Global NEST Journal, Vol 19, No 3, pp 464-478

Copyright© 2017 Global NEST

Printed in Greece. All rights reserved

Batch and fixed-bed column studies for the biosorption of Cu(II) and
Pb(II) by raw and treated date palm leaves and orange peel
Amin M.T.1,2, *, Alazba A.A.1,3 and Shafiq M.1
1Alamoudi Water Research Chair, King Saud University, P. O. Box 2460, Riyadh 11451, Kingdom of Saudi Arabia
2Department of Environmental Sciences, COMSATS Institute of Information Technology, Abbottabad, 22060, Pakistan
3 Agricultural Engineering Department, King Saud University, P. O. Box 2460, Riyadh 11451, Kingdom of Saudi Arabia

Received: 09/03/2017, Accepted: 25/08/2017, Available online: 22/10/2017

*to whom all correspondence should be addressed: e-mail: [email protected]

Abstract disposal of extremely large quantities of untreated

wastewater from industrial, agricultural, and household
Herein, we describe the batch and fixed-bed column sources into natural water bodies (oceans, rivers, and lakes).
adsorption of Cu2+ and Pb2+ by raw and treated date palm The above wastewater can contain acids, plating metals, and
leaves (DP) and orange peel (OP) waste biomass. Contact toxic chemical residues, with heavy metals being of particular
time, pH, adsorbent dose, and particle size were optimized in concern due to their long-term persistency in soils and
batch adsorption experiments, while breakthrough curves sediments. Since heavy metals are not biodegradable, they
obtained in fixed-bed adsorption experiments were used to can accumulate in the environment and the food chain,
determine the effects of bed height, initial metal posing severe health hazards to humans, animals, and plants
concentration, particle size, and flow rate. The use of treated (Singh et al., 2011). Excessive exposure to heavy metals can
DP and/or OP in batch adsorption mode increased the result in cancer, retarded growth and development, organ
removal efficiency of metal ions by 20–30% compared to that damage, elevated blood pressure and blood sugar levels,
observed for raw adsorbents. The equilibration time was joint diseases, and, in extreme cases, sudden death (Chary et
estimated as 0.5 h, with rapid metal removal observed during al., 2008; Titi and Bello, 2015).
the first 15 min at an optimum pH value of ~5. Increasing the
adsorbent dose from 0.5 to 6–7 g enhanced the metal Among toxic metals, the major environmental contaminants
removal efficiency by ~60%, whereas a particle size increase present in drinking water and industrial wastewater are
from 50 to 300 µm decreased this value by about 30% for copper and lead (Osman et al., 2010; Soliman et al., 2016),
both Cu2+ and Pb2+ and both raw and treated DP/OP. Both originating from battery manufacturing waste, erosion of
breakthrough and exhaust times increased with increasing natural deposits, leather finishing, and metal plating (Song et
bed height of the fixed-bed column, and the effect observed al., 2013). The maximum allowable limits for copper and lead
for treated DP exceeded that observed for raw DP by a factor in discharged wastewater set by the Environmental
of two. Conversely, both breakthrough and exhaust times Protection Agency (EPA) equal 1.3 and 0.05 mg L–1,
decreased with increasing initial metal concentration, respectively (Barakat, 2011; Djeribi and Hamdaoui, 2008;
particle size, and flow rate. Increasing the particle size from Zahra, 2012). Hence, methods of controlling and reducing the
100–150 to 300 µm changed the exhaust time by 8 h when levels of these metal ions in wastewater to comply with EPA
treated DP was used for Pb2+ adsorption. The obtained linear guidelines are urgently required to maintain a sustainable
regression coefficients (R2 = 0.9–0.99) suggest that both global ecosystem (Ertaş and Öztürk, 2013).
Thomas and Yoon–Nelson models are well-suited for The removal of heavy metals from (waste)water has been
predicting the adsorption performance of the present attempted using various physical, chemical, and biological
system. techniques, e.g., reverse osmosis (Gupta et al., 2012), hybrid
Keywords: adsorption, date palm, fixed bed, orange peel, electrocoagulation membranes (Mavrov et al., 2006),
pre-treatment, Thomas, Yoon-Nelson chemical precipitation, ion exchange (Da̧ browski et al., 2004),
chemical coagulation and flocculation (Amuda et al., 2006),
1. Introduction ozonation, hybrid flotation/membrane filtration (Blöcher et
Mitigation of the rapidly progressing contamination of al., 2003), and advanced oxidation (Oller et al., 2011).
aquatic environments with heavy metals has recently However, these techniques are not widely used due to their
become a challenge for researchers (Han et al., 2006; high energy cost, production of oxidation by-products, and
Sternberg and Dorn, 2002), being attributed to the daily membrane fouling during filtration. Most of these methods

Amin M.T., Alazba A.A. and Shafiq M. (2017), Batch and fixed-bed column studies for the biosorption of Cu(II) and Pb(II) by raw and treated
date palm leaves and orange peel, Global NEST Journal, 19(3), 464-478.
BATCH AND FIXED-BED COLUMN STUDIES FOR THE BIOSORPTION OF Cu(II) AND Pb(II) 465

are also ineffective for metal ion concentrations of 10–100 2.1. Chemicals and adsorbents
mg L–1 (Bulut and Tez, 2007). Hence, extensive research
Stock solutions of Cu2+ and Pb2+ (1000 mg/L each) in
efforts are now focused on developing new, cost-effective,
deionized water were prepared by dissolving appropriate
and eco-friendly techniques for removing such toxic
amounts of copper sulfate pentahydrate (CuSO4·5H2O; AR
pollutants.
grade, Merck, Germany) and lead nitrate (Pb (NO3)2, Tianjin
Biosorption is a technology developed in the last few years to Benchmark Chemical Reagent Co., Ltd. Tianjin, China) in a
mitigate contamination by toxic metals, presenting a 1000-mL volumetric flask, respectively. The solution pH was
potential alternative to traditional water decontamination adjusted using aqueous HCl or NaOH (0.1 M each), and pH
treatment due to its low cost, abundant raw materials, measurements were carried out utilizing a microprocessor-
minimal utilization of chemicals, generation of minimal based pH meter (PHS-3CW, China). Stock solutions were
amounts of biological sludge waste, and absence of nutrient stored at 4 °C for long-term use, with 2 mL of concentrated
requirements (Aksu, 2005; Sarı et al., 2007). The efficiency of HCl added as a preservative. Different standard solutions
biosorption relies on the adsorption of dissolved metal ions with initial concentrations of 50−150 mg/L were prepared
onto the adsorbent surface. Recently, agricultural waste and from stock solutions by serial dilution with deionized water.
byproducts such as tobacco stems, peat, wood, pine cones,
To prepare raw adsorbents, both DP and OP were collected
banana peels, cotton balls, coffee leaves, wheat straws, rice
from various locations in Riyadh, Saudi Arabia, and were
husk, sawdust, and orange peel have been widely
initially washed with tap water and thoroughly rubbed to
investigated as sorbents for metal removal from
remove all foreign particles. The adsorbents were further
(waste)water (Annadurai et al., 2003; Ho et al., 2002;
washed with distilled water, filtered, and placed in a drying
Momcilovic et al., 2011; Riaz et al., 2009; Saka et al., 2012;
oven held at ~70 °C for 24 h. The dried materials were
Sciban et al., 2007; Tan, 1985; Wong et al., 2003), making this
crushed by a crushing machine and ground (Planetary Mono
process both cost-effective and environmentally friendly and
Mill Pulverisette 6, FRITSCH, Germany) to an average particle
simultaneously helping to reduce surface pollution.
size of 0.045–0.3 mm.
Saudi Arabia is the biggest market for oranges and dates,
To obtain pre-treated adsorbents, ~50-g samples of raw DP
which are important fruit crops occupying a large percentage
and OP were reacted with 250 mL of 1% ethanolic NaOH at
of cultivated land. Three large Saudi Arabian cities (Riyadh,
room temperature (25 °C) for 24 h. Further modification was
Jeddah, and Dammam) annually produce more than six
performed by stirring approximately 30 g of the dry product
million tons of biowaste, with values of 600,000 kg/day
in 1 L of 1% mercaptoacetic acid (C2H2O2S) for 12 h at room
observed during pilgrimage and local fasting festivals (Khan
temperature to improve adsorption capacity, as reported
and Kaneesamkandi, 2013). A large fraction of the generated
earlier (Amin et al., 2016).
food left-overs is represented by orange and date palm
waste. On average, about 20 million kg of date palm waste 2.2. Batch adsorption experiments
(leaves and stems) is produced annually as a result of farming
Batch adsorption experiments were performed to measure
practices (such as thinning and pruning) and disease
the effectiveness of Cu2+ and Pb2+ adsorption for both raw
treatment. Similarly, a large amount of orange peel waste is
and treated DP and OP. These experiments were carried out
produced by domestic orange juice industries. These biomass
in duplicate, utilizing 100-mL conical flasks and an orbital
wastes can potentially be used as low-cost green adsorbents
shaking incubator (Wise Cube Orbital Shaker, Daihan
for removing lead and copper from wastewater, helping
Scientific Co. Ltd., Wisd. ThermoStable IS-20, South Korea) at
reduce surface pollution and decontaminate aqueous media.
a certain controlled temperature and 220 rpm. Samples were
In this study, we focused on the removal of copper (Cu2+) and drawn every 5 min, centrifuged (Elektromag M815P) at 1000
lead (Pb2+) using both raw and treated (i.e., chemically rpm, and filtered through a nitrocellulose filter (0.45 µm)
modified) date palm leaves (DP) and orange peel (OP) waste using a vacuum filtration assembly. The filtrates were diluted
biomass employing batch and fixed-bed methods. The to obtain metal levels corresponding to the linear range of
removal efficiencies of Cu2+ and Pb2+ achieved by the above calibration curves and were analyzed using a flame atomic
low-cost agricultural byproducts were determined in batch absorption spectrometer (Perkin Elmer AAnalyst 200). Batch
experiments, whereas the industrial-scale applicability of adsorption data were analyzed using Eqs. (1) and (2) to obtain
these sorbents was analyzed in fixed-bed column the adsorption capacity and the removal effectiveness of
experiments. All experiments were carried at room selected heavy metal ions.
temperature by varying certain parameters while keeping
other ones constant. Finally, the process of column C0 -Cf
qe = ( )V (1)
adsorption was analyzed using different kinetic models for m
estimating the breakthrough performance of the fixed-bed
column reactor. C0 -Cf
Removal efficiency (%)= ( ) ×100 (2)
C0
2. Materials and methods
466 AMIN et al.

where qe is the metal uptake (mg g–1), C0 is the initial metal before and after Cu2+/Pb2+ adsorption at different
concentration (mg L–1), Cf is the residual metal concentration magnifications (×2400, ×3000, and ×6000) shown in Fig. 1.
(mg L–1) after adsorption, and V (L) and m (g) are the volume Images in Figs. 1a and 1b show raw DP and OP surfaces before
of the heavy metal–containing solution and adsorbent mass, adsorption.
respectively. After adsorption, the pores were covered by heavy metal ions
Fixed raw and treated adsorbent masses of 0.5 and 1 g —per (Figs. 1c and 1d), making their structural analysis
litre of the heavy metal ion’s solution, respectively, were complicated. Prior to adsorption, however, rough
used in different experiments. To determine the equilibration asymmetric pores with different diameters and cylinders
time, batch experiments were conducted at regular time were observed on the surface of both adsorbents, which
intervals during the first 3 h. Similarly, batch adsorption improved their interactions with heavy metal ions. Cylindrical
experiments were also performed to optimize the contact shaped structures seem to be composed of multicellular
time, pH, adsorbent dose, adsorbent particle size, and the fibres bound together by lignin. One can also observe the
pre-treatment procedure. Table 1 summarizes the results of central void inside the fibre, known as the lumen (Fig. 1a).
batch experiments and the used parameters. Secondary pores were also seen inside the primary pores on
the surface of both adsorbents before the adsorption of
2.3. Column adsorption
heavy metal ions. These primary and secondary pores were
Fixed-bed column adsorption experiments were carried out critical for the sorption of heavy metal ions.
in a cylindrical glass column with an internal diameter of 2.5 The surfaces of both raw and treated DP exposed to heavy
cm and a height of 60 cm. The top and bottom of the column metal solutions exhibited closed pore structures and a
were covered with a 3-mm layer of glass beads and glass smooth and shiny appearance owing to the physicochemical
wool, respectively, and the column was filled with adsorbents interaction between the above ions and the functional
to a bed height of ~50 cm. Adsorbents with different particle groups present on the rough surface of these adsorbents. The
sizes were used, as specified for each experiment in Table 2. attachment of metal ions could be seen clearly on the surface
In every experiment, a heavy metal–containing solution of a of the adsorbents and inside the pores and the change of the
certain initial concentration (50–150 mg L–1) was pumped to structure of adsorbents after adsorption can be linked to the
the top of the column using a peristaltic pump at a fixed flow influence of metal ions.
rate (2–10 L min–1), as shown in Table 2. All experiments were
carried out at room temperature and had a pH of 4–5 (Table (a)
(c)
2). Samples for determining the concentration of metal ions
were collected at regular time intervals at the bottom of the
column, and continuous adsorption experiments were
stopped only after the column was fully exhausted. After
plotting the breakthrough curves (Ct/C0 vs. time), the 50%
breakthrough capacity (i.e., Ct/C0 = 0.5) was calculated using
Eq. (3):

(t0.5 × Q × C0 ) (b) (d)

Q0.5 = (3)
m
where Q0.5 is the 50% breakthrough capacity (mg of metal
adsorbed per gram of adsorbent, mg g–1), t0.5 is the
breakthrough time at 50% (i.e., at Ct/C0 = 0.5), C0 and Ct are
the initial and effluent metal concentrations (mg L –1),
respectively, and Q (mL min–1) and m (g) are the flow rate and
adsorbent mass, respectively. Finally, the obtained data were
analyzed using Thomas and Yoon-Nelson kinetic models as
well as the bed depth service time (BDST) model to Figure 1. SEM images of (a) raw DP, (b) raw OP, (c) treated
determine the kinetic parameters, adsorption capacity, and DP after Cu2+ adsorption, and (d) treated OP after Pb2+
breakthrough performance of the utilized fixed-bed column adsorptionResults and discussion
reactor.
3.2. Analysis of batch adsorption data
3. Results and discussion
Batch experiments were performed to measure the
3.1. Surface characterization of adsorbents adsorption effectiveness of specific metals. In this section,
The availability of pores and internal surfaces was the selected results for the potential of raw and treated
determined by scanning electron microscopy (SEM, Tescan DP/OP for removing Cu2+ and Pb2+ in batch systems is
Vega 3 SBU, USA), with images of raw/treated adsorbents presented. The effects of different process variables
BATCH AND FIXED-BED COLUMN STUDIES FOR THE BIOSORPTION OF Cu(II) AND Pb(II) 467

including pre-treatment effects, contact time, pH, adsorbent

dose, and particle size were investigated while keeping other
relevant process parameters constant, as shown in Table 1.
Table 1. Selected process variables and constants used in different batch experiments
Constant parameters
Variable parameters Value/range Adsorbent/metal Contact Initial metal Adsorbent Particle
pH
time, min conc. mg L–1 dose, g size, µm
Raw and treated DP/Cu2+
Pre-treatment
Raw and treated OP/Pb2+
- 5 50 1 45
Treated DP and OP/Cu2+
Contact time, min 0–1500
Raw DP and OP/Pb2+
Raw DP/Cu2+
Initial solution pH 2–6 15 - 50 1 75
Treated OP/Pb2+
Raw DP/Cu2+
Adsorbent dose, g 0.5–7 15 5 50 - 75
Treated OP/Pb2+
Raw and treated DP/Cu2+
Particle size, µm 50–300 15 5 50 1 -
Raw and treated OP/Pb2+

3.2.1. Effects of pre-treatment and contact time on metal or chemical modification of raw/natural biosorbents was
adsorption efficiency reported to improve the adsorption capacity by enhancing
adsorbent porosity and stability as well as by controlling the
The effects of pre-treatment (i.e., chemical modification) on
coloration and release of organic materials in solution (Ali et
the Cu2+ and Pb2+ adsorption capacities of raw DP and OP,
al., 2014; Jiménez-Cedillo et al., 2013; Mohan and Pittman,
respectively, are shown in Fig. 2. Batch adsorption
2007; Zhu et al., 2008; Khosa et al., 2013).
experiments for determining pre-treatment effects were
performed at an initial metal concentration of 50 mg L–1, To establish an equilibrium, which is essential for designing
adsorbent dose of 1 g, adsorbent particle size of 45 µm, and batch adsorption experiments, it was important to evaluate
an initial solution pH of 5 (Table 1). the effect of contact time on Cu2+ and Pb2+ adsorption
capacity. Kinetic measurements were conducted to
After ~3 h of adsorption, a 20 % higher Cu2+ removal
determine the time required to reach adsorption equilibrium,
efficiency was observed for treated DP compared to that of
with results obtained for the removal of Cu 2+ with treated
raw DP, with this difference slightly increasing after 1 d.
DP/OP and that of Pb2+ using raw DP/OP presented in Fig. 3.
Similarly, treated OP exhibited a ~30% higher Pb2+ adsorption
As described in Table 1, a pH of 5, an initial metal
efficiency than raw OP (Fig. 2b). The observed adsorption
concentration of 50 mg L–1, an adsorbent dose of 1 g, and
enhancement was attributed to the increased number of
particle size of 45 µm was used.
functional groups generated on the surface of modified
adsorbents (Abia et al., 2002). Moreover, the pre-treatment
100 100
(a) Cu+2 (b) Pb+2
90 90
80 80
DPtrd
70 70
DPraw
Removal (%)

60 60
50 50 OPtrd
40 40 OPraw
30 30
20 20
10 10
0 0
0 30 60 90 120 150 180 400 800 1200 0 30 60 90 120 150 180 400 800 1200
Time (minutes) Time (minutes)

Figure 2. Effects of pre-treatment on the removal of (a) Cu2+ by DP and (b) Pb2+ by OP
468 AMIN et al.

100 100
(a) Cu+2 (b) Pb+2
90 90
80 80
OPraw
70 70
Removal (%)
DPraw
60 60
50 50
40 OPtrd 40
30 DPtrd 30
20 20
10 10
0 0
0 30 60 90 120150 180 600 900 1200 1500 0 30 60 90 120 150 180 400 800 1200
Time (minutes) Time (minutes)

Figure 3. Effects of contact time on the removal of (a) Cu2+ and (b) Pb2+ by DP and OP

Figure 3 shows the effect of contact time on the adsorption (0.5 to 7 g), with other parameters being constant, at an
of Cu2+ and Pb2+ by raw and treated DP and OP, revealing initial solution pH of 5.
rapid adsorption during the first 15–20 min that was ascribed The maximum efficiency of Cu2+ removal by raw DP was
to the availability of unreacted adsorbent surface at the initial observed at pH of 5, whereas the corresponding efficiency of
stage (Qadeer and Akhtar, 2005). Cu2+ and Pb2+ adsorption Pb2+ removal by treated OP was maximal at pH of 5–5.5 (Fig.
equilibria were established in ~30 min, although the 4a). The maximum adsorption capacity was estimated as 17.5
efficiency of Pb2+ removal by raw DP/OP was less (35–40%) and 28 mg g-1 for Cu2+ and Pb2+ using raw DP and treated OP,
than that of Cu2+ removal by treated DP/OP (50–70%). For respectively. Similar pH dependencies have previously been
other batch experiments, an equilibration time of 30 min was investigated for the adsorption of heavy metal ions onto
used to optimize the adsorption process. plant wastes of various types (Yadav et al., 2015; El Nemr et
3.2.2. Effects of pH and adsorbent dose al., 2008; Rajamohan et al., 2014). The enhanced removal of
Cu2+ and Pb2+ under acidic conditions was ascribed to the
pH variation significantly influences the adsorption competition between metal cations and protons (H+) for
mechanism, resulting in efficient removal of cationic biosorption sites and increased electrostatic repulsive
molecules by biosorbents (Areco and Afonso, 2010). The interactions at low pH (Chieng et al., 2015; El-Bindary et al.,
effect of initial solution pH was investigated in the range of 2 2014).
to 6 (Fig. 4a), while other parameters, i.e., initial metal
concentration (50 mg L–1), adsorbent dose (1 g), particle size The adsorbent dose influences the economic viability of the
(75 µm), and contact time (15 min) were kept constant (Table adsorption process, making it critical to achieve maximal
1). Figure 4b shows the effects of different adsorbent doses removal efficiency using a minimal amount of adsorbent.

100 100
(a) (b)
90 +2
DPraw, Cu
80 80 +2
DPraw, Cu
+2 OPtrd, Pb
70
Removal (%)

+2
60 OPtrd, Pb 60
50
40 40
30
20 20
10
0 0
0 1 2 3 4 5 6 1 2 3 4 5 6 7
pH Adsorbent dose (g)

Figure 4. Effects of (a) pH and (b) adsorbent dose on the removal of Cu2+ and Pb2+ by DP and OP
BATCH AND FIXED-BED COLUMN STUDIES FOR THE BIOSORPTION OF Cu(II) AND Pb(II) 469

100 100
(a) Cu+2 (b) Pb+2
90 90
80 DPtrd 80
70 OPtrd
DPraw 70

Removal (%)
OPraw
60 60
50 50
40 40
30 30
20 20
10 10
0 0
0 50 100 150 200 250 300 0 50 100 150 200 250 300
Particle size (µm) Particle size (µm)

Figure 5. Effects of particle size on the removal of (a) Cu2+ by DP and (b) Pb2+ by OP

A 60–70% increase of metal removal efficiency was observed 2012; Boudrahem et al., 2011; Ghorbani et al., 2012; Hikmat
for Cu2+ by raw DP and for that of Pb2+ by treated OP when et al., 2014; Haleem and Abdulgafoor, 2010).
the adsorbent dose was increased from 0.5 to 5–7 g (Fig. 4b).
3.2.3. Effects of particle size
The enhanced removal efficiency of both Cu2+ and Pb2+ at an
adsorbent dose of 5–7 g, as compared to those observed at The effects of particle size were investigated for the removal
lower dosages of 1–4 g, was attributed to the larger available of Cu2+ by raw and treated DP and for that of Pb2+ by raw and
surface area with more binding sites in the former case treated OP, as shown in Figs. 5a and 5b, respectively, with
(Aydın et al., 2008; Uzunoğlu et al., 2014). The stable removal initial metal concentration (50 mg L–1), adsorbent dose (1 g),
efficiencies beyond 5 g shows that this value is the optimum pH (5), and contact time (15 min) kept constant, and the
dose of both adsorbents and was estimated as 5 g at which average particle size varied between 50 and 300 µm (Table
the maximum adsorption capacity of 38 and 49 mg g-1 was 1).
recorded for Cu2+ and Pb2+ using raw DP and treated OP, As shown in Fig. 5, increasing the particle size from 50 to 300
respectively. µm decreased the removal efficiency of both Cu2+ and Pb2+ by
The maximum adsorption of both metal ions was observed at ~30–35%, which could be ascribed to the decreased
contact times of about 10 min when the dose increased to 6- adsorbent surface area and number of available binding sites
7 g using same values of other process parameters. (Al-Ghouti et al., 2010). Moreover, larger particles are known
Increasing the adsorbent dose increased the adsorption to result in increased internal diffusion related to adsorbate
capacity, concomitantly increasing the removal efficiency, as penetration, delaying the establishment of an equilibrium
reported in previous studies (Yadav et al., 2013; Hilal et al., and consequently decreasing adsorption capability.
Table 2. Selected process variables and constants used in different fixed-bed column experiments
Constants parameters
Variable Bed
Value/range Adsorbent/metal Contact Initial metal Particle Flow rate,
parameters pH height,
time, h conc., mg L–1 size, µm mL min–1
cm
5, 10, 15 Raw DP/Cu2+ 6.67 4
100 2
Bed height, cm Raw DP/Pb 2+
10.83 - 300
5, 10 5
Treated DP/Pb2+ 21.67 50 4
50, 100, 150 Raw DP/Cu2+ 6.67 4 300
Initial metal
100, 200 Raw DP/Pb2+ 10.83 5 - 150 2
conc., mg L–1 5
50, 100 Treated DP/Pb2+ 21.67 300
150, 300 Raw DP/Pb2+ 10.83
Particle size,
100, 200, 5 5 100 - 4
µm Treated DP/Pb2+ 21.67
300
Flow rate, mL 4, 7, 10 Raw DP/Cu2+ 6.67 100
5 5 300 -
min–1 2, 4, 6 Treated DP/Pb2+ 21.67 50
470 AMIN et al.

3.3. Fixed-bed column adsorption adsorption of Pb2+, a breakthrough time increase of ~1 h and
a significant exhaust time increase of more than 6 h were
The continuous adsorption of Cu2+ and Pb2+ in a fixed-bed
observed (Fig. 6c). The increased breakthrough and exhaust
column was investigated using both raw and treated DP and
times observed for deeper beds are attributed to their
OP, however only selective results are presented in this
increased surface area and a larger amount of binding sites
section. Breakthrough curves (plots of normalized
for heavy metal ions. Similar results were reported for
concentration (Ct/C0) vs. time) under specified operating
adsorption of Cu2+ by magnetized sawdust (Kapur and
conditions were predicted for the successful design and
Mondal, 2016), in line with other investigations on the
operation of fixed-bed adsorption. The shape of these curves
adsorption of different dyes onto plant-based adsorbents
and breakthrough times are important characteristics
(Yagub et al., 2015; Sajab et al., 2015).
influenced by individual transport in the column and the
adsorbent, reflecting the loading behavior of the heavy metal 3.3.2. Effect of initial metal concentration
ions being removed (Vázquez et al., 2006; Guo and Lua, 2003;
Breakthrough curves obtained for different initial metal
Ahmad and Hameed, 2010). The effects of parameters such
concentrations (50–200 mg L–1) at a constant flow rate (2 mL
as bed height, initial metal concentration, particle size, and
min–1) and a bed height of 5 cm are shown in Fig. 7.
flow rate were evaluated separately by keeping the values of
Adsorption of Cu2+ onto raw DP was conducted at an initial
other relevant parameters constant, as shown in Table 2
solution pH of 4 and an adsorbent particle size of 300 µm (Fig.
3.3.1. Effects of bed height 7a), whereas adsorption of Pb2+ by raw and treated DP was
performed at an initial pH value of 5 and adsorbent particle
The effects of bed height (5, 10, and 15 cm) on the adsorption
sizes of 150 and 300 µm, respectively. For the adsorption of
of Cu2+ by raw DP and on that of Pb2+ by raw and treated DP
Cu2+ onto raw DP, increasing the initial metal concentration
were investigated for solutions with initial pH values of 4–5
from 50 to 150 mg L–1 decreased the breakthrough and
and initial metal concentrations of 50 and 100 mg L–1 at flow
exhaust times by ~30 and 90 min, respectively (Fig. 7a). A
rates of 2 and 4 mL min–1 and an adsorbent particle size of
similar decrease of breakthrough time (about 30 min) and
300 µm (Fig. 6). Figure 6a shows that increasing the bed
exhaust time (more than 2 h) was observed for the
height from 5 to 15 cm resulted in a slight breakthrough time
adsorption of Pb2+ onto raw DP when the initial metal
increase of ~0.5 h for Cu2+ adsorption by raw DP, whereas the
concentration was increased from 100 to 200 mg L–1 (Fig. 7b).
exhaust time was increased by ~3 h. A similar insignificant
When treated DP was used, the decreases of breakthrough
breakthrough time increase and nearly unchanged exhaust
and exhaust times was observed as ~ 1 h and > 6 h,
time were observed for the adsorption of Pb2+ by raw DP
respectively, as the initial Pb2+ concentration was increased
when the bed height was doubled from 5 to 10 cm, as shown
from 50 to 100 mg L–1 (Fig. 7c).
in Fig. 6b. However, when treated DP was used for the

1.0 (a) DP - Cu+2 1.0 (b) DP - Pb+2 1.0 (c) DP - Pb+2

0.8 0.8 0.8

0.6 0.6 0.6

Ct/Co

5 cm 5 cm
0.4 10 cm 0.4 10 cm 0.4 5 cm
15 cm 10 cm

0.2 0.2 0.2

4 pH, 100 ppm, 300 µm, 2 mL min-1 5 pH, 100 ppm, 300 µm, 2 mL min-1 5 pH, 50 ppm, 300 µm, 4 mL min-1
0.0 0.0 0.0
0 50 100 150 200 250 300 350 400 0 100 200 300 400 500 600 0 200 400 600 800 1000 1200
Time (minutes) Time (minutes) Time (minutes)

Figure 6. Effects of bed height on the adsorption of (a) Cu2+ by raw DP and Pb2+ by (b) raw and (c) treated DP.

1.0
(a) DP - Cu+2 1.0 (b) DP - Pb+2 1.0 (c) DP - Pb+2

0.8 0.8 0.8

0.6 0.6 0.6

Ct/Co

-1
50 mg L -1 -1
-1 100 mg L 50 mg L
0.4 100 mg L 0.4 -1 0.4 -1
-1 200 mg L 100 mg L
150 mg L
0.2 0.2 0.2

4 pH, 5 cm, 300 µm, 2 mL min-1 5 pH, 5 cm, 150 µm, 2 mL min-1 5 pH, 5 cm, 300 µm, 2 mL min-1
0.0 0.0 0.0
0 50 100 150 200 250 300 350 400 0 100 200 300 400 500 600 0 200 400 600 800 1000 1200
Time (minutes) Time (minutes) Time (minutes)

Figure 7. Effects of initial metal concentration on the adsorption of (a) Cu2+ by raw DP and Pb2+ by (b) raw and (c) treated DP
BATCH AND FIXED-BED COLUMN STUDIES FOR THE BIOSORPTION OF Cu(II) AND Pb(II) 471

smaller particles (150 µm) were employed (Fig. 8a). For

The above breakthrough time decline observed for increasing adsorption of Pb2+ onto treated DP, both breakthrough and
initial metal concentrations was attributed to slower mass exhaust times decreased by almost 0.5 and 8 h, respectively,
transport caused by the reduced metal concentration as the average particle size increased from 100 to 300 µm
gradient, which consequently decreased the diffusion or (Fig. 8b). The left-to-right breakthrough curve shift with
mass transfer coefficient (Teng and Lin, 2006). decreasing particle size resulted in enhanced metal ion
removal. Consequently, the increased breakthrough and
3.3.3. Effects of particle size
exhaust times observed for smaller particle sizes imply that
The effects of average particle size on the adsorption of Pb2+ the column is more difficult to exhaust under these
onto raw and treated DP are exemplified by the conditions than in the case of larger particles.
breakthrough curves in Figs. 8a and 8b, respectively, which
3.3.4. Effects of flow rate
were recorded at constant pH (5), bed height (5 cm), initial
metal concentration (100 mg L–1), and flow rate (4 mL min–1), The adsorption of Cu2+ and Pb2+ at flow rates in the range of
as shown in Table 2. 2–10 mL min-1 was studied using raw and treated DP,
No influence of particle size on breakthrough time was respectively, with breakthrough curves shown in Fig. 9 An
observed when raw DP was used for Pb 2+ adsorption. initial solution pH of 5 with a bed height of 5 cm and an
However, the exhaust time was decreased by 2 h when larger average particle size of 300 µm was used, whereas initial
particles (300 µm) were used, as compared to the case when metal concentrations of 100 and 50 mg L–1 were used for Cu2+
and Pb2+, respectively.

1.0 (a) DP - Pb+2 1.0 (b) DP - Pb+2

0.8 0.8

0.6 0.6 300 µm

200 µm
Ct/Co

300 µm
150 µm 100 µm
0.4 0.4

0.2 0.2
5 pH, 5 cm, 100 mg L-1, 4 mL min-1 5 pH, 5 cm, 100 mg L-1, 4 mL min-1
0.0 0.0
0 100 200 300 400 500 600 0 200 400 600 800 1000 1200 1400
Time (minutes) Time (minutes)

Figure 8. Effects of particle size on the adsorption of Pb2+ by (a) raw and (b) treated DP

(a) DP - Cu+2 - Pb+2

1.0 1.0 (b) DP

0.8 0.8
-1
10 mL min -1
0.6 7 mL min
-1
0.6 6 mL min
Ct/Co

-1
4 mL min
-1 4 mL min
-1
0.4 0.4 2 mL min

0.2 0.2
5 pH, 5 cm, 100 mg L-1, 300 µm 5 pH, 5 cm, 50 mg L-1, 300 µm
0.0 0.0
0 100 200 300 400 0 200 400 600 800 1000 1200 1400
Time (minutes) Time (minutes)

Figure 9. Effects of flow rate on the adsorption of (a) Cu2+ by raw DP, and (b) Pb2+ by treated DP.

The breakthrough and exhaust times for Cu2+ adsorption onto the flow rate from 4 to 10 mL min–1 (Fig. 9a). Similarly, both
raw DP were decreased by slightly less than 1 h by increasing breakthrough and exhaust times gradually decreased by
472 AMIN et al.

slightly more than 1 h and ~4 h, respectively, for Pb2+ where the Thomas rate constant or kinetic coefficient (KTh, L
adsorption onto treated DP as the flow rate was increased min–1 mg–1) and the maximum or equilibrium sorption
from 2 to 6 mL min–1 (Fig. 9b). This result shows that the capacity of the fixed-bed column (q0, mg g–1) can be
column is difficult to exhaust at smaller flow rates due to the determined from the plot of ln[(C0/Ct)−1] vs. time (t, min) at a
higher removal efficiency of heavy metal ions in the bed. given flow rate using linear regression analysis. In the above
Besides, the low contact time between adsorbents and heavy formula, C0 and Ct are the initial and effluent metal
metal ions observed at higher flow rates can reduce the concentrations (mg L–1), Q is the flow rate (mL min–1), and m
adsorption efficiency of the packed bed. Furthermore, the is the amount of adsorbent in the column (g). Both KTh and q0
faster adsorption zone movement at high flow rates may calculated from linearized plots were used to describe the
reduce the time for Cu2+/Pb2+ adsorption onto the surface of column behavior (Pilli et al., 2012). For adsorption of Cu2+ in
packed DP/OP in the fixed-bed column (Sadaf et al., 2015). a fixed-bed column packed with raw DP, KTh increased and q0
decreased with increasing flow rate (Table 3a). Table 3b
3.4. Breakthrough curve prediction and column adsorption
presents the results of Pb2+ adsorption onto treated DP,
models
showing that q0 increased and KTh decreased with increasing
3.4.1. Thomas model initial metal concentration, which can be attributed to the
increased driving force related to the concentration
The Thomas model, based on the Langmuir
difference between the metal ions onto the surface of the
adsorption/desorption model and second-order reversible
adsorbent and in the solution (Aksu and Gönen, 2004; Malkoc
reaction kinetics, is most commonly used to describe the
et al., 2006). Moreover, KTh and q0 decreased with increasing
behavior of breakthrough curves in fixed-bed columns
bed height although the difference in q0 was not significant
(Thomas, 1944; Futalan et al., 2011; Apiratikul and Pavasant,
by increasing the bed height from 5 to 15 cm (Table 3a). The
2008), being helpful for predicting the maximum adsorption
diminution in the equilibrium sorption capacity with decrease
capacity of adsorbents required for treatment plant design.
in bed height signifies that the effluent concentration ratio of
This model was applied to calculate the maximum solid-
heavy metal ions increased more rapidly at smaller bed
phase concentrations of Cu2+/Pb2+ and the corresponding
height than for a higher bed height. Hence, the lower bed
adsorption rate constants using the data obtained for the
depth improve the adsorption of both heavy metal ions on
fixed-bed column in continuous mode. The linearized form of
the studies adsorbents to a limited extent and the bed is
the Thomas model can be expressed as Eq. (4):
saturated in less time for smaller bed heights which
C0 KTh q0 m corresponds to less amount of adsorbent. These results are
ln ( -1) = -(KTh C0 )t (4) similar to those obtained by other researchers (Futalan et al.,
Ct Q
2011; Cheraghi et al., 2016; Kapur and Mondal, 2016).
Table 3a. Thomas model parameters obtained by regression analysis at various conditions of Cu2+ adsorption onto raw DP.
Initial conc. Flow rate KTh
Bed height (cm) q0 (mg g–1) R2
(mg L–1) (mL min–1) (mL min–1 mg–1)
50 5 3 0.508 1.657578 0.9077
100 5 3 0.173 4.416846 0.9817
100 10 3 0.09 3.659286 0.9531
100 15 3 0.068 3.415889 0.8765
100 5 7 0.385 3.077403 0.9033
100 5 10 0.42 2.253571 0.891
150 5 3 0.165 5.190193 0.8847
Table 3b. Thomas model parameters obtained by regression analysis at various conditions of Pb2+ adsorption onto treated DP.
Flow rate KTh
Initial conc. (mg L–1) Bed height (cm) q0 (mg g–1) R2
(mL min–1) (mL min–1 mg–1)
50 5 2 0.148 7.647201 0.8539
100 5 2 0.049 9.63586 0.891
100 10 2 0.033 6.962264 0.8871
50 5 4 0.16 5.366374 0.9396
50 5 6 0.194 3.477099 0.9466

These conditions can be attributed to the high driving force earlier for the adsorption of phosphate and nitrate on waste
due to the high amount of heavy metal ions perforated into solids (Olgun et al., 2013). Thus, the adsorption of Cu2+ and
the packed bed of DP. Similar results have been reported Pb2+ onto raw and treated DP, respectively, can be enhanced
BATCH AND FIXED-BED COLUMN STUDIES FOR THE BIOSORPTION OF Cu(II) AND Pb(II) 473

at higher initial concentrations, lower flow rates, and smaller where KYN is the Yoon-Nelson rate constant (min−1), T is the
bed depths. R2 values of ~0.9 and high indicated an average time required for 50% adsorbate breakthrough (min), C0 and
to good fits of the adsorption data to the Thomas model Ct are the initial and effluent metal concentrations,
suggesting that internal and external diffusion were not rate- respectively (mg L–1), and t is the breakthrough (sampling)
limiting steps (Rao et al., 2011; Aksu and Gönen, 2004; time (min). KYN (slope) and T (= intercept/KYN) can be
Cheraghi et al., 2016). determined from the plot of ln(Ct/(C0− Ct)) vs. sampling time
(t, min).
3.4.2. Yoon-Nelson model
This model was applied to experimental data obtained at
The Yoon-Nelson model, a simple theoretical model based on different flow rates (2–10 mL min–1), initial metal
the theory of adsorption and probability of adsorbate concentrations (50, 70, and 100 mg L–1), and bed depths
breakthrough, was also used to investigate the breakthrough (between 5 and 15 cm), with Tables 4a and 4b showing the
behavior of both Cu2+ and Pb2+ for raw and treated DP. This results obtained for adsorption of Cu2+ onto raw DP and that
model is applicable to single-component adsorption systems of Pb2+ onto treated DP, respectively.
and assumes that the rate of adsorption probability decrease
for each adsorbate molecule is proportional to the The above calculations show that KYN increased with
probability of adsorbate adsorption and breakthrough on the increasing initial metal concentration and flow rate, but
adsorbent (YOON and NELSON, 1984). The linearized form of decreased with increasing bed height. The values presented
the Yoon-Nelson model can be expressed as: in Tables 4a and 4b indicate that the time required to achieve
a 50% adsorbate breakthrough decreased with increasing
Ct initial metal concentration and flow rate, increasing with
ln =K t-TKYN (5) increasing bed height for adsorption of both Cu2+ and Pb2+
Co -Ct YN
onto raw and treated DP.
Table 4a. Yoon-Nelson model’s constants calculated for Cu2+ adsorption onto raw DP.
Parameter KYN (min–1) Ƭ (min) R2 Percentage error
Initial conc. (mg L–1)
50 0.0572 140.9423 0.9338 1.120879
100 0.0681 114.3805 0.9667 0.33373
150 0.0705 96.92057 0.9765 2.02165
Flow rate (mL min–1)
3 0.0481 114.3805 0.9667 0.33373
7 0.0615 94.17236 0.938 1.570526
10 0.0637 82.18367 0.9142 2.741215
Bed height (cm)
5 0.0481 114.3805 0.9667 0.33373
10 0.0321 138.5327 0.9944 1.048064
15 0.0287 166.9477 0.9799 1.05416
Table 4b. Yoon-Nelson model’s constants calculated for Pb2+ adsorption onto treated DP.
Parameter KYN (min–1) Ƭ (min) R2 Percentage error
Initial conc. (mg L–1)
50 0.0125 440.192 0.9415 2.37023
100 0.0156 188.7756 0.9546 1.49175
Flow rate (mL min–1)
2 0.0125 440.192 0.9415 2.37023
4 0.0138 314.8333 0.9238 1.96667
6 0.0144 267.7986 0.9985 1.7615
Bed height (cm)
5 0.0156 188.7756 0.9546 0.49175
10 0.0097 441.7113 0.9588 1.4278

The enhanced rate of metal uptake at higher initial metal previously reported by other researchers (Han et al., 2009;
concentrations could be due to the competition between Hamdaoui, 2006; Bhaumik et al., 2013). The rate constant
adsorbate molecules for adsorption sites, with similar results extents were improved with increase in the flow rate
whereas the Ƭ (min) showed the reverse trend. An opposite
474 AMIN et al.

behavior was seen for both of the rate constant extents and of the BDST model (Sadaf and Bhatti, 2014; Baral et al., 2009),
Ƭ (min) by increasing the bed depth from 5 to 15 cm. The describing the service time (t, min) at a breakthrough point:
longer time required for attaining the breakthrough or
saturation in the greater bed depths of column is due to the Nb 1 Co
t= z- ln ( ) (6)
large amount of adsorbent that provides a greater number of Co U Ka Co Cb -1
sites for the binding of heavy metal ions. On the other hand, where z is the bed height (cm), C0 and Cb are the initial and
columns with short bed height were saturated more quickly breakthrough concentrations of metals (mg L–1), respectively,
owing to lesser amount of adsorbent and the available U is the linear velocity (cm min–1), Nb is the bed biosorption
binding sites. Similar pattern was reported in the previous capacity (mg L–1), and Ka is the rate constant of the BDST
research (Kapur and Mondal, 2016). The insignificant model (L mg–1 min–1). Thus, Ka and Nb can be determined from
percentage error (describing the deviation of T values the slope (Nb/C0U) and the intercept ((1/KaCo) ln [(C0/Ct)−1)])
calculated using this model with experimental data (τ50% exp.)) of the linear plot of service time vs. bed height, respectively.
and high linear regression coefficients (R2 = 0.9–0.99)
The breakthrough times for Pb2+ adsorption onto treated OP
indicate that the Yoon-Nelson model could well fit the
obtained for various bed heights (5, 7, 10, and 15 cm), initial
experimental data.
metal concentrations (50, 100, and 150 mg L–1), and flow
3.4.3. BDST model rates (4, 7, and 10 mL min–1) were introduced into the BDST
model. The linear velocity U was calculated by dividing flow
The BDST model, based on the Bohart-Adams equation
rate by the cross-sectional area of the fixed-bed column
modified by Hutchins, is the most simplified fixed-bed
(diameter = 2.5 cm). BDST model parameters were also
analysis method (El-Kamash, 2008; Hutchins, 1973; Santhy
calculated for different initial metal concentrations at a fixed-
and Selvapathy, 2006; Lee et al., 2001), predicting the
bed height of 5 cm and a flow rate of 4 mL min–1 and for
relationship between bed height and service time while
different flow rates at a fixed-bed height of 5 cm and an initial
ignoring the resistances of external film and intraparticle
Pb2+ concentration of 100 mg L–1 (results not shown).
mass transfer (Ko et al., 2000). This model assumes that the
Similarly, BDST model parameters calculated from the slopes
rate of adsorption is controlled by the surface reaction
and intercepts of linear plots for different bed heights at a
between the adsorbate and the adsorbent with unused
fixed flow rate of 4 mL min–1 and an initial metal
capacity (Goel et al., 2005). Eq. (6) shows a linearized version
concentration of 100 mg L–1 are listed in Table 5.
Table 5. BDST model’s parameters for adsorption of Pb2+ onto treated OP at various bed heights.
Bed height Nb (mg L–1) Ka R2
5 2313.309 0.203447 0.87
7 2545.455 0.18259 0.99
10 2769.455 0.149064 1
15 2973.091 0.135631 1

As the bed height increased from 5 to 15 cm, the volumetric The effectiveness of pre-treatment was investigated by
sorption capacity of the bed (N0) increased, and the rate comparing the performances of raw and treated DP and OP.
constant (K0) decreased, indicating that the breakthrough Batch adsorption experiments were carried out to optimize
was delayed (Table 5). This behavior was probably due to the contact time, pH, adsorbent dose, particle size, and pre-
increased residence time of the metal solution inside the treatment effects. Similarly, fixed-bed adsorption was
column, allowing the ions to diffuse deeper into the treated analyzed using breakthrough curves under specified
OP, as reported in earlier studies (Khitous et al., 2016; Han et operating conditions to evaluate the effects of bed height,
al., 2007). The volumetric sorption capacity of the bed was initial metal concentration, particle size, and flow rate.
also increased by increasing the flow rate and initial metal For batch adsorption, a ~20% higher Cu2+ removal efficiency
concentration, which, however, resulted in an increase and was observed for treated DP compared to that of raw DP. The
decrease of the BDST rate constant, respectively. The use of treated OP also enhanced the adsorption of Pb2+ by
observed high correlation coefficients (R2 > 0.99) indicate the ~30%, probably due to the increased number of functional
validity of the BDST model for describing the adsorption of groups present on the surface of modified adsorbents and
Pb2+ onto treated OP; however, a worse correlation was their enhanced porosity and stability. The rapid adsorption
observed at a lower bed height (5 cm in Table 5). observed during the first 15 min of contact could be linked to
4. Conclusions the availability of unused adsorbent surface area at the initial
stage, and the equilibrium for Cu2+ and Pb2+ adsorption was
This study revealed that locally available DP and OP can be established within 30 min. The removal of both Cu2+ and Pb2+
used to remove Cu2+ and Pb2+ from aqueous solutions in both using raw and treated DP/OP was most efficient at pH 5–5.5.
batch and continuous flow systems, i.e., fixed-bed columns.
BATCH AND FIXED-BED COLUMN STUDIES FOR THE BIOSORPTION OF Cu(II) AND Pb(II) 475

The removal efficiencies of Cu2+ and Pb2+ were increased (by considered when selecting an adsorbent. This study leaves
~60–70%) by increasing the adsorbent dose from 0.5 to 6–7 plenty of room for further investigation due to the complex
g for both raw and treated adsorbents. A 30–35% decrease and diverse chemical composition of real wastewater, which
of the above removal efficiencies was observed when the contains a variety of toxic metals and exhibits dynamic
particle size was increased from 50 to 300 µm. characteristics.
For the adsorption of Cu2+ onto raw DP in a fixed-bed column, Acknowledgments
increasing the bed height from 5 to 15 cm resulted in a slight "This project was funded by the National Plan for Science,
breakthrough time increase of about 30 min, as compared to Technology and Innovation (MAARIFAH), King Abdulaziz City for
the 3-h increase of exhaust time. However, both Science and Technology, Kingdom of Saudi Arabia, Award Number
breakthrough and exhaust times for the adsorption of Pb2+ (11-WAT1875-02)".
onto treated DP increased by 1 h and ~6 h, respectively, when
Conflict of Interest
the bed height was increased from 5 to 10 cm. An increase of
initial metal concentration from 50 to 150 mg L–1 resulted in Authors declare no conflict of interest.
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