Journal of Environmental Management 132 (2014) 237e249

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Journal of Environmental Management

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Treatment and decolorization of biologically treated Palm Oil Mill

Effluent (POME) using banana peel as novel biosorbent
Rafie Rushdy Mohammed a, b, *, Mei Fong Chong a
a
Department of Chemical and Environmental Engineering, Faculty of Engineering, University of Nottingham Malaysia campus, 43500 Semenyih, Selangor,
Malaysia
b
Department of Chemical Industries, Mosul Technical Institute, Al-Majmoa’a Al-Thaqafiya, Mosul, Iraq

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

Article history: Palm Oil Mill Effluent (POME) treatment has always been a topic of research in Malaysia. This effluent
Received 27 June 2013 that is extremely rich in organic content needs to be properly treated to minimize environmental hazards
Received in revised form before it is released into watercourses. The main aim of this work is to evaluate the potential of applying
11 November 2013
natural, chemically and thermally modified banana peel as sorbent for the treatment of biologically
Accepted 18 November 2013
Available online
treated POME. Characteristics of these sorbents were analyzed with BET surface area and SEM. Batch
adsorption studies were carried out to remove color, total suspended solids (TSS), chemical oxygen
demand (COD), tannin and lignin, and biological oxygen demand (BOD) onto natural banana peel (NBP),
Keywords:
Palm Oil Mill Effluent
methylated banana peel (MBP), and banana peel activated carbon (BPAC) respectively. The variables of
Adsorption pH, adsorbent dosage, and contact time were investigated in this study. Maximum percentage removal of
Biosorbent color, TSS, COD, BOD, and tannin and lignin (95.96%, 100%, 100%, 97.41%, and 76.74% respectively) on BPAC
Banana peel were obtained at optimized pH of 2, contact time of 30 h and adsorbent dosage of 30 g/100 ml. The
isotherm data were well described by the RedlichePeterson isotherm model with correlation coefficient
of more than 0.99. Kinetic of adsorption was examined by Langergren pseudo first order, pseudo second
order, and second order. The pseudo second order was identified to be the governing mechanism with
high correlation coefficient of more than 0.99.
Ó 2013 Elsevier Ltd. All rights reserved.

1. Introduction (Azhari et al., 2010). POME is a highly polluting wastewater that

Malaysia currently accounts for 39% of world palm oil produc-
tion and 44% of world exports. The oil palm planted area in 2011
reached 5.00 million hectares, an increase of 3.0% against 4.85
million hectares recorded in the previous year. Crude palm oil
(CPO) production in 2011 increased by 11.3% to reach a record of
18.91 million tons (MPOC, 2013), which produced 30 million tons of
Palm Oil Mill Effluent (POME) (Tengku et al., 2012). Palm oil pro-
cessing is carried out in palm oil mills, where oil is extracted from a
palm oil fruit bunch, and about 50% of the waste that results is
POME. Despite high economical returns to the country, the industry
also generates large amounts of waste in the form of empty fruit
bunch (EFB) (23%), mesocarp fiber (12%), shell (5%), and POME
(60%) for every ton of fresh fruit bunch (FFB) processed in the mills
* Corresponding author. Department of Chemical Industries, Mosul Technical
Institute, Al-Majmoa’a Al-Thaqafiya, Mosul, Iraq. Tel.: þ964 7701622984.
E-mail addresses: rafie59.che@gmail.com, rafaa59@yahoo.com (R.
R. Mohammed).
pollutes the environment if discharged directly into rivers due to its
high chemical oxygen demand (COD), biochemical oxygen demand
(BOD), phenol, and color concentrations. It is worth mentioning
that no chemical is added during palm oil mill processing (Zahrim
et al., 2009).
Thus, the treatment of POME has gained interest from many
researchers due to the abundant amount generated in the mills,
and this treatment is an important issue for the minimization of
water pollution. The high organic content, mainly oil and fatty
acids, enables POME to support bacterial growth that reduces its
polluting strength. Anaerobic process is the most suitable approach
for its treatment (Azhari et al., 2010). Many technologies have been
studied and applied for treating raw POME and biologically treated
POME such as biological digestion (Chotwattanasak and
Puetpaiboon, 2011), membrane technology (Ahmad et al., 2006),
coagulation and flocculation (Saifuddin and Dinara, 2011),
adsorption (Igwe et al., 2010b), tertiary treatment (Shakila, 2008),
and Fenton oxidation (Ooi, 2006) systems. A good review of
treating POME is presented by Yeong et al. (2010). Every treatment
has its own advantages and disadvantages. Membrane technology

0301-4797/$ e see front matter Ó 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.jenvman.2013.11.031
238 R.R. Mohammed, M.F. Chong / Journal of Environmental Management 132 (2014) 237e249
has the highest removal efficiency in COD but the treatment is very
costly. As for carbon based adsorption, despite of its prolific use,
granular activated carbon (GAC) is considered an expensive mate-
rial. While many studies have been conducted about the use of
activated carbon in treating various types of contaminants, there
has been limited reporting of its application in treating POME. Also,
there is little information in the field about using biosorbents or
activated carbon made from waste materials to treat POME. This
study intends to fill the existing knowledge gaps.
POME retains its color even after biological treatment, both
aerobic and anaerobic. The color of the effluent is due to plant
constituents such as lignin and phenolic compounds as well as re-
polymerization of coloring compounds after anaerobic treatment
(Chanida and Poonsuk, 2011). The removal of color from effluents is
one of the major environmental problems. In this concern,
adsorption process has been found to be a more effective method
for the treatment of dye containing wastewater. The most efficient
and commonly used adsorbent is commercially available activated
carbon which is expensive and has regeneration problems. Recent
investigations focused on effectiveness of low cost adsorbents like
pearl millet husk, neam leaf powder, coconut husk, wheat straw,
wood, peat, banana pith, and agricultural waste in the removal of
dyes from wastewater effluent (Verma and Mishra, 2010). However,
there is still scarcity of information in the literature on the use of
low cost adsorbents for decolorization of POME.
As one of the most consumed fruits in the world, banana is a
very common fruit. The main banana residue is the fruit peel, which
accounts for 30e40% of the total fruit weight. Preliminary in-
vestigations show that several tons of banana peels are produced
daily in marketplaces and household garbage, creating an envi-
ronmental nuisance and disposal problem. Various chemical
groups exist on the banana peel surface, including carboxyl, hy-
droxyl and amide groups, which have been extensively proven to
play a critical role in the biosorption processes (e.g. enhancing
biosorption capacity and shortening stable time) (Cong et al., 2012).
In this study, efficiencies of removal of color, TSS, tannin and
lignin, BOD, and COD from the final biologically treated POME were
investigated using 3 types of adsorbents: natural banana peel
(NBP), methylated banana peel (MBP), and banana peel activated
carbon (BPAC). The effects of various parameters such as agitation
time, pH, and adsorbent dosage were investigated in batch exper-
iments. Equilibrium isotherms were analyzed by using the Lang-
muir, Freundlich, Redlich, and Sips models. The adsorption kinetic
was determined by fitting with pseudo-first-order, pseudo second
order, and second order adsorption kinetic models. Determination
of the isotherm and kinetic concepts provided a sound basis for the
process of designing an adsorption unit for POME final polishing to
achieve optimal treatment results. Thus, banana peel can be used in
removing color from biologically treated POME as the final pol-
ishing step before discharge.
2. Materials and methods
2.1. Biologically treated POME
The effluent was collected in plastic containers from the final
pond effluent of a palm oil mill in Dengkil, Selangor, Malaysia. The
containers were properly washed and rinsed with the effluent
before collection to avoid contamination and dilution. Containers
were then brought back to laboratory and stored in refrigerator at
temperature of 4  C for tests and analysis. COD, pH, TSS, tannin and
lignin, BOD, and color units were determined. The characteristics of
the biological POME sample obtained are summarized in Table 1.
It has been observed that the biologically treated POME excee-
ded the standard discharge limit of Environmental Quality Act
Table 1
Properties of biologically treated POME.
Property Values Standard discharge limits Units
(Saifuddin and Dinara, 2011)
pH 8.4 5e9
Color 9900 e PtCo/l
TSS 1800 400 mg/l
COD 4700 mg/l
BOD5 1350 100 mg/l
Tannin and lignin 215 e mg/l
(EQA) 1974, Department of Environment (DOE), Malaysia
(Saifuddin and Dinara, 2011). The final treated effluent still con-
tained high concentrations of COD, color, BOD and TSS. On the other
hand, the pH indicated that the effluent was alkaline.
All chemicals used in this study were of analytical grade sup-
plied by Aldrich Chemicals. All solutions used in this study were
diluted with distilled water as required.
2.2. Collection and preparation of adsorbents
2.2.1. Natural banana peel (NBP)
Mature banana with yellow peel was collected as solid waste.
The collected material was then washed three times with tap water
and three times with distilled water to remove external dirt. The
washed material was cut into small pieces (1e2 cm) then dried in a
hot air oven (Memmert Universal oven Model UFE 600 - Germany)
at 80  C until it reached a constant weight, which was accom-
plished after 48 h. In the final stage, the material was grounded by
using Retsch Cutting Mill SM 100 (Germany) with mesh size 0.2,
and screened by using ELE international laboratory sieve shaker
(USA) with mesh size of 300e425 mm.
2.2.2. Methylated banana peel (MBP)
Modification of the carbonyl groups on the surface of the banana
peel (esterification) was achieved by using acidic methanol. 9 g
from the previously prepared NBP was suspended in 633 ml of
99.9% methanol to which 5.4 ml of concentrated hydrochloric acid
37% was added to give a final concentration of 0.1 M. Then the
solution was heated at 60  C and stirred continuously for 48 h by
using digital orbital shaker (Heidolph unimax 1010, Germany). The
solid material was then separated and washed three times with
deionized water at (20  C) in order to halt the esterification reac-
tion. The material was then dried in the oven at 100  C for a period
of 8 h (Jamil et al., 2008).
2.2.3. Banana peel activated carbon (BPAC)
The NBP was used for BPAC preparation. It was prepared by a
carbonized temperature of 500  C for 1 h under a nitrogen atmo-
sphere in a tubular furnace (Carbolite CTF 12/100/900, United
Kingdom) and then was left to cool to room temperature. The
carbonized material was then subjected to potassium hydroxide
(KOH) activation. The material was agitated by using (cermaic
stirring; IKA 3581000; Vernon Hills, IL, USA) in KOH (45% aqueous
solution) at a ratio of 1:4 carbonized material to KOH weight by
weight basis. After 12 h of agitation, the carbonized slurry was left
for 24 h at room temperature. The sample was then dried at 110  C
for another 24 h. The dried sample was then activated in nitrogen
atmosphere using (Carbolite CTF 12/100/900, United Kingdom)
with temperature maintained at 700  C for 1 h before cooling. After
cooling for 12 h, the activated carbon was washed 3 times with
0.2 N hydrochloric acid (HCl). The washing was completed with hot
water until the pH became neutral, and finally with cold water to
 R.R. Mohammed, M.F. Chong / Journal of Environmental Management 132 (2014) 237e249
remove the excess KOH compounds. The washed samples were
dried at 110  C for 8 h to get the final product (Mopoung, 2008).
2.3. Adsorption isotherm experiments
Adsorption isotherm experiments were carried out in 250 ml
conical flasks into which 15 g of adsorbent and 100 ml of biologi-
cally treated POME were added with different concentrations
respectively. The desired concentrations were achieved by diluting
the biologically treated POME with distilled water. The samples
were then shaken at 200 rpm for 40 h by using digital orbital shaker
(Heidolph unimax 1010, Germany). At the end of the adsorption
period, the solution was centrifuged for 5 min at 3000 rpm and
then the concentrations of the residual color, TSS, and COD were
determined.
The adsorption capacity of these parameters on the adsorbent
was calculated from the mass balance equation as follows
qe ¼ ðCo  Ce ÞV=M (1)
where qe is the amount of constituent adsorbed per unit mass of
adsorbent at equilibrium (mg/g), Co and Ce are the initial and
equilibrium liquid-phase concentrations of solution (mg/L)
respectively, V is the volume of effluent solution (L), and M is the
mass of adsorbent sample used (g).
2.4. Adsorption experiment
In each adsorption experiment, 100 ml of effluent solution was
added to different amounts of adsorbent (5, 10, 15, 20, 25 and 30 g)
respectively in closed flasks and the samples were stirred at
200 rpm in a rotary orbital shaker (Cermaic Stirring; IKA 3581000;
Vernon Hills, IL, USA) at room temperature for a period of time
ranging from 2 to 36 h. Shaking step was done after noting down
the initial pH of the solutions (2, 5, 7, 8.4, and 12). The initial pH of
each solution was adjusted to the required value by adding either
1 M HCl or 1 M sodium hydroxide (NaOH) solution. Samples were
withdrawn from each of the flasks at predetermined time intervals.
The adsorbents were separated from the solution by centrifugation
(Eppendorf 5430, Hamberg, Germany) at 3000 rpm for 5 min. Color,
TSS, COD, BOD, and tannin and lignin were measured to determine
the concentration of the residue.
The percentage of removal (%R) of each parameter and the
amounts adsorbed by the adsorbents were calculated by the
following equations:
%R ¼ fðCo  Ct Þ=Co g  100 (2)
qt ¼ ðCo  Ct ÞV=M (3)
Here, Ct is the concentration of the solution at any time (mg/L)
and qt is the amount adsorbed at any time for each parameter
investigated (mg/g).
Three repeatable experiments were tested and the average
values with their standard deviations were recorded and used for
discussion.
2.5. Analytical methods
COD measurement was carried by APHA Standard method 8000
using the colorimetric method. 2 ml of sample was added into COD
vial (HR 20e1500 mg/L) and digested for 2 h by using HACH
digester (DRB200, Loveland, CO). The COD concentration was then
measured with a HACH spectrophotometer (DR2800, Loveland,
CO). Total suspended solids were also measured by following the
239
APHA Standard method 8006 using HACH spectrophotometer (DR
2800, Loveland, CO) by placing 10 ml of sample in a specially
designed square quartz sample cell. The color analysis was carried
out by following platinum-cobalt standard method 8025 and the
color was detected at a wavelength of 455 nm using HACH spec-
trophotometer (DR 2800, Loveland, CO) by placing 10 ml of sample
in the same previous sample cell. Tyrosine method 8193 was used
with the aid of HACH spectrophotometer (DR 2800, Loveland, CO)
to measure the concentration of tannin and lignin in the sample.
After adding 0.5 ml of tannin-lignin reagent and 5.0 ml of sodium
carbonate solution to 25 ml of the sample, 10 ml of the mixture was
poured into square sample cell and the measured result was in mg/l
tannins. The BOD tests were carried out using standard procedure
APHA Standard method with a dissolved oxygen (DO) probe (YSI
model 5100, USA). Seeds and nutrient buffer pillows were added to
the samples (1.5e3.5 ml). Samples were diluted 15 times followed
by aeration to make sure enough dissolved oxygen will remain after
five days of incubation. 300 ml standard BOD bottles were used in
these tests which were incubated at 20  C in a dark incubator
(Memmert Model IN110 e Germany). After five days, the differ-
ences in oxygen consumption were measured by using a DO meter
(YSI model 5100, USA) to estimate BOD5. Solutions pH were
measured with a HACH sension1 pH meter using a combined glass
electrode. Finally, surface morphology and BET surface areas of NBP,
MBP and BPAC were studied using Quanta 400 Field Emission
Scanning Electron Microscope (FESEM), and N2 adsorption
isotherm by Nano Porosity System (Micrometrics ASAP 2020, USA)
respectively.
3. Results and discussion
In this study, the adsorption behavior of biologically treated
POME onto 3 different types of biosorbents, namely NBP, MBP and
BPAC prepared from banana peel was investigated. The BET surface
area of NBP was found to be 24.2572 m2/g. This BET surface area
was higher than that of chitosan flakes and pine bark (Ngah and
Fatinathan, 2006; Vázquez et al., 2007) but lower than that of
palm oil fruit shell (Hossain et al., 2012). On the other hand, the
surface area was low compared to chemically (MBP), (168.3648 m2/
g), and thermally (BPAC), (875.2914 m2/g), treated banana peel.
Nevertheless, it could be considered a good alternative as it was
produced from non-treated, low cost material using a simple pro-
cess. It is evident that specific surface area of banana peel bio-
sorbent is fully dependent on the preparation method.
In general, acidic methylation and alkali treatment of the NBP to
produce MBP and BPAC respectively could alter its lattice structure
effectively compared to the raw material. These treatments led to
remarkable increase in the specific area and the major change
achieved in the material’s structure promoted considerably its ca-
pacity for all contaminants removal compared to original untreated
peel.
3.1. Performance study
In the present study the adsorption performance is measured on
the basis of the percentage of removal for the parameters of color,
TSS, and COD from biologically treated POME as in Equation (2). The
influence of operating parameters in terms of biosorbent dosage,
contact time, and initial pH on the adsorption performance was
investigated for all types of biosorbents. Fig. 1 shows the effect of
adsorbent dosage at room temperature (25  C) by varying the
sorbent amounts from 5 to 30 g with varying contact times. Fig. 1
shows the effects of NBP, MBP and BPAC dosage on the percent-
age of removal of color, TSS, and COD. It is obvious that, regardless
of the type of biosorbent used, the percentage of removal increases
 240
R.R. Mohammed, M.F. Chong / Journal of Environmental Management 132 (2014) 237e249
Fig. 1. Effect of dosage on the percentage removal of (i) color, (ii) TSS, and (iii) COD for (a) NBP, (b) MBP and (c) BPAC respectively with varying contact time at pH 8.4.
 R.R. Mohammed, M.F. Chong / Journal of Environmental Management 132 (2014) 237e249 241

rapidly with increase in the amount of adsorbent due to greater

availability of surface area for adsorption. This leads to the intro-
duction of more binding sites for adsorption. A significant increase
in uptake was observed when the dosage was increased from 5 to
25 g/100 ml. Any further addition of adsorbent beyond this amount
did not cause significant change in adsorption performance. This
may be due to the overlapping of adsorption sites as a result of
overcrowding of adsorbent particles (Goud et al., 2005; Verma and
Mishra, 2008). For all types of biosorbents, maximum removal of all
studied contaminations was obtained at the adsorbent dosage of
30 g/100 ml.
It can be seen from Figs. 1 and 2 that by increasing the contact
time from 2 h to 36 h the removal percentage increases until
adsorption equilibrium is reached. It also illustrates that the
contaminant removal was rapid in the first 24 h during which
nearly 70e80% of the total uptake appeared to have been adsorbed
depending upon the adsorption ability of different biosorbents.
This can be attributed to the availability of sites for the sorbate. In
addition, a very high adsorption driving force at the beginning Fig. 3. Effect of pH on the percentage removal of color, TSS and COD on 30 g/100 ml
MBP adsorbent at 24 h.
resulted in a higher adsorption rate. After the initial period, slower
adsorption may be attributed to the slower diffusion of molecules
into the interior pores of the adsorbent (Shavandi et al., 2012), and Suspended and dissolved particles in water influence color.
the molecules subsequently occupy the positions within the Dissolved organic matter, such as humus, peat, or decaying plant
adsorbent framework. This observation is in support of the findings matter can produce a yellow or brown color. Concentrations of
reported by several authors (Goud et al., 2005; Shavandi et al., naturally dissolved organic acids such as tannins and lignins may
2012; Zahangir et al., 2009). also have an effect by giving water a tea color. Tannins that are
yellow to black are the most abundant kind found in POME and can
have a great influence on its color, as well as a musty smell. The
brown coloring comes from tannins leaching into runoff water from
the manufacturing process of palm oil (Clean Water team, 2013).
From the previous facts, it is obvious that color removal is strongly
dependent on the removal of total suspended solids and tannin and
lignin. This is revealed by Fig. 1(i), (ii), and 2(a). LAB Fit curve fitting
software V7.2.48 was used to establish a new correlation between
the adsorption capacities of color with TSS and tannin and lignin on
BPAC. This correlation is represented by:

Y ¼ 37:18ðX1 *X2 Þ0:0468 (4)

where Y, X1 and X2 are the adsorption capacity of color, TSS and

tannin and lignin respectively. The statistical data for the predicted
correlation are (Correlation Coefficient: R2 ¼ 0.9938680Eþ00,
ChiSq. ¼ 0.145292Eþ00, Red. ChiSq. ¼ 0.363231E-01 ¼> P(Red.
ChiSq.) ¼ 0.997 and Average absolute residual ¼ 0.138289Eþ00).
This correlation may offer a basis for the estimation of color
removal as a function of total suspended solids and tannin and
lignin removal from POME. This correlation is also indicates that
TSS and tannin and lignin contents of POME are responsible for its
color.
The effect of variation of pH on adsorption performance in terms
of color, TSS, and COD onto MBP at constant time of 24 h and
adsorbent dosage of 30 g/100 ml are shown in Fig. 3. As other
biosorbents of NBP and BPAC follow a similar trend as that in Fig. 3

Table 2
Comparison of biosorption capacity of color, TSS and COD on NBP, MBP and BPAC
adsorbent dose (5e30 g/100 ml), contact time (2e36 h) and pH (2e12).

Parameters (% removal) Biosorbent

NBP MBP BPAC

Min. Max. Min. Max. Min. Max.

Color 18.182 61.111 41.414 73.737 64.646 96.464

Fig. 2. Effect of contact time on the percentage removal of (a) tannin and lignin with
TSS 5.556 90.278 5.556 91.667 50.000 w100
varying dosage and (b) BOD with the dosage of 5 g/100 ml on BPAC with constant pH of
COD 70.213 99.468 80.850 w100 84.04 w100
8.4.
242 R.R. Mohammed, M.F. Chong / Journal of Environmental Management 132 (2014) 237e249
at different levels of intensity, the removal efficiency at minimum
and maximum percentages for various contaminants is tabulated in
Table 2. The maximum percentages of removal in Table 2 are for
30 g/100 ml adsorbent dose, 30 h contact time and pH 2. The
minimum values are for 5 g/100 ml, 2 h contact time and pH 12. A
deterioration of adsorption performance as pH increased was
observed for all types of biosorbent with the maximum percentage
of removal recorded at pH 2. The same trend for NBP was found in
another study where Khan et al. (2012) found that banana peel
Fig. 4. Adsorption isotherm of (a) color, (b) TSS, and (c) COD on NBP.
adsorbent was effective in the adsorption of Reactive Yellow 15
from aqueous solution and maximum adsorption occurred at pH 2.
The most possible explanation may be related to the presence of
excess Hþ ions accelerating the removal of the contaminants with
the anion OH- in the solution. It is also possible that the surface
properties of the adsorbent depend on the pH of the solution.
Higher uptakes obtained at lower pH may be due to the electro-
static attractions between negatively charged functional groups
located on the contaminants and positively charged adsorbent
surface. Hydrogen ion also acts as a bridging ligand between the
Fig. 5. Adsorption isotherm of (a) color, (b) TSS, and (c) COD on MBP.
 R.R. Mohammed, M.F. Chong / Journal of Environmental Management 132 (2014) 237e249
adsorbent wall and the contaminants molecules (Zawani et al.,
2009). Malik (2004) and Mohamed (2003) reported that at low
pH region the surface of the sorbent will be largely protonated. The
positive ions (Hþ) provide an electrostatic attraction between the
fiber’s surface and the contaminant’s molecules leading to
maximum adsorption. On the other hand, at pH above 2 (i.e., pH
range of 3e12) the degree of protonation of the surface of the fibers
will be less, which results in a decrease in diffusion and adsorption
due to electrostatic repulsion. Furthermore, lower adsorption of the
contaminants in alkaline medium can also be attributed to the
Fig. 6. Adsorption isotherm of (a) color, (b) TSS, and (c) COD on BPAC.
243
competition between excess hydroxide ions (OH) and the anionic
contaminant molecules for the adsorption sites (Khan et al., 2012).
In all, it is clear that NBP, MBP, and BPAC were capable of
reducing the concentrations of color, TSS, COD, BOD, and tannin and
lignin from biologically treated (POME). The adsorptive removal of
these contaminants could be explained based on the modes of
sorption of materials or contaminants on biosorbents.
The adsorptive removal of contaminants may be attributed to
two main terms; intrinsic adsorption and coulombic interaction.
The coulombic term results from the electrostatic energy of in-
teractions between the adsorbents and adsorbates. It can also be
observed in the adsorption of cationic species versus anionic spe-
cies on adsorbents. The intrinsic adsorption of the materials is
determined by their surface areas. Moreover, both factors can
interact, thereby influencing the adsorption capacity. It has been
reported that the surface area has a great effect on the sorption
capacities of adsorbents (Igwe et al., 2010a). Thus, increase in sur-
face area increases sorption capacity. The trend of this sorption
capacity can be put as COD > BOD > TSS > tannin and lignin > color
(Figs. 1 and 2 and Table 2). This trend can be explained based on
solubility and diffusion processes. COD and BOD are defined as the
amount of dissolved oxygen needed to break down the carbona-
ceous component of the waste (Igwe et al., 2010a). This means that
both COD and BOD involve dissolved components of the effluent.
Also, color is a consequence of dissolved components and TSS of the
effluent. Diffusion takes place before adsorption of the contami-
nants because dissolved contaminants diffuse faster than sus-
pended particles, hence they will be more adsorbed. Therefore, in
our opinion, this is the reason for the sorption trend observed. The
pH could be considered as resulting from the interactions of the
other parameters. That is, changes in pH of the effluent are
dependent on the changes in the hydrogen ion concentration which
in turn is dependent on the dissolved components of the effluent.
It was found that BPAC biosorbent exhibited the highest per-
formance in terms of color, TSS, COD, BOD, and tannin and lignin
removal efficiency followed by MBP and NBP. This may be attrib-
uted to the carbonization followed by chemical (KOH) activation of
the banana peel. Chemical activation of carbons is a very common
method for obtaining activated carbons with very high surface
areas. KOH is one of the most effective agents employed for organic
materials. KOH may be more selective in the activation process,
causing a more localized reaction with the carbon precursor and is
more effective for highly ordered materials (Mopoung, 2008). The
effectiveness of KOH activation relative to either physical activation
methods or activation by other chemical agents can be attributed to
the ability of potassium (K) to easily form intercalation compounds
with carbon. In addition, the potassium oxide (K2O) formed during
the process of KOH activation, in-situ, can easily infiltrate into the
pores. K2O is reduced to K by carbon resulting in carbon gasification
with a subsequent emission of carbon dioxide (CO2) leading to the
formation of pores. Also K atoms that intercalate into the lamella of
the carbon crystallites widen the space between the adjacent car-
bon layers (intercalation phenomenon), resulting in an increase in
the value of specific surface area (Yong et al., 2007). The carboxyl
groups on banana surface are responsible to some extent for the
binding of sorbate ions. This means that increasing the number of
carboxylate ligands in the biomass can enhance the sorbate binding
capacity. Some groups from cellulose, pectin, and hemicelluloses,
which are major constituents of banana peel, can be modified to
carboxylate ligands by treating the biomass with KOH, thereby
increasing the sorbate-binding ability of the biomass (Baig et al.,
1999).
In general, acidic methylation, alkali, and thermal treatment of
the NBP to produce MBP and BPAC respectively could alter their
lattice structure more effectively compared to the raw material.
244 R.R. Mohammed, M.F. Chong / Journal of Environmental Management 132 (2014) 237e249

Table 3
Adsorption isotherm parameters, correlation coefficient and relative average error for Langmuir, Freundlich, RedlichePeterson and Sips isotherm for adsorption of Color, TSS
and COD using NBP, MBP and BPAC.

Biosorbent NBP MBP BPAC

Parameter Color TSS COD Color TSS COD Color TSS COD

Langmuir isotherm
qm (mg/g) 49.751 28.409 67.563 87.719 47.17 147.059 135.135 62.893 200
b (L/mg) 3.559  104 1.983  103 9.113  104 3  104 1.206  103 3.717  104 1.675  103 3.721  103 1.91  103
R 2
98.84  102 91.19  102 96.71  102 98.04  102 89.72  102 87.43  102 99.7  102 98.3  102 92.6  102
Relative av. error 0.027004 0.087318 0.033989 0.132826 0.122038 0.039245 0.03911 0.055281 0.102418
RL 22.1  102 21.9  102 18,9  102 25  102 31.5  102 36.4  102 5.69  102 13  102 1  101
Freundlich isotherm
Kf 28.5  102 46.2  102 39.1  102 46.7  102 50.5  102 16.3  102 662.7  102 110.6  102 187.1  102
n 1.805 1.85 1.578 1.745 1.7 1.26 2.837 1.719 1.613
R2 0.9624 0.937 0.9939 0.9776 0.9908 0.9975 0.9532 0.9602 0.9935
Relative av. error 0.062819 0.088169 0.025039 0.048738 0.035662 0.022178 0.062763 0.074782 0.029085
RedlichePeterson Isotherm
KRP 1.408  102 39.27  102 12.16  102 2.555  102 133.5 987.6 26.70  102 19.94  102 85.74  102
aRP 1.500  105 53.42  102 6.312  102 1.899  105 286.6 6970 3.352  103 8.486  104 11.38  102
b 1.321 52.07  102 55.28  102 1.279 39.98  102 18.63  102 93.94  102 1.197 57.07  102
R2 0.9945 0.9750 0.9933 0.9950 0.9979 0.9980 0.9986 0.9994 0.9982
Relative av. error 0.017747 0.086435 0.022765 0.04144 0.034923 0.020235 0.036194 0.043963 0.023811
Sips Isotherm
KS 3.489  103 53.07  102 24.88  102 1.754  102 37.14  102 18.26  102 57.15  102 7.565  102 1.354
bS 1.234 52.01  102 73.11  102 1.081 64.67  102 76.67  102 84.31  102 1.251 71.65  102
aS 8.083  105 1.248  104 1.502  103 1.802  104 1.107  103 3.253  104 3.948  103 1.438  103 3.988  103
R2 0.9927 0.9449 0.9914 0.9939 0.9939 0.9981 0.9952 0.9969 0.9951
Relative av. error 0.020385 0.090476 0.023493 0.045303 0.03716 0.019674 0.038162 0.047905 0.025001

These treatments led to remarkable increase in the specific area,
and the major change achieved in the material’s structure consid-
erably promoted its capacity for all contaminants removal
compared to the original untreated peel.
3.2. Equilibrium isotherms
In this study equilibrium isotherm equations are used to
describe the experimental sorption data. The equation parameters
and the underlying thermodynamic assumptions of these equilib-
rium models often provide some insight into the sorption mecha-
nism and the surface properties as well as affinity of the sorbent.
The most common isotherms applied in solid/liquid systems are the
theoretical equilibrium isotherm, the Langmuir, which is the best
known and most often used isotherm for the sorption of a solute
from a liquid solution; the Freundlich, which is the earliest known
relationship describing the adsorption equation; the Redliche
Peterson and the Sips, which are the isotherms containing three
parameters. These equilibrium isotherm models were used to
analyze the adsorption behavior in this study. Table S1 supple-
mentary data shows a summary of the models used. The equilib-
rium isotherm data were fitted with Langmuir and Freundlich
models by using linear regression method. Non-linear regression
was used for data fitting on RedlichePeterson and Sips models with
the aid of Graphpad Prism version 6 package. The degree of fitness
for all models was determined by least squares error analysis.
From Table S1 supplementary data, qm is the maximum uptake
capacity under the given conditions (mg/g), b is the equilibrium
constant related to free energy of adsorption (L/mg), Kf (mg/g)(L/
mg)1/n and n are the Freundlich constants characteristic of the
system and the indicators of the adsorption capacity and adsorp-
tion intensity respectively, KRP (L/g) and aRP (L/mg)(1/b) are Redliche
Peterson isotherm constants, Ks (mg/g)(L/mg)bs and as (L/mg)bs are
Sips isotherm constants, b and bs are the isotherm exponents.
The comparison of the experimental and estimated data by
Langmuir, Freundlich, RedlichePeterson, and Sips models for the
parameters of color, TSS, and COD with different biosorbents of
NBP, MBP and BPAC at 25  C are presented in Figs. 4e6 with the
corresponding goodness of fit in Table 3. Generally, both two-
parameter and three-parameter models show good fitness with
experimental data for adsorption of most parameters. This can be
attributed to the presence of both heterogenous and homogenous
surfaces on the banana peel (Febrianto et al., 2009). However, based
on values of mean residual square (R2) and relative average error as
criteria for goodness of fit, RedlichePeterson isotherm provides a
better correlation between the theoretical and experimental data
for the whole concentration range for all types of biosorbent
compared to the other models. This is expected as the form of the
RedlichePeterson equation includes features of the Langmuir and
Freundlich isotherms. So it may be used to represent adsorption
equilibrium over a wide concentration range of adsorbate.
The values of adsorption capacity qm for adsorption of color, TSS
and COD onto BPAC are higher than for both MBP and NBP. The
higher adsorption capacity for all parameters for the BPAC in
comparison to the other studied adsorbents may be attributed to
the higher pore fraction capable of adsorbing the contamination
molecules and is in-line with the trend observed from the previous
section of performance study. However, heterogeneity of the car-
bon surface and the wide range of pore sizes and surface properties
extremely complicate analysis of the observed behavior.
3.3. Adsorption kinetics
The experimental sorbate uptake rates onto the biosorbents
were investigated by using kinetic models in this study. The ki-
netics of adsorption based on the overall adsorption rate by the
adsorbents were analyzed by the Pseudo-first-order, pseudo-sec-
ond-order, and second order kinetic models as shown in Table S2
supplementary data.
In Table S2 supplementary data, qt is the amount adsorbed at
time t (mg/g); K1 is the rate constant of first order adsorption (L/
min), K2 and K are the rate constants of pseudo second order and
second order-adsorption respectively (g/mg.hr).
Figs. 7e9 show that for the pseudo first order kinetic model
there is a deviation from the experimental data and the data were
fitted with a poor correlation coefficient and high relative average
 R.R. Mohammed, M.F. Chong / Journal of Environmental Management 132 (2014) 237e249
error for most parameters (Table 4). This indicates that the rate of
removal of color, TSS, and COD onto banana peel does not follow the
pseudo-first-order sorption rate expression of Lagergren.
The pseudo-second-order equation is based on the sorption
capacity of the solid phase. It predicts the behavior over the whole
range of data. Furthermore, it is in agreement with chemisorption
being the rate controlling step. Model parameters K2 and qe values
Fig. 7. Comparison of different kinetic models for (a) color, (b)TSS and (c) COD on NBP
biosorbent.
245
were determined from the slope and intercept of the plots of t/qt
against t. The values of the parameters, correlation coefficients and
relative average errors are also presented in Table 4. The correlation
coefficients of all examined data were found to be very high
(R2 > 0.99) and the relative average errors were very low. Also the
calculated values of equilibrium sorption capacity, qe, are very
much in agreement with experimental data for all studied systems.
This shows that the model can be applied for the entire adsorption
process and confirms that the sorption of color, TSS, COD, BOD, and
Fig. 8. Comparison of different kinetic models for (a) color, (b)TSS and (c) COD on MBP
biosorbent.
246 R.R. Mohammed, M.F. Chong / Journal of Environmental Management 132 (2014) 237e249
tannin and lignin onto NBP, MBP and BPAC follow the pseudo-
second-order kinetic mechanism.
Figs. 7e9 also show the kinetic modeling of color, TSS, and COD
adsorption by the second order model equation. Correlation co-
efficients, relative average errors and the second order model rate K
for all studied systems are listed in Table 4. The correlation co-
efficients, R2, of the second-order kinetic were found to be rela-
tively low compared to the pseudo second order model, but still
better than those of the first order kinetic model. Relative average
Fig. 9. Comparison of different kinetic models for (a) color, (b)TSS and (c) COD on BPAC
biosorbent.
errors were higher than that of the pseudo second-order model, but
still lower than those of the pseudo first-order model.
The kinetics of sorption processes are concerned with forces
between sites and adsorbate molecules, and this forms an impor-
tant area of surface chemistry. Banana peel surface is cellulose
based and contains carboxylic and amine groups. Also the esteri-
fication process of the banana peel introduces specific functional
groups on the fibril surface by which significant improvement of
hydrophobicity may be obtained. On contact with water and
depending on pH, these groups become negatively charged and are
likely sites for chemical reaction to take place on the banana peel
surface. According to Ho and McKay (1999), pseudo-second order
model is based on the assumption that the rate-limiting step may
be chemical sorption or chemisorption involving valency forces
through sharing or exchange of electrons between sorbent and
sorbate. The adsorption system obeys the pseudo second-order
kinetic model for the entire adsorption period and thus supports
the assumption behind the model that the adsorption is due to
chemisorption.
3.4. Scanning Electron Microscopy (SEM)
The surface physical morphology of NBP, MBP, and BPAC as
observed in Fig. 10 show progressive changes in the surface of the
particles. Fig. 10(a) reveals that microporous structures, heteroge-
nous, rough surface with crater-like pores exist in banana peel. The
NBP particles are of irregular shape and their surface exhibits a
micro-rough texture, which can promote the adherence of
adsorbates.
Fig. 10(b) shows that the treatment with methanol and acid has
changed the surface morphology of NBP. The surface of MBP has
more irregular and porous structure than that of NBP, and therefore
explains the higher BET surface area with higher adsorption ca-
pacity. Fig. 10(b) also shows that the pores within the particles are
more homogenous. Also, this slightly rough surface provides suit-
able binding sites for adsorbate molecules.
It is obvious from Fig. 10(C1) that the BPAC activated by KOH lost
its original cellular structure and looked broken. The KOH reagent is
a strong base. It is able to interact with carbon atoms and thus
catalyze the dehydrogenation and oxidation reactions, leading to
the increment of tar evolution and development of porosity (Hsu
and Teng, 2000).
White spheres and some fluffy materials can be seen in the
pores of BPAC (Fig. 10(C2)). The white spheres and fluffy materials
may be due to the presence of K2O, potassium carbonate (K2CO3), or
K residues. It may be argued that during the KOH activation process,
various reactions can take place with such products as hydrogen
gas (H2), K, K2CO3, and K2O (Babel and Jurewicz, 2004). At high
activation temperature, the formation of K2O is thermodynamically
the most stable. The high KOH ratio of 4 to 1 in samples containing a
large amount of K may cause the production of more K2CO3 and K2O
during pyrolysis. It appears that larger amounts of K2CO3 cause
larger pore size and structural deformation (Fig. 10(C3)). This pro-
posed mechanism causes BPAC to have a higher performance than
NBP and MBP (Yupeng et al., 2002). These findings are in agreement
with the findings of Mopoung (2008).
3.5. Optimum conditions for treatment and decolorization of
biologically treated POME
Treatment of POME requires a sound and efficient system to face
the current challenges. With the present situation where there are
some mills still failing to comply with the DOE standard discharge
limit even after they have applied the available treatment system, it
is believed that adsorption technology will be able to further polish
 R.R. Mohammed, M.F. Chong / Journal of Environmental Management 132 (2014) 237e249 247

Table 4
Parameters, correlation coefficient and relative average error of kinetic models obtained by using the linear methods for adsorption of color, TSS, COD, Tannin & lignin and BOD
on NBP, MBP and BPAC.

Adsorbent Adsorbate qe(exp.) (mg/g) Pseudo first-order model Pseudo second-order model Second-order model

K1 (1/hr) R2 Relative av. Error K2 (g/mg/hr) R2 Relative av. Error K (g/mg/hr) R2 Relative av. Error
3
NBP Color 65.0 0.2633 0.9550 0.056534 6.762  10 0.9983 0.033199 0.0314 0.9265 0.145756
TSS 19.0 0.1275 0.9960 0.06474 2.913  103 0.9940 0.027864 0.0190 0.9709 0.339175
COD 85.0 0.2829 0.6710 0.102363 11.710  103 0.9996 0.016083 0.0156 0.9931 0.021715
MBP Color 94.0 0.4505 0.9150 0.073979 39.400  103 w1 0.006587 0.0911 0.9327 0.023886
TSS 13.0 0.2195 0.9710 0.114048 19.700  103 0.9940 0.050348 0.0910 0.9568 0.304766
COD 85.0 0.4501 0.8090 0.074324 47.200  103 w1 0.00709 0.8810 0.9523 0.038508
BPAC Colour 176.0 0.2183 0.7742 0.148375 6.436  103 0.9999 0.012703 0.0663 0.9034 0.087279
TSS 28.5 0.1854 0.7166 0.153404 23.600  103 0.9988 0.035884 0.0871 0.9135 0.097595
COD 91.5 0.2472 0.7920 0.15139 26.400  103 0.9995 0.018225 0.0861 0.8577 0.027888
Tannin & lignin 1.4 0.1153 0.9788 0.17692 90.400  103 0.9988 0.010357 0.4209 0.9664 0.07071
BOD 27.0 0.1257 0.9674 0.10591 4.965  103 0.9991 0.070284 0.0609 0.7092 0. 09533

the biologically treated POME in a more beneficial way. For all
studied biosorbents, the optimum condition was found at contact
time of 24 h, dosage of 30 g/100 ml, and pH of 2. The BPAC was
found to be the optimum biosorbent as compared to NBP and MBP.
Under optimum conditions, the color of biologically treated POME
(dark brown) was significantly different after adsorption process.
The color after adsorption by NBP and MBP turned to light and very
light yellow respectively. The color degree of biologically treated
POME after undergoing BPAC adsorption treatment was further
reduced, as more than 96.46% of its initial value was removed, and it
was found to be colorless to the naked eye. The final color con-
centration at the optimum conditions of this work was 350 PtCo/L
after treatment with BPAC adsorption compared to a final color
concentration of 1350 PtCo/L found by Kutty et al. (2011) after
treating POME with microwave incinerated rice husk ash
adsorption.
The test results for TSS removal showed that the maximum
extent of removal was approximately 90% after treating with NBP.
This is equivalent to a residual concentration of 180 mg/L which is
much lower than the standard discharge limit. This removal per-
centage is slightly higher when treating with MBP where it reaches
91.667% of the initial value, while the final TSS concentration after
BPAC adsorption treatment was close to 0 mg/L.
COD shows a reduction by 99% after adsorption with NBP. The
MBP and BPAC treatments brought down the COD value nearly to
0 mg/L from the original COD value of biologically treated POME.
For BOD reduction, a similar trend to the COD reduction was ob-
tained from each type of biosorbent. However, it can be seen that
NBP treatment process reduced the BOD percentage by more than
90%, which is well below the allowable limit set by the Malaysian
Department of Environment, which is 100 mg/L. Similarly, a BOD
reduction to near 0 mg/L was observed for both MBP and BPAC
treatment processes.
Adsorption processes were expected to reduce tannin and lignin
content of biologically treated POME effectively. Results revealed
that BPAC adsorption processes were capable of reducing tannin
and lignin by up to 76.744% (as compared to initial level). Due to the
fact that there is no chemical addition during palm oil processing,
the color of this effluent is due to plant constituents such as lignin
and phenolics as well as repolymerizsation of coloring compounds
after anaerobic treatment (Zahrim et al., 2009). Considering the
results of this research, it is believed that decolorization of bio-
logically treated POME is a function of its TSS and tannin and lignin
concentrations.
In addition, with the final pH adjustment to 7, the resulting
biologically treated POME using this technology is in compliance
with standard discharge regulations and the resulting high-quality
treated water can be recycled back to the plant to be reused.
4. Conclusion
Research was carried out to explore banana peels as a high ca-
pacity, economically viable and low cost adsorbent for treating
biologically treated POME. The experimental results showed that
NBP has the ability to reduce the concentrations of biologically
treated POME to meet the POME discharge standard. Results
showed that modification of NBP by acidified methanol or KOH and
thermal treatment can further improve the sorption removal for
color, TSS, and COD. The optimum adsorption capacity of NBP was
found at 97 mg/g for color, 25 mg/g for TSS, and 90.5 mg/g for COD
removals respectively. The MBP has optimum adsorption capacity
of 137.5 mg/g, 28.5 mg/g and 93 mg/g for color, TSS, and COD re-
movals respectively, while BPAC has 184.5 mg/g, 34.5 mg/g, 94 mg/
g, 26.76 mg/g and 1.4 mg/g for color, TSS, COD, BOD, and tannin and
lignin removals respectively. In the present study, the optimum
adsorption conditions were found at dosage of 30 g of adsorbent/
100 ml of sample and after 24 h contact time. The pH played an
obvious effect on the sorbate adsorption capacity onto all types of
banana peel biosorbents. The decrease in the solution pH led to a
significant increase in the adsorption capacities of all parameters
on the banana peel biosorbents with maximum adsorption capacity
occurring at acidic pH of 2, although, the adsorption efficiency is
still high at the original effluent pH (8.4).
Four adsorption isotherm models were studied. The sorption
data of color, TSS, and COD on banana peel biosorbents fitted into
two-parameter isotherm models (Langmuir and Freundlich) and
three-parameter isotherm models (RedlichePeterson and Sips). An
excellent prediction in all the studied concentration range can be
obtained by the three-parameter equations. Among all the tested
equations, an excellent and perfect representation of the experi-
mental results is obtained using the RedlichePeterson model. and
the mechanism of adsorption is a hybrid unique and does not
follow ideal monolayer adsorption.
Kinetic study showed that sorption behavior of color, TSS, COD,
BOD, and tannin and lignin onto banana peel biosorbents had a
better fit with the pseudo second order equation than the Lagerg-
ren first order and second order equations. Following the pseudo
second-order kinetics indicates that the biosorption process oper-
ates through chemisorption mechanism. Chemical sorption can
occur by the active functional groups of biosorbents as chemical
bonding agents.
The addition of KOH raised the pore size and porosity of BPAC
which is due to the aggressive action on the cellular structure,
indicating that carbon gasification was enhanced by the addition of
KOH which led to widened pores.
The present work reveals that the waste banana peel is a
promising material for the treatment of biologically treated POME.
248 R.R. Mohammed, M.F. Chong / Journal of Environmental Management 132 (2014) 237e249

Fig. 10. Surface images of (a) NBP, (b) MBP, (C1) BPAC, (C2) BPAC with the white spheres and fluffy materials and (C3) BPAC with large pores.

Acknowledgment
This work has been carried out during sabbatical leave granted
to the author (Rafie R. Mohammed) from Mosul Technical Institute
during the academic year 2012, so the author thanks Ministry of
Higher Education/Iraq, and Foundation of Technical Education/
Iraq, for their support. Authors would like to acknowledge and
extend their heartfelt gratitude to Dr. Vasanthi Sethu who has
made the completion of this research possible. We are deeply
indebted to Andrew, Y.S., Farahwahida B.M., and Filza M.F. for their
technical assistance. This research has been supported by the
University of Nottingham/Malaysia Campus as a research scholar
fellowship.
Appendix A. Supplementary data
Supplementary data related to this article can be found at http://
dx.doi.org/10.1016/j.jenvman.2013.11.031
 R.R. Mohammed, M.F. Chong / Journal of Environmental Management 132 (2014) 237e249 249

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