Inuence of impregnation ratio on coffee ground activated carbon as landll leachate

adsorbent for removal of total iron and orthophosphate

Sim Lan Ching
a
, Mohd Sufan Yusoff
a,
, Hamidi Abdul Aziz
a
, Muhammad Umar
a, b
a
School of Civil Engineering, Engineering Campus, Universiti Sains Malaysia, 14300, Nibong Tebal, Penang, Malaysia
b
School of Civil, Environmental and Chemical Engineering, RMIT University, Melbourne 3001, Victoria, Australia
a b s t r a c t a r t i c l e i n f o
Article history:
Received 18 January 2011
Received in revised form 19 May 2011
Accepted 5 June 2011
Available online 24 June 2011
Keywords:
Coffee ground
Activated carbon
Landll leachate
Semi-aerobic
Adsorption
Coffee grounds waste was used to prepare activated carbon with particle size between 1.18 and 2 mm by
chemical activation with sulphuric acid. The inuence of impregnation ratio on physical properties of
activated carbon and removal efciency of total iron and orthophosphate (PO
4
P) was studied. Impregnation
ratio of 0.5 was found optimum for preparing activated carbon with high pore surface area (224.7 m
2
/g) and
micropore volume (0.07986 cm
3
/g). Batch experiments were conducted to study the effects of contact time,
pH, particle size and adsorbent dosage. Impregnation ratios of 2.5 and 0.5 were found to be optimum for the
adsorption of total iron and PO
4
P, respectively at doses of 10 g and pH 8.1. pH 13 was optimum for iron
removal while pH b5 and N11 was optimum for PO
4
P removal. The adsorption capacity increased with
increasing adsorbent dosage for total iron. However, this trend was exceptional for PO
4
P with uctuating
adsorption capacity. The smaller particle size yielded larger adsorption capacity.
2011 Elsevier B.V. All rights reserved.
1. Introduction
Coffee is produced all over the world. In 2008, according to the
International Coffee Organization the production of coffee
amounted to about 680,000,000 tons [1]. In Malaysia, 45% of all the
waste dumped to landlls is composed of kitchen waste including
coffee grounds [2]. The coffee grounds, which are the residues of the
soluble coffee industry, are highly pollutant due to the presence of
organic material that demands a great quantity of oxygen in order to
degrade [3]. The amount of carbon dioxide (CO
2
) produced by burning
1000 g of coffee grounds was 538 g [4].
In Malaysia, coffee production for 2009/10 was forecasted at
450,000 bags (60 kg) for both green coffee beans and Robusta coffee
beans. The import of green coffee beans for 2009/10 was forecasted at
650,000 bags (60 kg) [5]. Usually, the locally produced coffee product
is in soluble powder form. Initially, 1.86 kg of spent coffee grounds
was produced for each kilogramof soluble coffee. With improvements
to the industry, this gure dropped to 1.27 kg in 1967, and it was
0.91 kg in 1997 [3].
A new Nestl plant in Shah Alam will feature Nestl standard of
environment-friendly manufacturing practices such as incineration of
spent coffee grounds and will eventually join the list of more than 20
Nescaf factories around the world that are currently using spent
coffee grounds as renewable fuel which reduces the needs for landll
dumping.
The adequacy and suitability of natural, renewable and low cost
materials (palm shell, pall ber, palm stone, bamboo dust, peat,
chitosan, lignite, fungi, moss, bark husk, chitin, coir pith, maize cob,
pinewood sawdust, rice husk, sugar cane bagasse, tea leaves, and sago
waste) as alternative precursors have currently been executed [6,7].
Various non-conventional low cost adsorbents have shown good
adsorption capacities in removing COD from landll leachate such as
rice husk with 70% of COD removal [8] oil palm shell with 50% of COD
removal [9] and peats with 69% of COD removal [10].
Landll leachate is a complex wastewater produced as a result of
interaction of waste with water percolating through the body of a landll
[1113]. To date, previous studies on non-conventional low cost
adsorbents were limited to the application for basic dye or COD removal
fromlandll leachate. Not much attempt has so far been made to obtain a
comprehensive overviewof leachate treatment interms of the adsorption
capacity of low cost adsorbents for other parameters such as ion
phosphate and heavy metals. Thus, there is a need to explore the use of
coffee grounds as lowcost adsorbents for other parameters' removal and
to optimize their removal conditions. Furthermore, limited investigations
about the effect of impregnation ratio on the adsorption capacities of
activated carbons prepared from coffee grounds by sulphuric acid
activation have been reported.
The aims of this study were to characterize coffee grounds
activated carbon (CGACs) based on difference H
2
SO
4
impregnated
ratios and to study the effects of shaking time, pH, adsorbent dosage
and particle size on the adsorption of total iron and PO
4
from leachate
produced at semi-aerobic Pulau Burung Landll Site (PBSL).
Desalination 279 (2011) 225234
Corresponding author. Tel.: +60 45996223; fax: + 60 45941009.
E-mail address: sufan@eng.usm.my (M.S. Yusoff).
0011-9164/$ see front matter 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.desal.2011.06.011
Contents lists available at ScienceDirect
Desalination
j our nal homepage: www. el sevi er. com/ l ocat e/ desal
2. Materials and methods
2.1. Analytical techniques
Landll leachate samples were collected from PBLS using plastic
containers and stored at 4 C until analysis was carried out. pH was
measured onsite using a portable pH meter (Hach, sens ion 1, USA).
COD was determined using Colorimetric Method (5220-D). NH
4
N
was determined using Nesslerization method (4500-NH
3
). The
removal of total iron and PO
4
P was determined using UV
spectrophotometer (HACH DR2500). PO
4
P and total iron concentra-
tion was determined using Molybdovanate and FerroZine Method at
wavelength of 255 nm and 480 nm, respectively. The readings were
taken after ltering the sorbents from the leachate samples. The
amount adsorbed was determined by taking the difference between
the initial concentration and the concentration of the solution at the
time of sampling. pH was adjusted by using 0.1 M H
2
SO
4
or NaOH.
2.2. Preparation of adsorbent
Coffee grounds were collected from a local coffee making shop
located in Kampung Baru, Bukit Mertajam, Penang. The coffee grounds
were washed with boiled water to eliminate the impurities, dust and
water soluble substances followed by washing with distilled water.
The washed coffee grounds were oven dried at 105 C for 24 h prior to
their activation. The dried coffee grounds were impregnated with a
weighted amount of H
2
SO
4
aqueous solution. The impregnation ratio
is dened as the ratio of the weight (g) of H
2
SO
4
to the weight of
precursor (g of dried coffee grounds). Coffee grounds activated
carbons (CGAC) were prepared with different impregnation ratios
namely IR 0.5, IR 1.5 and IR 2.5. The impregnation ration was
determined according to the following formula.
Impregnation ratio =
Weight of the H
2
SO
4
Weight of the coffee ground activated carbon CGAC
Dried coffee grounds were impregnated by putting 200 g of coffee
grounds each in 3 conical asks in contact with 600 mL of H
2
SO
4
solutions for 24 h. The concentration of acid was 96% by weight. The
activated samples were subsequently oven dried at 105 C for 24 h.
The resulting samples were then carbonized for 60 min at 600 C in a
vertical tube furnace (Carbolite Type MTF 12/38/250) under nitrogen
atmosphere. After cooling, the char was washed with boiled and
distilled water in order to eliminate the residual organic and mineral
matter. Washing with water easily removed most of the residues from
activating agents. The completion of washing was carried out until the
nal pH of washing water was neutral. It was then dried at 105 C for
24 h. The carbon product was sieved to a uniform size (1.182 mm)
and stored in closed bottles. The yield of the activated carbon
synthesis is dened as the ratio of the weight of the activated carbon
after activation, carbonization and washing (w
1
) to that of the dry
coffee grounds (w
0
): yield%=(w
1
/w
0
)100. The burn off is the
weight loss percentage due to the activation and carbonization step.
2.3. Characterization of adsorbents
The N
2
adsorptiondesorption isotherms of the activated carbons
were measured using an automatic adsorption instrument (AutoSorb
I, Quantachrome) at liquid nitrogen temperature (77 K). The specic
surface areas (S
BET
) of the activated carbons were calculated using the
BrunauerEmmettTeller (BET) equation by assuming the area of the
nitrogen molecule to be 0.162 nm
2
. The micropore volume and
microporous surface area were determined by the t-plot method [14].
The capacity of adsorbents to remove color can be evaluated
through iodine adsorption from aqueous solutions using test
conditions referred to as iodine number determination which
indicates their relative activation level and the surface area available
for micropores [15]. Usually adsorbents with a high iodine number
have a high surface area and are suitable for adsorbing small
compounds [15]. The iodine number corresponding to the produced
adsorbent was determined according to the procedure established by
the Standard Test Method (ASTM D4607-86) [16]. According to this
test, 0.1 g of activated carbon was placed in a 250 mL dry Erlenmeyer
ask and fully wetted with 10 mL of diluted HCl (5% by weight).
100 mL of iodine solution (0.1 mol/L) was poured into the ask and
the mixture was vigorously shaken for 30 s. After ltration, 50 mL
solution was titrated with 0.1 mol/L sodium thiosulfate. The iodine
number expressed in mg/g was reported as the amount of iodine
adsorbed per gram of adsorbent at a residual iodine concentration of
0.02 N.
Fourier transform infrared (FTIR) transmission spectra of carbon
samples were obtained through potassiumbromide technique [17] on
FTIR spectrometer (Model PerkinElmer Spectrum One) in 400
4000 cm
1
wave number range, with a 2 cm
1
resolution. FTIR was
used to provide information on the chemical structure of the activated
carbon before and after adsorption. Pellets made of a mixture of
0.6 mg of activated carbon and 200 mg of KBr were pressed at
350 MPa, and oven-dried for 48 h at 110 C before analysis.
2.4. Adsorbate
The leachate samples used in this study were obtained from semi-
aerobic PBLS, which is situated within Byram Forest Reserve in
Penang, Malaysia. The site has a natural marine clay liner with the
total area of 33 ha and it is equipped with a leachate collection pond.
The PBLS was developed into a semi-aerobic system employing a
controlled tipping technique and leachate recirculation system in
March 2001 and is one of the only three sites of its kind in Malaysia
[18]. The site receives approximately 1800 tons of solid waste daily
from Penang Island [19]. No pretreatment was done for the collected
Table 1
Characteristics of leachate from Pulau Burung landll site.
Raw 1 2 3 4 5 6 Average
pH 7.89 7.71 7.12 7.67 7.43 7.57 7.5
COD (mg/L) 1200 1010 1450 1620 1773 1815 1478
BOD
5
(mg/L) 271 256 184 215 338 218 247
BOD
5
/COD 0.23 0.25 0.13 0.13 0.19 0.12 0.17
TKN (mg/L) 1771.84 1699.4 1711.36 1644.16 1563.52 1520.5 1651.8
NH
4
N (mg/L) 2609 2670 2208 2388 2405 2780 2510
Nitrite (mg/L) 43.3 36.7 42.5 46.7 36.7 43.3 41.5
Nitrate (mg/L) 1.33 1.67 3.2 1.33 2.67 2.33 2.1
PO
4
P (mg/L) 284 276 290 220 250 240 260
Color point (Pt.Co) 4153 4030 3527.5 3670 3679.5 3720.5 3796.75
SS (mg/L) 434 366 450 490 458 463 443.5
Total iron (mg/L) 4.25 4.61 4.42 4.82 4.73 4.59 4.57
226 S.L. Ching et al. / Desalination 279 (2011) 225234
leachate samples. The collected samples were stored in darkness at
4 C with minimum exposure to surrounding air to keep the leachate
characteristics unchanged. The characteristics of leachate samples
were based on 6 samplings collected for 3 months from January to
March, 2010. All experiments were undertaken in triplicates. The
detailed composition is shown in Table 1.
The COD strength of the leachate varied between 1010 and
1200 mg/L, while the BOD
5
concentration was less than 500 mg/L.
This gives a BOD
5
/COD ratio of about 0.17, which indicates that most
of the organic compounds in the landll leachate were poorly
biodegradable. Ammonium strength is also a major pollutant in the
landll leachate and its strength was around 2510 mg/L. In each
experiment, the same sample was used and the initial characteristics
were determined in order to take consideration of the changes in
composition and to reduce the background interferences.
2.5. Batch adsorption experiments
This study was divided into four parameters with four different
factors. Different impregnation ratios of 0.5, 1.5 and 2.5 were studied for
each of the parameters with four different factors and the treatment
performance was evaluated and reported as percent removal. Moreover,
the study was concentrated on the identication of the condition that
provides the best treatment performance. Four different aspects of the
experimental effect factors such as contact time, pH, particle size and
adsorbent dosage were evaluated based on the range as follows:
2.5.1. Contact time
Adsorption experiments were carried out by adding a xed
amount of sorbent into a number of 250 mL conical asks containing
leachate, at different impregnation ratios of coffee ground activated
carbons at pH 8.1 and temperature 30 C. The volume of leachate
samples was 100 mL in each case while a xed amount of 10 g CGAC
was used in each experiment. Already impregnated CGAC was added
to the conical asks.
The asks were placed in an orbital shaker (PROTECH Model 720)
and agitation was provided at 300 rpm for 150 min. The leachate
samples were taken at preset time intervals after 30, 60, 90, 120, 150,
180, 210, 240 and 270 min. The concentrations of total iron and PO
4
P
were similarly measured.
2.5.2. pH
Adsorption experiments were carried out by adding a xed
amount of sorbents (10 g) into a number of 250 mL conical asks
containing leachate (100 mL in each case), at different impregnation
ratios of coffee ground activated carbons at 30 C. The asks were
placed in an orbital shaker (PROTECH Model 720) and agitation was
provided at 300 rpm for 150 min. The pH was varied at 2, 5, 7, 11 and
13 by using either 0.1 M H
2
SO
4
or NaOH. The concentrations of total
iron and PO
4
P were similarly measured.
2.5.3. Adsorbent dosage
Adsorption experiments were carried out by adding various amount
of sorbents (5, 10, 15, 20and25 g) intoa number of 250 mL conical asks
containing leachate (100 mL in each case), at different impregnation
ratios of coffee ground activated carbons at pH 8.1 and temperature
30 C. The asks were placed in an orbital shaker (PROTECHModel 720)
and agitation was provided at 300 rpm for 150 min. The concentrations
of total iron and PO
4
P were similarly measured. The equilibrium time
was taken as 150 min for each IR by xing the CGAC dosage at 10 g for
each case of different impregnation ratios and kinetics of adsorption
were measured for both total iron and PO
4
P.
2.5.4. Particle size
Adsorption experiments were carried out by adding a xed
amount of sorbents (10 g) into a number of 250 mL conical asks
containing leachate (100 mL in each case), at different impregnation
ratios of coffee ground activated carbons at pH 8.1 and temperature
30 C. The asks were placed in an orbital shaker (PROTECH Model
720) and agitation was provided at 300 rpm for 150 min. The particle
sizes were varied at 1.182, 0.61.18, 0.4250.6, 0.30.425 and 0.15
0.3 mm. The concentrations of total iron and PO
4
P were similarly
measured.
2.6. Calculation analysis
In this work, calculation analysis was carried out to determine the
value of yield, weight loss, and percentage of removal.
2.6.1. Yield and weight loss calculation
The yield of activated carbon is dened as the ratio of the weight of
the resultant activated carbon to that of the original coffee grounds
(dry basis). The percentage yield of activated carbon was calculated as
follows:
Yield % = w
1
= w
0
100 1
where w
0
is the weight of original coffee grounds (dry basis) and w
1
is
the weight of the resulted activated carbon.
The weight loss or the weight ratio of the nal product to that of
raw materials was calculated from:
Weightloss % = w
0
w
1
= w
0
100 2
where w
0
is the weight of original coffee grounds (dry basis) and w
1
is
the weight of the resulted activated carbon.
2.6.2. Percentage of removal calculation
The removal percentage of PO
4
and Fe can be calculated as follows:
Removal % = C
0
C
e
= C
0
100 3
where C
0
and C
e
(mg/L) are the liquid-phase concentrations of total
iron and PO
4
P at initial and equilibrium, respectively.
3. Results and discussion
3.1. Characterization of activated carbon
Characterization of activated carbon included weight loss and
yield, iodine number, specic surface area, micropore volume and
FTIR.
3.1.1. Weight loss and yield
Table 2 illustrates that an increase in sulphuric acid resulted in an
increase in the weight loss and hence a reduced yield of the carbon
product. The weight loss was 49, 48.15 and 57.23% for IR 0.5, IR 1.5 and
IR 2.5, respectively. The yield was 51, 51.85 and 42.77% for IR 0.5, IR
1.5 and IR 2.5, respectively. H
2
SO
4
reacted with char and volatile
matter and diffused quickly out of the surface of particles during the
activation process. Therefore, with high H
2
SO
4
content, the gasica-
tion of surface carbon atoms became predominant leading to an
increase in the weight loss and a low carbon yield.
3.1.2. Iodine number
Iodine numbers are indications of the adsorption capacity in
micropores, and therefore are often employed to examine the
adsorption capacity of the activated carbon. Table 2 demonstrates
that the iodine number increased with an increase in the impregna-
tion ratio. The iodine number was 71.33, 93.67 and 96.5 for IR 0.5, IR
1.5 and IR 2.5, respectively. As acid content increased, more reaction
took place and consequently, more surface area was developed. A
higher acid content generally lead to formation of the product with a
227 S.L. Ching et al. / Desalination 279 (2011) 225234
higher level of volume and surface area which could then provide a
higher adsorption capacity; however, it was difcult to establish this
concept with only three impregnation ratios studied in this work.
3.1.3. Specic surface area and pore structure
An important property of the activated carbon is its adsorptive
capacity, which is related to the specic surface area. Table 2 shows
the BET surface area obtained for each impregnation ratio. The specic
surface areas for IR 0.5, IR 1.5 and IR 2.5 were 146.1, 55.43 and
121.5 m
2
g
1
, respectively. Using H
2
SO
4
as the activating reagent, the
maximum surface area was obtained for IR 0.5. Interestingly, with
increasing impregnation ratio from 0.5 to 2.5, surface area decreased
from 146.1 to 121.5 m
2
g
1
. There were also signicant reductions in
micropore and total pore volumes with increasing impregnation ratio.
In a study of the preparation of the activated carbon from cattle-
manure by ZnCl
2
activation [20], it was found that when the
impregnation ratio was higher than 1.5 in the activation process, a
decrease in both BET surface area and micropore volume of the
activated carbon was observed. Experimental results suggested that
the impregnation ratio strongly affects characteristics of the activated
carbon; hence an appropriate impregnation ratio should be selected
for the production of the activated carbon with the highest surface
area and pore volume. As a comparison, micropore volume obtained
in this study for IR 0.5 was smaller in comparison to that obtained by
using H
3
PO
4
activated CGAC in a recent study conducted by Reffas et
al. [1]. It was not possible to draw a comparison for IR 1.5 and IR 2.5
used in this study because they [1] used different impregnation ratios.
3.1.4. FTIR of CGACs
The infrared spectra of CGACs before and after adsorption are
illustrated in Fig. 1. The more intense bands are reported in Table 3. It
is clear that CGACs has considerable numbers of heterogeneous layers
of pores where there was a good possibility for total iron and PO
4
P to
be adsorbed. The FTIR spectrum of CGACs (Fig. 1 and Table 3) shows
that some peaks were shifted or disappeared but no new peak was
detected. The changes observed in the spectrum indicate the possible
involvement of those functional groups on the surface of the CGACs in
the adsorption process.
Fig. 1 indicates that functional groups OH, NH and CH stretching
in alkyl or aryl existed in the CGACs at wavenumber 32323839 cm
1
(before adsorption) and 32463839 cm
1
(after adsorption). Amino
groups were also detected in CGACs at wavenumber 2299
2395 cm
1
(before adsorption) and 2347 cm
1
(after adsorption),
while C_O groups were found at wavenumber 1521 cm
1
(before
adsorption) and 1543 cm
1
(after adsorption). The OH and CO
bending (in-plane) was detected at 1433 cm
1
(before adsorption)
and 1415 cm
1
(after adsorption). POC strongest band highest
frequencies for aliphatic amines (1053 cm
1
) and CH out-of-plane
deformation (825 cm
1
) were also detected before and after
adsorption.
3.2. Effect of adsorbent dosage
The removals of total iron and PO
4
P as a function of adsorbent
dosage at different IR of 0.5, 1.5 and 2.5 were calculated. Initial
concentration of total iron was 4.57 mg/L while 260 mg/L for PO
4
P.
Fig. 2a shows the variations in total iron adsorption at different
dosages of CGAC while Fig. 2b shows the variations in PO
4
P
adsorption at different CGAC dosages. These results indicate that the
removal percentage of total iron increased with an increase in the
adsorbent dosage from 5 to 25 g (Fig. 2a). A similar trend was
observed for PO
4
P removal (Fig. 2b). These results were expected as
with increased adsorbent dosage, the available sorption surface and
availability of more adsorption sites increase which results in more
adsorbate attached to the surfaces [21,22]. Although an increase in
adsorption occurred with respect to increase in dosage, the trend of
amount adsorbed per unit mass decreased by increasing dosage as
shown in Fig. 2 (a, b).
The removal percentage of total iron increased in the order of IR of
0.5, 1.5 and 2.5 (Fig. 3a). The removal percentage of total iron
improved by 19.5, 18.6 and 12.5% for IR 0.5, IR 1.5 and IR 2.5,
respectively when the adsorbent dosages were increased from 5 to
25 g. A higher increment in removal percentage was seen for IR 0.5
compared to other impregnation ratios. The best removal of 72.6% for
total iron was achieved for IR 2.5 by using 25 g of adsorbent. The PO
4

P removal percentage for IR 1.5 decreased by 27% and 3.8% as the

adsorbent dosage increased from 10 to 15 g and 15 to 20 g,
respectively. Meanwhile, the removal percentage for IR 1.5 increased
from 50% to 57.7% when the dosage increased from 20 to 25 g. For IR
2.5, the percentage removal decreased by 11.54 and 19.23% when the
adsorbent dosage increased from 5 to 10 g and 10 to 15 g,
respectively. As mentioned earlier, it was rather difcult to establish
an optimum impregnation ratio in this study; however, a higher
impregnation ration generally leads to higher ash content due to
consumption of more carbon atoms in activation reaction [23]. This
could be veried from more uctuations that occurred in the PO
4
removal for IR 1.5 and 2.5. The unstable trend that occurred for IR 1.5
and 2.5 could have been due to the reactions of various anions present
in leachate consequently leading to reduced removal performance.
However, no uctuation was observed for IR 0.5 curves which refer to
increased conductivity of activated carbon.
Although percent adsorption increased with increase in adsorbent
dosage, the amount adsorbed per unit mass decreased. This statement
can be supported from the results plotted in Fig. 3 (a, b). The decrease
in adsorption density with increase in adsorbent dose is mainly owing
to unsaturation sites through the adsorption process [24,25]. Another
reason might be the particle interactions such as aggregation,
resulting from high sorbent concentration. Such aggregation would
lead to a decrease in the total surface area of the adsorbent [26].
3.3. Effect of contact time
The removal of total iron and PO
4
P as a function of contact time at
different impregnation ratios of 0.5, 1.5 and 2.5 was observed. The
results are presented in Fig. 4 (a, b). As expected, the removal
percentage increased with time until the equilibrium was attained
between the amounts of adsorbate adsorbed on the adsorbent and
that remained in solution.
In the total iron adsorption curve shown in Fig. 4 (a), the uptake of
total iron for IR 0.5 was slow in the rst 90 min and the removal
increased rapidly by 18% as the contact time increased from 180 to
270 min. Among the three different impregnation ratio of adsorbents,
IR 2.5 performed a constant removal percentage of around 73% as
different stage of increment was not seen in the adsorption curve. In
contrast, adsorption curve for IR 0.5 increased rapidly after contact
time 180 min and the removal percentage kept increasing instead of
slowing down. Such trend indicates that the adsorption process took
Table 2
Physical properties of activated carbon prepared at various impregnation ratios.
Impregnation ratio H
2
SO
4
/coffee
Parameter 0.5 1.5 2.5
Particle size (mm) 1.182 1.182 1.182
Weight loss (%) 49 48.15 57.23
Yield (%) 51 51.85 42.77
Iodine number (mg/g) 71.33 93.67 96.5
BET surface area (m
2
/g) 146.1 55.43 121.5
Pore specic volume V
tot
(cm
3
/g) 0.0705 0.01938 0.05925
Micropore area (m
2
/g) 224.7 86.64 187.2
Micropore volume (cm
3
/g) 0.07986 0.03079 0.06653
Average pore diameter (nm) 1.6 1.398 1.951
228 S.L. Ching et al. / Desalination 279 (2011) 225234
more than 270 min to reach equilibrium. In the case of IR 1.5, the
removal of total iron increased gradually with increasing contact time
at the early stage of adsorption until the contact time reached
210 min. The increase in removal rate from76 to 84% towards the end
of the experiments indicates that IR 1.5 took more than 270 min to
reach the equilibrium.
The adsorption curve for PO
4
P as shown in Fig. 4 (b) uctuated
more in comparison to total iron. The tremendous uctuation trend
was seen both in the studies of effect of contact time and adsorbent
dosage for IR 2.5 on PO
4
removal. These results proved that IR 2.5 was
not suitable to be used for PO
4
P adsorption. The efciency of PO
4
P
reduction for the three different impregnation ratio of adsorbents was
of the order IR 0.5NIR 1.5NIR 2.5. In order to explain this behavior, the
dependency of the removal capacity on the physical structure of the
sorbent was considered. The removal capacity was clearly dependent
on the total pore volume and the mean pore diameter as shown in
Table 2. As IR 0.5 had higher pore volume and the mean pore
diameter, phosphate uptake by the sorbent was higher. The
enhancement of the removal capacity seemed to be due to the
contribution of the wide pores created, which maintained the
diffusional transport of PO
4
P from the liquid phase into the internal
surface of the sorbent. A slight uctuation was observed in the
adsorption curves of IR 0.5 and IR 1.5. This phenomenon might have
been due to the effect of foreign anions such as SO
4
2
, Cl

and NO
3

which reduced the percent removal of PO

4
P [27]. In case of IR 0.5 and
IR 1.5, the uptake of PO
4
P increased gradually with increasing
contact time, then slightly dropped at contact time 150 min, and
thereafter reached equilibrium with 69% removal at 270 min.
Optimum removal efciency for both IR 0.5 and IR 2.5 was 84.6 and
69.2%, respectively at contact time of 150 min. Hence, the contact time
of 150 min was considered as the optimum.
3.4. Effect of pH
The removal of total iron and PO
4
P as a function of pH at different
impregnation ratios of 0.5, 1.5 and 2.5 was studied. The results are
presented in Fig. 5 (a, b). Adsorption capacity for total iron at various
4000.
0
360
0
320
0
280
0
240
0
200
0
180
0
160
0
140
0
120
0
100
0
80
0
60
0
400.
0
16.
0
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
cm-1
%T
Before
After
3839
3736
3650
3246 2347
1543
1053
569
442
1241
1415
825
3839
3736
3616
3504
3232
2395
2299
1433
1244
1053
568
441
825
1521
(b)
(a)
Fig. 1. FTIR of CGAC: (a) before adsorption and (b) after adsorption.
Table 3
FTIR of CGACs.
Main observed bands
(cm
1
)
Before
adsorption
After
adsorption
Differences Assignment
3839 3839 0 OH, NH, CH stretching in alkyl or aryl
3736 3736 0
3616 3650 34
3232 3246 14
2395 2347 48 Amino groups
2299
1521 1543 22 C_O stretching
1433 1415 18 in-plane OH bending and CO stretch of
dimmers
1244 1241 3 CO stretching
1053 1053 0 POC strongest band highest frequencies
for aliphatic amines
825 825 0 CH out-of-plane deformation
Fig. 2. Effect of different adsorbent dosage on the amount adsorbed of (a) total iron, and
(b) PO
4
P using CGAC.
229 S.L. Ching et al. / Desalination 279 (2011) 225234
pH values is presented in Fig. 5 (a). The pH of the aqueous solution is
an important operational parameter in the adsorption process
because it affects the solubility of the metal ions, concentration of
the counter ions on the functional groups of the adsorbent and the
degree of ionization of the adsorbate during reaction [28]. Thus, the
role of hydrogen ion concentration in the removal of total iron was
examined. The maximum removal efciency achieved by IR 0.5, IR 1.5
and IR 2.5 was 96, 86 and 100%, respectively at alkaline pH range 11
13. The removal efciency increased signicantly with increasing pH
for all adsorbents. It could be observed that increasing pH of the
solution from 2 to 11 caused linear increase in total iron removal
efciency for IR 0.5 and IR 1.5. The removal efciency increased
rapidly above pH11. However, different trend was observed for IR 2.5.
The adsorption increased rapidly from pH 5 to 11, and thereafter
maintained at 100% at pH 11 and 13. Better adsorption performed by
IR 2.5 could be due to increasing number of micropores which are
proved by the highest iodine number for IR 2.5 compared to IR 0.5 and
IR 1.5, making total iron easier to penetrate into the micropores [29]. It
could be concluded that the adsorbent achieved a good total iron
removal at pH13 with a minimumvalue of 80% (Fig. 5a). These results
could be attributed to the positive charge of total iron which would
react and attach onto adsorbent surface's functional groups. There are
four major functional groups on the surface of activated carbon which
are carboxyl, carbonyl, hydroxyl, and lactonized carboxyl [29].
However, the actual chemical reaction between the metal ion and
functional groups on the activated carbon surface was complex and
difcult to understand. The removal efciency of metal ions generally
increased when the initial pH of solution was increased. This was
because the adsorbents were highly selective for H
3
O
+
ions when the
concentration of H
3
O
+
ions was high at low pH value. Thus, at lower
pHvalues, H
3
O
+
ions competed with metal ions for the exchange sites
in adsorbents [30,31]. A higher pH value also leads to the formation of
iron precipitates resulting in enhanced total iron removal.
Maximum removal of PO
4
P occurred at pH 5 for IR 1.5 with
removal efciency of 58% as shown in Fig. 5 (b). In contrast, IR 0.5 and
IR 2.5 reached the maximum removal efciency at pH 13 with the
removal of 73 and 77%, respectively. At pH 2, IR 0.5 had the lowest
removal efciency of 34.6%. IR 1.5 and IR 2.5 had the lowest removal
efciency in pH range 713 and 711, respectively. Phosphate exists
as H
3
PO
4
, H
2
PO
4

, HPO
4
2
, and PO
4
3
, depending on the pH of the
Fig. 3. Percent removal of (a) total iron, and (b) PO
4
P using CGAC.
Fig. 4. Effect of different contact time on the removal performance of (a) total iron, and
(b) PO
4
P using CGAC. Fig. 5. Effect of pH on removal performance of (a) total iron, and (b) PO
4
P using CGAC.
230 S.L. Ching et al. / Desalination 279 (2011) 225234
system. The predominant species of phosphate is H
3
PO
4
at lower pH.
These protonated species are weakly attached to the sites of the
adsorbent. With increased pH, other species of phosphate such as
H
2
PO
4

and HPO
4
2
were prevalent; hence their adsorption occurred
at high pH. At pH value more than 8, the concentration of OH

in
solution, which competes with the PO
4
3
species, became higher. The
highly negatively charged adsorbent sites did not favor the adsorption
of oxyanions due to the electrostatic repulsion [32,33]. Thus, it could
be concluded that optimum pH suitable for PO
4
P removal was in pH
range 57 and pH more than 13.
3.5. Effect of particle size
The removal of total iron and PO
4
P as a function of particle size at
different impregnation ratios of 0.5, 1.5 and 2.5 was determined. The
results are presented in Fig. 6 (a, b).
The adsorption of total iron as shown in Fig. 6 (a) gradually
decreased with a decrease in particle size. The percentage removal of
total iron at particle size of 0.153 mm was the minimum which was
around 40, 54 and 53% for IR 0.5, IR 1.5 and IR 2.5, respectively. The
optimum size range for total iron adsorption was 0.4250.6 mm, 0.6
1.18 mm, and 1.182 mmfor IR 0.5, IR 1.5 and IR 2.5, respectively. The
efciency of Fe reduction for the three different impregnation ratios of
adsorbents was of the order IR 2.5NIR 1.5NIR 0.5. The maximum
removal percentages of 47, 61 and 72% were achieved for IR 2.5, IR 1.5
and IR 0.5, respectively. There was a linear decrease in removal
efciency for IR 2.5 from size range 1.182 to 0.4250.6 mm but it
remained constant for size range 0.30.425 and nally dropped by
8.5% at 0.150.3 mm. For IR 1.5, the adsorption curve decreased by
6.3% in the beginning and thereafter maintained at 54% from size
range 0.4250.6 mmto 0.150.3 mm. While for IR 0.5, the uptake only
dropped by 11.6% from size range 0.4256 mm to 0.30.425 mm. The
results indicated that the total iron adsorption was more inuenced
by other elements than its particle size. It possibly shows that the total iron adsorption occurred by chemical adsorption rather than physical
adsorption (outer sphere complex) [34].
The similar trend was observed in PO
4
P adsorption performance
as shown in Fig. 6 (b). In the case of IR 2.5, PO
4
uptake decreased
linearly from size range 0.61.18 mm to 0.150.3 mm. The maximum
removal efciency of 65.4% and minimum removal efciency of 19.2%
occurred at size range 0.61.18 mm and 0.150.3 mm, respectively.
For IR 1.5, PO
4
P uptake decreased slightly from size range 0.6
1.18 mm to 0.30.425 mm. The maximum removal efciency of 76.9%
and minimumremoval efciency of 57.7% occurred at size range 0.15
0.3 mm and 0.30.425 mm, respectively. The maximum removal at
smallest size range could be attributed to the dilution error during the
preparation of samples for spectrophotometer analysis. While for IR
0.5, the removal efciency was the minimum at low size range 0.15
0.3 mmwhich removed only 19% of PO
4
P. The PO
4
P uptake capacity
decreased with the decrease in particle size. The PO
4
P uptake
capacity was a function of iron content that was bound in the
adsorbent adsorption sites. Since the uptake of iron increased with
increasing particle size, it could possibly result in the larger particle
size providing a greater amount of iron for phosphate removal from
solution. Similar theory was proved in a study conducted by Eberhardt
and Min [35].
3.6. Adsorption isotherms
Equilibrium isotherms were analyzed using the Langmuir and
Freundlich isotherms. Both Langmuir and Freundlich isotherms are
the most common isotherm models used to describe the adsorption
characteristics of the adsorbents used in water and wastewater
treatments [36]. The Langmuir isotherm is a typical model for
monolayer adsorption based on assumption that sorption takes
place at specic homogenous sites within the adsorbent [37].
Fig. 6. Effect of particle size on removal performance of (a) total iron, and (b) PO
4
P
using CGAC.
Fig. 7. Langmuir (a) and Freundlich isotherm (b) for total iron.
231 S.L. Ching et al. / Desalination 279 (2011) 225234
The Langmuir isotherm is expressed as:
1= q
e
= 1= Q
0
+ 1= Q
0
b

C
e
: 4
The Freundlich isotherm is an empirical equation based on the
assumption that adsorption takes place on heterogeneous surfaces.
The Freundlich isotherm model is described as [38]:
logq
e
= logK + 1= n logC
e
5
where qe is the amount of solute adsorbed per unit weight of
adsorbent (mg/g), Ce is the equilibrium concentration of adsorbate in
solution after adsorption (mg/L) and K(mg/g(L/mg)1/n), n, Q
0
(mg/g)
and b (L/mg) are the constants.
The results of the total ironadsorption obtained by each isothermare
shown in Fig. 7 (a, b). According to the results shown in Fig. 7 (a) for
Langmuir isotherm and Fig. 7 (b) for Freundlich isotherm, both these
isotherms showed very good ts for adsorbate with corresponding
coefcient (R
2
) values above 0.9 except for IR 0.5 in case of Langmuir
isotherm. Thus, it could be concluded that both isotherms described the
adsorption mechanism of total iron using the CGAC as adsorbent
indicating that the adsorption of total iron on CGAC took place as
monolayer adsorptiononthe surface homogenous inadsorptionafnity.
In case of PO
4
P (Fig. 8a), Langmuir isothermt the data better for
IR 2.5 as indicated by the value of R
2
greater than 0.9. However, the
Langmuir isotherm for IR 0.5 and 1.5 showed values of R
2
lower than
0.9 representing that the data was not described by the isotherm. A
similar behavior was observed for Freundlich isotherm with lower
values of R
2
(Fig. 8b).
3.7. Adsorption kinetics
Several kinetic models may be used to examine the controlling
mechanism of adsorption process and the potential rate limiting steps
such as transfer and chemical reaction [39]. In this study, the adsorption
kinetics was predicted by two common models which were pseudo-
rst-order and pseudo-second-order model. The pseudo-rst-order
kinetic equation is based on the sorption capacity of the solid phase. It
predicts the behavior over the whole range of adsorption which is in
agreement with chemical adsorption mechanism being the rate
controlling step which may involve valency forces through sharing or
exchange of electrons between adsorbate anions and adsorbent [39].
The pseudo-rst-order model is generally expressed as:
d
q
= d
t
= k
0
1
q
e
q : 6
The pseudo-second-order model is expressed as:
d
q
= d
t
= k
0
2
q
e
q 7
where q
e
is the amount of solute adsorbed at equilibrium per unit
weight of adsorbent (mg/g), q the amount of solute adsorbed at time t
per unit weight of adsorbent (mg/g) while k
1
(min
1
) and k
2
(g/
mg min) are the constants.
It was observed that total iron did now t very well in pseudo-rst-
order model (Fig. 9a), however it tted very well in pseudo-second-
order model with R
2
values more than 0.9 (Fig. 9b). The high correlation
coefcient (R
2
) values indicated that the model successfully described
the adsorption kinetics of the parameters. Similar was true in the case of
PO
4
P where the values of R
2
were less than 0.9 for pseudo-rst-order
model while they were higher than 0.9 for pseudo-second-order model
except IR2.4 (Fig. 10). Overall, it impliedthat the adsorptionof bothtotal Fig. 8. Langmuir (a) and Freundlich isotherm (b) for PO
4
P.
Fig. 9. Pseudo rst (a) and second order kinetic model (b) for total iron.
232 S.L. Ching et al. / Desalination 279 (2011) 225234
iron and PO
4
P followed second-order kinetics suggesting that the
adsorption was controlled by chemisorption [37].
4. Conclusions
The experimental impregnation ratios strongly affected the physical
characteristics of coffee grounds activated carbon. The optimum
impregnation ratio was found to be 0.5 to obtain higher specic surface
area (224.7 m
2
/g) andmicropore volume (0.07986 cm
3
/g). FTIRindicated
that the presence of functional groupOH, NH, CH, C_O, OH, COand
POC in coffee grounds activated carbon. Impregnation ratio of 2.5 and
0.5 was optimum for the removal of total iron (77%) and PO
4
P (84%),
respectively at 10 g dosages and pH8.1. The optimumpHwas 13 for total
iron removal and pHb5 and pHN11 for PO
4
P removal onto the coffee
grounds. The adsorption capacity of total iron increased with an increase
of the adsorbent dosage. But it was exceptional for PO
4
P removal which
showed uctuationtrend possibly due to the effect of foreignions present
in the leachate.
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