber and Stuckey, 1999)
Advantage
Construction
1. Simple design
2. No moving parts
3. No mechanical mixing
4. Inexpensive to construct
5. High void volume
6. Reduced clogging
7. Reduced sludge bed expansion
8. Low capital and operating costs
Biomass
1. No requirement for biomass with unusual settling properties
2. Low sludge generation
3. High solids retention times
4. Retention of biomass without fixed media or a solid-settling chamber
5. No special gas or sludge separation required
Operation
1. Low HRT
2. Intermittent operation possible
3. Extremely stable to hydraulic shock loads
4. Protection from toxic materials in influent
5. Long operation times without sludge wasting
6. High stability to organic shocks
Fig. 2: Schematic diagram of the MAIB bioreactor experimental set-up.
2.3. Experimental Analysis procedure
The RPM wastewater collected from Muda Paper Mill
Penang were subjected to the analysis of the following
parameters, i.e. pH, chemical oxygen demand (COD),
biochemical oxygen demand (BOD), total dissolved
solids (TDS), total suspended solids (TSS), total
solids (TS), volatile suspended solids (VSS) and
biogas methane concentration. These parameters
analyses were performed according to American
Public Health Association (APHA, 1995). They were
analyzed using specialized equipments, such as
Spectrophotometer DR-2800, Shimadzu Gas
Chromatography-FID (GC) with FID column and
COD reactor digest.
The MAIB-R was operated continuously until
steady-state condition achieved. The MAIB-R
samples were monitored each two days for pH,
temperature, COD and biogas. During the steady state,
the influent, each compartment and effluent samples
were collected. Samples were collected starting from
the last compartment towards the first compartment to
Zwain and Dahlan
Biological Treatment of Recycled Paper Mill Wastewater Using Modified Anaerobic Inclining-Baffled (MAIB)
Bioreactor
79
prevent air intrusion and maintain anaerobic
condition. All the parameters were determined
according to APHA Standard Method (APHA, 1995)
Biogas generated (methane gas) in each
compartment of MAIB bioreactor was collected from
the upper part of each compartment using biogas bag.
Volume of biogas was measured daily by using biogas
bag with a volume of 1 L per bag and pipette bulb
with 40 ml per pump. Shimadzu Gas
Chromatography-FID (GC) with propack N column
equipped with Flame ionization detector (FID) and
data acquisition system with computer software was
used to determine methane concentration in biogas
collected. Nitrogen gas was used as carrier gas. The
temperature of detector was set to 100C and injector
temperature at 90C. Methane concentration was
analyzed by injecting 1.0 ml of biogas sample in
column of GC using airtight glass syringe. Then, the
methane concentration was taken.
3. RESULTS AND DISCUSSION
3.1 Characteristic of Recycled Paper Mill
Wastewater
The characteristic of the RPM wastewater generated
depends on the type of processes, process technology
applied, management practices internal recirculation
of the effluent for recovery, and the amount of water
to be used in the particular process (Pokhrel and
Viraraghavan, 2004). Table 9 shows the characteristic
of RPM wastewater generated by Muda Paper Mill
Penang, Malaysia. The RPM wastewater generated
contained a considerable high amount of pollutants
characterized by various physico-chemical
constituents. If the untreated RPM wastewater
discharges into streams and other water bodies, it can
cause disastrous environmental consequences,
including the destruction of fisheries and the
contamination of drinking and irrigation water.
Table 9: Characterization of RPM wastewater
pH - 6.2-7.8
Temperature C 35-45
Biological oxygen demand (BOD) mg/L 1650-2565
Chemical oxygen demand (COD) mg/L 3380-4930
BOD
5
/ COD - 0.488-0.52
Total Solids (TS) mg/L 3530-6163
Total dissolved solids (TDS) mg/L 1630-3025
Total suspended solids (TSS) mg/L 1900-3138
Total volatile solids (VSS) mg/L 840-2920
These physico-chemical constituents were
relatively high compared to Malaysian Standard of
parameter limits of effluent discharge in Fifth and
Seventh Schedules of Environmental Quality
(Industrial Effluent) Regulations as shown in Table 10
and Table 11, respectively. There are two standards
stipulated in EQA 1974, namely Standard A and
Standard B. Standard A is for effluent discharges
upstream of a raw water intake and is more stringent.
On the other hand, Standard B is for effluent
discharges downstream of raw water intake. These
standards are interpreted as absolute standards, which
sewage and industrial effluent must comply before
being discharged; in this study is RPM wastewater.
This wastewater standard is established for the main
purpose of regulating the disposal pollutants into a
receiving water course to protect aquatic ecosystems,
public health and welfare.
Table 10: Environmental Quality Act 1974 and Regulations. Environmental Quality (Industrial Effluent) Regulations (PU (A)
434), Fifth Schedule
Parameters Units
Standard
A B
Temperature C 40 40
pH value - 6.0-9.0 5.5-9.0
Suspended solids mg/l 50 100
Table 11: Acceptable conditions for discharge of industrial effluent containing chemical oxygen demand (COD) for specific
trade or industry sector
Trade/Industry Unit Standard A Standard B
(a) Pulp and paper industry
(i) pulp mill mg/L 80 350
(ii) paper mill (recycled) mg/L 80 250
(iii) pulp and paper mill mg/L 80 300
Wastewater Engineering: Advanced Wastewater Treatment Systems
Chapter 3: Wastewater Treatment by Biological Methods
80
By comparing Table 9 with Table 10 and 11, the
characterization of RPM wastewater was far from the
allowable limit set by EQA 1974 for discharge
industrial effluent, therefore a proper and systematic
wastewater treatment is required to treat the RPM
wastewater to make sure the parameters are in
allowable range before it is discharged.
From Table 9, the RPM wastewater generated had
relatively neutral pH with the range of pH 6.2 to 7.8.
Thus, the wastewater does not require alkaline
adjustment because the pH is within the allowable
discharge range by EQA 1974. The BOD
5
/COD
relationship of 0.5 showed that the wastewater is of
high strength organic type and has a potential to
increase in strength with time, hence its suitable to be
treated anaerobically (Nyanchaga and Elkanzi, 2002).
The BOD5/COD was found comparable to the
average BOD
5
/COD ratio of 0.59 reported by
Nyanchaga and Elkanzi (2002).
The ratio of BOD
5
/COD of a wastewater is a good
indication of amount of the total organic load (or
oxygen demand) is available for degradation.
Indirectly, BOD
5
/COD ratio is a measure of food
value. If the ratio is higher, it has higher food and less
toxicity. However, researchers used to describe
BOD
5
/COD ratio as biodegradability level of
materials by which organic matter containing
wastewater is readily broken down in the
environment. BOD
5
/COD ratio can be categorized
into toxic, biodegradable and acceptable or stable
zones (Samudro and Mangkoedihardjo, 2010).
3.2 Start-up at Continuous Feeding
The start-up was the most crucial and important part
of overall MAIB-R processes, it requires a long period
of time to reach steady state due to slow growth rates
of the anaerobic microorganisms inside the MAIB-R,
especially methanogens. The adaptation during this
period is very important for the bacterial population to
develop the microbial culture for treating wastewater
in an anaerobic environment in the MAIB-R.
The anaerobic digestion process was begun in the
absence of oxygen. During this stage, MAIB-R was
under close monitoring to ensure that the anaerobic
active sludge is well grown by monitoring the
temperature of the bioreactor, pH, COD. The
continuous operation of MAIB-R was started at
hydraulic retention time (HRT) of 5 days. To obtain a
good start-up, low initial organic loading rate was
being carried out to provide good condition for the
growth of anaerobic active sludge as well as to
prevent slow growing microorganisms from
overloaded in MAIB-R.
Later, COD removal efficiency and the varying of
pH curve of RPM wastewater were closely monitored
and studied to determine the performance efficiency
of MAIB-R during start-up. These parameters were
analyzed using the standard methods by American
Public Health Association (APHA, 1995).
3.2.1. pH Level at Continuous Feeding
The obtained result for pH of MAIB-R in each
compartment during continuous feeding period for 15
days is shown in Figure 3. The pH level of RPM
wastewater in influent was relatively stable at about
7.90. However, in first compartment, the pH level was
decreased drastically with the range from 6.70 to 6.21.
On day 2 to day 6, the pH in compartment 2 to 4 were
increased, but the pH level was decreased in
compartment 5 and slightly increased again to 7.20,
7.10 and 7.03 for the effluent pH on day 2, day 4 and
6, respectively.
The decreasing of the pH in first compartment
(acidification zone) is due to the presence of large
population of acidogenic bacteria. The optimum pH of
acidogenic bacteria was recorded in the range
between 5.8 and 6.2 (Zoetemeyer et al., 1982) which
has shown on day 15 in first compartment. The
substrate level was high thus contributing to the fast
growing bacteria. According to Hu and Li (2008), the
pH level of each compartment increased towards the
end of the reactor from compartment 2 to 5 which has
been proven through this study.
On day 11 to day 15, pH in compartment 2 to 4 is
relatively stable and not much of fluctuation. On day
11, pH of MAIB-R from compartment 1 to 5 showed
a smooth increase which is the same as predicted by
Hu and Li (2008) in their study. If the first
compartment has higher pH compared to other
compartment, it could be due to the substrate level
was insufficient to feed the fast growing bacteria and
some of them starved thus died. This shows that pH
has an important effect on the selection, survival, and
growth of microorganism. On day 15, the pH in every
compartment showed a smooth increase and had
almost negligible fluctuation, hence steady state was
reached.
Zwain and Dahlan
Biological Treatment of Recycled Paper Mill Wastewater Using Modified Anaerobic Inclining-Baffled (MAIB)
Bioreactor
81
Fig. 3: pH profiles for each compartment of MAIB bioreactor during continuous feeding period
3.2.2. COD Removal at Continuous Feeding
As shown in Figure 4, the influent COD concentration
was ranging from 717-752mg/L with an average of
737mg/L. It was greatly reduced with the COD
concentration in effluent was varied in the range of
264 to 60 mg/L. On day 2, the COD removal
efficiency was 63% with influent and effluent COD at
720mg/L and 264mg/L, respectively. COD removal
efficiency was slightly increased to 74% on day 4.
Then, the COD removal rate was further increased
steadily with the influent COD relatively constant at
737mg/L. It increased gradually from 63% to 92%
from day 2 to 15. On day 11 to 15, the COD removal
efficiency of MAIB-R showed relatively stable with
the range from 91% to 92%.
On day 15, the influent COD concentration
reduced from 750mg/L to 60mg/L with COD removal
efficiency at 92%. This could be the beginning day of
steady state in MAIB-R. Steady state of COD removal
of more than 80% is considered acceptable for
anaerobic bioreactor start-up and acclimatization
(Buitron G., 2003; Enright A.M., 2005). As for other
type of wastewater, ABR can remove up to 77% of
COD for treatment of textile dye effluent with HRT
of 4 days (Goel, 2010). The average COD removal
efficiency of ABR was constantly maintained at
around 65% and the total COD removal rate of the
system in treating chemical synthesis-based
pharmaceutical wastewater was as high as 95% to
98% (Lili et al., 2009).
Fig. 4: COD concentration and removal efficiencies in the MAIB bioreactor during continuous feeding
Wastewater Engineering: Advanced Wastewater Treatment Systems
Chapter 3: Wastewater Treatment by Biological Methods
82
3.2.3. Methane Gas Production at Continuous
Feeding
Table 12 shows the result of methane concentration in
biogas analyzed by GC. The methane gas production
rate during continuous feeding and at steady state was
monitored and analyzed from day 2 to 15. Methane
gas was produced along with degradation of organic
matter in MAIB-R. Methane concentration in biogas
was varied in the range of 46 to 70%. The average
methane concentration from day 2 to 15 was 67% to
57%. On day 2 to 6, the methane content was in the
range of 59 to 67% with 0.65L/d, 0.44L/day and
0.57L/day of biogas for day 2, 4 and 6, respectively.
The biogas yield was obtained by measuring the
volume of biogas produced within 24hours. Then, on
day 11 to 15, the methane content in biogas was
slightly higher than previous days in the range of 47 to
57% with varied amount of biogas by 0.67L/day,
0.77L/day and 0.77L/day for day 11, 13 and 15,
respectively.
Organic matter which is broken down by bacteria
without oxygen will produce significant quantities of
methane gas (CH
4
) with sufficient supply of nutrients
like nitrogen and phosphorus. The lack of nutrients or
substrate will limit biogas production. Having more
organic content in sludge will generate more methane
gas. Biogas mainly composed of methane and carbon
dioxide is a byproduct of anaerobic decomposition of
organic waste. Increase in biogas production and
methane content may be due to greater activity of
methanogenic bacteria in MAIB-R (Goel, 2010).
However, the quality of biogas and methane content
generated by organic waste materials does not remain
constant but varies with the period of digestion in
MAIB-R (Mahdi, 1986).
As for textile dye effluent, ABR generated up to
83% of methane content in biogas (Goel, 2010).
Meanwhile, methane content in biogas generated by
ABR in treating palm oil mill effluent was up to
67.4% (Setiadi et al., 1996).
Table 12: Methanogenesis of RPM wastewater using MAIB bioreactor at different time
Day Methane content (% v/v) Biogas yield
(L/d)
1 2 3 Average
2 70 65 66 67 0.65
4 69 64 62 65 0.44
6 52 60 65 59 0.57
11 46 50 46 47 0.67
13 58 53 59 57 0.77
15 55 57 59 57 0.77
3.3. Steady State Performance
3.3.1. pH Level
Steady state was achieved on day 15 of continuous
feeding. As shown in Figure 5, on day 15, influent pH
of RPM wastewater was 7.94 while effluent pH of
RPM wastewater dropped to 6.63 after anaerobic
digestion in MAIB-R. The pH level decreased
drastically to 6.21 in first compartment. However, the
pH level from compartment 2 to 5 increased smoothly
towards the end of the MAIB-R with pH of 6.39, 6.47,
6.59 and 6.60, respectively.
In the anaerobic digestion process, there are three
types of bacteria exist in anaerobic digestion process,
namely acid producing fermentation bacteria,
hydrogen-producing acetogenic bacteria and
methanogens. However, the pH demanded by the
three bacterial communities was different. The best
pH for the growth of methanogen ranged from 6.6 to
7.8. If the pH falls below 6, methanogenic bacteria
cannot survive. Hydrogen-producing acetogenic
bacteria and methanogen generate together. The pH
for hydrogen-producing acetogenic bacteria was
similar to that of methanogen, whose pH ranged from
6.0 to 8.0 (Guochen et al., 2009).
The pH level in the first compartment of MAIB-R
(acidification zone) has lower pH of 6.21. In the
acidogenesis process, acidogenic bacteria converts the
product of hydrolysis (amino acids, fatty acids, simple
sugars and glucose) into simple organic compounds,
mostly short chain acids, volatile acids (Metcalf &
Eddy, 2004). The transition of the high substrate
(carbon and energy source) level from organic
material to organic acids in the acid forming stages
causes the pH of the first compartment to drop
drastically and increase the growth rate of the
bacteria. This is beneficial for the acidogenic and
acetagenic bacteria that prefer a slightly acidic
environment and are less sensitive to changes in the
incoming feed stream.
The growth rate of scavenging bacteria becomes
slower towards the end of the reactor (methanogenic
zone) at higher pH (Hu and Li, 2008). In
methanogenesis, methane-producing bacteria,
methanogens are very sensitive towards changes and
prefer a neutral to slightly alkaline environment (Gas
Technology Inc, 2003). If the pH falls below 6,
Zwain and Dahlan
Biological Treatment of Recycled Paper Mill Wastewater Using Modified Anaerobic Inclining-Baffled (MAIB)
Bioreactor
83
methanogenic bacteria cannot survive. Thus, the
change in pH can be both an indicator to determine
the performance efficiency and the cause of process
imbalance in MAIB-R. At steady state, effluent pH of
RPM wastewater produced using MAIB-R was 6.63.
If compared with the regulations in EQA 1974 shown
in Table 10 and it was found to be complying and
within the limit of both Standard A (pH6.0-9.0) and
Standard B (pH5.5-9.0).
Fig. 5: pH profiles for each compartment of the MAIB bioreactor at steady state on day 15
3.3.2. COD Removal
Figure 6 shows the COD concentration in each
compartment at the steady state performance. The
removal efficiency of COD on day 15 was 92% when
the pH was recorded above 6. These results proved
that MAIB-R reactor has showed good bioreactor
performance. The COD concentration was further
decreased towards the end of the MAIB-R from
compartment 1 to 5. In compartment 1 of MAIB
bioreactor, the COD concentration was dropped
drastically to 328mg/L from initial 988mg/L of
influent COD concentration. As for compartment 2,
the COD concentration measured was 322 mg/L while
in compartment 3 was 316 mg/L. The COD
concentration for compartment 4 and 5 of MAIB-R
was 298 mg/L and 294 mg/L, respectively.
From this result clearly indicates that MAIB-R led to
a higher biological degradation of the organic matter
in RPM wastewater, and a better adaptation of the
biomass for the degradation of the substrates. Similar
observation was reported by Guochen et al (2009)
using ABR bioreactor, where the COD removal
efficiency up to 89%. Guochen et al. (2009) reported
that during stable stage, average COD removal rate of
ABR treating high-concentration sugar producing
wastewater was 85.5%. COD removal of ABR in
treating wheat flour starch industry wastewater was up
to 67% (Movahedyan et al., 2007).
At steady state, effluent COD concentration of MAIB-
R was 60mg/L. From Table 11, it showed that it
complied to EQA 1974 Standard B with COD limit of
100mg/L. However it failed to comply with Standard
A with COD limit of 50mg/L with a slight difference
by 10mg/L. Further studies need to be done for better
COD removal efficiency so that the effluent (RPM
wastewater) can be reached below 50mg/L.
Wastewater Engineering: Advanced Wastewater Treatment Systems
Chapter 3: Wastewater Treatment by Biological Methods
84
Fig. 6: COD concentration in the MAIB bioreactor at steady state on day 15
4. CONCLUSIONS AND RECOMMENDATIONS
Recycled paper mill wastewater contained a
considerable high amount of COD with the range of
3380mg/L to 4930mg/L; BOD with the range of
1650mg/L to 2565mg/L. The BOD
5
/COD relationship
(0.488-0.52) showed that RPM wastewater was of
high strength wastewater. In addition, RPM
wastewater also contained relatively high total solids,
total suspended solids and total dissolved solids. The
start-up process of MAIB-R in this study has been
shortly achieved and the steady state was obtained on
day 15. The MAIB-R after successful start-up can
achieve relatively high average COD removal of 92%.
The pH showed a smooth increased from
compartment 1 towards the end of the MAIB-R,
compartment 5. Influent pH of RPM wastewater was
7.94 and dropped to 6.63 (effluent pH). On the other
hand, the COD concentration in each compartment
was slightly decreased from compartment 1 to
compartment 5. The removal efficiency of COD on
day 15 was 92%. Methane content in biogas generated
by MAIB-R was up to 57% with biogas yield of
0.77L/d on day 15. Although, this MAIB-R start-up
was successfully carried out, however further study is
needed to enhance the performance of the MAIB-R at
wide range of OLR, HRT and temperature. It is also
suggested that effort should be made to investigate the
microbial growth kinetic of the MAIB-R.
ACKNOWLEDGMENT
The authors wish to acknowledge the financial
support from the Universiti Sains Malaysia (RU-I
Grant A/C. 1001/PJKIMIA/814148).
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Available online at http://www.ijsrpub.com/books
2014 IJ SRPUB
87
Augmentation of Biological Nitrogen Removal via Optimization of Support Media
Size and Aeration Strategy in Moving Bed Sequencing Batch Reactor
Jun-Wei Lim
1
, Mohammed J.K. Bashir
1,*
, Si-Ling Ng
2
, Sumathi Sethupathi
1
, Lai-Peng Wong
1
1
Department of Environmental Engineering, Faculty of Engineering and Green Technology (FEGT), University Tunku Abdul
Rahman, 31900 Kampar, Perak, Malaysia
2
School of Science, Monash University Sunway Campus, 46150 Petaling Jaya, Selangor, Malaysia
*Corresponding Author: jkbashir@utar.edu.my; Tel: 605-4688888 ext: 4559; Fax: 605-4667449
Abstract. As the discharge of wastewater containing nitrogen is in soaring trend, the objectives of this research aim to
optimize the size of support media and aeration strategy in moving bed sequencing batch reactor (MBSBR) for the biological
nitrogen removal enhancement. In accordance with these objectives, MBSBRs packed with polyurethane (PU) foam cubes of
sizes 8 to 125-mL as the support media and operated with continuous aeration (CA) strategy was initially experimented to
determine the optimum size of support media, reflected by the highest total nitrogen (TN) removal. Subsequently, the
operation of MBSBR packed with optimum size of support media was converted to intermittent aeration (IA) strategy and its
performance in terms of TN removal was investigated again. The results of these two steps experiments vindicated that the
MBSBR packed with 8-mL PU foam cube and operated with IA strategy removed the highest TN removal, signifying the
optimum condition. This optimum condition had eventually resulted the MBSBR procured the highest total weight of attached-
growth biomass that was associated to the maximum amount of internally stored carbon source in which favorable the
simultaneous nitrification and denitrification (SND) process.
Keywords: Nitrogen Removal, Sequencing Batch Reactor, Biological Method
1. INTRODUCTION
The increasingly discharge of nitrogen wastes from
industrial, livestock and agricultural wastewaters
without prior channeling to a proper treatment can
adversely contaminate the quality of receiving waters.
Serious concern related to the adverse impacts of
nitrogen wastes particularly ammonium-nitrogen
(NH
4
+
-N) includes dissolved oxygen (DO) depletion,
toxicity and eutrophication (Gerardi, 2002; Magri et
al., 2013). Therefore, the necessity to remove NH
4
+
-N
in wastewaters before the disposal is utmost crucial to
comply with the stringent discharged limits for
wastewaters containing nitrogen.
Biological nitrogen removal has been widely
recognized to offer a more economical and
environmentally friendly approach in removing NH
4
+
-
N via nitrification and denitrification processes
(Gerardi, 2002; Jokela et al., 2002; Leta, 2004;
Dempsey et al., 2005; Aslan et al., 2009; Yao et al.,
2013). Over the decades, various operational
parameters had been studied with intention to
optimize the biological nitrogen removal (Deguchi
and Kawashiwaya, 1994; Pochana and Keller, 1999;
Katsogiannis et al., 2003; Daniel et al., 2009; Chu and
Wang, 2011).
1.1. Nitrification Process
The nitrification process is a two steps aerobic
process. The first step involves the oxidation of NH
4
+
-
N to nitrite-nitrogen (NO
2
-
-N) which is subsequently
oxidized to nitrate-nitrogen (NO
3
-
-N) in the second
step mediated by Nitrosomonas sp. and Nitrobacter
sp., respectively (Kotlar et al., 1996; Qiao et al.,
2008). The oxidation of NH
4
+
-N to NO
2
-
-N is
conventionally known as nitritation process, whereas
the oxidation of NO
2
-
-N to NO
3
-
-N is typically
identified as nitratation process (Zeng et al., 2009;
Fukumoto et al., 2011).
Nitritation process performed by Nitrosomonas sp.:
NH
4
+
+ 1.5O
2
NO
2
-
+ 2H
+
+ H
2
O (1)
Nitratation process performed by Nitrobacter sp.:
NO
2
-
+ 0.5O
2
NO
3
-
(2)
Overall nitrification process:
NH
4
+
+ 2O
2
NO
3
-
+ H
2
O + 2H
+
(3)
The nitrifying bacteria of Nitrosomonas spp. and
Nitrobacter spp. are categorized as
chemolithoautotrophs, indicating that the nitrifying
bacteria obtain carbon from the inorganic carbon, i.e.,
carbon dioxide, and energy from the chemical
reactions (Eqs. 1 and 2, respectively) for growth and
multiplication. Carbon dioxide is accessible to
nitrifying bacteria in the form of bicarbonate in the
wastewaters (Gerardi, 2002; Liao et al., 2008). As
more energy can be reaped from the oxidation of
NH
4
+
-N to NO
2
-
-N than NO
2
-
-N to NO
3
-
-N, the
population size of Nitrosomonas spp. is always greater
than Nitrobacter spp. Besides, Nitrosomonas spp. also
has a shorter generation time which enables its
numbers to faster than Nitrobacter spp. (Gerardi,
2002). Therefore, in the activated sludge system, the
Lim et al.
Augmentation of Biological Nitrogen Removal via Optimization of Support Media Size and Aeration Strategy in
Moving Bed Sequencing Batch Reactor
88
ability of being oxidized for NH
4
+
-N is always higher
than for NO
2
-
-N, causing a transient accumulation of
NO
2
-
-N which is removed when NH
4
+
-N is completely
oxidized. However, during unfavourable operational
conditions such as low DO concentration, excessive
sludge washout, extreme change in temperature, etc.,
significant accumulation of NO
2
-
-N concentration can
be detected in the mixed liquor of the bioreactors
(Ruiz et al., 2006; Jubany et al., 2009; Lim et al.,
2010; Gu et al., 2012).
Although the activated sludge system is commonly
used to treat wastewaters containing NH
4
+
-N in many
treatment plants, it is actually not an ideal system for
the nitrification process. As demonstrated by Gerardi
(2002), the typical population size of nitrifying
bacteria in the activated sludge system is merely in the
range of 3% to 10% with the remaining consisting of
organotrophs. This is due to the nitrifying bacteria has
a very low reproductive rate as large amounts of
NH
4
+
-N and NO
2
-
-N are required during the
assimilation process.
1.2. Denitrification Process
The sole nitrification process is only partially
fulfilling the objective of biological nitrogen removal
as the NH
4
+
-N is merely bio-transformed to the
oxidized nitrogen, viz., NO
3
-
-N and NO
2
-
-N, by the
nitrifying bacteria. These oxidized nitrogen species
must be later reduced to nitrogen gas (N
2
) and
released to the atmosphere in order to remove nitrogen
from wastewaters. The reduction process is known as
denitrification process which reduces the oxidized
nitrogen to N
2
with the sequence shown hereafter
(Gerardi, 2002):
Nitrate ion (NO
3
-
) Nitrite ion (NO
2
-
) Nitric
oxide (NO) Nitrous oxide (N
2
O) Ntrogen gas
(N
2
)
The process of denitrification can be achieved by a
broad range of facultative anaerobes which make up
an approximately 80% of the bacteria in the activated
sludge system. The largest numbers of facultative
anaerobes that can perform the denitrification process
are from genera of Alcaligenes, Bacillus and
Pseudomonas (Gerardi, 2002). More so, the
facultative anaerobes that denitrify are also termed by
several names including denitrifying bacteria,
organotrophs, denitrifiers and heterotrophs.
In assuring the feasibility of denitrification
process, the carbon source must be made available to
the denitrifying bacteria under an anoxic environment
with DO concentrations of lower than 1.0 mg/L or 2%
saturation in the mixed liquor of the bioreactors (Goh,
2007; Lim et al., 2012). As the denitrifying bacteria
can reap more energy through the aerobic respiration,
the denitrification process has to be strictly
commenced in the anoxic environment to enable the
added carbon source is primarily utilized to reduce the
oxidized nitrogen instead of being aerobically
degraded (Gerardi, 2002). According to Gerardi
(2002), the reduction of NO
3
-
ion in the presence of
carbon source under the anoxic environment can be
expressed in two simplified biochemical reactions
shown hereafter:
NO
3
-
+ Carbon Source NO
2
-
+ CO
2
+ H
2
O (4)
NO
2
-
+ Carbon Source N
2
+ CO
2
+ OH
-
(5)
1.3. Moving Bed Sequencing Batch Reactor -
Support Media Size and Aeration Strategy
Sequencing Batch Reactor (SBR) system has been
extensively manipulated for the treatment of domestic,
municipal and industrial wastewaters and also offers
an attractive option in the biological wastewater
treatment systems with the advantages as below
(Irvine and Ketchum, 1989; Wobus et al., 1995;
Louzeiro et al., 2002; Goh, 2007):
(a) Resistant to influent loading fluctuation;
(b) Simplicity and cost effective;
(c) Flexibility in terms of sequence and cycle time;
(d) Ideal quiescent settling condition;
(e) Ability of combining aerobic and anoxic phases in
a single reactor.
Incorporated with an activated sludge system, SBR
is primarily running on the fill and draw principle.
The operation of the SBR is usually achieved by five
sequential periods, namely FILL, REACT, SETTLE,
DRAW and IDLE in a single tank instead of
simultaneously in the separate tanks as typically
observed in the conventional activated sludge system
(Arora et al., 1985). Thus, permits the construction of
smaller treatment plant which is suitable in the area
with limited land availability. Nevertheless, a
conventional SBR system is generally incapable of
executing an effective biological nitrogen removal
(Goh, 2007; Li et al., 2011). As a result, an
improvement of SBR system is deemed essential
when the bio-treatment of wastewater containing
nitrogen is to be addressed.
For years, numerous attempts have been
committed to modify the SBR system in order to
enhance the performance. Among others, the moving
bed sequencing batch reactor (MBSBR) which is
developed by retrofitting support media into the SBR
has attracted much interest among the researchers in
the field of biological wastewater treatment (Garzon-
Zuniga and Gonzalez-Martinez, 1996;
Sirianuntapiboon and Yommee, 2006; Goh et al.,
2009; Hosseini Koupaie et al., 2012). In general, three
Wastewater Engineering: Advanced Wastewater Treatment Systems
Chapter 3: Wastewater Treatment by Biological Methods
89
categories of support media, namely Kaldnes
(polyethylene media), Liapor (ceramic media) and
Linpor (plastic media with high porosity) are used to
pack the MBSBR (Valdivia et al., 2007). The mobility
of the support media in MBSBR is usually conserved
by the aeration or mechanical mixing systems
(Odegaard et al., 1994). Once the attached-growth
biomass (biofilm) has grown on the surfaces of
support media, the MBSBR which contains both
suspended-growth and attached-growth biomasses are
anticipated to outperform the SBR which consists of
only suspended-growth biomass.
Among of these three types of support media used,
Valdivia et al. (2007) reported that the MBSBR
packed with Linpor performed better than either
Kaldnes or Liapor in removing chemical oxygen
demand (COD) and NH
4
+
-N at the organic loading
rate higher than 3.0 g COD/m
3
day. The polyurethane
(PU) foam which belongs to the Linpor type of
support media has a high porosity and is an ideal
medium for biomass immobilization through
attachment. In addition, PU foam also has a good
mechanical strength and is relatively low cost (Golla
et al., 1994; Chu and Wang, 2011).
Nitrogen removal via simultaneous nitrification
and denitrification (SND) process had been
investigated in previous studies (Kotlar et al., 1996;
Daniel et al., 2009; Chu and Wang, 2011). The SND
process is potentially reducing the operational period
which ultimately results in the reduction of operation
cost. The oxygen concentration and the availability of
the carbon source for denitrification were found to be
the important parameters for the commencement of
SND process (Pochana and Keller, 1999). By using
the PU foam cubes as a support media for biofilm
formation, studies had demonstrated the occurrence of
decreasing dissolved oxygen (DO) gradient within the
inner layer of biofilm and also deep inside the PU
foam which leads to the creation of an anoxic zone
(Morper, 1994; Guo et al., 2010). Furthermore, as the
carbon source is also an important constituent to
ensure the viability of the denitrification process, the
SND process is frequently inhibited in treating
wastewaters containing low COD/N ratio.
Nevertheless, in the study of Guo et al. (2010), the
SND process was still detected in the anoxic zone of
the PU foam. The occurrence of the SND process
without the addition of the external carbon source in
their study could be explained by the possibility of
carbon storage in the deeper biofilm layers which was
also reported by several researchers (Morgenroth and
Wilderer, 1999; Pastorelli et al., 1999; Gieseke et al.,
2002). The presence of carbon storage together with
anoxic zone within the biofilm and deep inside the PU
foam could be used to kindle the denitrification
process which eventually stimulated the SND process.
Based on the results of previous studies, PU foam
was found to be a good support media in the MBSBR
system. Its porous structure will allow the formation
of attached-growth biomass, the establishment of
anoxic zone and the storage of carbon which enhance
the nitrogen removal via SND process. However, to
date, relatively little is documented on the effect of
different sizes of the PU foam cubes on the nitrogen
removal in the MBSBR system. In addition, the
biomass growth onto the surfaces and into the interior
porous structure of the various sizes of PU foam cubes
along with the role of these various sizes of PU foam
cubes in the SND process in treating low COD/N ratio
wastewaters have not been thoroughly investigated.
The main advantage of intermittent aeration (IA)
strategy application in treating wastewater containing
nitrogen includes the reduction of the operational cost
due to a decrease of continuous aeration (CA) supply
and the amount of external carbon source required for
the subsequent denitrification phase (Li et al., 2008).
In the IA system, the high DO concentration during
the aeration period enables the aerobic nitrifiers to
oxidize NH
4
+
-N to NO
2
-
-N and then to NO
3
-
-N.
During the subsequent non-aeration period, the DO
concentration will decrease to such a low level that
the NO
2
-
-N and NO
3
-
-N species are reduced to N
2
mediated by the denitrifiers (Li et al., 2008).
Nonetheless, the feasibility of IA strategy
application in removing nitrogen from low COD/N
ratio wastewaters is still questionable due to
inadequate supply of carbon source which results in
an incompetency of denitrification process. In view of
the carbon storage in the deeper layers of biofilm
within the support media which can serve as the
carbon source, the integration of IA strategy in
MBSBR (IA-MBSBR) packed with PU foam cubes is
not expected to face the aforesaid problem. The
carbon storage is not only found in the biofilm on the
external surfaces which is typically exhibited by most
of the support media but is also located within the
interior porous structure of the PU foam cubes which
is being occupied by the attached-growth biomass.
However, to date, the available information to sustain
the viability of IA-MBSBR in the enhancement of
nitrogen removal is still lacking. The availability of
the carbon storage located onto and into the
acclimated PU foam cubes with attached-growth
biomass also needed to be further substantiated.
In light of relatively little information on the
potential of MBSBR in the removal of nitrogen, the
objectives of this study are to optimize the size of
support media, i.e., PU foam cubes, and aeration
strategy in MBSBR system for biological nitrogen
removal via SND process.
Lim et al.
Augmentation of Biological Nitrogen Removal via Optimization of Support Media Size and Aeration Strategy in
Moving Bed Sequencing Batch Reactor
90
2. METHODOLOGY
To achieve the aforementioned objectives, two major
experiments were carried out with the first experiment
aimed to determine the optimum size of support media
used to pack the MBSBR and the subsequent
experiment targeted to investigate the optimum
aeration strategy; both emphasized on the
enhancement of biological nitrogen removal via SND
process.
2.1. Determination of Optimum Support Media
Size Packed in MBSBR
Five plexiglass reactors were inoculated with the
activated sludge collected from municipal sewage
treatment plant and fed with synthetic wastewater
simulating the municipal wastewater composition
with NH
4
+
-N and COD concentrations of
approximately 48 and 200 mg/L, respectively. The
reactors were operated with a cycle time of 24 h in the
following sequencing periods: instantaneous FILL, 0
h; aerobic REACT, 10 h; anoxic REACT, 2 h;
SETTLE, 1.5 h; DRAW, 1 h and IDLE, 9.5 h.
Adequate amount of ethanol solution was
instantaneously added into the reactor as a carbon
source at the beginning of the anoxic REACT period
to reduce the oxidized nitrogen to N
2
. At the end of
the REACT period, mixed liquor was wasted to
maintain the sludge age of suspended-growth biomass
at 40 days. During the DRAW period, the supernatant
or treated effluent was drawn out with an exchange
volume of the reactor being retained at 70.3%. The
residual settled solids in the reactor were left to rest
throughout the IDLE period in preparation for the next
cycle.
After achieving the quasi-steady state, four rectors
were transformed to the MBSBR by introducing PU
foam cubes into its mixed liquor for the development
of attached-growth biomass. The packing volume of
the PU foam cubes in each MBSBR was fixed at 8%
(v/v) of the working volume. The performance of
MBSBRs were investigated using four different sizes
of PU foam cubes, namely 8-, 27-, 64- and 125-mL
cubes which were labeled as R2 - R5, respectively.
One of the reactors was continuously operated without
the addition of support media to serve as the SBR
system (R1) for comparison. The schematic diagram
of the MBSBR is shown in Figure 1. The
performances of all reactors were monitored in terms
of nitrogen removal consisting of NH
4
+
-N, NO
2
-
-N
and NO
3
-
-N species.
Fig. 1: Schematic diagram of the MBSBR: (a) plexiglass reactor; (b) aquarium air pumps; (c) addition of feed solution by the
peristaltic pump; (d) addition of ethanol solution by the peristaltic pump; (e) draw out tubing to remove treated effluent
containing unsettled suspended solids by the peristaltic pump; (f) support media of PU foam cubes; (g) ejector; (h) air
diffusers; (i) aeration tubing; (j) working volume of 12.8 L; (k) residual volume of 3.8 L.
Wastewater Engineering: Advanced Wastewater Treatment Systems
Chapter 3: Wastewater Treatment by Biological Methods
91
2.2. Determination of Optimum Aeration Strategy
in MBSBR
The selected MBSBR with optimum size of PU foam
cubes from the experiment as outlined in Section 2.1
was then converted to IA-MBSBR in which the
REACT period was converted to begin with 1 h of
aeration period followed by 1 h of non-aeration period
and the pattern was repeated throughout the 12 h
REACT period. The instantaneous addition of
adequate amount of ethanol solution to serve as a
carbon source was only implemented at the beginning
of the last non-aeration period in every cycle to reduce
the oxidized nitrogen to N
2
. The performance of IA-
MBSBR in terms of nitrogen removal was compared
with its former stage of aeration strategy, i.e., CA
strategy.
3. RESULTS AND DISCUSSIONS
The comparative study of MBSBRs packed with
various sizes of PU foam cubes each and with SBR
was initially discussed in this section. Optimum size
of PU foam cubes used to pack the MBSBR was
culled based on the highest nitrogen removal
efficiency via SND process. Subsequently, the
MBSBR packed with optimum size of PU foam cubes
was operated with IA strategy during the REACT
period and the results obtained were compared with its
former stage, i.e., CA strategy, to determine the
optimum aeration strategy for the enhancement of
biological nitrogen removal.
The image of Scanning Electron Microscope of
support media, i.e., PU foam cube, added into the
MBSBR is presented in Figure 2. There are many
pores on and into the surfaces of PU foam cubes; thus,
permitting the growth and attachment of biomass.
Figure 2: SEM image of PU foam cube with 40X magnification and captured at WD of 7 mm using EHT and
signal of 5.00 kV and SE2, respectively.
3.1. Optimization of Support Media Size Packed in
MBSBR
The concentration profiles of nitrogen species during
the REACT period for SBR and MBSBRs are shown
in Fig. 3. For SBR, a small NO
2
-
-N concentration peak
was observed during the initial stage of the aerobic
REACT period and a constant NO
3
-
-N concentration
was attained when the nitrification process was
completed. In contrast, for MBSBRs, the formation of
NO
2
-
-N was barely observed in the aerobic REACT
period. Figure 3 shows that the NO
3
-
-N concentrations
in R2 to R5 decreased gradually after the completion
of nitrification, with the most obvious reduction seen
in R2. The percentages of total nitrogen (TN) removal
during the aerobic REACT period for R1 to R5 were
15%, 37%, 31%, 24% and 19%, respectively. If only
nitrification process was involved, the TN should
remain constant during the aerobic REACT period.
Instead, an increasing percentage of TN removal was
observed in the order of R1 < R5 < R4 < R3 < R2.
The removal of nitrogen can be plausibly
explained by the assimilation and SND processes
(Valdivia et al., 2007). Several studies have reported
the aeration condition and carbon source as the
parameters affecting the yield of the SND process
(Pochana and Keller, 1999; Third et al., 2003; Walters
et al., 2009; Khor et al., 2011). The percentage of TN
removal was found to be the lowest in R1. The
occurrence of SND process was not favored in R1 due
to the high DO and low COD concentrations in the
mixed liquor (Pochana and Keller, 1999; Chu and
Wang, 2011; Seifi and Fazaelipoor, 2012). Therefore,
the TN removal in R1 was deemed to be caused by
only assimilation process in which the lost TN was
used to build cell mass. In MBSBRs, aerobic
condition was kept on the surface of the acclimated
PU foam cubes whereas, distinctive DO gradient
Lim et al.
Augmentation of Biological Nitrogen Removal via Optimization of Support Media Size and Aeration Strategy in
Moving Bed Sequencing Batch Reactor
92
occurred along the acclimated PU foam cubes inward
depth (Uemura et al., 2002; Guo et al., 2010).
Moreover, the carbon source required for
denitrification process could be obtained from the
storage inside the deep layer of acclimated PU foam
cubes (Pastorelli et al., 1999; Gieseke et al., 2002).
According to Gray (2004), the denitrification process
is dependent on the size of microorganism population.
The total weight of attached-growth biomass of all
MBSBRs were measured and found to be 49, 35, 33
and 30 g for R2 to R5, respectively, which was in
accordance with the decreasing trend of TN removal
from R2 to R5 as abovementioned. The lower weight
of attached growth biomass measured in larger PU
foam cubes was due to the failure of biomass to
diffuse into the internal surface of cubes to form
attachment viz--viz the smaller cubes as shown by
the SEM images in Figure 4. Hence, among the
MBSBRs, R2 packed with 8-mL acclimated PU foam
cubes was the most optimum reactor due to the
highest achievable of TN removal.
Fig. 3: Profiles of nitrogen species concentrations during the REACT period for (a) R1, (b) R2, (c) R3, (d) R4 and (e) R5.
Fig. 4: SEM images of (a) internal surface of acclimated 8-mL PU foam cube, (b) internal surface of acclimated 27-mL PU
foam cube, (c) internal surface of acclimated 64-mL PU foam cube and (d) internal surface of acclimated 125-mL PU foam
cube all with 40X magnification and captured at WD of 7 mm using EHT and signal of 5.00 kV and SE2, respectively. The
internal surface of each size of the PU foam cube is referring to the surface of the cube cross sectional area.
3.2. Optimization of Aeration Strategy in MBSBR
The study in Section 3.1 had underscored the
advantages of using 8-mL PU foam cubes as the
support media in MBSBR for the removal of nitrogen
from low COD/N ratio wastewater as opposed to
larger PU foam cubes. The highest growth of
attached-growth biomass was achieved in the MBSBR
packed with this size of PU foam cubes which led to
the highest TN removal mainly via SND process.
However, the application of continuous aeration (CA)
strategy in MBSBR (CA-MBSBR) during the 10 h of
(a) (b) (c) (d)
Wastewater Engineering: Advanced Wastewater Treatment Systems
Chapter 3: Wastewater Treatment by Biological Methods
93
aerobic REACT period increases the operation cost
especially when the nitrification process has
completed. Besides, the CA strategy would also
deplete the carbon storage in the acclimated PU foam
cubes which plausibly led to the slowing down of
SND process. Thus, the potential of integrating IA
strategy in MBSBR (IA-MBSBR) packed with 8-mL
PU foam cubes as the support media for nitrogen
removal enhancement was investigated.
Figure 5 shows that the NH
4
+
-N was completely
removed only at the third aeration period. During the
first and second non-aeration periods, the oxidation of
NH
4
+
-N was impeded due to the exhausted supply of
DO in the mixed liquor, resulting in a relatively flat
region of the NH
4
+
-N concentration profile. The NO
3
-
-
N concentration, however, decreased gradually during
the non-aeration period due to the denitrification
process. Figure 5 also shows that the NH
4
+
-N was
swiftly oxidized to NO
3
-
-N during the nitrification
process with negligible accumulation of NO
2
-
-N.
Based on Figure 5, the calculated percentage of TN
removal in IA-MBSBR during the REACT period
prior to the addition of ethanol solution was 57%. The
TN removal could be explained by the occurrence of
the SND process within the anoxic zone in the
acclimated PU foam cubes. The percentage of TN
removal in the IA-MBSBR was also found to be
higher than the CA-MBSRB of R2, which was
reported to be only 37%. The better performance of
IA-MBSBR was plausibly due to the presence of
higher total weight of attached-growth biomass in the
IA-MBSBR (57 g) than in the CA-MBSRB of R2 (49
g) as the quantity of stored carbon source which is
used to facilitate the denitrification process, increases
with increasing amount of attached-growth biomass.
Therefore, the integration of IA strategy in MBSBR
was considered optimum since higher percentage of
TN removal could be attained as compare with the
CA-MBSBR. Additionally, IA strategy was also more
economical since the overall aeration period of IA-
MBSBR had reduced to almost half of the CA-
MBSBR.
4. CONCLUSIONS
The highest TN removal could be noticed when the
CA-MBSBR was packed with 8-mL PU foam cubes
as the support media as compare with other sizes of
cubes. The percentage of TN removal was later
improved when the IA strategy was retrofitted into the
REACT period of MBSBR packed with similar size of
support media, signifying the optimum condition. The
dominance of this MBSBR in removing nitrogen was
due to the presence of the highest amount of attached-
growth biomass that could store carbon source, a
crucial substance to promote the SND process.
Fig. 5: Profiles of nitrogen species concentrations during the REACT period for IA-MBSBR.
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Wastewater Engineering: Advanced Wastewater Treatment Systems
Available online at http://www.ijsrpub.com/books
2014 IJ SRPUB
96
Wastewater Engineering: Advanced Wastewater
Treatment Systems
Chapter 4: Electrochemical Methods
Wastewater Engineering: Advanced Wastewater Treatment Systems
Available online at http://www.ijsrpub.com/books
2014 IJ SRPUB
97
Electrochemical Oxidation Process Contribution in Remediating Complicated
Wastewaters
Mohammed J. K. Bashir
1,*
, Jun-Wei Lim
1
, Shuokr Qarani Aziz
2
, Salem S. Abu Amr
3
1,*
Department of Environmental Engineering, Faculty of Engineering and Green Technology, Universiti Tunku Abdul Rahman,
31900 Kampar, Perak, Malaysia
3
Department of Civil Engineering, College of Engineering, University of SalahaddinErbil, Iraq
2
School of Civil Engineering, Engineering Campus, Universiti Sains Malaysia,14300 Nibong Tebal, Penang, Malaysia
*Corresponding Author: jkbashir@utar.edu.my; Tel: 605-4688888 ext: 4559; Fax: 605-4667449
Abstract. In recent years, electrochemical oxidation process has gained increasing interest due to its exceptional technical
features to eliminate a wide range of pollutants exist in various types of wastewaters, e.g., refractory organic matter, nitrogen
species, microorganisms, etc. Serve as a clean, adaptable and powerful tool in removing pollutants, this review paper focuses
on the fundamental mechanisms of electrochemical oxidation process and provides discussions on the possible applications in
wastewater treatment. To top it off, special attention on the most recent developments and challenges are as well highlighted in
this review.
Keywords: Electrochemical, Wastewater, Oxidation Process
1. INTRODUCTION
Basically, wastewater treatment aims to improve the
quality of wastewater before discharging to the
receiving water bodies by using reliable technology.
The conventional sequence of wastewater treatment
starts with draining the wastewater in a central,
separated location and subjecting the wastewater to
several treatment processes. Wastewater treatment can
be generally categorized by the character of the
treatment process operation being used such as
biological, chemical or physical methods. Wastewater
treatment via biological technology is the most
economical means of treatment and normally utilizes
for the removal of biodegradable organic pollutants
presented in the wastewater. Nevertheless, the
presence of toxic and refractory substrates in the
wastewater would virtually foil the biological
treatment process as these substrates are potentially
inhibiting the bioactivity of microorganism (Grimm et
al., 1998). Among the various techniques, the use of
electro-chemical oxidation process in the wastewater
treatment has engrossed many researchers attention,
particularly in remediating industrial wastewater. To
date, electrochemical oxidation processes have been
shown to be a valuable option for the elimination of
refractory organic compounds from various types of
wastewaters (Bashir et al., 2013). Electrochemical
oxidation is highly capable and efficient in reducing
the organic compounds from various types of
wastewater as compared with other types of physio-
chemical technologies which only bring about phase
transfer of the contaminants in question with no
chemical destruction is taking place.
Similarly, Kapalka et al. (2009) stated that the
electrochemical oxidation process is a clean, versatile
and powerful tool for the destruction of organic
pollutants in wastewater. Furthermore,
electrochemical method presents many significant
gains since it does not require any ancillary chemical,
appropriate for large range of pollutants removal and
does not require high pressures and temperatures for
the reaction to commence. However, the efficiency of
the electro-oxidation techniques depends strongly on
the operation conditions and on the nature of the
electrode materials (Wang et al., 2008). Recently, the
strict wastewater discharge limits with health quality
standards obligation set by legislation may be met by
applying electrochemical oxidation. Wastewaters
generated from municipal landfill and a wide diversity
of industries including the food, textile, and tannery
productions have been successfully treated by this
process. Thus, due to its high competence together
with its disinfection capabilities, electro-oxidation is a
suitable technique for water reuse programs. On the
other hand, treatment costs have to be cut down prior
to full-scale application of this technology.
Accordingly, the employment of electrochemical
oxidation together with other technologies and the use
of renewable energy sources to operate this process
are two significant steps required to reduce the overall
operational cost (Anglada et al., 2009).
2. ELECTROCHEMICAL OXIDATION
PROCESS
Electrochemical oxidation process has been
recognized as one of the most effective techniques in
degrading pollutants present in textile wastewater,
landfill leachate, simulated wastewater, olive mill
wastewater, paper mill effluents, and industrial paint
wastewater (Krbahti and Tanyola 2003; Un et al.,
2008; Bashir et al., 2009 ). The electrochemical
reactor in the laboratory experiments is shown in
Bashir et al.
Electrochemical Oxidation Process Contribution in Remediating Complicated Wastewaters
98
Figure 1. Figure 2 shows the conceptual diagram of
electrochemical reactor for wastewater treatment,
which includes a direct current (DC) power supply, a
cathode, an anode, and the electrolyte (a medium that
provides the ion transport mechanism between the
anode and the cathode necessary to maintain the
electrochemical process).
Fig. 1: The electrochemical reactor in the laboratory experiments. (1) DC power supply, (2) magnetic stirrer, (3) cover, (4)
electrodes, (5) magnetic bar-stirrer, (6) wastewater and (7) electric wire (Source: Bouhezila et al., 2011).
Fig. 2: Conceptual diagram of an electrochemical reactor (Source: Anglada et al., 2009)
Electrochemical oxidation of impurities in
wastewater is accomplished through two different
mechanisms as demonstrated in Figure 3: (1) direct
anodic oxidation, where the pollutants are destroyed at
the anode surface and (2) indirect oxidation where
mediators (NaCL, HClO, H
2
S
2
O
8
, etc) are
electrochemically produced to achieve the oxidation.
It should be clear that during electro-oxidation of
aqueous effluents, both oxidation mechanisms may
coexist (Chiang et al., 1995). Generally, the
mechanism of electrochemical degradation of
wastewater is a complex phenomenon involving
coupling of electron transfer reaction with a dissociate
chemisorptions step.
Wastewater Engineering: Advanced Wastewater Treatment Systems
Chapter 4: Electrochemical Methods
99
Fig. 3: Schemes for direct and indirect electrolytic treatment of pollutants (Chiang et al., 1995).
2.1. Direct oxidation
Direct oxidation of pollutants takes place in two steps:
(i) diffusion of pollutants from the bulk solution to the
anode surface and (ii) oxidation of pollutants at the
anode surface. As a result, the effectiveness of the
electrochemical oxidation will depend on the
correlation between mass transfer of the substrate and
electron transfer at the electrode surface. The rate of
electron transfer is determined by the electrode
activity and current density. In general, there are two
different pathways of anodic oxidation of organic
substances as shown henceforth (Drogui et al., 2007):
Electrochemical conversion. Organic
substances (R) are partially oxidized as presented in
Eq. 1. Thus, a following treatment is needed to
completely destroy the oxidized substrates.
R RO + e (1)
Electrochemical incineration (combustion).
Organic substances are transformed into water, carbon
dioxide and other inorganic constituents as presented
in Eq. 2.
R CO
2
+ H
2
O + Salts + e (2)
2.1. Indirect oxidation
During indirect electrochemical oxidation, a strong
oxidizing agent is electro-generated at the anode
surface and subsequently destroys the organic
compounds in the bulk solution. The most widespread
electrochemical oxidant is chlorine which is produced
via the oxidation of chloride at the anode. Throughout
indirect oxidation, the agents produced on the anode
that are responsible for oxidation of inorganic and
organic matters could be chlorine and hypochlorite,
hydrogen peroxide, peroxodisulfuric acid, and ozone
(Li et al., 2010; Scialdone et al., 2009). Accordingly,
throughout the electrochemical oxidation of
wastewater, the impurities removal principally
occurred due to indirect oxidation, utilizing
chlorine/hypochlorite produced by anodic oxidation of
chlorine that existing or being added in the aqueous. A
chain of reactions that involve chlorine/hypochlorite
indirect oxidation are presented in Eqs. 3-9.
Anodic reactions:
2Cl
Cl
2
+ 2e
(3)
6HOCl + 3H
2
O 2ClO
3
+ 4Cl
+ 12H
+
+ 1.5O
2
+
6e
(4)
2H
2
O O
2
+ 4H
+
+ 4e
(5)
Bulk reactions:
Cl
2
+H
2
O HOCl + H
+
+ Cl
(6)
HOCl H
+
+ OCl
(7)
Cathodic reactions:
2H
2
O + 2e
-
2OH
+ H
(8)
OCl
+ H
2
O + 2e
Cl
+ 2OH
(9)
The hypochlorite (OCl
are almost unaffected by desorption of gases and they
can act as oxidizing reagents in the total volume of
wastewater (Canizares et al., 2006).
2.3.4 Energy Consumption
The energy expenditure should be reduced to
minimize the power costs. The total power
requirement has contributions for both electrolysis and
movement of either the solution or the electrode. The
design of both electrodes and cell has a chief role in
reducing power needed. Therefore, a very open flow-
through porous electrode will have a low pressure
drop linked with it, giving rise to modest pumping
costs and facilitating reactor sealing. A high surface
area electrode which itself a turbulence promoter in
bed electrode, will give rise to a moderately high mass
transfer coefficient and active area without the need
for high flow rates through the cell; the pumping cost
will again be moderately low (Klamklang et al.,
2012). The maintenance of a low cell voltage requires
awareness to electrodes and cell design. The following
aspects should be considered:
(a) The counter electrode reaction should be
selected to reduce the reversible cell voltage. Thus, a
suitable and stable electrode material is required.
(b) The over-potentials at both electrodes should
be minimized through using electro catalysts.
(c) The electrodes, current feeders, and connectors
should be prepared from greatly conducting materials.
(d) Electrode and cell design should allow a small
inter-electrode or electrode membrane gap. The
electrode may touch the membrane as in zero-gap or
solid polymer electrolyte cells.
(e) A separator should be avoided by suitable
selection of the counter electrode chemistry or a thin
conductive membrane should be applied.
3. APPLICATIONS OF ELECTROCHEMICAL
OXIDATION IN WASTEWATER TREATMENT
Being touted as an effective treatment process, the
performance of electrochemical oxidation process in
treating various types of complicated wastewater
containing various pollutants has been studied. Also,
considerable efforts have been contributed recently to
elimination micro-contaminants using electrochemical
oxidation process. In general, microorganisms can be
deactivated via direct electrochemical process or by
the creation of killer agents, for example OH
(Lazarova and Spendlingwimmer 2008; Polcaro et al.,
2007). The combination of pollutants removal with
disinfection of wastewaters in a single treatment step
poses an attractive option, mainly in water recovery
and reuse where effectual removal of pathogens is
critical to protect public health. Table 2 presents the
effectiveness of electrochemical oxidation process in
treating variety of wastewaters.
Post-treatment of slaughterhouse wastewater via
electrochemical oxidation process was studied by
Awang et al. (2011). The most favorable conditions
were determined as 220 mg/L influent COD, 30
mA/cm
2
current density and 55 min reaction time.
This resulted in 96.8% of color removal, 81.3% of
BOD removal and 85.0% of COD removal. Under the
optimal operation conditions (initial pH 6.9, current
density of 10 mA/cm
2
, conductivity of 3,990 micro
S/cm, and electrolysis time of 10 min), the removal
efficiencies of the textile wastewater by
electrochemical oxidation were 78% of COD and 92%
of turbidity. The energy and electrode consumptions
at the optimum conditions were calculated to be 0.7
kWh/kg COD (1.7 kWh/m
3
) and 0.2 kg Fe/kg COD
(0.5 kg Fe/m
3
), respectively (Kobya et al., 2009).
Landfill leachate treated electrochemically using
graphite carbon electrodes by Bashir et al. (2009), the
highest COD removal of 68% was achieved under the
operational conditions of 4 h reaction time and 79.9
mA/cm
2
current density, while the initial COD was
Wastewater Engineering: Advanced Wastewater Treatment Systems
Chapter 4: Electrochemical Methods
103
1414 mg/L. In another study conducted by Moraes
and Bertazzoli (2005), about 73% of COD, 57% of
TOC, 86% of color removals at a current density of
116.0 mA/cm
2
and 180 min of reaction were attained.
They used oxide-coated titanium as an anode
electrode. The electrochemical treatment of industrial
water-based paint wastewater was examined in a
continuous tubular reactor. The effects of reaction
time on COD, color and turbidity removals was
investigated at 30 C, 35 g/L electrolyte and
7496 mg/L of initial COD concentrations with
66.8 mA/cm
2
current density. The optimum residence
time in the reactor was fixed at 6 h for a cost driven
approach, enabling COD, color and turbidity removal
of 44.3%, 86.2% and 87.1%, respectively (Krbahti
and Tanyola, 2009).
Electrochemical treatment of organic pollutants
from paper mill effluent was investigated by El-
Ashtoukhy et al. (2009). The results showed that the
percentage of COD and color removals were 97% to
100%, respectively. Energy consumption calculation
shows that energy consumption ranges from 4 to
29 kWh/m
3
of effluent depending on the operating
conditions. In another study, the electrochemical
oxidation of paper mill effluents was investigated via
a dimensionally stable anode of composition Ti/RuPb
(40%) Ox. The results indicated that about 99% of
COD and 95% of color and polyphenols were
removed after 15 min of electrolysis. The UV-Vis
spectrum illustration confirmed the formation of
hypochlorite ions (ClO
-
) during the electrolysis
process, indicating that the electrochemical oxidation
proceeds via an indirect mechanism with the
participation of hypochlorite ions (Zayas et al., 2011).
In the case of olive oil mill wastewater, the removal
rates of organics increased with the increase of
applied current density, sodium chloride level,
recirculation rate and temperature. The original COD
concentration of 41,000 mg/L was reduced to 167
mg/L, 99.85% of turbidity removal, 99.54% of oil-
grease removal were achieved after 7 h electrolysis at
the conditions of 135mA/cm
2
, 2M NaCl, 7.9 cm
3
/s,
and 40
(3)
where D
is diffusion coefficient and d is membrane
thickness. For steady state diffusion across a thin
membrane, only one dimension can be considered. By
applying the mass transfer coefficient k
k = D/d (4)
Equation (3) can be simplified and integrated to give
J = k ([S
s
] [S
f
]) = k ([S
f
] [S
s
]) (5)
where [S
f
] and [S
s
] are the concentrations of the
species in feed phase and stripping phase, respectively
(Kislic, 2010).
Fig. 4 shows a schematic of solute transfer from
the aqueous feed phase, through the LM and extracted
in the aqueous stripping phase in BLM system. The
basic concept of liquid membrane can be described as
follows:
Feed phase and receiving (stripping) phases are
divided by an immiscible organic solution either with
or without carrier (modifier). Different types of LM
are based on this organic phase installation and
position: if it is a thin layer of emulsion sphere
(globule), then it is called ELM, while in BLM the
organic phase is an independent bulk layer and in
SLM, the impregnated microporous membrane
support is considered as the organic phase.
The diffusion of a solute from the feed phase, into
the LM and consequently the extraction of it in
stripping phase, is the main direction of liquid
membrane extraction process. There is not any routine
and unique model for all different types of LM
diffusions (Kislic, 2010); however, the basic
diffusion-chemical reactions in LM can be described
based on diffusion, partition and interdiffusion of the
solute in different stages of LM process, as shown in
Fig. 5.
First the diffusion inside the aqueous feed phase:
J
f
= k
f
([S
f
] [S
fm1
]) (6)
This is the first step of all three LM configurations
(BLM, SLM and ELM). [S
f
] is solute concentration at
feed phase and [S
fm1
] is solute concentration at the
feed phase-LM interface.
After this step, solute partition takes place due to
thermodynamic conditions and the solute
concentration changes from [S
fm1
] to [S
fm2
].
The second step is after solute partition and
complexations, which is solute diffusion through the
liquid membrane (interdiffusion):
J
m
= k
m
([S
fm2
] [S
ms1
]) (7)
where [S
fm2
] is solute concentration at feed phase-LM
interface and [S
ms1
] is the solute concentration at
LMstripping phase interface.
Similar to the first step, after this step the solute
concentration changes from [S
ms1
] to [S
ms2
] as a result
of different thermodynamic conditions.
The third step is diffusion through the stripping phase:
J
s
= k
s
([S
ms2
] [S
s
]) (8)
where [S
s
] is the solute concentration at the stripping
phase.
Teng et al.
Supported Liquid Membrane in Wastewater Treatment
140
Fig. 4: Solute transport configuration from aqueous feed phase to aqueous stripping phase through BLM
3.1. Liquid Membrane Types Based on Transport
Mechanism
Three different types of liquid membranes (BLM,
SLM and ELM) can be divided by three different
types based on transport mechanism:
3.1.1. Simple Transport
The solubility of the solute in the liquid membrane
plays an important role. Because the LM is not
impregnated with any modifier then no chemical
reaction occurs between the solute and the LM and
hence it is in the same form in stripping phase as it has
been in feed phase and LM. The permeation stops at
equilibrium level (Schlosser et al., 1993; Schlosser
and Sabolova, 1999; Wodzki and Nowaczyk, 2002).
Fig.6. shows the mechanism of solute transport
through the LM; [S
f
] is solute concentration in the
feed phase, [S
m
] is the solute concentration in the
liquid membrane and [S
s
] is the solute concentration
in the stripping phase. In simple transport mechanism,
the solute permeation stops when concentration
equilibrium is reached.
Wastewater Engineering: Advanced Wastewater Treatment Systems
Chapter 6: Wastewater Treatment by Membrane Techniques
141
Fig. 5: Solute concentration [S] Vs distance (H) profile from the aqueous feed phase through the LM to the aqueous stripping
phase
Fig. 6: Simple transports of Species (S) from Feed phase (F), through LM (M) to Stripping phase (S)
3.1.2. Facilitated Transport
The most important transport mechanism in LM
technique is based on carrier facilitated transport.
Partitioning, complexations and diffusion are the
major parts of facilitated transport mechanism. This
type of LM accelerates the flux rate and extraction
process. However, subsequent mechanisms like
coupled counter transport or coupled co-transport can
be derived from the facilitated transport mechanism.
Fig.7. shows the schematic of the solute facilitated
transport through LM. The first stage is the solute (S)
partitioning in LM, diffusing from feed phase to feed-
LM interface due to chemical potential, then a
chemical reaction between the solute and the carrier
(C) at the interface occurs to form solute-carrier
complex (S=C) and the complex moves through the
LM (due to the solubility of the solute) towards the
LM-stripping interface (reverse reaction and
partitioning the solute in stripping phase and
decomplexation) and stripping in the stripping phase
due to different thermodynamic conditions at LM-
stripping phase interface and diffusion to the stripping
phase (SA formation due to chemical reaction with
anion (A
(2)
Where,Jv = the permeate flux of salt aqueous
solution or pure water flux (m
3
/m
2
s); A = the effective
area of membrane (m
2
); t = the time (s); V = Volume
of permeate solution collected, (m
3
)
For pure water flux, the permeability of each
membrane was determined by the measurement of
water flux as a function of applied pressure, shown as
Equation 3.
P
Jv
P
m
(3)
Where, P
m
= Permeability (m
3
/m
2
s Pa); Jv = Flux
(m
3
/m
2
s); P = Applied Pressure (Pa)
5. RESULT AND DISCUSSION
Polyethersulfone UF membranes were formulated by
varying the polymer concentration in the range of 13
wt% to 17 wt%. This concentration range is usually
used for the preparation of ultrafiltration membranes.
High concentration of the polymer that is more than
19 wt.% may produce nanofiltration while polymer
concentration lower than 11 wt.% may produce
membranes in micofiltration. To achieve high
performance membrane (high rejection to solute with
acceptable flux rate), the membrane cannot be too
loose for the structure as it will decrease the rejection
ability, neither too tight which will decrease the flux
production. Range of polymer concentration used in
this study was in the middle of the UF range, which
means higher possibility to achieve the objectives. All
the compositions were obtained through turbidimetric
titration measurement. Composition for membrane
solution is presented in Table 2.
Table 2: Casting solution formulation for ternary system
5.1. Pure Water permeation (PWP) measurement
According to Figure 2 below, flux for produced
membranes increased when the pressure increased
from 1 bar to 5 bar. The flux increased linearly with
the increase in pressure. This is an important step to
shows that the produced membranes were stable in
producing flux and were suitable application. Figure 2
also shows the flux production increased as the
concentration of PES decreased in solution. Detail of
permeability coefficient of each membrane is as
shown in Table 3.
From Table 3, membrane with polymer
concentration of 17 wt.% produced the least flux if
compared to other membranes. It might cause by the
thickness of the membrane posts greater hindrance
effect on the permeate through the membrane. By
decreasing 2 wt.% of polymer, produced membrane
Components
Before titration, in wt.%
(binary system)
After titration, in wt.%
(ternary system)
Casting
Solution 1
Casting
Solution 2
Casting
Solution 3
Casting
Solution 1
Casting
Solution 2
Casting
Solution 3
PES 15 17 19 13.60 15.40 17.70
NMP 85 83 81 77.40 75.30 75.70
Water 0 0 0 9.00 9.30 6.60
Wong et al.
Challenges in Fabricating Suitable Membrane for Water Treatment Application
176
was showed a good result by increasing the flux rate
to around 100 times. This shows that membrane was
more porous and permeate could pass through it
faster. A deduction of polymer by 2 wt.% again
produced a membrane with a permeability coefficient
which was more than 4 times higher than the 15 wt.%
PES membrane, and 500 times than the 17 wt.% PES
membrane. It was found that PES 13 wt.% was the
best flux production membrane among the produced
membranes. Although having a great flux, there is
another important factor for membrane performance,
which is rejection. Produced membrane was tested
with 0.01 M NaCl and the result is explained in the
following section.
Fig. 2: PWP at different pressure
5.2. Electrolyte Rejection by ternary system
Based on Figure 3, once again the membrane with
PES concentration of 13 wt.% produced the highest
flux compared to other membranes. It was found that
flux produced has increased as the concentration of
PES in solution decreased. It shows a huge difference
in the amount of flux produced compared to the others
at the same pressure given (1 bar to 3 bar). Membrane
with 15 wt.% of PES produced second highest flux,
followed by membrane with 17 wt.% of PES which
produced the least flux at the same pressure provided.
Table 3: Permeability coefficient for membrane
Wastewater Engineering: Advanced Wastewater Treatment Systems
Chapter 6: Wastewater Treatment by Membrane Techniques
177
0
300
600
900
1200
1500
1800
2100
2400
2700
3000
3300
3600
3900
4200
4500
0 1 2 3 4 5 6
Pressure (Bar)
F
l
u
x
[
L
/
m
2
.
h
]
PES 13 wt.%
PES 15wt.%
PES 17wt.%
Fig. 3: Fluxes of NaCl (0.01M) vs pressure for fabricated membrane with different polymer concentration
Detail for permeation produced by membranes in
salt water (NaCl 0.01 M) rejection is shown in Table 4
below. Membrane with the concentration of PES 17
wt.% showed a low flux rate of 5.5 21.1 L/m
2
.h
when 1-5 bar of pressure was provided. Decreasing 2
wt.% of polymer increased significantly the flux to
260-1120.8 L/m
2
.h, which is around 50 times higher
than the flux for membrane with 17 wt.% PES. By
decreasing 2 wt.% more of polymer concentration,
which brought it to 13 wt.%, the flux produced has
increased to a range of 1027.4 4109.6 L/m
2
.h when
low pressure (1-5 bar) was provided.
Table 4: Salt water flux produced by membranes at pressure given
It shows a great increase with more than 200% for
flux produced with decreasing PES concentration
from 17 wt.% to 13 wt.%. For 15 wt.% of PES
concentration, even it was showing better increase in
flux produced if compared to membrane with 17
wt.%, decrease of 2 wt.% more will provide the
membrane with greater performance in flux
production.
A high performance membrane should be able to
offer high flux and high solute rejection Salt rejection
(0.01 M NaCl) studies was tested on the membranes
and results are as shown in Figure 4.
Wong et al.
Challenges in Fabricating Suitable Membrane for Water Treatment Application
178
0
20
40
60
80
100
120
0 1 2 3 4 5 6
Pressure (Bar)
R
e
j
e
c
t
i
o
n
(
%
)
PES 13wt.%
PES 15wt.%
PES 17wt.%
Fig.4: Electrolyte rejection vs pressure for fabricated membrane with different polymer concentration
It was shown in Figure 4 that the membranes
performed differently in the solute rejection tests. The
lowest rejection range (40-60%) was provided by 17
wt.% membrane. Meanwhile, membrane with 15 wt.%
showed good rejection even at low pressure where the
performance increased with increasing pressure. For
membrane with 13 wt.% of polymer, it again achieved
highest rejection (100%) among the membranes even
only low pressure (1 and 2 bar) was provided. As
presented by Table 5, solute rejection for membranes
shows an increase in the sequence of membrane with
17 wt.%, 15 wt.% to 13 wt.%. This shows that the
concentration of PES had great effect on the rejection
performances.
Table 5: Rejection of NaCl (0.01M)
5.3. SEM Cross Section Analysis
Generally membrane with higher concentration of
polymer gives higher rejection, but in this study,
membrane with 17 wt.% PES performed poorly
compared to other membranes, which gave rejection
of 50% to 60%. By reducing the concentration of
polymer to 15 wt.%, the rejection increased to higher
range of 87% to 99%. When it came to membrane
with the PES concentration of 13 wt.%, again it gave
the total rejection ability to salt water, where it
achieved 99% rejection at low pressure (1-2 bar), and
even achieved 100% rejection when higher pressure
was applied (3-5 bar). The experimental data were
then confirmed by the cross sectional images taken by
scanning electron microscope (SEM) at magnification
of 700X. SEM images shown in Figure 5 revealed the
membranes cast at low polymer concentration tend to
posses thicker membrane layer, large pore radius and
larger macrovoids, thus exhibiting a highest rejection
and highest flux rate.
Wastewater Engineering: Advanced Wastewater Treatment Systems
Chapter 6: Wastewater Treatment by Membrane Techniques
179
A thick skin layer, nicely formed finger-like
structure, and large macrovoids was observed in the
cross section SEM view for membrane with 13 wt.%
PES. The structure provided a good condition to
produce high flux rate and high rejection. When 2
wt.% more polymer being added, macrovoid was
found to be absent and skin layer became thinner. This
situation explain the reduction in flux rate and
rejection ability of PES 15 wt.% compare to PES 13
wt.% membrane. SEM images of the membranes
sample showed that a finger-like structure provided
good membrane porosity and higher flux rate. As
polymer concentration increased, the larger macro
voids disappeared. This is a factor for the reduction of
flux rate. At 17% of polymer concentration, the
membrane pore size and membrane active layer were
reduced which resulted in the lowest flux rate.
However, the increasing number of membrane pores
did not influence the higher flux and rejection due to a
thinner active layer.
The result for the ternary system showed that
membrane with 13 wt.% of polymer concentration
was the best among the produced membranes. It not
only showed the outstanding performances in flux
produced, but also for the rejection of 0.01 M NaCl.
5.3. Bacteria Filtration Application
One of the important parameters in water treatment is
bacteria rejection for the system. If the system failed
to do so, then all the users are exposed to the bacteria
contaminated water, which will definitely jeopardize
their health. In this study, the bacteria removal studies
at low pressure (1-3 bar) were carried out for the
ternary system membrane with PES concentration of
13 wt.%, since it was found that the membrane with
13 wt.% PES gave the best performance. Pure cultures
for E. coli and E. Faecalis were applied in feeding
solution and result for flux production and removal
ability were shown as Table 6 and Table 7.
Table 6: Filtration result in log form for E. coli
Wong et al.
Challenges in Fabricating Suitable Membrane for Water Treatment Application
180
Fig. 5: SEM cross-sections of novel AULP membranes at different composition; (a) 13 % polymer; (b) 15 % polymer and (c)
17 % polymer
Wastewater Engineering: Advanced Wastewater Treatment Systems
Chapter 6: Wastewater Treatment by Membrane Techniques
181
Table 7: Filtration result in log form for E. faecalis
According to the result obtained, removal of
bacteria which was higher than 6 logs (totally
removed) was achieved by the PES 13 wt.%
membrane even high concentration was used as feed
solution. Changing pressure did not post significant
effect on change of the removal ability of the
membrane. However, increasing pressure during
application enhance significantly the flux production.
As totally rejection obtained, it means that produced
UF membrane had a smaller pores size than the
bacteria. According to Tsummi et al. (1990), in the
cell separation by such porous membrane, molecular
size exclusion effect is dominant factor. When the size
of the solute is much larger than pore size of the
membrane, effective cutoff occurs. Once it achieved
totally rejection to the bacteria, it shows that produced
membrane was safe to be used for bacteria filtration
process as it was impossible for bacteria which have
bigger size than the membrane pores can pass through
it.
6. CHALLENGES IN FABRICATING
SUITABLE MEMBRANE FOR WATER
TREATMENT APPLICATION
There are several parameters must be considered in
order to produce high performance membranes, such
as dope formulation, casting condition, ambient
temperature during membrane casting, shear rate,
membrane thickness and so on. Changes on each
parameter, may affect membrane properties, and
hence changing the membrane performance in
different application. In order to reproduce a high
performance membrane, all the parameters involved
during membrane fabrication must be recorded in
detail.
Another challenge is to produce membranes which
give good fluxes and rejection. These always become
a limitation when it comes to the flux and selectivity
problems. Generally a membrane with bigger pore
size and loose structure will have higher flux, but
lower rejection ability. By increasing polymer
concentration in the solution, it will make the
membrane become denser and usually rejection ability
will be improved as well, but flux production will be
decreased. This is supported by Li (1993) where in his
study, he found out that as flux increase, membrane
selectivity will decrease and as the selectivity
increased, fluxes will be decreased.
Even though there is no perfect membrane, which
can serve all application with perfect rejection and
high flux production, but still there is optimum
membrane which can serve in specific application
with the acceptable range of removal ability and flux
production.
7. CONCLUSION
Based on the experimental data, this study had proven
that membrane with ternary system and concentration
of PES 13.60 wt.% was the best among the produced
membranes. It showed excellent performance in terms
of flux (2700 L/m
2
.h) and achieved 99.97% for salt
rejection (NaCl 0.01 M). In addition, the membrane
also achieved 100% rejection for the bacteria (E. coli
and E. faecalis) with an average flux of 320 L/m
2
.h
and 400 L/m
2
.h at low pressure provided (1 bar). SEM
cross sectional images clearly observed that this
asymmetric membrane provides great properties and
excellent separation performances. As the produced
membrane able to totally remove the bacteria in water,
this may help to provide a safe and clean drinking
water for those needed.
Pressure
(Bar)
Feed
Concentration,
Cf (cfu/ml)
Permeate
Concentration,
Cp (cfu/ml)
Flux
(L/m
2
.h)
BRI
(%)
BRLI
(log)
1
7x10
6
1 342.47 100 >6
7x10
8
1 286.72 100 >6
2
7x10
6
1 616.44 100 >6
7x10
8
1 440.31 100 >6
3
7x10
6
1 725.22 100 >6
7x10
8
1 513.70 100 >6
Wong et al.
Challenges in Fabricating Suitable Membrane for Water Treatment Application
182
ACKNOWLEDGEMENTS
We would like to extend our gratitude to Ministry of
Science, Technology and Innovation (MOSTI) for
the fund with project No. 03-02-11-SF0161.
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Wastewater Engineering: Advanced Wastewater Treatment Systems
Available online at http://www.ijsrpub.com/books
2014 IJ SRPUB
183
Removal of Copper from Aqueous Solution by Using Thermo-responsive Polymer
Hydrogel as Copper Chelator via Polymer-enhanced Ultrafiltration (PEUF)
J.J. Chen, A.L. Ahmad, B.S. Ooi*
School of Chemical Engineering, Engineering Campus, Universiti Sains Malaysia, Seri Ampangan, Nibong Tebal 14300 Pulau
Pinang, Malaysia, Tel: +6045996418; Fax :+6045941013;
* Corresponding Author: chobs@eng.usm.my
Abstract. Membrane based separation is another efficient method for separating inorganic substances from aqueous effluents
due to its simplicity to scale-up and low energy consumption. Nevertheless, application of this method to remove heavy metals
from wastewaters is still a challenge to most researchers owing to the fact that heavy metals exist in aqueous solution as
hydrated ions with low molecular weights that can easily pass through most membranes except membranes for reverse osmosis
(RO) and nanofiltration (NF). However, RO and NF membranes with denser structures and narrower pores have very low
selectivity where nearly all types of solutes in the effluent are retained instead of separating only the targeted metal ions.
Furthermore, high energy is consumed and high operating pressure is required to achieve adequate permeation of solvent
through these types of membrane. Advanced materials combined with smart membrane systems could provide low energy and
highly sustainable metal recovery process. For example, polymer enhanced ultrafiltration combined with thermo-responsive
hydrogel could offer such attractive process. Compared to the conventional adsorbents, the adsorption capacity of the thermo-
responsive hydrogel is a function of solution pH, ligand density as well as temperature. The separation of hydrogel from the
waste stream can be realized through temperature induced agglomeration as well as steric retention by the membrane. The
separation process could be almost instantaneous with the metal recovery obtained even at very trace concentrations. Lower
temperature is more favorable due to the swollen hydrogel that exerts less diffusional resistance for metal to bind within the
interior marix. Low temperature is also favorable as it promises less membrane fouling phenomenon.
Keywords: Copper removal, Polymer-enhanced Ultrafiltration, Aqueous Solution
1. INTRODUCTION
Heavy metals are inorganic pollutants commonly
found in wastewaters discharged from industries like
metal-plating, tanneries, batteries, automobile and
fertilizer manufacturing. The pollution of natural
water-bodies especially rivers by the metal-
contaminated industrial effluents is becoming one of
the most serious environmental problems. Several
conventional methods had been widely adopted to
scavenge metal ions from aqueous solution including
ion exchange resins, electrodialysis, chemical
precipitation, adsorption and membrane separation.
However, the efficiency of these methods has been
constraint by some unsolved challenges such as
production of secondary sludge, low selectivity and
low metal-recovery efficiency (Lazaridis et al., 2004,
Dermentzis et al., 2009, Ghodbane et al., 2008).
In terms of low energy consumption and high
solute-rejection efficiency, ultrafiltration (UF) is
deemed as a promising membrane separation process
for the treatment of industrial wastewaters. The
average pore diameters of UF membranes fall within
the range of 10 1000 (1 100 nm). The pore
structures at this range of pore diameters allow
permeation of microsolutes with molecular weight
(MW) less than 300 g/mol. Nevertheless, copper
divalent ion (Cu
2+
) as a transition metal ion with
molar mass of merely 63.55 g is too low to be retained
by a UF membrane. The shortcoming of UF process
on metal removal is currently resolved by integration
of both metal-polymer complexation and UF
(Micheals, 1990). This combination is known as
polymer-enhanced ultrafiltration (PEUF).
In PEUF operation, water-soluble polymer with
metal-chelating ability is used as chelating agent to
complex with a targeted metal ion. The metal ion is
chelated by functional ligands of the polymer such as
carboxylic (-COOH) and amide (-CONH) groups via
electrostatic interaction to form metal-polymer
complexes. The complex can then be retained by UF
membrane effectively (Almutairi and Lovitt, 2012,
Camarillo et al., 2012, Zerze et al., 2013).
Complexation of metal in aqueous solution is deemed
as a major type of metal ion adsorption by polymeric
substances through chelation process. Polymer with
metal-chelating ligands are known as chelating agent
(chelator) that bind with free metal ions in aqueous
solution to form complex molecules known as
chelates. A chelator contains one or more ligands
that are ionic or neutral such as SO
3
H, -COOH, -NH
2
,
-OPO
3
H and -C=O. Each ligand could possess mono-,
bi- or even polydentate enabling it to form ring
structure with a metal ion (Flora and Pachauri, 2010,
Butvin et al., 1988).
Chen et al.
Removal of Copper from Aqueous Solution by Using Thermo-responsive Polymer Hydrogel as Copper Chelator via
Polymer-enhanced Ultrafiltration (PEUF)
184
1. COMPLEXATION OF COPPER IONS BY
POLYMER WITH METAL-CHELATING
LIGANDS
The metal-ligand complex formation between a metal
ion and ligands of a polymer can be described by the
following reaction:
(1.0)
where M refers to a free metal ion; L is a ligand of
polymer, and n is known as the number of ligands
involved in chelation with the metal ion.
The chelation of metal ion by acidic ligands of a
polymer involves dissociation of acidic functional
groups like carboxylic groups (-COOH) into both
anionic carboxylates (-COO
-
) and H
+
protons at pH
higher than pK
a
of the acidic ligand involved, for
example, pK
a
of acrylic acid (AA) is around 4.3.
Hence, it is important to determine their dissociation
equilibrium prior to analyzing the copper binding
equilibrium. Camarillo et al. (2012) elucidated that the
dissociation equilibrium constant, K
a
of protonated
ligands is expressed as:
(1.1)
where L
-
is the deprotonated ligands of polymers,
whereas HL refers to protonated ligands and
represents a constant depending on each polymer
ligand which accounts for nearest neighbouring
interaction (Camarillo et al., 2012, Porasso et al.,
2000). This expression is also applicable to other
polymers with acidic ligands in which their chelating
ability is mainly contributed by their acidic functional
groups.
Since the dissociation of carboxylic groups is
dependent on pH, therefore solution pH in the absence
of metallic ions is expressed as a function of K
a
, and
the degree of protonation, . The expression is known
as modified Henderson-Hasselbach equation as shown
in Equation 1.2:
(1.2)
The protonation degree, is usually expressed as
molar ratio of added base (NaOH) to carboxylic acid
(-COOH) of AA moieties in a PNIPAM-co-AA
polymer hydrogel:
(1.3)
where [NaOH] represents molar concentration of
NaOH added into the reaction solution; C
H
is the total
molar concentration of carboxylic (-COOH) and
carboxylate (-COO
-
) of hydrogel (Camarillo et al.,
2012, Flora and Pachauri, 2010). Hence in the
presence of metal ions, the concentration balance of
protonated ligands, [LH], deprotonated ligands [L] and
chelated ligands [ML
n
] is expressed as:
(1.4)
where [L]
total
is the total ligand concentration in the
solution. In addition, the extent of metal-ligand
complexation is described by a complex formation
constant, K
f
which is defined as: (1.5)
where: [ML
n
] = concentration of metal-ligand
complex formed; [M] = concentration of metal ion; [L]
= concentration of protonated ligand
The value of this formation constant is highly
dependent on solution pH, and it is also expected to be
influenced by temperature for thermo-responsive
PNIPAM-co-AA polymer hydrogels.
For ease of experimental measurements and
calculation, the chelating ability of a polymer is
usually quantified by its chelating capacity in
equilibrium state, which is always expressed as a
parameter known as equilibrium adsorption capacity,
q
e
in most of the metal adsorption studies as shown in
Equation 1.6:
(1.6)
where V (L) is the total volume of reaction solution,
M (g) is the dry mass of chelating polymer.
2. APPLICATION OF THERMO-RESPONSIVE
PNIPAM-co-AA POLYMER HYDROGEL AS
NOVEL CHELATING AGENT
Selection of a suitable chelating agent is important for
optimizing the efficiency of metal ions-complexing in
PEUF. Water-soluble polymers are usually chosen as
potential metal chelators due to the presence of
hydrophilic functional groups that act as ligands for
metal chelation such as amide (-CONH), carboxylate
(-COO
-
) and carbonyl (-C=O). These functional
ligands are Lewis acids or bases that donate electron
pair to fill the unoccupied d-orbital of a metal ion to
form a chelated complex (Flora and Pachauri, 2010,
Hancock and Martell, 1989).
There are numbers of studies reported on the use of
different water-soluble polymers as metal chelating
agents in PEUF processes. Among them,
polyethyleneimine (PEI), poly(vinyl sulfonic acid)
(PVSA) and poly(acrylic acid) (PAA) are the most
common chelators for the evaluation studies of PEUF.
Ca izares et al. (2002) applied water-soluble PEI
(MW = 25,000 g mol
-1
) and PAA (MW = 250,000 g
mol
-1
) for recovering Cu
2+
, Ni
2+
, Pb
2+
and Cd
2+
cations.
The affinity of these two types of polymer toward
metal ions are attributed to their metal-chelating
ligands like amines (-NH) groups in PEI and
carboxylic (-COOH) in PAA (Ca izares et al. 2002).
PEI also attracted interest from slamolu et al. (2006)
Wastewater Engineering: Advanced Wastewater Treatment Systems
Chapter 6: Wastewater Treatment by Membrane Techniques
185
to study the effect of ionic strength on its
complexation with Cd
2+
and Ni
2+
in PEUF process.
They found that in the absence of NaNO
3
salt, the
retention value of Cd
2+
was higher than that for Ni
2+
.
In contrast, as 0.5 N NaNO
3
was added to the binary
metal solution, the retention of Ni
2+
became higher
instead (slamolu et al. 2006).
In 2008, Llanos and partners synthesized a novel
derivative of PEI known as partially ethoxylated
polyethylenimine (PEPEI) as chelator for Cu
2+
recovery in PEUF. The results show a maximum
retention percentage over 97 % obtained with feed
loading ratio of 208 mg Cu per g. of PEPEI at pH 6
(Llanos et al., 2008). Labanda et al. (2009) compared
the ethoxylated PEI (EPEI) with polyvinyl alcohol
(PVA), polyacrylic acid-co-maleic acid (PACM) and
PEI on the recovery of Cr
3+
in PEUF. They discovered
that among these four types of chelating agents,
PACM with carboxylic groups formed relatively
stable irreversible complex with Cr
3+
, whereas
alcoholic PVA with hydroxyl groups did not chelate
with Cr
3+
at all. The amines of PEI and EPEI formed
hydroxo-complexes with Cr
3+
ions under varying pH
(Labanda et al., 2009).
Since water-soluble polymers like PEI form highly
stable metal complex in aqueous solution, it is not
easy to be dissociated in low pH medium to achieve
objective of metal recovery. A type of intelligent
polymeric microgel with thermo-responsive property
known as poly(N-isopropylacrylamide-co-acrylic acid)
(PNIPAM-co-AA) polymer hydrogel is applied as a
novel chelating agent in PEUF for removal of divalent
copper ions (Cu
2+
) from aqueous solution. This
polymer hydrogel consists of a cross-linked network
structure with a shape of globule conformation which
makes each hydrogel structure a discrete nano-size gel
particle in aqueous phase. It undergoes a temperature-
induced volume phase transition (VPT) process
manifested as swelling-shrinking behaviour under
varying temperature (Yang et al., 2004, Burmistrova
et al., 2011, Chen et al., 2013, Zhang and Wang, 2009,
Yamashita et al., 2003).
3. THERMO-RESPONSIVENESS OF PNIPAM-
co-AA POLYMER HYDROGEL
Physically, the hydrogel swells below its volume
phase transition temperature (VPTT) (~32 C)
because its hydrophilic functional ligands like amides
(-CONH) and carboxylic (-COOH) and carbonyl (-
C=O) tend to form hydrogen bonds with water
molecules which leads to expansion of the hydrogel
network. As temperature increases above its VPTT,
the hydrophilic groups are hidden and forming strong
inner hydrogen bonds within hydrogel interior. The
formation of short-range hydrogen bonds among
ligands causes expulsion of water from hydrogel and
shrinkage of the entire hydrogel network
conformation. On the other hand, hydrophobic groups
like isopropyl and methyl groups are gradually
exposed to the exterior of hydrogel at temperature
above VPTT, and the shrinking mechanism causes
hydrogel to be separated from aqueous phase (Chen et
al., 2013, Zhang and Wang, 2009, Yamashita et al.,
2003).
The thermo-responsive behaviour of PNIPAM-co-
AA polymer hydrogel before and after copper
complexation is characterized by using dynamic light
scattering (DLS) technique. The change of
hydrodynamic diameter, D
h
is plotted within
temperature range of 25 50 C. Figure 1(a) and (b)
show the temperature-induced D
h
curves for PNIPAM
before and after complexing with copper ions,
respectively. The D
h
of hydrogel before complexation
with copper decreases from 610 to 380 nm with
increasing temperature from 25 to 50 C. After
copper-hydrogel complexation, the sharp reduction in
D
h
above VPTT had disappeared. This indicates that
the binding of Cu
2+
with functional groups had
replaced the water-associated hydrogen bonds. The
ordinary trend of D
h
change with temperature as in
Figure 1(a) is disturbed. The curve in Figure 1(b)
shows that the rate of D
h
change is lowered for both
heating and cooling cycles. More pronounced
hysteresis effect is observed between heating and
cooling curves in Figure 1(b). This is because copper
chelation had reduced water-associated ligands and
chelation of Cu
2+
ion by different ligands causes
certain extent of irreversible shrinkage (Chen et al.,
2013, Zhang and Wang, 2009, Yamashita et al., 2003,
Zhang et al., 2005, Sun et al., 2011).
4. FACTORS THAT AFFECT COMPLEXATION
OF COPPER BY PNIPAM-co-AA
The affinity of chelating ligands in PNIPAM-co-AA
toward copper ions in aqueous solution are sensitively
influenced by several factors including pH, density of
ligands (chelating functional groups) and temperature
(thermo-responsive polymers) (Flora and Pachauri,
2010, Hancock and Martell, 1989).
Chen et al.
Removal of Copper from Aqueous Solution by Using Thermo-responsive Polymer Hydrogel as Copper Chelator via
Polymer-enhanced Ultrafiltration (PEUF)
186
(a) (b)
Fig. 1: Thermo-responsiveness of hydrogels: (a) before and (b) after copper complexation
4.1. Effect of pH
pH is a critical parameter for influencing the rate,
efficiency and stability of metal-polymer complex
formation by altering the charges of ligands. Most of
the polymers bearing functional groups like NH
(amine) and -COOH (carboxylic acid) as chelating
ligands are inactive for chelating metal ions at low pH
(< pK
a
) due to protonation of the functional groups
and electron donors are not available for donating
electrons to metal ion. As pH increases above pK
a
of
the acidic ligand of polymer, the functional group
(ligand) is deprotonated and increases affinity of the
ligand toward metal ion. Nevertheless, at high pH (
pH 6), the formation of insoluble metal hydroxide
precipitates reduces free metal ions from being
chelated by polymer ligands leading to a decline in
metal-chelating efficiency of the polymer.
In the case of copper, it exists as a hydrated
tetracopper cationic complex, [Cu(H
2
O)
4
]
2+
at pH 6
in aqueous solution. At pH range of 3 5,
mononuclear complexes of one ligand (LM
+
) or two
ligands (L
2
M) are formed. In condition where the
concentration ratio of ligands to copper cations is low
(<10), formation binuclear complexes (two central
copper ions) is induced at pH 4 8. Then at pH 6,
insoluble hydroxide species of copper, Cu(OH)
2
is
precipitated. In the presence of high concentration of
carboxylate ligands, Cu(OH)
2
tends have hydrophilic
interaction with the polymer ligands through hydrogen
bonds. The formation of binuclear, mononuclear
copper-ligand complexes and Cu(OH)
2
species leads
to the increase in adsorption capacity of polymer
hydrogels with increasing solution pH at range of pH
4 7 (Yao et al., 2010, Powell et al., 2007, 2011).
Figure 2 shows the pH effect on copper removal
efficiency in percentage % in the presence of
PNIPAM-co-AA hydrogels. A sharp increase
observed from 26.6% to 53.4% when the solution pH
changed from 4.0 to 5.0. It is because increase in pH
value leads to increase in OH
-
hydroxyl ions from the
base added (NaOH) that consume H
+
ions in the
solution. Consequently, lesser free H
+
ions compete
with Cu
2+
ions for the chelation sites of ligands. From
pH 6 to pH 9, copper removal was increased linearly
from 63.2% to 87.6% due to the fact that hydroxides
of copper started to form at pH 6 and it was increasing
at higher pH. The dominating species of copper at pH
3 5 is Cu
2+
while at pH 6 and above, insoluble
Cu(OH)
2
is dominating. At pH 6, Cu
2+
is still
dominant in the solution, but the presence of
monohydroxo Cu(OH)
+
which possess single charge
was adsorbed to a greater extent than divalent Cu
2+
and slight Cu(OH)
2
were also formed under this
condition. Thus, the increase in removal efficiency at
pH 5 is owed to deprotonation of AA ligands, whereas
at pH 6 and above, Cu(OH)
+
and Cu(OH)
2
species had
significant effect towards enhancement of copper
removal (Yao et al., 2010, Powell et al., 2007, 2011).
4.2. Effect of Ligand Density
The density of chelating functionalities (ligands)
indicates the amount of dentates present in a polymer
hydrogel. As previously discussed, a ligand could be
mono-, bi- or poly-dentate (electron pairs) which acts
as donor groups donating electron pairs to a metal ion.
The arrangement and spacing among chelating
functionalities are also important in determining the
interactions among ligands. Increase in ligand density
results in narrower spacing among ligands and eases
more ligand-ligand interaction through hydrogen
bonds that may reduce active dentates for chelating
metal ion (Yang et al., 2004, Burmistrova et al., 2011,
Yamashita et al., 2003, Zhang et al., 2005).
Wastewater Engineering: Advanced Wastewater Treatment Systems
Chapter 6: Wastewater Treatment by Membrane Techniques
187
Fig. 2: Effect of pH on copper removal %.
Figure 3 shows the equilibrium adsorption capacity,
q
e
of hydrogels increased from 0.0943 to 0.8397 mmol
g
-1
as AA content incorporated in a hydrogel increased
from 0 mol% (PNIPAM monopolymer) to 30 mol%.
Nevertheless, as it was increased to 50 mol%, there is
a slight fall from 0.8397 to 0.7868 mmol g
-1
. This is
ascribed at too high AA content (50 mol% AA),
hydrogels has high tendency to agglomerate and
aggregate into colloids owing to excessive ligand-
ligand interaction. The active chelating sites and
surface area of hydrogel networks are greatly reduced.
This results in the lowering ratio of copper-binding
sites to total Cu
2+
concentration (Yamashita et al.,
2003, Zhang et al., 2005).
Fig. 3: Effect of AA content in PNIPAM-co-AA on q
e
.
4.3. Effect of Temperature
Figure 4 compares the curves of q
e
versus initial Cu
2+
concentrations (C
0
) at three different temperatures:
303, 313 and 323 K. It shows that at lower C
0
ranging
from 20 to 50 mg L
-1
, temperature effect is apparently
significant on q
e
, where it decreases with increasing
temperature. This trend agrees with the postulates
proven by Morris et al. (1997) and Kagz et al. (2006)
that diffusional resistance is a problem for metal ions
adsorption as the reductions in both interior volume
and active chelating sites (ligands) at higher
temperature (Morris et al., 1997, Kagz et al., 2006,
Hou et al., 2008). However, as C
0
rose from 60 to 80
mg L
-1
, the increase in q
e
is getting independent of
temperature effect. At higher concentration of Cu
2+
,
higher concentration gradient and osmotic pressure
created by the copper ions is prevailing and
overcomes diffusional resistance within hydrogel
interior.
5. MEMBRANE FOULING BY
CONCENTRATION POLARIZATION (GEL
LAYER FORMATION)
Most of the PEUF systems are operated at constant
applied pressure typically in the range of 1 5 bar,
where the feed is circulated at a fixed pressure across
a membrane and the permeate is collected for
measurements over time. As steady pressure is
maintained throughout an operation, convective
transport of complex solutes by the bulk feed stream
Chen et al.
Removal of Copper from Aqueous Solution by Using Thermo-responsive Polymer Hydrogel as Copper Chelator via
Polymer-enhanced Ultrafiltration (PEUF)
188
towards membrane could cause the accumulation of
retained solute particles at the active layer of
membrane. These retained solutes remain stagnant at
the membrane surface because their large size and
solute-membrane interactions prevent them from
diffusing back into the bulk stream (Porter, 1990,
Baker, 2012, Wang et al., 2011, Palencia et al., 2009,
Camarillo et al., 2010).
As the concentration of solutes deposited at
membrane surface (C
s
) rises to the point of incipient
gel precipitation, the solute particles consolidate by
solute-solute interaction and form a gel layer which
acts as if a secondary membrane on the membrane
surface. This gel layer of retained solutes creates a
fouling resistance (R
f
) as secondary barrier to the
permeation of solvent flow through membrane. This
type of fouling phenomenon is known as
concentration polarization (CP). Concentration
polarization is the major fouling mechanism in nearly
all PEUF studies. It is reversible in nature when
solute-solute interaction is dominating in the process
as the gel layer can easily be scavenged by
backwashing or feed flow scouring, whereas it could
also become irreversible if solute-membrane
interaction is dominant instead (Wang et al., 2011,
Palencia et al., 2009).
Fig. 4: Plot of q
e
of PNIPAM-co-AA as a function of C
0
at different temperatures (303, 313 and 323 K).
Since the gel layer offers resistance to the
permeation of solvent through membrane, it leads to
decline in permeate flux. Hence, the formation of gel
layer is usually described in term of permeate flux
which is expressed mathematically as follows:
(1.7)
where is the solution dynamic viscosity (Pas);
P represents transmembrane pressure difference,
whereas R
m
and R
c
refer to hydraulic resistances of
membrane and gel layer, respectively (Porter, 1990,
Baker, 2012, Wang et al., 2011).
5.1. Effect of hydrogel (Chelator) Concentration
Figure 5(a) presents the permeate fluxes obtained for
different polymer PNIPAM-co-AA hydrogel
concentration, C
h
. Increasing concentration of
hydrogel in the feed enhances the formation of gel
layer at membrane surface. As expected, the permeate
flux plunged sharply from 72.38 L m
-2
h
-1
for the feed
with 0.01 g L
-1
hydrogel to 11.75 L m
-2
h
-1
in the
presence of 0.1 g L
-1
hydrogel. Subsequently, the flux
decreases slowly from 11.75 to 6.90 L m
-2
h
-1
as the
concentration increases from 0.1 to 0.7 g L
-1
. The
increase in hydrogel concentration provides more
available active site for chelating Cu
2+
cations in the
feed. This factor in turn contributes to more copper-
hydrogel complexes formed and eases the formation
of gel layer at the membrane surface.
Figure 5(b) illustrates the percentage of copper
retained under different hydrogel concentrations. In
the absence of hydrogels, around 13.1% of Cu
2+
was
retained by the functional groups at membrane active
layer. As hydrogel was added into the feed at
concentration of 0.1 g L
-1
, retention rises up to
81.45% and slightly increases again until 84% as
hydrogel concentration increased further to 0.7 g L
-1
.
Two phenomena responsible for the improved copper
rejection are: 1) gel layer formation due to CP driven
by the convective transport of hydrogels onto
membrane surface 2) The increase in hydrogel
concentration provides more ligands for chelating
Cu
2+
(da Silva et al., 2007, Childress and Elimelech,
1996, Tokuyama et al., 2005, Wijmans et al., 1985).
Wastewater Engineering: Advanced Wastewater Treatment Systems
Chapter 6: Wastewater Treatment by Membrane Techniques
189
(a) (b)
Fig. 5: Effect of P-30 hydrogel concentrations on: (a) permeate flux and (b) Cu
2+
rejection (50 ppm Cu
2+
in feed; T = 303 K;
pH =5; transmembrane pressure, P = 1.5 bar).
The AFM images shown in Figure 6 illustrate the
effect of different hydrogel concentrations (0.01, 0.1,
0.5 and 0.7 g L
-1
) toward the membrane (cellulose
acetate) surface characteristic. At 0.01 g L
-1
, the
lowest density of hydrogels in its spherical structure
was found to be bound on the membrane surface with
a lot of unblocked membrane pores as shown in
Figure 6.0(a). These accounts for the highest permeate
flux (72.38 L m
-2
h
-1
) and the lowest Cu
2+
rejection
(33.1 %). As hydrogel concentration increases, more
hydrogel particles are bound and consolidated at the
membrane surface as shown in Figure 6.0(b-d). At
higher concentration of 0.7 g L
-1
, hydrogels tend to
agglomerate into lumps by intense hydrophobic
interaction. However, these lumps did not improve
permeate flux at 50C owing to the fact that under
such high concentration, the feed is relatively more
viscous and hydrogels are more densely packed within
gel layer. As a result, the more rigid hydrophobic gel
layer hinders permeation of solvent.
6. CONCLUSION
PNIPAM-co-AA hydrogel is a potential chelating
agent for copper ion which present in abundance in
most of the industrial effluent. The chelating ability
of the hydrogel is very much depending on the
solution pH, ligand density as well as temperature due
to its thermoresponsive properties. At low copper
concentration, the adsorption process is highly
diffusional control therefore very sensitive to the
operating temperature. Lower temperature is more
favorable due to the swollen hydrogel that exerts less
diffusional resistance for copper to bind within the
interior marix. In a PEUF system, filtration at low
temperature (< 40 C) encountered low permeation
flux due to formation of gel layer of polymer
hydrogels at the membrane surface. However, high
copper rejection was achieved owing to the copper-
ligand complexation and gel layer provides hydraulic
resistance to the permeation of copper through
membrane. The same phenomenon was observed for
high polymer loading which shows that hydrogel
agglomeration at the surface greatly reduces the
membrane flux. Continuos effort to enhance both
copper removal as well as permeation flux is required.
ACKNOWLEDGEMENT
The authors wish to thank the financial support
granted by Ministry of Higher Education Malaysia
(MOHE) FRGS (203/PJKIMIA/6071252)
Chen et al.
Removal of Copper from Aqueous Solution by Using Thermo-responsive Polymer Hydrogel as Copper Chelator via
Polymer-enhanced Ultrafiltration (PEUF)
190
(a) (b)
(c) (d)
Fig. 6: AFM images of membrane surface after PEUF processes for different hydrogel concentration: (a) 0.01 g L
-1
, (b) 0.1 g
L
-1
, (c) 0.5 g L
-1
and (d) 0.7 g L
-1
.
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Wastewater Engineering: Advanced Wastewater Treatment Systems
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Wastewater Engineering: Advanced Wastewater
Treatment Systems
Chapter 7: Wastewater Treatment by
Phytoremediation Technologies
Wastewater Engineering: Advanced Wastewater Treatment Systems
Available online at http://www.ijsrpub.com/books
2014 IJ SRPUB
194
Wastewater Treatment by Phytoremediation Methods
Hossein Farraji
School of Civil Engineering, Engineering Campus, University Sains Malaysia, 14300 Nibong Tebal, Penang, Malaysia
Email: hosseinfarraji@gmail.com
Abstract. Nowadays many technologies are using for treatment of environmental pollutions and phytoremediation as a green
technology is going on to convert to one of the main ecofriendly technologies which scientist using in their researches. Aquatic
media as a fundamental and critical part of human environment have main role in water resources and food chain. In this
chapter we present different aspect and types of phytoremediation in aquatic media purification from metallic elements.
Keywords: Wastewater, Treatment, Phytoremediation
1. INTRODUCTION
The anthropogenic emissions of metallic elements
globally ends up to wastewater and industrialization
caused a lot of environmental problems .Heavy metals
spectacular Zn, Cu, Ni and Cr are most common
contain of industrial wastewater (Sun and Shi, 1998).
For example recently report from China indicate that
anthropogenic emissions of cadmium to atmosphere
from 1990 to 2010 increased from 474 to 2186 ton
(Shao et al., 2013). Most Cd is emitted to the
atmosphere at the first stage and then precipitate on to
water and soil (Yamagata, 1979). Meanwhile
vulnerability of ground water as drinking water
sources, is higher than surface water (Landmeyer,
2012). levels of arsenic in groundwater sources is
higher in comparing with surface-water sources
(Bissen and Frimmel, 2003). On the other hands,
concentrate ions and accumulation of some pollutants
same as
137
Cs in aquatic media are higher than
sediment or soils (Ashraf et al., 2013), so it shows
critical statue of decontamination of wastewater (Shao
et al., 2013).
2. PYTOREMEDIATION
Phytoremediation is vast, emerging term which has
been used in recent decades for a group of green
ecofriendly technologies that fundamentally based on
plants (aquatic, semiaquatic and terrestrial) and
related associated enzymes, microorganism and water
consumption, uptake, remove, retain, transform,
degrade or immobilize contamination (organic and/or
inorganic) with different origin, from soil, sediment
and aquatic media or atmosphere (Mueller et al., 1999,
Pivetz, 2001, Ghosh and Singh, 2005; Vishnoi and
Srivastava, 2007; Mulbry et al., 2008; Ridzuan et al.
2010, Dhir 2013). To sum it up, phytoremediation in
aquatic media is directly up take and accumulation of
contaminant from water media and assimilation by
plants (Ndimele and Ndimele, 2013). Two approaches
have been presented in literatures about
phytoremediation, natural or continuous
phytoremediation and chemically enhanced
phytoremediation (Lombi et al., 2001; Alkorta et al.,
2004).
2.1. Continuous or natural phytoremediation
This type of phytoremediation fundamentally based
on using natural hyperaccumulator plants with not
only exceptional metal accumulation in shoots but
also extraordinary tolerance to metal toxicity in root
around media (Assuno et al., 2003; Prasad, 2004).
2.2. Chemically enhanced phytoremediation
Natural phytoremediation have following drawbacks
(Hem, 1970; Prasad, 2004; Yoonet al., 2006):
(a) Low biomass and slow growth in
hyperaccumulator plants; (b) Low translocation of
metals in hyperaccumulator plants; (c) Insolubility or
immobility of metallic elements in media; (d) Low up
taking element by roots.
A chemical enhancement for phytoremediation
helps to overcome these limitations. Chelating ligands
like as ethylene diamine tetra-acetic acid (EDTA), 1,
3-propylene-diaminetetra-aceticacid (PTDA), nitrilo-
tri-acetic acid (NTA), diethyl triamine penta-acetic
acid (DTPA), etc. Which are microbial poorly
degradable and present in g/L concentration in
aquatic media (Knepper, 2003), reduce net shoot and
root biomass production (Rmkens et al., 2002).
Several aspect of phytoremediation improved and
established based on mechanism of decontamination,
kind of pollutions, affected factors and media of
remediation (Stout and Nsslein 2010; Dhir, 2013).
Table 1 is summarized typical kind of this green
technology and its process.
Faraji
Wastewater Treatment by Phytoremediation Methods
195
Table1: Phytoremediation process (Dhir, 2013)
2.3. Advantages of aquatic phytoremediation
These green technologies as an ecofriendly present
many advantages for decontamination of aquatic
polluted media comparing other treatment systems
(Ximnez-Embn et al., 2001; Bissen and Frimmel
2003; Ghosh and Singh, 2005; Kirkham, 2006; Verma
et al., 2007; Olgun and Snchez-Galvn, 2010;
Landmeyer, 2012; Wang and Calderon, 2012; Delmail
et al., 2013).
(a) Greatly cost effective; (b)
Environmentally Compatible, green aesthetically; (c)
Feasible globally technology (no need to high-tech
equipment or material); (d) Easy maintenance (supply
and energy) solar powered; (e) In situ and ex situ
operation available; (f) Inhibiting deployment of
contamination to atmosphere or soil by in situ
operation; (g) Suitable for shallow depth contaminated
water to hydrologic control of ground water; (h)
Periodic treatment against continued treatments; (i)
Different types of many contaminations can be treated
in one time; (j) Produce biomass for renewable energy
production; (k) Rapid mass propagation by tissue
culture available; (l) Almost treatable for all kind of
contaminations (organic, inorganic and radionuclides);
(m) Operable approximately in all media (aquatic,
sediment, soil and atmosphere); (n) Broad acceptable
pH (2-10) for treatment; (o) Chelating molecules
positively affected phytoremediation;
2.4. Disadvantages of aquatic phytoremediation
Same as each technology, phytoremediation suffer
from disadvantages which should considered through
applying (Mojiri et al. 2013; Assuno et al., 2003,
Alkorta et al., 2004; Ghosh and Singh, 2005; Shiyab
et al., 2009; Delmail et al., 2013, Kumar et al., 2013;
Nan et al., 2013).
(a) Harvested biomass contains hazardous
pollution; (b) Long time need for effective treatment;
(c) Deep polluted media are limited treating; (d)
Limited to climate growth condition (tropical,
subtropical and tempered zoon); (e) Restricted to low
concentration of polluted site; (f) Harvested biomass
managing required; (g) Limited hyperaccumulator
species introduced for aquatic media; (h) Leaves fall
may cause spread contaminant; (i) Most of
hyperaccumulator plants have limited roots and slow
growing; (j) Most of hyperaccumulator species up
take only limited elements; (k) Many of
hyperaccumulators propagation system is sexual; (l)
Recycling to soil and water by rain in volatilized
pollutions; (m) Possibility of entering contaminated
biomass to animal and human food chain
2.5. Phytovolatilization
This kind of phytoremediation involves the utilization
of plants to take up pollutions from contaminated
media, transforming them into volatile form and
finally transpiring them into the air.
phytovolatilization normally occurs in plants for up
taking water, organic and inorganic compounds so
some of contamination can pass through the plant
parts to the leaves and at low concentration ,volatilize
into the atmosphere (Mueller et al., 1999) In a
nutshell, the use of plant species for volatilize
contaminants from the leaves which can use for soil
and sediment pollutions (Mueller et al., 1999) air
contaminations (Burken and Schnoor, 1999) and water
Wastewater Engineering: Advanced Wastewater Treatment Systems
Chapter 7: Wastewater Treatment by Phytoremediation Technologies
196
pollution (Baeder-Bederski-Anteda, 2003). The
phytovolatilization radionuclides such as Tritium(3H)
from soil (Dushenkov, 2003),significantly up taking
selenium compounds contain dimethyldiselenide and
dimethylselenide by Brassica species (Bauelos et al.,
2000) are some sample studies on phytovolatilization.
Disadvantages of mercury phytovolatilization is
recycling by rain and a residue back into the
ecosystem (Alkorta et al., 2004).
2.6. Phytodegradation
Phyodegradation or phytotransformation refers to two
kind of plant reactions it is independent on
rhizospheric microorganisms (Vishnoi and Srivastava,
2007) contain phytoreduction which is the reductive
transformation of oxidized organic compounds by
reducing plant enzymes and phytooxidation which is
the oxidative transformation reactions catalyzed by
plant oxidizing enzymes (Nzengung and Jeffers,
2001).Plant enzymes contain five various
nitroreductaces (Schnoor et al., 1995), dehalogenase
and oxygenase (Vishnoi and Srivastava, 2007)
degrade organic compounds. The main
phytodegradation process for organic contamination in
plants are, uptake, translocation and metabolism
(Dzantor et al., 2002).Taken up of most of Polycyclic
aromatic hydrocarbons (PAHs)is hard for plants and
less suitable for phytodegradation (Reichenauer and
Germida, 2008). Some of the main organic compound
that successfully degraded by plant species are
hexachloroethane (HCA),
dichlorodiphenyltrichloroethane (DDT) (Nzengung
and Jeffers, 2001) and carbon tetrachloride (Wang et
al., 2004). Inorganics compounds like as sulfur oxides
and atmospheric nitrogen oxides can be taken up by
plants for degradation. Genetically modified plant
species also had been used for phytodegradation (Doty
et al., 2000).
2.7. Rhizodegradation
Rhizodegradation is breakdown organic
compounds(fuels and solvents) to plants nutrients in
rhizospher trough microbial (fungi, yeast , bacteria
and other microorganisms )activity which is very
slower than phytodegradation process and also called
phytostimulation (Hutchinson et al., 2003; Ghosh and
Singh, 2005; Ridzuan et al., 2010).This technology
widely applied in treatment of soils so that in
Germany there are more than 100 years background
for rhizoremediation (Wand et al., 2002). Generally,
plant exudates same as carboxylic , amino acids and
carbohydrates are capable to stimulate entire
rhizosphere microbial action and enhance
rhizodegradation proceeding (Dzantor, 2007) Some of
plants which applied for Rhizodegradation are
Hibiscus cannabinus for used lubricating oil (Abioye
et al., 2012), Sorghum bicolor L. for crude oil (Banks
et al., 2003), Broadleaf plantain plant (Plantago
major L.) for Imidacloprid (insecticide) in water and
soil (Romeh, 2009), willow (Salix babylonica)used for
perchlorate in soil and water (Mwegoha et al.
2007).Some treatments used for enhancing
rhizodegradation like as supplying organic carbon
(Yifru and Nzengung, 2008),chicken manure
(Mwegoha et al., 2007) and organic waste treatment
(Dadrasnia and Agamuthu, 2013).
2.8. Phytomining
Phytomining or bio-ore is a green technology which
could generate revenue from saleable metallic
elements that accumulated in ash of plants biomass
(Ghosh and Singh, 2005). Mining of nickele has been
already a patented technology (Chaney et al., 1998).
Normally phytomining occurs in situ at the
contaminated mine lands or sub-economical ore
(Anderson et al., 1998). Phytoextraction or
bioextraction of metals for commercial gain contain
cropping, harvesting, drying and ashing are main
process of phytomining (Sheoran et al., 2009). Cattails
(Typha latifolia) used for absorbing boron (B) from
the effluent of biggest borax mine of the world and
250mgkg-1 boron absorbed in constructed wetland
system (Trker et al., 2013).
2.9. Phytostabilization
This technology applied for decreasing bioavailability
of contamination from environment and stabilizing of
pollutants occurs more than removing
them(commonly metallic elements) by plants
(hydraulic control) ? (Padmavathiamma and Li, 2007).
Enhancing appropriate soil modification by plants
,caused to decreasing bioavailability of metallic
elements on the other hands plant cover decreased
leaching and enhance environmental protection
(Houben et al., 2011).Plants can help to stabilize
pollutants with up taking in adsorption system or
accumulate them in root system (Vangronsveld et al.,
2009). Plant selection for phytostabilizing is a critical
issue and perennial species, well local
environmentally adapted ,high biomass production
and high resistance to pollution recommended (Pilon-
Smits, 2005). Since there is no natural
hyperaccumulator phytoremediator for mercury
controlling this toxic metallic element is critical so
Indian mustard (Brassica juncea L.) reported as a
suitable plant species for stabilization of mercury in
soil and wastewater (Shiyab, Chen et al. 2009).
Aquatic plant Hydrilla verticillata reported as
Faraji
Wastewater Treatment by Phytoremediation Methods
197
potential species for phytostabilization of wastewater,
in this plant has high translocation factor (TF) and low
bio concentration factor (BCF) for toxic metals
(Pb,Cr) (Ahmad et al., 2011). Rapeseeds (Brassica
napus), sunflowers (Helianthus annuus), tomatoes
(Solanum lycopersicum) and soapworts (Saponaria
officinalis) reported as capable plants for
phytostabilization with less than one bioaccumulation
coefficients obtained in all of these plants (Sung et al.,
2011). Major metallic element removal in plant
species phragmites (Phragmites australis), Typha spp,
Juncus spp, Spartina spp and Scirpus spp from
different wastewater contaminated area are
phytoextraction and phytostabilization (Bhatia and
Goyal, 2013).
2.10. Phytofiltration
Phytofiltration or rhyzofiltration is a green technology
for removing contaminations by plants roots in aquatic
media like as ground water, most of wastewaters and
extracted ground water (Pivetz, 2001; Mukhopadhyay
and Maiti, 2010). Terrestrial, aquatic and wetland
plants are suitable material for phytofiltration and
constructed wetlands are the best method for
removing metallic elements from wastewater (Cheng
et al., 2002). Limnocharis flava (L.) reported as
suitable plant species for phytofiltration of low
concentration Cd contaminated water (Abhilash et al.
2009) Wolffia globosa is a suitable nominated for
arsenic metabolism studying via phytofiltration
(Zhang et al. 2009).For effective accumulation of
cadmium and hyperaccumulation of arsenic,
micranthemum umbrosum introduced as suitable
macrophyte (Islam et al., 2013). Indian mustard
(Brassica juncea (L.) Czern) could uptake 95%
mercury from contaminated water via phytofiltration
(Moreno et al., 2008). Aquatic plants, Pteris
creticacvMayii (Moonlight fern) and Pteris.vittata
(Chinese brake fern) as arsenic hyperaccumulator
plants, used via phytofiltration (Alkorta et al., 2004;
Tu et al. 2004; Baldwin and Butcher, 2007). The
mechanism of phytofiltration is similar to
phytoextraction containe 1) chemisorption 2)
complexation 3) ion exchange 4)micro precipitation
5)hydroxide condensation 6) surface adsorption
(Cheng et al., 2002; Gardea-Torresdey et al., 2004).
Plant specification in phytofiltration should be 1)
tolerance to high level of metallic elements 2) facile
handling 3) high root biomass or surface area 4)
reasonable maintenance cost 5) least secondary waste
requirement (Dushenkov, 2003).
2.11. Phycoremediation
Phycoremediation is using macro and micro algae for
bio transforming or removing pollutions from
wastewater furthermore CO
2
as air pollution from
waste air (Mulbry et al., 2008; Rawat et al., 2011).
Algae is a suitable plant for decontamination of
metallic elements, xenobiotic, nutrients in various
wastewater and consume of carbon dioxide from
exhausts (gu, 2003). Micro algae is a capable
plant for treatment of various type of wastewater such
as industrial wastewater ,domestic wastewater and
solid wastes both aerobically and anaerobically
(Safonova et al., 2004). For this technology ,oldest
scientific research carried out in half century ago
(Oswald and Gotaas, 1957). In a pilot study on
chrome sludge, phycoremediation with Desmococcus
olivaceus could effectively decrease nitrate,
phosphate, ammonia, TDS ,TSS and chrome
(Sivasubramanian et al., 2010). Fresh water blue green
algae used successfully for treatment of dairy manure
effluent(Mulbry et al., 2008). Sewage water treated by
different algae and Chlorella vulgaris could remove
almost all of contaminations and after treating process
it can be thrown in water bodies 1n 2013.
2.12. Phytoextraction
Phytoextraction /phytoaccumulation (Khan et al.,
2000) can be considered as suitable green technology
for removing metallic elements from aquatic media
(Wang et al., 2008). This kind of remediation used for
accumulation of Zinc by duckwood (Lemna gibba)
(Khellaf and Zerdaoui, 2009), Cadmium by water
spinach (Ipomea aquatic) (Wang et al., 2008),
Chromium with small pondweed (Potamogeton
pusillus) in presence of Cu
2+
(Monferrn et al., 2012).
recently reported study carried out for accumulation of
Pb by Ceratophyllum demersum and Myriophyllum
spicatum and finally introduced as phytoremediator
and bioindicator of Pb. (El-Khatib et al., 2014) Water
hyacinth (Eichhornia Crassipes) used for removing
heavy metals from coastal water (Agunbiade et al.,
2009), Crude oil from artificial wastewater amended
by urea fertilizer (Ndimele and Ndimele 2013) and
palm oil mill effluent treatment (Christwardana and
Soetrisnanto, 2013). Furthermore, heavy metals from
industrial wastewater have been removed by vetiver
(Chrysopogan zizanioides) (Roongtanakiat, 2009).
3. HEAVY METAL
Generally speaking, heavy metals which nowadays
known as metallic elements (Mbengue et al., 2014),
confined as element with density higher than 4.5- 5
mg mL
-1
/kg dm
-3
(Sarkar, 2002)but the collective
Wastewater Engineering: Advanced Wastewater Treatment Systems
Chapter 7: Wastewater Treatment by Phytoremediation Technologies
198
term includes arsenic(As), cadmium(Cd), lead(Pb),
Mercury (Hg), nickel(Ni), chromium (Cr), zinc (Zn),
copper (Cu), aluminum (Al), cesium (Cs), Ferrum
(Fe), manganese (Mn), molybdenum (Mo), radium
(Ra), uranium (U), strontium (Sr), platinum (Pt),
palladium (Pd), beryllium (Be) (McIntyre 2003)
Metallic elements are persistent and non-
biodegradable (Mahmood et al., 2010) .cooperation of
several disciplines engineering such as environmental,
civil, and chemical is fundamental requirement for
remediation of heavy metals (Bradl, 2005).
3.1. Metal removal rate
The rate of metallic elements removal from polluted
wetland depended on plant spices, climacteric
condition, statue of substrates, type of element
(Hg>Mn>Cd=Fe>Cr=Pb>Cu=Zn>Al>Ni>As), their
ionic forms (Marchand et al., 2010). Remediation
habit of plants species hyperaccumulator>
acuumulator> indicator> excluder (Figure 1) (Bradl,
2005).PH less than 5 is harmful for plants meanwhile
there is a report for a plant species (Lupinus) that can
growth in pH<2 and uptake 98% metallic elements
(Ximnez-Embn et al., 2001).Results of five aquatic
species indicated that all aluminum uptake increased
in low pH (Gallon et al., 2004).
3.2. Indexs of phytoremediation
There are some index that helps to calculate efficiency
of phytoremediation and assessment of plant ability in
up taking and translocation or mobilization (Kisku et
al., 2000) of metallic elements. these index use for
collecting hyperaccumulator plant species (McGrath
and Zhao, 2003).
3.2.1. Bioconcentration factor (BF)
The ratio of concentration of metallic elements in
plants tissue (roots, shoots) to that in contaminated
site (Tu et al., 2002),it also termed as bio
concentration factor (BCF) (Marchiol et al., 2004).
3.2.2. Enrichment Coefcient (EC)
It termed as degree of metallic elements accumulation
in plants (shoot, roots) to concentration of metallic
elements at contaminated site (Kisku et al., 2000). It
also termed as biological accumulation coefficient
(BAC).
3.2.3. Translocation (mobilization) factor (TF)
This factor calculated to determine the translocation of
metallic elements from the root of plant to shoot
(McGrath and Zhao, 2003).
where; TF in hyperaccumulator species is more than
one
3.2.4. Relative treatment efficiency index (RTEI)
Introduced by (Marchand et al., 2010)which is based
on comparing control treatment metal removal with
influent metal concentration and effluent treatment
metal removal ,meanwhile previous index are suitable
now (Kumar et al., 2013).
Fig. 1: Relative uptake and biological accumulation potential in plant species (Bradl, 2005)
Faraji
Wastewater Treatment by Phytoremediation Methods
199
4. HYPERACCUMULATORH
Hyperaccumulator used as first time in 1948 by Italian
scientist (Fingerman and Nagabhushanam, 2005). The
plant spices which accumulate heavy metals more
than 1% dry weight, named hyperaccumulator
(Zavoda et al., 2001). Most common aquatic
hyperaccumulators are Spirodelta polyrhiza,
Eichhornia crassipes and Elodeu nuttali (Dhir et al.,
2009), meanwhile Marchand reported there is no
aquatic hyperaccumulator plant species(Marchand et
al., 2010). Tow pictures of native natural terrestrial
hyperaccumulator plants(Figure 2 and Figure 3)
collected in China and Malaysia(Xue et al. 2004; van
der Ent et al., 2013) .Effective phytoremediation
highly correlated to suitable plant selection
(Manousaki, Kadukova et al., 2008).High biomass
,deep and/or wide roots, easy harvesting easily
provide renewable energy and resistance to high
concentration of pollutant are common characters of
phytoremediators (Ghosh and Singh, 2005).
Collecting plants from high polluted area is scientist
preferred method for finding metallic elements
hyperaccumulators (Gleba et al., 1999).Through the
all plant species only 400 species (Brooks, 1998) or
500 species (Ma et al., 2001)reported as
hyperaccumulators. Heavy metals hyperaccumulators
belong to approximately 500 tax of angiosperm (less
than 0.2%) (Krmer, 2010). Recently study in China
introduced three aquatic hyperaccumulator species
for heavy metals Najas marina for arsenic (As) and
cadmium (Cd), Vallisneria natans for lead (Pb) and
Ceratophyllum demersum for cobalt (Co), chromium
(Cr) and ferrum (Fe) plant species selection for this
study carried out from native nominated plants from
studying site (Xing et al., 2013).Some of recently
carried out studies are listed in Table 2, and a number
of old researches added because of their importance.
5. FUTURE STUDIES
Micro propagation is the best way for mass production
of some aquatic machrophyte, since produce a lot of
unique genetically plants in short time for analytical
data collection (Kan et al. 1990),which may use for
phytoremediation of contamination particular metallic
elements, first report in this area reported by (Delmail
et al., 2013), There is no reports on natural Mercury
phytoremediator plants(Shiyab et al., 2009)and high
toxicity of this element for human (Harris et al.
2003)presents a critical circumstance for introducing
suitable candidate for phytoremediation of Mercury.
A genetically studying is trying to make Hg
hyperaccumulator by the Meagher laboratory
(Fingerman and Nagabhushanam, 2005).Nowadays
researches on different concentration of heavy metals
in sediments, soil and water, in unique case study also
(Falinski et al. 2014), introducing suitable spectacular
plant species for water, soil and sediment
phytoremediation(Nan, et al., 2013) and using
different enhancers like as microbial and Zeolite in
phytoremediation process(Karimzadeh et al., 2012) is
leading researches toward using constructed wetland
(CW) as a complete ecological system for treating
wastewater spectacular for continues
phytoremediation in practical treatment for example
removing metals from road runoff (Borne et al.
2014),electric industry wastewater (Yang et al., 2013)
fresh oilfield produced water (Alley et al., 2013).
Fig. 2: Nickel hyperaccumulator ultramafic area
Malaysia and the Philippine (van der Ent et al., 2013)
Fig. 3: Phytolacca acinosa Roxb.
Growing at Xiangtan manganese tailing ,China (Xue
et al., 2004)
Wastewater Engineering: Advanced Wastewater Treatment Systems
Chapter 7: Wastewater Treatment by Phytoremediation Technologies
200
Table 2: Summary of recent studies on aquatic hyperaccumulation
Plant species Metallic
elements
Results Media Reference
Salvinia Minima(fern)
Pb
2+
Phytochelatins cope with
pb
2
+ as one of mechanism
Artificially polluted
water
(Snchez-Galvn et al.,
2008)
Chara Australis (algae) Cd Chara is not a
hyperaccumulator
Sediment (Clabeaux et al., 2011)
Talinum Triangular Cu, Pb, Ni,
Cd
Stem cuttings are new Cu
hyperaccumulator
Hydroponic system (Rajkumar et al., 2009)
Cyperus rotundus L. Heavy
metals
New Sn
Hyperaccumulator
Soil and water media. (Ashraf et al., 2011)
Pteris vittata L.
As In pH:5.21 fern is
hyperaccumilator
hydroponic
experiment
(Tu et al., 2004)
Nasturtium officials
diplazium Esculentum
As These are not
Hyperaccumulator
Sediment soil
water
(Falinski et al., 2014)
Eichhornia crassipes
(Ash)
Heavy
metals
Pb,Zn,Cr,Cu and Ni
Hyperaccumulator
Artificially polluted
water
(Mahmood et al., 2010)
pistia stratiotens Cd Cd hyperaccumulator surface waters (Das et al., 2013)
Lemna minor Hg Phytoremediator Natural lake water (Isaksson et al., 2007)
Ceratophyllum demersum
Lemna gibba
Pb, Cr 2 Effective
phytoremediators
Artificially
contaminated water
(Abdallah, 2012)
Eleacharis acicularis Heavy
metals
Pb hyperaccumulators abandoned mining and
sediment
(Ha et al., 2009)
Salvinia minima (fern) Pb
2+
Accumulation of Pb
increased Glutathiane
synthase
artificially
contaminated
water
(Estrella-Gmez et al., 2012)
Echonrnnia crassipes
Spirodela polyrhiza
Fe, Mn,
Cu, Cd,
Pb, Cr
Suitable
Bioindicators or
bioaccumulator
electric industries
waste water
(Sahu et al., 2007)
Eichhornia crassipes
Spirodela polyrrhiza
pistia stratiotens
Fe,Zn,Cu,
Cr,Cd
3 Suitable
phytoremediators
artificially
contaminated
water
(Mishra and Tripathi, 2008)
Myriophyllum
aterniflorum
Cd,Cu Hyperaccumulator aquatic media (Delmail et al., 2013)
1-Najas marina
2-Ceratophyllum
demersum
3-Vallisneria natanas
Heavy
metals
1-As and Cd
hyperaccumulator
2- Co,Cr and Fe
hyperaccumulator
3-Pb hyperaccumulator
24 eutrophic lakes (Xing et al., 2013)
Alternantbera philoxeroids heavy
metals
Zn and Cd
hyperaccumulator
local river (Nan et al., 2013)
Myriophyllum vercillatum Pb,Cu,Cd
and Zn
May be hyperaccumulator
for Pb
2+
hydroponic system (Ucer et al., 2013)
Pistia stratiotes L. heavy
metals
Cr,Cu,Fe,Mn,Ni,Pb, and
Zn hyperaccumulator
Surface water (Pant and Singh, 2013)
Eichhorna crassipes Cd,Ni The roots are effective in
absorbing most of Cd and
Ni
Artificially
contaminated water
(Elfeky et al., 2013)
Potamogeton natans
Alismaplantago aquatica
Filipendula ulmaria
Cu,Zn,Pb These plants are the most
efficient plant for up taking
heavy metals
Storm water (Fritioff and Greger, 2003)
Catharanthus roseus
137
Cs
90
Sr
Ideal hyperaccumulator
For radionuclides
Artificially
contaminated water
(Eapen et al., 2009)
Chrysopagann zizanioides Mn,
Fe,Cu,Zn,
Pb
Harvested plant safely can
use for compost or
handicrafts
Industrial wastewater (Roongtanakiat, 2009)
Leersiahexandra Cr Hyperaccumulator electroplating factory
wastewater
(Zhang et al., 2007)
Callitriche cophocarpa Cr Suitable bioaccumulator Artificially
contaminated water
(Augustynowicz et al., 2013)
Eichhorna crassipes
Ipomea aquatic
Typha angustata
Zn,Cu,Pb,
Ni, Co,Cd
Three native aquatic plants
are suitable species for
phytoremediation
Sediment and water
Gujarat wetland
(Kumar et al., 2008)
Lemna minor Pb Suitable phytoremediator
in low concentration
Artificially
contaminated water
(Bianconi et al., 2013)
Faraji
Wastewater Treatment by Phytoremediation Methods
201
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Wastewater Engineering: Advanced Wastewater
Treatment Systems
Chapter 8: Landfill Leachate Treatment Techniques
Wastewater Engineering: Advanced Wastewater Treatment Systems
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Municipal Landfill Leachate Treatment Techniques: An Overview
Shuokr Qarani Aziz
1, 2, *
, Hamidi Abdul Aziz
2
, Mohammed J.K. Bashir
3
, Amin Mojiri
2
1
Department of Civil Engineering, College of Engineering, University of SalahaddinErbil, Iraq
2
School of Civil Engineering, Engineering Campus, Universiti Sains Malaysia, 14300 Nibong Tebal, Penang, Malaysia
3
Faculty of Eng. and Green Tech. (FEGT), Universiti Tunku Abdul Rahman, 31900 Kampar, Perak, Malaysia
*Corresponding Author, shoker71@eng-usalah.org, shoker71@yahoo.com, H/P: 00964 750 462 5426
Abstract. Production of raw leachate from landfills regards as shortcoming for the sanitary landfills. Unprocessed landfill
leachate requires treatment prior disposal to the natural environment. In this work, leachate channeling, biological, and
physical-chemical treatment processes for treatment of formed landfill leachate were presented in details. Definite treatment
processes were resulted in high removal of pollutants such as ammonia (NH
3
-N), chemical oxygen demand (COD),
biochemical oxygen demand (BOD
5
), phenols, color etc. Practically, age of produced leachate have influence on the treatment
systems. Efficient treatment methods were explained for fresh, medium, and stabilized landfill leachates.
Keywords: Landfill, leachate, treatment, municipal solid waste, pollutants, removal efficiency
1. INTRODUCTION
Sanitary landfill is the most common municipal solid
waste (MSW) disposal method due to such advantages
as simple disposal procedure, low cost, and landscape-
restoring effect on holes from mineral workings.
However, the production of highly contaminated
landfill leachate is a chief weakness of this system
(Aziz et al., 2010). The generation of highly
contaminated leachate that can seep into the ground
and contaminate the ground water, surface water, and
soil is principally a main negative aspect associated to
municipal sanitary landfill disposal method (Bashir et
al., 2012. Additionally, leachate is liquid contain large
amounts of organic compounds measured as chemical
oxygen demand (COD), biochemical oxygen demand
(BOD
5
), ammoniacal nitrogen (NH
3
-N), halogenated
hydrocarbons suspended solid, significant
concentration of heavy metals, and inorganic salts
(Aziz, 2013; Bashir et al., 2012; Aziz et al., 2010;
Uygur and Kargi, 2004).
If not treated and disposed safely, landfill leachate
could be a major source of water contamination
because it could percolate through soil and subsoil,
causing high pollution to receiving waters. Thus, the
treatment of hazardous leachate constituents before
discharge has been made a legal requirement to
prevent pollution of water resources and to avoid both
acute and chronic toxicities (Aziz et al., 2011).
To reduce the negative impacts of discharged
leachate on the environment, several techniques of
water and wastewater treatment have been used,
including aerobic and anaerobic biological treatment,
chemical and electrochemical oxidation processes,
chemical precipitation, adsorption using various
adsorbent, reverse osmosis, coagulationflocculation,
membrane processes, and ion exchange (Aziz et al.
2013; Bashir et al., 2012; Aziz et al., 2011; Abbas et
al 2009; Renou et al., 2008).
The current work was aimed to present appropriate
landfill leachate treatment techniques for unprocessed
landfill leachates. Giving detailed information on
leachate channeling, biological, and physical-chemical
treatment processes for raw leachates was another
goal for the present study. Furthermore, suggestion of
efficient treatment methods for different sorts of
produced landfill leachates from various sanitary
landfills was illustrated as well.
2. LANDFILL LEACHATE
2.1 Types of leachate based on landfill design
According to Yamamoto, (2002) and Matsufuji et al.
(1993), in an anaerobic landfill, solid wastes are
dumped in an excavated area of a plane field, which is
filled with water in an anaerobic condition. Typically,
anaerobic sanitary landfills are recognized by its
sandwich-shaped cover. On the other hand, semi-
aerobic landfills have a leachate collection duct. The
opening of the duct is surrounded by air, and the duct
is covered with small crushed stones. Moisture
content in solid waste is small, and oxygen is supplied
to the solid waste from the leachate collection duct.
The schematic diagram of anaerobic and semi-aerobic
(Fukuoka method) landfills is demonstrated in Figure
1 (JICA, 2005). Characteristics of fresh landfill
leachates at semi-aerobic and anaerobic landfills are
given in Table 1.
Aziz et al.
Municipal Landfill Leachate Treatment Techniques: An Overview
209
Fig.1: Schematic diagram of anaerobic and semi-aerobic landfill
2.2 Significance of leachate problem
Tatsi et al. (2003) and Renou et al. (2008) reported
that landfill leachate can be characterized by two main
factors: quantity (volumetric flow rate) and quality
(chemical composition). El-Fadel et al. (2002)
indicated that the quantity of leachate generation is
affected by landfill moisture distribution influencers
namely refuse age, pretreatment, permeability,
compaction, particle size and density and direct
landfill moisture contributors like rainfall, snowmelt,
groundwater intrusion, initial moisture and leachate
recirculation. Seriously, leachate production is rapid
in tropical countries such as Malaysia since the
rainfall normally exceeds the quantity that can be
evaporated during the rainy season (Lema et al.,
1988).
Usually, leachate contains a complex variety of
substances and organic compounds such as humic
substances, fatty acids, heavy metals and many other
hazardous chemicals. Regardless of the concentration
changes and show a discrepancy based on a complex
set of interconnected factors, the complexity of the
landfill leachate can be categorized on the basis of
four major groups of pollutants i.e. dissolved organic
substances, inorganic macro-components, heavy
metals and xenobiotic organic compounds
(Widziewicz et al., 2012; Schrab et al., 1993).
Bashir et al (2010; 2012) and Aziz et al. (2011)
reported that the common features of raw leachate
generated from Malaysian landfill sites are its high
strength of recalcitrant compounds (as reflected by its
chemical oxygen demand (COD) value) and high
concentrations of ammonia nitrogen (NH
3
-N).
Ammonia resulting from the decomposition process of
organic nitrogen, has been recognized not only as a
major long-term noxious waste, but also as the
primary cause of acute toxicity (Ernst et al., 1994;
Baun et al., 1999). Bashir et al. (2010) stated that the
existence of high amount of NH
3
N in leachate over a
long period of time is one of the most important
problems routinely faced by landfill operators. This
high quantity of unprocessed NH
3
N leads to the
depletion of dissolved oxygen which is also
recognized as eutrophication. Because NH
3
-N is stable
under anaerobic situations, it typically accumulates in
the leachate (Ernst et al., 1994). With a concentration
of higher than 100 mg/L, untreated NH
3
-N is highly
toxic to aquatic organisms (Widziewicz et al., 2012;
Burton and Watson-Craik, 1998; Silva et al., 2004;
Bagchi, 1994). Unless appropriately treated, leachate
that seeps from a landfill can get into and contaminate
the underlying groundwater.
In line with the abovementioned, if the leachate
escapes to the water bodies, it is very complicated and
costly to have it controlled and cleaned up,
consequently posing potentially serious hazards to
living organisms, as well as public health in the long
term. In most cases, it is very hard to restore the
contaminated water bodies to its original state.
Recently, the hazard of groundwater pollution due to
leachate seepage has turn out to be a main
environmental concern worldwide. Therefore, an
adequate engineering plan and design of a municipal
landfill can avoid or reduce the seepage of leachate
from reaching the water bodies.
Typically, the concentration of leachate parameters
changes with the age of the leachate. The phases of
leachate are transition (0 -5 years), acid-formation (5 -
10 years), methane fermentation (15 - 20 years), and
final maturation (greater than 20 years). The age of
the landfill is one of the most important factors that
affect leachate characteristics (Kostova, 2006; Aziz,
2013) The levels of some leachate characteristics such
Wastewater Engineering: Advanced Wastewater Treatment Systems
Chapter 8: Landfill Leachate Treatment Techniques
210
as biochemical oxygen demand (BOD
5
), COD, total
organic carbon (TOC), NH
3
-N, nitrite ( NO
2
-N) and
total dissolved salts (TDS) in different phases are
presented in Table 1.
According to the literature, as a landfill becomes
older, the biological decomposition of the deposited
wastes shifts from a relatively shorter initial period to
a longer decomposition period, which has two distinct
sub-phases: acidic and methanogenic. Leachates from
these distinct stages contain different constituents;
therefore, young leachates tend to be acidic due to the
presence of volatile fatty acids.
Fig. 2: Diagram of landfill leachate treatment techniques, based on Abbas et al. (2009); Renou et al. (2008)
3. RESULTS AND DISCUSSIONS
If raw leachate is disposed without treatment, it could
become a major source of water pollution because it
can percolate through soils and sub-soils, causing high
contamination of the receiving water. The treatment of
potentially hazardous constituents of leachate prior to
discharge is a legal requirement to avoid
contamination of water resources to prevent both
acute and chronic toxicity (Ziyang et al., 2009; Oman
and Junestedt, 2008; Sanphoti et al. 2006; ARRPET,
2004).
Aziz et al.
Municipal Landfill Leachate Treatment Techniques: An Overview
211
To reduce the negative impact of discharged
leachate on environment, several techniques of water
and wastewater treatment have been used. The
technologies which were developed for the treatment
of landfill leachate could be classified as physical,
chemical, and biological (Abbast et al., 2009; Renou
et al., 2008). Normally, the techniques are applied as
an integrated system because it is not easy to achieve
the satisfying treatment efficiency by using only one
technology. Traditional treatment techniques
generally demand multistage process treatment. To set
up acceptable treatment process for removal of
contaminates from leachates, various physicochemical
and biological techniques and/or their different
combinations could be applied.
The implementation of the most suitable technique
for the treatment of leachate is directly governed by
the characteristics of the leachate. An overview of
leachate treatment methods is shown in Figure 2,
(Abbas et al., 2009; Renou et al., 2008)
Comparison of the above techniques for different
landfill ages with changeable success is illustrated in
Table 2. In addition, the most important advantages
and disadvantages of the different leachate treatment
methods are reviewed in the following sections. In
general, biological treatment processes are effective
for young or freshly (<5 years) produced leachate, but
are ineffective for leachate from older landfills (>10
years old). In contrast, physicalchemical methods
which are not favoured for young leachate treatment
are advised for older leachate treatment (Ghafari et al.,
2009).
3.1. Leachate Channeling
3.1.1. Combined treatment with domestic sewage
General means of landfill leachate disposal is piping
into the sewerage system for discharge into the sea or,
if possible, for combined treatment with domestic
sewage at traditional wastewater treatment plant. It
was favoured for its low operating costs and simple
maintenance (Ahn et al., 2002). This alternative has
been increasingly inquired due to the presence of
organic inhibitory compounds in leachate with low
BOD
5
/COD and heavy metals that might decrease
treatment efficiency and increase concentrations in the
effluent (Cecen and Aktas, 2004). A disagreement to
this treatment option is that phosphorus (brought by
sewage) and nitrogen (brought by leachate) are not
required to be added to the treatment scheme (Abbas
et al., 2009).
Cecen and Aktas (2001) investigated the combined
biological treatability of domestic wastewater and
landfill leachate in both continuous flow and semi-
continuously fed batch activated sludges, with
recycling mechanism. In addition, the researchers
added powdered activated carbon (PAC) in order to
examine the improvement in nitrification process and
organic carbon removal. The obtained results showed
that in both types of operations, NH
3
-N and COD
removal efficiencies decreased with an increase in the
leachate to total wastewater ratio. When the leachate
ratio increased, the positive effects of PAC on the
removal of COD and nitrification process became
more obvious.
3.1.2. Recycling
A common system used in many landfills consists of
recycling landfill leachate back through the tip
because it was one of the cheapest alternatives (Lema
et al., 1988). Bae et al. (1998) explained that the
leachate recirculation increased the moisture content
in a controlled reactor method and offered the
distribution of enzymes and nutrients between
solids/liquids and methanogens. Chugh et al., (1998)
stated that lowering COD and methane production
was observed to be important as the recycled leachate
quantity was 30% of the initial waste bed quantity.
The recirculation of leachate not only improves the
leachate characteristics, but also shortens the required
time for stabilization of leachate from several decades
to 2-3 years (Reinhart and Al-Yousisfi, 1996). High
recirculation rates of leachate could negatively
influence anaerobic degradation of solid wastes.
Recirculation of leachate could cause the inhibition of
methanogenesis as it may lead to high concentrations
of organic acids, pH less than 5, which are toxic for
the methanogens. In addition, if the amount of
recycled leachate is very high, problems such as
saturation, acidic conditions, and ponding may happen
(Abbas et al., 2009).
Wastewater Engineering: Advanced Wastewater Treatment Systems
Chapter 8: Landfill Leachate Treatment Techniques
212
Table 1: Characteristics of raw leachate at semi-aerobic and anaerobic landfills (Aziz et al., 2010)
No. Parameter
Semi- aerobic Pulau Burung site Kulim site Standard B
Unaerated Intermittently aerated Anaerobic
Discharge limit
b
Range Average
a
Range Average
a
Range Average
a
1 Phenols (mg/L) 0.35-2.07 1.2 2.85-10.5 6.7 1-5.25 2.6
2 Total nitrogen (mg/L N-TN) 200-700 483 700-1800 1200 100-600 300
3 Ammonia-N (mg/L NH
3
-N) 360-730 542 1145-2150 1568 130-1039 538
4 Nitrate-N (mg/L NO
3
-
-N) 900-3200 2200 2900-7900 5233 400-2600 1283
5
Nitrite-N (mg/L NO
2
-
-N)
44-270 91 20-120 49 30-60 52
6
Total phosphorus (mg/L PO
4
3-
-TNT)
10-43.0 21 10.0-25 17 8.0-40 19
7
Ortho-Phosphorus (mg/L PO
4
3-
mv
)
84-274 141 94-210 159 57-197 94
8 BOD
5
(mg/L) 67-93 83 146-336 243 135-476 326 50
9 COD (mg/L) 600-1300 935 1680-4020 2345 630-2860 1892 100
10 BOD
5
/COD 0.051-0.12 0.096 0.036-0.186 0.124 0.088-0.35 0.205 0.5
11 pH 8.05-8.35 8.20 8.14-8.37 8.28 6.93-8.26 7.76 5.5-9
12 Electrical conductivity (ms/cm) 10.14-13.630 12.17 21.500-22.500 22.10 5.250-13.92 8.55
13 Turbidity (FAU) 600-3404 1546 149-211 180 490-4500 1936
14 Color (Pt Co) 1944-4050 3334 2310-4390 3347 1950-7475 4041
15 Total solids (mg/L) 5138-7404 6271 8860-11084 9925 4520-10568 6336
16 Suspended solids (mg/L) 906-2220 1437 374-1372 837 232-1374 707 100
17 Total iron (mg/L Fe) 2-29.5 7.9 0.9-8.8 3.4 0.6-11.4 5.3 5
18 Zinc (mg/L Zn) 0-3 0.6 0.01-2 0.5 0-1 0.2 1
19 Total coliform <50 (0.77-0.85)x10
4
0.81x10
4
20 E-Coli 0.00 (0.18-0.22)x10
4
0.20x10
4
a
Average value of six samples
b
Standard B of the Environmental Quality (Sewage and Industrial Effluents) Regulations 1979, under the Environmental Quality Act of Malaysia, 1974 (MDC, 1997).
Aziz et al.
Municipal Landfill Leachate Treatment Techniques: An Overview
213
Table 2: Effectiveness of leachate treatment techniques versus leachate age (Abbas et al., 2009)
No. Type of treatment Leacgate age (year)
Young (<5) Medium (5-10) Old (>10)
1 Combined treatment with
domestic sewage
Good Fair poor
2 Recycling Good Fair poor
3 Aerobic processes Good Fair poor
4 Anaerobic processes Good Fair poor
5 Coagulation/flocculation Poor Fair Fair
6 Chemical precipitation Poor Fair Poor
7 Adsorption Poor Fair Good
8 Oxidation Poor Fair Fair
9 Stripping Poor Fair Fair
10 Ion exchange Good Good Good
11 Microfiltration Poor - -
12 Ultrafiltration Poor - -
13 Nanofiltration Good Good Good
14 Reverse osmosis Good Good Good
3.2. Biological treatment
The biological purification processes have been well
recognized and effectively employed for the treatment
of domestic wastewater. Biological treatments are
categorized as aerobic or anaerobic depending on
whether or not the biological processing medium
needs oxygen (O
2
) supply. In aerobic treatment,
organic contaminants are mostly transformed into
carbon dioxide (CO
2
) and sludge by using the
atmospheric O
2
transferred to the wastewater. While,
in anaerobic processing, organic matter is converted
into biogas, a mixture mainly comprising of CO
2
and
CH
4
, and biological sludge (Lema et al., 1988).
Because of its simplicity, reliability, and high-cost
effectiveness, biological purification (suspended or
attached growth) is mainly employed to treat landfill
leachate containing extreme concentrations of BOD
5
(Renou et al., 2008). Biological techniques have been
recognized to be very effective for young leachate
treatment since the BOD
5
/COD ratio is high (> 0.5).
However, the biodegradability ratio commonly
decreases as the landfill ages, due to the presence of
pollutants that decrease biomass activity and/or are
refractory to biological processes (Lema et al., 1988).
The main fraction of mature or biologically treated
leachate is large unmanageable organic compounds
that are not easily removed through biological
treatment. Thus, to meet the allowable standards for
direct discharge of leachate into the environment, a
development of integrated treatment methods is
required, i.e. a combination of biological, physical,
and chemical, and other process steps (Tauchert et al.,
2006).
3.2.1 Aerobic treatment
Destruction of biodegradable organic matter occurs
via aeration in aerobic process. Aerobic biological
methods consist of suspended-growth and attached-
growth biomass processes. The former method has
been extensively applied for treatment of municipal
landfill leachate and wastewater (Abbas et al., 2009;
Renou et al., 2008).
i) Suspended-growth biomass process
Aerated lagoons
Aerated lagoons have commonly been viewed as a
successful and economical technique for the removal
Wastewater Engineering: Advanced Wastewater Treatment Systems
Chapter 8: Landfill Leachate Treatment Techniques
214
of pathogens, organic and inorganic matters. Low
operation and maintenance costs have made them an
accepted option for wastewater treatment, particularly
in developing countries. Further, it requires a little
professional skill to operate the system (Maynard et
al., 1999). Maehlum (1995) studied biological
treatment of leachate using anaerobicaerobic lagoons
and constructed wetlands and more than 70% of
nitrogen, phosphorus and ferrous removals were
obtained for diluted landfill leachate. Generally,
treatment of landfill leachate in lagoons and wetlands
need 10 to 20 days retention time (Robinson et al,
1992, Maehlum, 1995). In spite of its lower costs, this
process might not be entirely satisfactory treatment
option for leachate treatment (Zaloum and Abbott,
1997). Finally, large area requirements, aerosol and
formation are other shortcomings of this method
(Robinson et al, 1992, Maehlum, 1995).
Activated sludge process
Activated sludge process could be defined as a
suspended growth process that utilizes aerobic
microorganisms to biodegrade organic matters in
wastewater or leachate. Activated sludge technology
has been extensively used for the treatment of
wastewater and leachate. However this process has a
good ability in the removal of nutrients but it has
some weaknesses such as: 1) Excess sludge
production, 2) Sludge settleability (i.e. high SVI
values), 3) High energy requirements, 4) The need for
longer contact times, and 5) Microbial inhibition due
to high ammonium-nitrogen (NH
4
-N) strength
(Loukidou and Zouboulis, 2001; Lin et al., 2000;
Lema et al., 1988).
Hoilijoki et al. (2000) added plastic carrier
material to activated sludge process and examined
nitrification of anaerobically pre-treated landfill
leachate in a lab-scale at different temperatures (5-
10C). They stated that the concentration of effluent
parameters (COD, BOD
5
, and NH
3
-N) for aerobic
post-treatment were 150-500 mg/L, < 7 mg/L , and <
133 mg/L, respectively. PAC supplemented to
activated sludge processes improved nitrification
efficiency in biological treatment of landfill leachate.
Aghamohammadi (2006) studied treatment of
semi-aerobic landfill leachate from PBLS by using
PAC augmented activated sludge process. The author
reported that the leachate characteristic had great
affect on the removal of organic matter using
activated sludge treatment. Removal efficiencies of
colour, COD, and NH
3
-N during the treatment of
landfill leachate for leachate from PBLS were 21%,
29%, and 60%, respectively.
SBR (Sequencing batch reactor)
SBR process varies from activated-sludge
techniques, because SBR merges all treatment units
and processes into a single basin; whereas traditional
systems rely on various tanks. Typical SBR is divided
into five time periods: fill, react, settle, draw, and idle.
SBR is used for the treatment of wastewater and
landfill leachates (Mahvi 2008; Al-Rekabi et al.,
2007). Due to low BOD
5
/COD ratio, high
concentration of COD, NH
3
-N, heavy metals, and
other compounds in landfill leachate, the capability of
SBR in leachate treatment is relatively weaker than
for municipal and industrial wastes (Uygur and Kargi,
2004). In literature, SBR was used for the treatment of
leachate with low BOD
5
/COD ratio of 0.09 to 0.37
(Guo et al., 2010; Spagni et al., 2008; Klimiuk and
Kulikowska, 2006).
SBR augmented powdered activated carbon (PAC-
SBR) showed higher removal efficiencies of NH
3
-N,
COD, colour, and TDS when compared with normal
SBR. Furthermore, PAC-SBR improved sludge
volume index (SVI) (Aziz et al. 2011; 2013)
ii) Attached-growth biomass systems
A number of attached-growth biomass processes by
using biofilm have been recently developed to
overcome the problems of activated sludge,
specifically sludge bulking (Dollerer and Wilderer,
1996). These methods offer the advantage of not
suffering from loss of active biomass. In addition,
nitrification is less affected by low temperature than in
suspended-growth methods, and by inhibition due to
high nitrogen content.
Moving-bed biofilm reactor (MBBR)
MBBR technique is based on the use of suspended
porous polymeric carriers, kept in continuous
movement in the aeration basin; whereas the active
biomass grows like a biofilm on their surfaces. The
main advantages of this process compared to normal
suspended growth methods seems to be:1) Higher
biomass concentrations, 2) Lower sensitivity to toxic
compounds, 3) Lower sludge-settling periods, and 4)
Both organic and high NH
3
-N removals in a single
process. Based on literature, this system could remove
60-81% of COD and 85-90% of NH
3
-N from landfill
leachate (Loukidou and Zouboulis, 2001; Horan et al.,
1997). Welander et al. (1998) reported that MBBR
resulted in about 90% and 20% removal of nitrogen
and COD while no inhibition of nitrification was
encountered during the treatment of high strength
ammonia leachate. Further, using adsorbent (i.e.
granular activated carbon) offers a suitable surface to
adsorb organic substance and enhanced
biodegradation. Thus, a steady-state equilibrium is
Aziz et al.
Municipal Landfill Leachate Treatment Techniques: An Overview
215
recognized between adsorption and biodegradation
(Horan et al., 1997).
Trickling filters
Trickling filters have been tested for lowering the
biological nitrogen from landfill leachate. Because of
low-cost filter media, biofilters remain an attractive
and interesting alternative for nitrification process
(Jokela et al., 2002). In literature, biological nitrogen
removal from municipal landfill leachate was
examined by Jokela et al. (2002) and nitrification of
leachate over 90% was achieved by using biofilters.
They concluded that nitrification in a low-cost
biofilter followed by denitrification in a landfill body
appeared to be applicable for the removal of nitrogen
in landfill leachate in colder climates (Jokela et al.,
2002). Maximum NH
3
-N removal of 75 % was
obtained by Martienssen and Schops (1997).
3.2.2. Anaerobic treatment
Anaerobic digestion is the oldest system used for
treatment of wastewater. It is suitable for the
treatment of high strength organic pollutants, such as
young leachate. Opposite to aerobic processes,
anaerobic digestion method saves energy and
produces very few solids; but it suffers from low
reaction rates. Further, the produced CH
4
could be
used for warming the digester that generally works at
35C (Renou et al., 2008; Sung et al., 1997).
Anaerobic digestion comprises suspended-growth
digester (anaerobic SBR and up-flow anaerobic sludge
blanket reactor, UASBR) and attached-growth
biomass system (anaerobic filter, hybrid filter, and
fluidized bed filter).
i) Suspended-growth digester
Bull et al. (1983) and Sung et al. (1997) studied the
performances of conventional anaerobic suspended
growth digester. The researchers reported that the
typical values for COD removal in anaerobic lab-scale
basin at 35C and ambient temperature were 80-90%
and nearly 55%, respectively.
Anaerobic SBR
Anaerobic SBR is a type of suspended-growth
digester. Some studies have shown good
performances of anaerobic SBRs. These technologies
are able to obtain solid capture and organic lowering
in one reactor (Timur and Ozturk, 1999). Uygar and
Kargi (2004) used lab-scale SBR for the reduction of
nutrient from pre-treated leachate. The researchers
reported that, at the end of cycle time of 21 h,
sequential anaerobic/aerobic operations offered
removal efficiencies of 62% for COD, 31% for NH
3
-
N, and 19 % for PO
4
3-
-P. Kettunen and Rintala (1995)
explained that COD removal in the anaerobic stage
was 35%; whereas removal efficiencies of COD and
BOD
5
in the combined process were up to 75% and
99%, respectively.
Timur and Ozturk (1999) examined anaerobic
treatability of municipal landfill leachate by using lab-
scale anaerobic SBR at 35
o
C. Based on the obtained
results, about 83% of COD removed during the
treatment was converted to methane. In addition, the
average biomass yield was 0.12 g volatile suspended
solids per gram of COD removed.
Upflow-anaerobic sludge blanket reactor (UASBR)
UASBR technique is a modern anaerobic treatment
process that can have high treatment efficiency and a
short HRT (Lin et al., 2000). In addition, Garcia et al.
(1996) reported that UASBR exhibited higher
performances compared to other types of anaerobic
reactors, when they submitted to high volumetric
organic loading rates.
A pilot-scale UASBR at low temperature was used
for the treatment of municipal landfill leachate.
Removal efficiencies of COD and BOD
5
at organic
loading rate of 2-4 kg/m
3
/d of COD were 65-75 % and
up to 95 %, respectively (Kettunen and Rintala, 1995).
At organic loading rates between 6 and 19.7 g/L/d of
COD, Kennedy and Lentz (2000) obtained COD
removal efficiency of 92%. Generally, for anaerobic
treatment with UASBRs, the process temperatures are
reported to be between 2035
C. (Akkaya et al.,
2010). However, several studies were conducted at
temperatures between 11 to 23C (Kettunen and
Rintala, 1995; Garcia et al., 1996). Sensitivity to toxic
substances is the main disadvantages of UASBRs
(Sung et al., 1997).
ii) Attached-growth biomass systems
Anaerobic filter
Anaerobic filter method is a high rate system that
collects the advantages of other anaerobic methods
and decreases the shortcomings. The filtration process
may be down-flow or up-flow. Packed filter media
provides the mechanism for separating the solids and
the gas that are produced within the digestion process.
In an up-flow anaerobic filtration process, biomass is
retained as biofilms on the supporting material, such
as plastic rings (Nedwell and Reynolds, 1996). At
loading rates of 1.26-1.45 kg/m
3
/d of COD and for
different ages of landfill leachate, anaerobic filter
removed 90% of COD. Further, anaerobic filter
resulted in total biogas production ranged between
400 to 500 Lgas/kg COD destroyed and methane
content of 75% and 85% (Henry et al., 1987).
Wastewater Engineering: Advanced Wastewater Treatment Systems
Chapter 8: Landfill Leachate Treatment Techniques
216
Hybrid filter
Hybrid bed filter consists of an up-flow sludge
blanket at the bed and an anaerobic filter on the top.
This technique acts as a gas-solid separator and
improves solids retention without causing
channelling or short-circuiting. A hybrid bed filter
(consisted of anaerobic filter and up-flow anaerobic
sludge blanket reactor) with a filter volume of 2.75 L
and HRT of 2.4 d at temperature of 35
o
C resulted in
removal of about 37.5 to 76 % COD from landfill
leachate (Timur and Ozturk, 1997). Nedwell and
Reynolds(1996) showed steady state COD removal
efficiencies of 81-97% under methanogenic digestion
was based on organic loading rate; and effective
treatment occurred up to a volumetric COD loading
rate of 3.75 kg COD/m
3
d
1
. One disadvantage of
hybrid bed filter, as well as anaerobic filter, is the
additional cost of the supporting media.
Fluidized bed filter
Imai et al. (1993) applied microorganism-attached
activated carbon fluidized bed technique for the
treatment of real landfill leachate containing
refractory organics and a high concentration of NH
4
-
N. They reported that the microorganism-attached
activated carbon fluidized bed method removed about
60% and 70% of refractory organics and nitrogen,
respectively. A number of researches on carbon-
assisted fluidized beds have been conducted (Gulsen
and Turan, 2004; Suidan et al., 1993). Suidan et al.
(1993) stated that about 82% of COD was removed
from leachate via fluidized bed reactor at temperature
of 35
o
C and volume of 7.9 L.
3.3. Physical/chemical treatment
Physico-chemical processes are used along with the
biological processes generally to enhance treatment
efficiency or to enhance biodegradability when the
biological oxidation method is disadvantaged by the
occurrence of bio-refractory materials. A number of
physical/chemical treatment techniques which
includes coagulation/flocculation, flotation, chemical
precipitation, adsorption, ammonium stripping,
chemical oxidation, ion exchange, electrochemical
oxidation, and membrane filtration are used for
removing non-biodegradable (humic and fulvic acid)
and/or unwanted compounds (such as heavy metals)
from the landfill leachate (Abbas et al., 2009; Renou
et al., 2008; Zouboulis et al., 2004)
3.3.1. Coagulation/flocculation
Coagulationflocculation technique is considered as a
simple physicalchemical process in landfill leachate
treatment (Aziz et al. 2009; Ghafari et al., 2009). It is
an effective pretreatment process if used prior to
reverse osmosis or biological treatment or as a last
polishing treatment so as to remove or decrease non-
biodegradable organic matter in landfill leachate
(Amokrane et al., 1997). Due to its limited efficiency
for the removal of organic matter, it is not suitable for
a full treatment of landfill leachate. Duan and Gregory
(2003) reported that the removal mechanism of the
coagulation process mainly consists of charge
neutralization of negatively charged impurities by
cationic hydrolysis products followed by integration
of colloids in an amorphous hydroxide precipitate
during flocculation process.
In literature, aluminum sulfate, ferrous sulfate,
ferric chlorosulfate, and ferric chloride were generally
used as coagulants (Zouboulis et al., 2004; Amokrane
et al. 1997). Dialynas et al. (2008) investigated that
ferric chloride is more effective than alum in
eliminating organic constituent of landfill leachate,
particularly at pH values more than 9. It was sued to
the fact that ferric chloride enlarges floc size and
reduces settling time more than alum.
Ghafari et al. (2009) explained that by using alum
as coagulant, the optimum removal efficiencies of
COD, colour, turbidity, and suspended solids from
stabilized leachae were 62.8 %, 86.4%, 88.4%, and
90.1 %, respectively. Aziz et al. (2007) used
aluminum (III) sulphate (alum), ferric (III) chloride,
ferrous (III) sulphate and ferric (III) sulphate as
coagulants. The obtained results showed that ferric
chloride was better than the other coagulants with a
colour removal of 94 %.
However, coagulation/flocculation process have a
number of shortcomings, such as inefficiency in NH
3
-
N removal, low removal efficiency of high strength
landfill leachate, an increase on the concentration of
iron or aluminum could also be noticed in the liquid
phase, and production of huge volume of sludge
(Duan and Gregory, 2003; Tatsi et al., 2003; Silva et
al., 2004; Amokrane et al., 1997).
Al-Hamadani et al. (2011) studied the feasibility of
using psyllium husk as coagulant and coagulant aid
(with poly-aluminum chloride and aluminum sulfate)
for the treatment of semi-aerobic landfill leachate
from PBLS. When psyllium husk was used as primary
coagulant, the removal efficiencies for COD, colour
and suspended solids were 55 %, 80% and 95%,
respectively; whereas the removal efficiencies of
COD, colour, and suspended solids for psyllium husk
as coagulant aid with poly-aluminum chloride were
64, 90 and 96%, respectively. The researchers
reported that psyllium husk was more effective as
coagulant aid with poly-aluminum chloride in the
removal of COD, colour and suspended solids, as
compared to aluminum sulfate.
Aziz et al.
Municipal Landfill Leachate Treatment Techniques: An Overview
217
3.3.2. Flotation
Dissolved air flotation could be defined as
disconnection of suspended solids from liquids by
carrying the particles to the surface of the liquid (Al-
Shamrani et al., 2002). For many years, flotation
technique has been widely used and focused on the
reduction of ions, colloids, microorganisms,
macromolecules, and fibers (Zouboulis et al., 2003).
This technique was used extensively for the treatment
of oily wastewater.
Zouboulis et al. (2003) examined the use of
flotation in column, as a post-treatment step for the
removal of residual humic acids (non-biodegradable
compounds) from simulated landfill leachates. Under
optimum operational conditions, the researchers
obtained about 60% humic acids removal.
Lately, using dissolved air flotation process for the
treatment of landfill leachate in the presence and
absence of coagulation process was studied by Adlan
et al. (2011) and Palaniandy et al. (2010). Based on
the obtained results by Palaniandy et al. (2010), the
removal efficiencies of colour, COD, and turbidity
from leachate using dissolved air flotation process
(without coagulation process) were 36%, 33%, and
32%, respectively; whereas the removal efficiencies
with the coagulation process were 70%, 79%, and
42%, respectively.
3.3.3. Chemical precipitation
Chemical precipitation method has been extensively
employed as leachate pre-treatment because of its
simplicity, capability, and low-cost equipment used.
This method is efficient in removing NH
3
-N, non-
biodegradable compounds, and heavy metals from
landfill leachate (Akkaya et al., 2010; Zhang et al.,
2009; Calli et al., 2005; Ozturk et al., 2003).
Li et al. (1999) stated that the performance of a
conventional activated sludge technique could be
significantly affected by the high concentration of
NH
4
+
-N. Struvite (magnesium ammonium phosphate
hexahydrate, MgNH
4
PO
4
.6H
2
O) precipitation was
firstly distinguished as a phenomenon to be controlled
because it could cause problems throughout the
operation of wastewater treatment and other processes
where high concentrations of ammonium, magnesium,
and phosphate are present.
Ozturk et al. (2003) used Struvite as precipitant for
the removal of NH
3
-N from anaerobically pre-treated
leachate. The removal efficiency of NH
3
-N and COD
were 90% and 50%, respectively. It is confirmed that
the ammonium concentration in leachate could be
considerably reduced by struvite precipitation.
However, this process requires relatively expensive
chemicals (Kochany and Lipczynska-Kochany, 2009).
3.3.4. Adsorption
Adsorption technique is recognized as the efficient
and promising elementary approach in wastewater
treatment processes (Foo and Hameed, 2009). It is
used as a stage of integrated chemical-physical-
biological method for leachate treatment, or
simultaneously with a biological process. The most
commonly used adsorbent is granular activated carbon
or PAC (Abbas et al., 2009).
PAC as adsorbent improved performance of SBR
process. Results revealed that the PAC-SBR offered
better removal efficiencies of pollutants and improved
sludge characteristics (Aziz et al. 2011; 2013)
3.3.5. Ammonium stripping
Because of its high removal efficiency, the
ammonium stripping treatment method is the most
widely used for the removal of NH
3
-N from landfill
leachate. High concentrations of NH
4
-N are
commonly found in landfill leachates, which lead to
increasing wastewater toxicity. This method usually
changes dissolved NH
3
-N and dissolved CH
4
in
leachate to gases. High pH values must be provided in
this method so as the column works efficiently (Hao
et al., 2010; Ozturk et al., 2003; Marttinen et al.,
2002).
Sincero and Sincero (2003) explained that
stripping was completed via introducing wastewater at
the upper part of the stripping column and permitting
it to flow the air down in the column. Marttinen et al.
(2002) reported that this method at operation
condition of pH value equal to 11, temperature of
20C, and retention time of 24 h resulted in NH
3
-N
removal of 89%. In a research conducted by Silva et
al. (2004), the researchers obtained NH
3
-N removal
efficiency of 99.5%. Calli et al. (2005) explained that
the removal efficiencies of NH
3
-N and COD for initial
concentration of 3260 mg/L were 94 % and <15%,
respectively.
Comparing with other treatment techniques such as
reverse osmosis and nanofiltration ammonium
stripping discovered to be more economical in terms
of operational costs. Regardless of its advantages, the
main disadvantages of this technique are: 1) The
release of NH
3
-N gas to the atmosphere, 2) The
scaling of CaCO
3
when lime is used for pH adjustment
in the stripping tower, and 3) Adjustment of effluent
pH value prior discharge (Li et al., 1999).
3.3.6. Chemical oxidation
Oxidation and reduction process are based on transfer
of electrons. In this process, one compound gives
electrons whereas the other receives electrons. When
Wastewater Engineering: Advanced Wastewater Treatment Systems
Chapter 8: Landfill Leachate Treatment Techniques
218
biological treatments are inefficient, this method is
used to achieve desired objectives. Chemical
oxidation process is required for the treatment of
wastewater containing non-biodegradable and/or toxic
pollutants. So, this method is an efficient technique
for the treatment of low BOD
5
/COD (i.e. stabilized)
landfill leachates (Derco et al., 2010; Mohajeri et al.,
2010; Rivas et al., 2003; Droste, 1997; Marco et al.,
1997).
Amokrane et al. (1997) used oxidants, such as
chlorine, potassium permanganate, ozone, and
calcium hydrochloride, for landfill leachate treatment
and found COD removal of 2050%. Researchers
reported that the efficiency of COD reduction for
mature and biologically pretreated landfill leachates
were 60 to 75 %, respectively by using Fenton reagent
(Lopez et al., 2004; Kang and Hwang, 2000).
Fenton oxidation was used by Mohajeri et al.
(2010) for the removal of colour and COD from Pulau
Burung stabilized landfill leachate whereby colour
and COD removal were 78% and 58%, respectively
(Mohajeri et al., 2010). Additionally, Gotvajn et al.
(2009) mentioned that the removal efficiency of NH
3
-
N by using Fenton oxidation was 40%.
According to Lopez et al. (2004), Fenton process
seemed to be the best compromise because it is
technically simple. In spite of simplicity of Fenton
process, it requires low pH and a modification of this
parameter is necessary. Further, high demand of
electrical energy and high oxidant doses are other
disadvantages of this method that makes the process
expensive (Bashir, 2011).
3.3.7. Ion exchange
Ion exchange process could be defined as reversible
interchange of ions among the liquid and solid phases
where no significant change in the structure of the
solid is observed. This treatment process is capable of
efficiently removing the traces of metal impurities to
meet the increasingly strict discharge standards in
developed countries. However, the application of ion
exchange is not generally used for the treatment of
landfill leachate, but it received great attention in
Germany for the removal of non-biodegradable
compounds that contained humic substances (Fettig,
1999).
Researchers explained that ion exchange resins are
generally and capably used for the removal of organic
compounds and ions from water and wastewater and
as a polishing step in landfill leachate treatment. Prior
to ion exchange process, leachate should initially be
subjected to biological treatment (Bashir et al., 2010;
Kurniawan et al., 2006). All soluble metallic elements
(anionic or cationic) could be efficiently removed or
reduced by using ion exchange technique. The resin is
prepared of synthetic organic polymers or natural
zeolite. Ions such as H
+
, OH
-
, Na
+
, and Cl
-
are joined
to the resin by weak electrostatic forces. These ions
are exchanged with ions in the contaminated product
that have more similarity for the resin. Resins could
be prepared to pick particular ions. The application of
ion exchange is economically limited due to high
operational cost. Another limitation is the requirement
of suitable pre-treatment system such as the removal
of suspended solids from landfill leachate. However,
ion exchange process is proper for heavy metal
removal from leachate (Kurniawan et al., 2006).
3.3.8. Electrochemical oxidation
Recently, electrochemical oxidation process has
received important consideration for wastewater
treatment because of its efficient and simple
operation. This treatment process has the ability to
destroy refractory pollutants. In this process,
refractory pollutants could be destroyed by direct
anodic oxidation, electro-chemically, or by indirect
oxidation (Atmaca, 2009; Deng and Englehrdt, 2007,
Chiang et al., 1995). Several types of electrodes have
been examined for electrochemical treatment such as
Ti, TiO
2
, PbO
2
/Ti, SnO
2
/Ti, Fe, aluminum, iron, and
graphite (Atmaca, 2009; Irdemez et al., 2006; Shen et
al., 2006; Chiang et al., 1995).
Atmaca (2009) used cast iron plates for both
anodes and cathodes with surface area of 22.6 cm
2
. At
operational conditions of 20 min treatment duration,
constant DC current of 3A, H
2
O
2
concentration of
2000 mg/L, and at initial pH 3, removal efficiencies of
colour and COD were 90% and 72 %, respectively.
Electrochemical oxidation process was used for the
treatment of Pulau Burung semi-aerobic landfill
leachate, Malaysia. Sodium sulphate Na
2
SO
4
(as
electrolyte) and carbon electrodes were used in the
treatment process. At optimum operational conditions
(1414 mg/L influent COD, 79.8 m A/cm
2
current
density and 4 h reaction time), the removal
efficiencies of BOD
5,
COD, and colour were 69.8 %,
67.6 %, and 83.7 %, respectively. Further, graphite
carbon electrode showed better performance in the
removal of BOD
5
, COD and colour (Bashir, 2007).
The disadvantages of this method are: 1) It is more
expensive than other treatment processes because of
high energy consumption, 2) It is less widely used for
the treatment of stabilized leachate, 3) High current
density could increase corrosion rate of electrodes,
and 4) It is inefficient for the removal of inorganic
substances and NH
3
-N.
Aziz et al.
Municipal Landfill Leachate Treatment Techniques: An Overview
219
3.3.9. Membrane filtration
A membrane could be defined as a material that
creates a thin barrier capable of selectively resisting
the move of different constituents of a fluid and
therefore affecting separation of the constituents
(Visvanathan et al., 2000). Usually, a thin layer of
material with a high surface porosity and a narrow
domain of pore size affect the physical structure of the
membrane. Different membrane filtration techniques:
microfiltration, ultrafiltration, nanofiltration, and
reverse osmosis are used in landfill leachate treatment.
i) Microfiltration
Microfiltration with pore sizes of 0.05 to 10 microns
is employed to capture microbial cells, small particles,
and large colloidal. According to landfill leachate
treatment, this method is not suitable to be used alone.
It is recommended to be used as pretreatment process
with other membrane processes (i.e. ultrafiltration,
nanofiltration or reverse osmosis) or in combination
with chemical treatment processes so as to remove
suspended matters and colloids. Piatkiewicz et al.
(2001) used this method as pre-filtration stage and
obtained COD removal of 25% to 35 %.
ii) Ultrafiltration
Ultrafiltration is a selective process utilizing pressures
up to 10 bar. This technique is efficient to remove
suspended matters either by direct filtration or with
biological treatment to replace sedimentation unit. It is
strongly dependant on the kind of material
constituting the membrane. Syzdek and Ahlert (1984)
proposed that this process might prove to be useful as
a pre-treatment method for reverse osmosis. It could
be employed to eliminate the larger molecular weight
components of leachate that tend to foul reverse
osmosis membranes (Bohdziewicz et al., 2001;
Rautenbach et al., 1996). COD removal of 50% was
obtained by using ultrafiltration alone (Bohdziewicz et
al., 2001)
Lastly, Tabet et al. (2002) reported that
ultrafiltration membranes have been successfully
employed in full scale membrane bioreactor plants by
combination of bioreactors and membrane technology.
High levels for landfill leachate treatment have been
obtained by using this method.
iii) Nanofiltration
Because of its unique properties between
ultrafiltration and reverse osmosis membranes,
nanofiltration has discovered a place in the
elimination of refractory organic compounds and
heavy metals from landfill leachate (Ozturk et al.,
2003). Removals of COD and NH
3
-N from landfill
leachate by using this process were 60 % to 70 % and
50 %, respectively (Trebouet et al., 2001; Linde and
Jonsson, 1995). In another research conducted by
Trebouet et al. (2001), nanofiltration was employed in
combination with physical processes which offered
acceptable COD removal (70% to 80 %) from landfill
leachate. Based on the results achieved by Linde and
Jonsson (1995), removal efficiencies of sulphate salts,
chloride, and other (Pb
2+
, Zn
2+
, and Cd
2+
) from landfill
leachate were 88-96%, 12-47 %, and > 88 %,
respectively.
On the other hand, successful use of membrane
technique needs effective control of membrane
fouling. An extensive spectrum of components could
contribute to membrane fouling in leachate
nanofiltration which includes inorganic substances,
dissolved organic, suspended particles, and colloidals
(Trebouet et al., 2001).
iv) Reverse osmosis
Membrane techniques, specifically reverse osmosis, is
a relatively new method that seems to be a more
efficient alternative than traditional methods for
mature landfill leachate treatment. This method
involves separating two solutions with various
concentrations by using a semi-permeable membrane
(Kurniawan et al., 2006; Ahn et al., 2002; Chianese et
al., 1999).
Ahn et al. (2002) stated that a landfill leachate
treatment plant in Korea was retrofitted to improve
treatment efficiency by employing integrated
membrane technique that was composed of membrane
bioreactor and reverse osmosis method. The removal
efficiencies of COD and NH
3
-N from young landfill
leachate were 96 % and 97 %, respectively. Other
researchers stated that the removal of COD and NH
3
-
N from landfill leachate was 98% (Linde et al., 1995).
Although, reverse osmosis technique was reported
as the most efficient in the removal of COD among
various physical-chemical technologies assessed
(Peters 1998), some disadvantages have been noticed
for membrane techniques. They include membrane
clogging which reduces the overall process
performance by lowering the reject concentration
while the cleaning of such membranes also reduces
their lifetime. Additionally, the production of large
quantitities of residuals which are generally useless
and required to be discharged or need further
treatment (Li et al., 2009; Wiszniowski et al., 2006).
Wastewater Engineering: Advanced Wastewater Treatment Systems
Chapter 8: Landfill Leachate Treatment Techniques
220
4. CONCLUSIONS
Design of landfill, age of landfill leachate, climate etc.
have great effect on leachate treatment. In this work,
detailed review on various treatment techniques were
explained. Results revealed that combined treatment
with domestic sewage, recycling, and biological
systems are efficient for processing young landfill
leachate. Commonly, physical-chemical treatment
methods are competent for treating medium and
old/stabilized leachates. Further, augmenting physical
and chemical methods or biological and physical-
chemical processes enhanced treatment of stabilized
leachate.
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225
Wastewater Engineering: Advanced Wastewater
Treatment Systems
Chapter 9: Application of Optimization in Treatment
Wastewater Engineering: Advanced Wastewater Treatment Systems
Available online at http://www.ijsrpub.com/books
2014 IJ SRPUB
226
Application of Optimization in Wastewater Treatment
Yee Ling Lim, Yeek Chia Ho, Abbas F. M. Alkarkhi*
School of Industrial Technology, Universiti Sains Malaysia, 11800 Penang, Malaysia
*Corresponding Author: abbas@usm.my
Abstract. Design and analysis of experiments (DOE) helps researchers achieves the research objective with less effort, cost
and time. In wastewater treatment process, DOE is used to study the effect of input variables such as flow rate/speed,
temperature, chemical dosing and retention time on the output and then optimize the process by finding the best operating
conditions for the input variables that meet the objective for the output variables and summarize the results in terms of model
to describe the behavior of the process. First-order and second-order models are usually used to describe the behavior of most
cases.
Keywords: Optimization, Wastewater Treatment,
1. INTRODUCTION
Design and analysis of experiments (DOE) have been
widely used in planning, analyzing and running
experiments in different areas of research, such as
wastewater treatment, food analysis, material
production and medication intake helping the
researchers to achieve the research objective with less
effort, cost and time. The application of DOE in
wastewater industries has increased since the
application of experimental design and analysis of
experiments enables us to collect data effectively and
reduce the error by excluding non-significant factor/s
in the experiment and effectively improves the results
to the target range. Three basic principles should be
considered in using experimental design, namely,
replication, randomization and blocking. Replication
allows experimenter to get an estimation of
experimental error and to increase the precision.
Randomization is the allocation of the experimental
materials and the order that the individual runs or
trials of experiment are to be carried out in random
manner. Furthermore, randomization eliminates bias
and to make sure independence among the
observations. Blocking technique is used to enhance
the accuracy by reducing or eliminates variability that
may affect the response (output) such as the difference
in skills of two or more operators and weather
conditions (rainy, cloudy, sunny) (Montgomery, 2012).
Researchers should provide clear objective of the
project before using experimental design, for instance
number of input variables and levels of each variable
(the region of each selected variable). As an example,
an outcome of an experiment includes the
identification of which factors contribute to overall
wastewater treatment process, for instance the factors
involved may include chemical dosing and total
retention time, while their levels may be 100g/L or
500g/L of chemical dosing and 3 days or 7 days for
the total retention time.
Experimental design is frequently used in industry
to optimize different experiments in order to find the
best operating conditions that produce desirable
product. Moreover, the application of DOE enables a
wastewater treatment system to optimize the
effectiveness of the process in removing the impurities,
particularly to fulfill the government regulation on the
effluent water. Optimization enables processes to
achieve highest possible removal rate within the given
range of factors at the lowest cost possible. For
instance, in a conventional treatment plant, the input
factors are flow rate/speed, temperature, chemical
dosing and retention time and the response (output) is
often more than one responses such as biochemical
oxygen demand (BOD), chemical oxygen demand
(COD), pH, concentration of cadmium, concentration
of lead and others. Thus, it is not quite possible to run
and plan a proper design for the experiment for good
yield without finding the best operating conditions
which results in highest removal.
2. APPLICATION OF DOE IN WASTEWATER
RESEARCH
The applications of design and analysis of
experiments in wastewater researches can be listed
down as follows:
(a) Production of adsorbent for wastewater, factors
involved may include heating temperature, heating
time and chemical composition while the response
may include removal of heavy metal, color removal or
even COD removal.
(b) For the cultivation of bacteria for the usage in
treatment plant on the other hand may include dosage
of carbon supply, shaking speed and incubation
temperature while the response is the growth of
bacteria.
(c) Conventional batch study involves parameters
of shaking speed, temperature, chemical dosage and
pH while the response will be the removal of the
target compound.
Lim et al.
Application of Optimization in Wastewater Treatment
227
(d) Study of flocculating activity involving
different physico-chemical parameters such as pH,
concentration of polymer, and mixing speed.
3. FACTORIAL DESIGN
Factorial designs are designs consist of several factors
(input variables) that influence one or more responses.
The advantage of factorial designs is to study the
effect of several factors and the interaction between
different factors simultaneously whilst the
disadvantage appears when the number of factors
included in the study increases which result in
increasing of the number of experiments. General
factorial design studies experiments with more than
one factor; each has at least two levels while special
cases of factorial designs are two-level factorial
design 2
k
and three-level factorial design 3
k
.
3.1. Two-level Factorial Design
Two-level factorial design with k factors (2
k
) is more
commonly used for screening purposes in order to
identify insignificant factors and to prepare for
optimization step (Ryan, 2007). Researchers usually
collect experimental data by running only a fraction of
the factorial design which is known as fractional
factorial design (Srinivasan and Viraraghavan, 2010).
The two levels are represented by (-1) to indicate that
the factor is at low level and (+1) to represents the
high level. Two-level factorial design is used to fit
first-order polynomial model.
The levels of each factor in the actual form are
known as natural variable. The levels can be
converted into -1 and 1 by using Eq. 1, this formula is
called coded form. The relationship between the
natural variable
i
and the coded variables
i
X is
given in Eq.1.
2 / ) (
2 / ) (
level Low level High
level Low level High
x
i
i
+
=
(1)
The benefit of using fractional factorial design is to
reduce the number of runs (experiments) as long as
the purpose of the experiment is to choose influential
factors, for instance, assume that 5 factors involved in
a process (2
5
), the total number of runs is 32
experimental runs for each replicate to cover all
possible combinations whilst fraction factorial design
of 2
k-1
(half factorial design) will use only 16 runs
which means less effort, time and cost to identify the
influential factors.
Example 3.1
Suppose a 2
5-1
two-level fractional factorial designs
with 16 runs were used to study the effects of
concentration of phenolic compounds, adsorbent
dosage, contact time, temperature and shaking speed
on phenolic compound removal (y) in wastewater.
The levels of each factor in coded and actual forms
are given in Table 1. The data for this experiment in
actual levels are given in Table 2.
Table 1: The factors and levels used for screening experiment
Factor Symbol Levels
Actual Coded
Concentration of phenolic compound (mg/L) x
1
20 40 -1 1
Adsorbent dosage (g/100ml) x
2
0.10 0.30 -1 1
Contact time (hours) x
3
120 300 -1 1
Temperature (
o
C) x
4
50 80 -1 1
Shaking speed (rpm) x
5
300 400 -1 1
Wastewater Engineering: Advanced Wastewater Treatment Systems
Chapter 9: Application of Optimization in Treatment
228
Table 2: The results of two-level fractional factorial design
Concentration of
phenolic compound
(mg/L)
Adsorbent
dosage
(g/100ml)
Contact
time
(hours)
Temperature (
o
C)
Shaking speed
(rpm)
% Removal by
phenolic
compounds
20 0.1 2 50 400 30.29
40 0.1 2 50 300 8.16
20 0.3 2 50 300 67.70
40 0.3 2 50 400 46.36
20 0.1 5 50 300 35.04
40 0.1 5 50 400 10.16
20 0.3 5 50 400 66.45
40 0.3 5 50 300 52.08
20 0.1 2 80 300 29.69
40 0.1 2 80 400 11.11
20 0.3 2 80 400 58.52
40 0.3 2 80 300 30.06
20 0.1 5 80 400 33.40
40 0.1 5 80 300 7.17
20 0.3 5 80 300 57.82
40 0.3 5 80 400 39.83
This experiment represents one-half fractional
factorial design with 16-runs, since the number of runs
is 16 which is not enough to provide degrees of
freedom to the error term in the analysis of variance
(ANOVA). Thus, in order to analyze this experiment
we will use normal probability plot or half normal
probability plot. Minitab statistical software (version
16) was used to analyze the data obtained from this
experiment. The analysis in the form of normal
probability plot is shown in Fig. 1. It can be seen that
shaking speed and contact time did not exhibit a
significant effect on the percentage removal of
phenolic compound. Only three factors showed
significant effect, namely concentration of phenolic
compound, adsorbent dosage and temperature.
Fig. 1: Normal probability plot of effects
An ANOVA table can be built after excluding non-
significant terms and analyze the result with only
three factors, concentration of phenolic compounds,
adsorbent dosage and temperature as a 2
3
design with
two replicates. Table 3 shows the results of ANOVA
for phenolic compound removal.
Lim et al.
Application of Optimization in Wastewater Treatment
229
Table 3: ANOVA table for phenolic compound removal
Source of variation DF Sum of square Mean sum of square F-value P-value
Main effects 3 6065.58 2021.86 173.85 0.000
2-Way interaction 3 131.83 43.94 3.78 0.059
3-Way interaction 1 10.47 10.47 0.90 0.371
Residual error 8 93.04 11.63
Pure error 8 93.04 11.63
Total 15 6300.92
It can be seen that three-factor interaction and two-
factor interaction were insignificant whilst the main
effect for selected factors was significant. Two-factor
interaction will be included in the model since this
interaction is significant at p<0.07.
The results are summarized in a regression model
to describe the behavior of the process. Regression
model for this experiment in coded units is given in
Eq. 2.
4 2 1 4 2
4 1 2 1 4 2 1
81 . 0 2.76 -
53 . 0 60 . 0 3.04 - 86 . 15 87 . 10 49 . 36
x x x x x
x x x x x x x y
+ + =
(2)
3.2. 3
k
Factorial Design
Three-level factorial design (3
k
) is a special case of
factorial design where all factors included in the study
have three levels. This design is used for fitting
second-order polynomial model to the experimental
runs. The levels in 3
k
design are denoted as low,
intermediate and high with the assumption of 0 for
low, 1 for intermediate and 2 for high, given that k
represents the number of factors included in the study.
If the factors are quantitative, we may denote the low,
intermediate and high level as 1, 0 and +1 respectively
to facilitate the calculation.
4. RESPONSE SURFACE METHODOLOGY
(RSM)
Response Surface Methodology is very well known by
RSM which consists mathematical and statistical
techniques that are useful for modeling and analysis of
problems in which the objective is to optimize the
response or responses by finding the best operating
conditions of the input variables (independent
variables) that influence the response
(Prakobvaitayakit and Nimmannit, 2003; Montgomery,
2012).
The objective of RSM is to guide the researcher to
find the levels of independent variables that optimize
the response which means maximize, minimize or
keep in a range. RSM is widely used in water and
wastewater treatment to evaluate the effect of several
independent variables and their interactions such as
speed, flow rate and chemical dosage on a response or
responses such as COD, BOD, colour, turbidity etc.
Special designs are used to carry out experiment in
RSM. These designs are capable to fit second-order
and second-order models for instance central
composite design (CCD) with Box-Behnken design
(BBD) and three-level factorial design.
4.1. Steps in RSM
The main purpose of using RSM is to optimize a
process. This purpose can be achieved by using the
following steps:
(1) Choosing the right design that serves your
objective. All information regarding the experiment
should be available to help in choosing the design by
involving all people who work in the project.
(2) Run the experiment and analyze the data
obtained then summarize the data in a model form
usually first-order or second-order model.
(3) Validate the model obtained by checking its
precision in predicting the response and whether this
model can be used for finding the optimum conditions.
(Montgomery, 2012)
To optimize the response, it is necessary to
approximate the functional relationship between the
independent variables and the response surface. For
example, suppose an engineer would like to know the
best condition for the highest removal (yield, y) of
heavy metal from its wastewater, given the
independent influencing factors are temperature (x
1
)
and heavy metal concentration (x
2
) in wastewater.
The yield for this process can be represented by the
following function:
Removal of heavy metal = f(temperature, heavy
metal concentration)
Wastewater Engineering: Advanced Wastewater Treatment Systems
Chapter 9: Application of Optimization in Treatment
230
5. OPTIMIZATION
Optimization is a procedure to select the best target
output from a process. This selection is made from a
series of experiments testing from a range of values
and the combination of each all factors. Optimization
may be a maximizing, minimizing and to keep the
target within range depending on the objective.
5.1. Concept of optimization
Concept of optimization is to select a combination of
the levels of factors which will result in a product with
desirable properties. This means solving problems
involving the optimization of several responses
(output), which depends upon a number of factors or
sets of parameters (input). Each desirable output
requires a special setting of input factors. For instance,
in an experimental study to maximize dye adsorption
capacity of an adsorbent made from coconut husk, the
two responses involved are decoloration and COD
removal of the dye wastewater. It can be achieved by
having higher temperature and retention time and at
the same time, reducing the rotation speed and
concentration of dye. In this optimization process, an
attempt was made to fulfill the requirement of the
wastewater treatment plant discharge (maximize the
dye adsorption capacity to reduce the discharge of dye
concentration in wastewater) while at the same time
reduces the material used (chemical dosage), obtain an
energy saving condition and reduces the duration of
the runs and most importantly to save cost. .
5.2. Desirability approach for Multiple Response
As we have mentioned before, optimization of a
process begins with selecting a proper design which
suit the process and then build a response surface
model for the response/s. The process of choosing a
set of operating conditions that is able to meet the
properties of each response is a challenge task;
however, it is possible in most cases to optimize all
responses by finding a combination of the levels of
input variables that meet the criteria of each response.
In such case, desirability approach is employed to
optimize the multiple responses process. This method
enables the process to obtain the most desirable
response/s by finding the suitable sets of operating
conditions, which means finding the most suitable
combination of the input variable (parameters). Given
that the process has a number of factors, all of these
selected factors must be in the desirable range.
A desirability function D(y) derives from the
process responses range from 0 to 1 and d(y) = 0
means the solution cannot be obtained and the
properties for one or more responses should be
changed while d(y) = 1 means the solution is possible
and is located in the desire region (Derringer and
Suich, 1980). This equation was modified by
Harrington, 1965 (Harrington, 1965). Desirability
function of each factor can be written in the form of
geometric mean as given in (3).
D = [(d
1
y
1
) (d
2
y
2
) (d
3
y
3
) (d
k
y
k
)]
1/k
(3)
with k representing the number of responses.
Upon the need of the output, the response of the
yield, y can be either maximize, minimize or at a
selected target value. Assume that L, U and T
represent the lower, upper and target value,
respectively, for the desired response y. Desirability
function for optimizing a process to the target yield is
given in (4).
>
>
=
U y if
U y T if
U T
y U
T y L if
L T
L y
L y if
y D
n
m
0
] [
] [
0
) (
(4)
Whereas, for a process response that requires a maximum yield, then the desirability function would be;
>
<
=
T y if
T y L if
L T
L y
L y if
y D
m
1
] [
0
) ( (5)
Lim et al.
Application of Optimization in Wastewater Treatment
231
Lastly, for a process response that requires a minimum yield, then the desirability function would be:
>
<
=
U y if
U y T if
U T
U y
T y if
y D
n
0
] [
1
) ( (6)
with notation m and n vital in determining the
relationship of the target value and yield, respectively.
If m=n=1, then the desirability function is linear
towards the target value. However, if m<1 and n<1,
the function would be convex and if m>1 and n>1,
the function would be concave.
6. DESIGNS USED FOR OPTIMIZATION
Selecting a suitable experimental design will greatly
help in describing the real behaviour of the process
over the region of interest. Some important properties
should be provided by the design such as rotatability
which means the predicted response is a function of
distance and not a function of direction and uniform
precision. As the location of optimum solution is
unknown before running the experiment, rotatability
provides equal precision of estimation in all directions.
Designs that have these properties are CCD and BBD
while three-level factorial design is not rotatable.
CCD and BBD design required a small number of
runs to fit a response surface model to the data
compared with full factorial designs such as three-
level factorial design and higher order. The model
obtained will be either first-order or second-order
polynomial model that fits the data. The model should
be checked for normality assumption, and model
adequacy.
6.1. Model
The most commonly response surface models used to
fit the data are first-order and second-order
polynomial models.
6.1.1. First order model
In most experimental condition, the relationship
between the response or the yield and independent
factors are unknown. In order to obtain a suitable
approximation for the relationship, a linear function or
lower order polynomial is engaged. This function is
known as a first-order model. The first order model
with k variables is given in (7).
i
k
i
i o x y
1 =
+ = | |
(7)
where,
i
| | and ,
0
are regression coefficients, and
i
x are the coded variables.
Two-level factorial (2
k
) is usually used since the
number of runs is smaller than other designs and
allows the assessment of linear effects of the factors
and interactions.
6.2.2. Second order model
Second-order model is used if there is a curvature in
the first order model which means that the first-order
model is insufficient, then a higher degree of
polynomial should be used to describe the real
relationship between the response and selected
independent variables. A second-order model is given
in (8).
2
0
1 1
k k
i i ii i ij i j
i i i j
y x x x x | | | |
= = <
= + + +
(8)
where, , , ,
0 ii i
| | | and
ij
| are regression
coefficients, and
i
x are the coded variables
(Montgomery, 2012).
It is important for the second-order model to
provide good prediction throughout the region of
interest. Hence, Box and Hunter (1957) suggested that
a second-order response surface design should be
rotatable. BBD and CCD are the most commonly used
designs to fit second-order model while three-level
factorial design is less use compared to other designs.
There is other second-order designs, which are not
frequently used, for instance, Hoke designs, Box
Draper saturated designs, uniform shell and hybrid
designs (Khuri and Mukhopadhyay, 2010).
6.2.2.1. Central Composite Design
CCD is a very efficient design for fitting a second-
order model. CCD is a rotatable design that provides
equal precision for fitted response at points (factor
level combinations) that are at equal distances from
the center of the factor space. CCD usually has axial
Wastewater Engineering: Advanced Wastewater Treatment Systems
Chapter 9: Application of Optimization in Treatment
232
or star points () outside the cube. The value of
depends on the number of variables in the design.
Furthermore, the choice of in the CCD is usually
based on the region of interest. CCD consists of three
components (i) a complete 2
k
factorial design with n
F
runs, (ii) 2k axial runs and (iii) n
0
center runs
(Montgomery, 2012). Therefore, the total number of
runs is equal to 2
k
+2k+n
0
. The response surface plots
can be employed to study the surfaces and locate the
optimum. An example for CCD with two factors in
coded form is given below:
x
1
x
2
-1 -1
Factorial
Points
1 -1
-1 1
1 1
-1.41421 0
Axial
Points
1.41421 0
0 -1.41421
0 1.41421
0 0
Centre
Points
0 0
0 0
0 0
0 0
It can be seen that there are three parts of CCD, (i)
factorial points n
F
= 4, (ii) axial (star) points = 4 and
(iii) four or five runs at the centre. In case of axial
point equals to 1 the CCD is called face centred
design (FCCD) (Montgomery, 2012).
Example 6.1
Suppose a chemist would like to extract vegetable
oil by using supercritical CO
2
from a sample prepared
without giving any pretreatment. Three factors are
thought to be influential factors, namely, pressure,
temperature and time. The levels of each factor in
actual and coded forms are given in Table 4. FCCD
was used to carry out the experiment. The data are
given in Table 5.
Table 4: Experimental conditions in actual and coded form
Factor Symbol Levels
Actual Coded
Pressure (MPa) x
1
27.58 48.26 -1 1
Temperature (C) x
2
40 80 -1 1
Time (min) x
3
45 70 -1 1
Lim et al.
Application of Optimization in Wastewater Treatment
233
Table 5: Face centred composite design in natural variables
Pressure (MPa) Temperature (C) Time
(min)
Percent yield
(%)
27.58 80 45 42.5
48.26 80 45 35.0
27.58 40 70 27.1
48.26 40 70 66.7
27.58 80 70 59.5
48.26 80 70 50.1
27.58 60 57.5 38.2
48.26 60 57.5 75.9
37.92 40 57.5 44.3
37.92 80 57.5 68.9
37.92 60 45 46.8
37.92 60 70 74.4
27.58 40 45 65.4
48.26 40 45 67.6
37.92 60 57.5 67.1
37.92 60 57.5 66.9
37.92 60 57.5 68.3
37.92 60 57.5 68.7
37.92 60 57.5 68.3
19 runs were required to cover all possible
combination of factor levels. Design Expert statistical
software (version 6) was used to analyze the data
obtained from this experiment. The results of
ANOVA are given in Table 6.
Table 6: ANOVA table for vegetable oil extraction
Source of variation Sum of squares Degree of Freedom
Mean
sum square F-value
P-value
Model 3911.79 9 434.64 13.25 <0.0003
Pressure 892.95 1 892.95 27.22 <0.0006
Temperature 50.90 1 50.90 1.55 <0.2444
Time 1200.73 1 1200.73 36.60 <0.0002
PressurePressure 663.93 1 663.93 20.24 <0.0015
TemperatureTemperature 296.65 1 296.65 9.04 <0.0148
TimeTime 10.30 1 10.30 0.31 <0.5888
PressureTemperature 13.42 1 13.42 0.41 <0.5383
PressureTime 785.76 1 785.76 23.95 <0.0009
TemperatureTime 119.00 1 119.00 3.63 <0.0892
Residual 119.00 1 32.80
Total 4207.03 18
The results of the ANOVA for vegetable oil
extraction showed that the main effects of pressure
and time of extraction are statistically significant.
Furthermore, the quadratic contribution for pressure
and temperature over the main effect was significant,
whilst time did not show a significant effect. In
addition, the interaction between pressure and time
was significant at P < 0.10.
A model that best describes the yield result was
built in order to optimize the process by finding the
optimal settings of pressure, temperature, and time so
as to maximize the yield for each response. A second-
order model for the yield of oil extracted from the
sample in terms of coded variables was obtained as
given in Eq. 9. Three-dimensional response surface
plot is given in Fig. 6 to illustrate the maximum yield.
Wastewater Engineering: Advanced Wastewater Treatment Systems
Chapter 9: Application of Optimization in Treatment
234
3 2 3 1 2 1
2
3
2
2
2
1 3 2 1
86 . 3 91 . 9 30 . 1
94 . 1 42 . 10 59 . 15 96 . 10 26 . 2 45 . 9 83 . 65
x x x x x x
x x x x x x Yield
+ +
+ + =
(9)
Fig. 2: Three-dimensional response surface diagram of percent yield as a function of pressure and temperature
It was found that the maximum yield in percent
can be achieved at 41.68 MPa, 74.54C and at
duration of 62.16 min may achieved 70.07% yield.
6.2.2.2. Box behnken design
The BBD is one of the most efficient designs used to
fit a second order model. It is a three-level design
based upon the combination of two-level factorial
designs and incomplete block designs. BBD is
rotatable or nearly rotatable and spherical design
(contains no embedded factorial or fractional factorial
design), in which the treatment combinations are at
the midpoints of the edges of the process space and at
the center. The advantage of the BBD is that it does
not contain combinations for which all factors are
simultaneously at their highest or lowest levels. Hence,
these designs are useful in avoiding experiments
performed under extreme conditions, in which
unsatisfactory results are often obtained. Furthermore,
BBD does not have axial points. Thus, all design
points fall within the safe operating zone. These
designs also ensure that all factors are never set at
their high levels, simultaneously (Ragonese, Macka et
al., 2002; Govender, 2005; Ferreira, 2007).
BBD is popular to be employed in industrial
research due to its economical design and requires
only three levels for each factor (-1, 0, 1). Typically,
BBD has the number of design arrangements of k is 3,
4, 5, 6, 7, 9, 10, 11, 12, and 16 factors (Khuri and
Mukhopadhyay, 2010).
An example for BBD with three factors will
consist of 3 sets of 2
2
factorial points, and 3 center
points or intermediate points. The total number of runs
is 15 as given below:
x
1
x
2
x
3
-1 -1 0
Factorial
Points
1 -1 0
-1 1 0
1 1 0
-1 0 -1
1 0 -1
-1 0 1
1 0 1
0 -1 -1
Lim et al.
Application of Optimization in Wastewater Treatment
235
0 1 -1
0 -1 1
0 1 1
0 0 0
Center Point/
Intermediate
0 0 0
0 0 0
Example 6.2
A biopolymer clarifies turbid water added during
coagulation-flocculation process. The performance of
clarifying water is examined by using the turbidity
reduction as response. The experimental ranges for all
independent variables were based on the preliminary
trials as depicted in Table 7.
Table 7: Experimental range for turbid water treatment
Factor Symbol Levels
Actual Coded
pH x
1
3 9 -1 1
Cation concentration (mM) x
2
0.1 1.0 -1 1
Biopolymer dosage (mg/L) x
3
10 50 -1 1
Seventeen runs were required to cover all possible
combination of factor levels. The experiments were
designed and analyzed using the Design Expert
statistical software (version 6). The experiment was
carried out randomly to minimize the effect of
unexpected variability in the observed responses. The
experiment runs are given in Table 8. The results of
the analysis are summarized in Table 9.
Table 8: Box-Behnken design in natural variables
pH Cation concentration
(mM)
Biopolymer dosage
(mg/L)
Turbidity reduction
(%)
3 0.10 30 55.5
9 0.10 30 91.1
3 1.00 30 99.7
9 1.00 30 98.8
3 0.55 10 97.0
9 0.55 10 98.4
3 0.55 50 68.7
9 0.55 50 99.7
6 0.10 10 99.0
6 1.00 10 99.8
6 0.10 50 76.2
6 1.00 50 99.7
6 0.55 30 99.6
6 0.55 30 99.7
6 0.55 30 99.0
6 0.55 30 99.3
6 0.55 30 99.4
Wastewater Engineering: Advanced Wastewater Treatment Systems
Chapter 9: Application of Optimization in Treatment
236
Table 9: The result of analysis of variance (ANOVA) for turbidity reduction
Source of variation
Sum of
squares
Degree
of
Freedom
Mean
sum
square F-value
P-value
Model 2685.11 9 298.35 21.25 <0.0003
pH 562.80 1 562.80 40.08 <0.0004
Cation concentration 725.81 1 725.81 51.69 <0.0002
Biopolymer dosage 311.25 1 311.25 22.17 <0.0022
pH pH 264.44 1 264.44 18.83 <0.0034
Cation concentration Cation
concentration 113.85 1 113.85 8.11 <0.0248
Biopolymer dosage
Biopolymer dosage 1.16 1 1.16 0.083 <0.7821
pH Cation concentration 333.06 1 333.06 23.72 <0.0018
pH Biopolymer dosage 219.04 1 219.04 15.60 <0.0055
Cation concentration
Biopolymer dosage 128.82 1 128.82 9.18 <0.0191
Residual 98.28 7
Total 2783.39 16
As can be seen, the analysis of variance revealed
that a second-order model adequately fitted the
experimental data. As shown in Table 6.6, the linear
effects of pH, cation concentration and biopolymer
dosage were significant. The contribution of quadratic
effect over the linear effect for pH and cation
concentration was significant, whilst the quadratic
contribution of biopolymer dosage was insignificant.
On the other hand, the interaction between pH and
cation concentration, pH and cation concentration,
cation concentration and biopolymer dosage was
significant at P<0.10. A second-order models that
describe the behavior of turbidity reduction are built
in order to optimize the process by finding the best
settings of pH, cation concentration and biopolymer
dosage that maximize turbidity reduction. The second-
order model for turbidity reduction in terms of coded
variable are given in Eq. 10,
3 2 3 1 2 1
2
3
2
2
2
1 3 2 1
68 . 5 40 . 7 13 . 9 - 52 . 0
20 . 5 - 93 . 7 - 24 . 6 - 53 . 9 39 . 8 40 . 99
x x x x x x x
x x x x x reduction Turbidity
+ +
+ + =
(10)
Lastly, to better present the optimization setting,
three dimensional response surface plot is given in Fig.
3 to have a clear picture on the maximum turbidity
reduction.
Fig. 3: Three-dimensional response surface for turbidity reduction as a function of pH and concentration of cation
Optimization process showed that maximum
turbidity reduction can be achieved at 99% in the
region of pH around 7.45, cation concentration at 0.67
mM and biopolymer dosage at 13.53 mg/L.
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