Hindawi

Journal of Chemistry
Volume 2021, Article ID 5514118, 13 pages
https://doi.org/10.1155/2021/5514118

Research Article
Using Pomegranate Peel and Date Pit Activated Carbon for the
Removal of Cadmium and Lead Ions from Aqueous Solution

Wedad A. Al-Onazi ,1 Mohamed H.H. Ali ,2 and Tahani Al-Garni 1

1
Department of Chemistry, College of Science, King Saud University, Riyadh, Saudi Arabia
2
National Institute of Oceanography & Fisheries, Cairo, Egypt

Correspondence should be addressed to Wedad A. Al-Onazi; walonazi@ksu.edu.sa

Received 21 January 2021; Revised 24 June 2021; Accepted 23 August 2021; Published 6 September 2021

Academic Editor: Shafaqat Ali

Copyright © 2021 Wedad A. Al-Onazi et al. This is an open access article distributed under the Creative Commons Attribution
License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is
properly cited.
Some agricultural byproducts are useful for solving wastewater pollution problems. These byproducts are of low cost and are
effective and ecofriendly. The study aim was to investigate the possibility of using pomegranate peel (PP) and date pit (DP)
activated carbon (PPAC and DPAC, respectively) as sorbents to remove Cd(II) and Pb(II) from aqueous solutions. Agricultural
wastes of DPs and PPs were subjected to carbonization and chemical activation with H3PO4 (60%) and ZnCl2 and used as
adsorbents to remove Cd(II) and Pb(II) from their aqueous solutions. The physical characterizations of PPAC and DPAC,
including determination of surface area, scanning electron microscopy, energy-dispersive X-ray spectroscopy, and Fourier-
transform infrared spectroscopy, were performed. The following factors affected adsorption: solution pH, adsorbent dosage, initial
metal ion concentration, and contact time. These factors were studied to identify the optimal adsorption conditions. The results
showed that the maximum adsorptions of Cd(II) and Pb(II) were achieved at pH ranging from 6 to 6.5, 90 min contact time, and
0.5 g/L for PPAC and 1 g/L for DPAC dosage. Furthermore, the adsorption efficiencies for both Pb(II) and Cd(II) were higher for
PPAC than for DPAC. However, the recorded Qmax values for PPAC were 68.6 and 53.8 mg/g for Pb(II) and Cd(II) and for DPAC
were 34.18 and 32.90 mg/g for Pb(II) and Cd(II), respectively. The Langmuir isotherm model fit the adsorption data better than the
Freundlich model. Kinetically, the adsorption reaction followed a pseudo-second-order reaction model, with qe ranging from 12.0
to 22.37 mg/g and an R2 value of 0.99.

1. Introduction photo-oxidation [4, 5], advanced oxidation [6, 7], and

bioremediation using biomasses [8]. These processes have
The recent notable deterioration of water quality mainly due certain disadvantages, mainly high operational costs and
to urbanization, anthropogenic wastes, increasing pop- maintenance. In addition, they have some complicated steps
ulation growth, progressive industrialization, and unsafe and may generate toxic byproducts of their own [9].
water resources utilization [1] has led to water resources Recently, adsorption processes using activated carbon
contaminated with different pollutants (e.g., toxic metal from agricultural wastes, sludge, or other carbonaceous
ions, pesticides, agricultural fertilizers). The progressively precursors have been used because they are ecofriendly, are
increasing amounts of different pollutants have caused alarm of low cost, and enable use of simple procedures. This
about water quality [2]. Minimization and control of water technique has been used for removing various contaminants
pollution problems have become an urgent necessity, and from water, including metals and dyes [10–13]. Currently,
great efforts have been made to develop ecofriendly, low- adsorption reactions are considered the most ecofriendly,
cost, and effective techniques to remove pollutants from low-cost, selective, and efficient treatment technique for
aquatic environments [3]. Several technological processes removing heavy metals and other organic pollutants from
have been developed by different researchers, including wastewater [14, 15]. This technique involves surface
2 Journal of Chemistry

adsorption in which adsorbate particles are attached and 2.2. Activated Carbon (AC) Preparation. Date pit (DP) and
held to the adsorbent surface until reaching equilibrium pomegranate peel (PP) wastes were collected from local
between free and bound molecules in the carrier liquid or markets in Riyadh City, Saudi Arabia. In the laboratory, the
gas [16]. DPs and PPs were washed well with hot deionized water and
Recently, agricultural wastes are used to produce porous dried in an open-air oven (Genlab–Mino 50) at 105°C for
activated carbon (AC), which is considered one of the most 24 hr. After reaching constant weight, the DPs and PPs were
popular and widely used adsorbents for the removal of heavy crushed and ground in a mill to a fine powder and then
metal ions from wastewater. Various agricultural wastes are sieved through progressively finer sieves to yield a final
found in huge quantities, which provide the advantages for particle size of <120 μm. AC from DPs (DPAC) and PPs
this method such as high availability, low cost, high ad- (PPAC) was prepared by soaking dry fine particles of DPs
sorption efficiency, and high removal capacity [17]. These and PPs with H3PO4 (60%) and ZnCl2 (50 wt%) at a ratio 1 : 1
wastes include orange peel [12], rice husks [18], coconut by volume for 24 hr to chemically activate them. Then, the
shells [19], Kiwi, mandarin, and banana peels [20, 21], mixtures were dried in an oven at 105°C. Finally, carbon-
pomegranate peel modified with zerovalent iron nano- ization was performed in a muffle furnace (Nabertherm L5)
particles [22], pomegranate peel [23–25], and date pits at 500°C for 60–70 min in the absence of air.
[26–28]. Some modified natural wastes were used as sub-
strates to remove heavy metals.
2.3. Characterizations. The surface area (SBET) of the pre-
In this study, pomegranate peels (PPs) and date pits
pared AC was estimated by using the Brunauer–Emmett–
(DPs) were used because they are the most locally available
Teller method (SBET) using a Coulter SA3100 instrument
precursors in Saudi Arabia for the preparation of AC ma-
with outgas for 15 min at 150°C. A scanning electron mi-
terials. PP is a byproduct of tanneries and pomegranate juice
croscope (model: JEM-2100-JEOL; Tokyo, Japan) was used
industries [29]. Additionally, DPs are common commercial
for scanning electron microscopy (SEM) and energy-dis-
agricultural wastes in the palm food industry [30]. Hence,
persive X-ray (EDX) measurements. Fourier-transform in-
DPs and PPs are suitable for AC preparation because of their
frared spectroscopy (FTIR) analysis was performed to
good natural structure, renewable sources, low cost, and low
identify the different principal functional groups using a
ash content [31]. Therefore, AC from PPs (PPAC) and DPs
spectrometer (6700 FTIR; Nicolet, America).
(DPAC), which are characterized by large surface area, high
micropore volume, and extremely high adsorption effi-
ciency, potentially can be used to prepare efficient sorbents 2.4. Batch Adsorption Study. A series of serial standard
for the removal of pollutants from water. Therefore, the solutions was prepared by dissolving Pb(NO3)2 and
prepared PPAC and DPAC adsorbents are considered ex- Cd(NO3)2 salts in deionized water. The effect of solution pH,
cellent novel adsorbents because of their low cost and highly contact time, initial metals’ concentrations, and sorbent
effective substrates. However, the hydrothermal chemical dosage was investigated as important factors that could affect
activation processing modified the adsorbents’ characteris- the adsorption process. A 100 ml aliquot of the metal ions
tics that made them have great abilities to remove toxic mixture was used for each experiment under fixed condi-
metals (Cu(II) and Ni(II)) and Pb(II) in a single-step process tions. All experiments were performed at room temperature
from aqueous solutions due to their high surface area, en- between 22 and 25°C and a fixed shaking speed of 250 rpm.
larged pore size, and existence of several different functional Then, samples were centrifuged at 10,000 rpm for 10 min,
groups onto their surfaces. the solution was withdrawn, and the concentrations of
The study aim was to investigate the possibility of using Pb(II) and Cd(II) were measured by using inductively
PPAC and DPAC as sorbents to remove Cd(II) and Pb(II) coupled plasma–atomic emission spectroscopy (ICP-AES;
from aqueous solutions. Some factors that affect the ad- Agilent 5800). The metal adsorption capacity (qe, mg/g) and
sorption process, such as solution pH, sorbent dose, dura- removal efficiency (R%) are calculated as follows:
tion time, and initial metal concentrations, were studied.
C0 − Ce 􏼁 x V
Furthermore, different kinetic and isotherm models for qe � ,
Pb(II) and Cd(II) adsorption were investigated. M
(1)
C − Ce 􏼁x100
2. Materials and Methods R% � o ,
Ce
2.1. Chemicals and Reagents. Lead nitrate, cadmium ni- where qe is the equilibrium metal concentration; C0 and Ce
trate, sodium hydroxide, and hydrochloric acid used in are the initial and final metal ion concentrations in solution
this study were of analytical grade and purchased from (mg/L), respectively; V is the volume of metal ions in so-
Sigma (Germany). Cd(II) and Pb(II) stock solutions of lution (L); and M is the sorbent mass (g).
1000 mg/L were prepared by dissolving Pb(NO3)2 and
Cd(NO3)2 in deionized water. For each experiment, serial 3. Results and Discussion
dilutions were prepared using deionized water to obtain
the required concentrations. The pH of each solution was 3.1. Characterization. SEM is useful for describing the po-
adjusted using 0.1N HCl or 1N NaOH to the required rous heterogeneity and surface morphological structures of
experimental value. the adsorbents. Figures 1(a) and 1(b) show the SEM
Journal of Chemistry 3

HV mag WD 50 µm HV mag WD 50 µm
5.00 kV 2 500 × 4.9 mm A 5.00 kV 2 000 × 4.8 mm C

(a) (b)

Figure 1: Scanning electron microscopy (SEM) images: (a) DPAC sorbent and (b) PPAC sorbent.

micrographs for DPAC and PPAC at different magnifica- function groups onto the surface of PPAC (Table 1).
tions. The SEM micrographs showed that both sorbents had However, five peaks were observed for DPAC before ad-
amorphous irregular surface structures. A smoother texture, sorption at 3460, 2935, 1750, 1470, and 1025 cm−1 and were
a more porous surface, and a lower particle size were ob- attributed to carboxylic acid −OH stretching, C–H sym-
served for PPAC than for DPAC, which have been shown to metric vibrations, nonionic carboxyl groups (COOH), C–H
be associated with the compositional nature of the initial bending in cellulose, and C–O stretching in the alcoholic
precursor and lignin content [32]. However, pomegranate hydroxyl group, respectively [39]. These bands are signifi-
peel contains a higher level of lignin than date pits, and cantly shifting to 3451, 2927, 1741, 1461, and 1022 cm−1 after
therefore, the morphological structures of PPAC and DPAC adsorption of metal ions (Table 1). FTIR spectroscopy in-
are different after carbonization and activation [33, 34]. EDX dicated the presence of oxygen-containing functional groups
spectroscopy was performed to determine the elemental (e.g., –OH, –COOH, –O�C�O, and –C–O) onto the surface
composition of DPAC and PPAC (Figures 2(a) and 2(b)). of PPAC and DPAC adsorbents, and this indicates that the
The EDX spectra showed the presence of two major peaks of main mechanism of metal ions adsorption is the typical
oxygen and carbon with abundance percentages of 52.48% oxidation process due to the presence of functional groups
and 25.43% in the DPAC adsorbent, respectively, while the containing oxygen, leading to enhancing the adsorption of
corresponding abundance ratio were 52.2% and 24.2% in the heavy metals [40].
PPAC adsorbent. In general, the high percentages of oxygen Determination of the specific surface area is most im-
and carbon are closely related to the nature of the PPs and portant for showing the capacity of adsorption onto an AC
DPs used [35]. Additionally, some minor peaks were de- sorbent. Table 2 and Figure 4 show the calculated values of
tected in the PPAC adsorbent, which belong to Mg (5.1%), Si SBET for DPAC and PPAC. Compared with DPAC
(3.1%), and K (3%). A slightly higher difference was observed (278.18 m2/g), PPAC has a higher SBET (350.22 m2/g). These
in the minor peaks that detected in DPAC than PPAC, and SBET values were less than those obtained by Abedi et al. [41]
the minor peaks are Si (5.5%), Mg (4.2%), K (2.1%), and who reported 887 m2/g for the surface area of AC from PP
S (1.1%). modified by iron and by Manel et al. [42] who recorded
FTIR spectroscopy was used to identify and characterize 1354 m2/g for PP activated thermally at 800°C. The maxi-
different functional groups present on the surface of the mum SBET for date seeds was previously found to be 860 m2/
PPAC and DPAC sorbents. Table 1 and Figure 3 show the g after thermal activation at 800°C [43].
different function groups existing on the surface of the two
sorbents. Before the adsorption process, a narrow band at
3950 cm−1 was observed on the surface of PPAC that at- 3.2. Batch Biosorption Experiments
tributed to the −OH stretching of water molecules; this band
was shifted after adsorption to 3949 cm−1, indicating the 3.2.1. Effect of pH. The adsorption process was greatly af-
interaction between metal ions adsorbed onto the active fected by the pH values of aqueous solutions of metal ions
sites. A broad band at 3600–3150 cm−1 was attributed to the since it not only controls active sites dissociation on the
carboxylic acid −OH stretching in lignin and cellulose [36], sorbent surface but also governs the ionization degree and
asymmetric stretching O�C�O of the CO2 group appeared metals speciation in the solution [41]. To study the effect of
at 2370 cm−1. A carboxyl peak was observed at 1650 cm−1, pH values on the adsorption efficiency of DPAC and PPAC,
and a band at 565 cm−1 was attributed to out-of-plane C–H a pH range of 2.5–7 was selected to show the removal ca-
vibrations [37, 38]. After the adsorption process, all these pacity of Cd(II) and Pb(II) onto both adsorbents’ surface at a
bands were significantly shifted to other wave numbers, 100 mg/L metal concentration for a 90-min contact time and
indicating successful binding of metal ions with different 0.5 g/L PPAC and 1 g/L DPAC adsorbent doses (Figure 5).
4 Journal of Chemistry

910
O K
O K 1.08 K
819
0.96 K
728
0.84 K
637
Ca Kα 0.72 K Mg K Si K
546
0.60 K
455
C K Mg K
0.48 K Si L
364 Si L Si K C K
0.36 K Ca L
273 Ca L S Kα S Kα
K L K L
0.24 K CI Kα
182 Cl Kα CI L Ca Kα
Cl L
K Kα S L Na K K Kα
S L Na K Ca Kβ 0.12 K AI K
91 CI Kβ
Al K S Kβ Cl Kβ K Kβ N K S Kβ K Kβ Ca Kβ
N K
0.00 K
0
0.00 1.00 2.00 3.00 4.00
0.00 1.00 2.00 3.00 4.00

Lsec: 30.0 0 Cnts 0.000 keV Det: Octane Pro Det Reso
Lsec: 30.0 0 Cnts 0.000 keV Det: Octane Pro Det Reso

(a) (b)

Figure 2: EDX spectra: (a) DPAC adsorbent and (b) PPAC adsorbent.

Table 1: The main functional groups detected on the surfaces of DPAC and PPAC.
Frequency (cm−1) DPAC PPAC
Before adsorption After adsorption Band function groups Function groups
∗
3956 3949 −OH stretching
∗
3600–3150 3590–3142 Carboxylic acid −OH stretch
∗
3460–3350 3451–3339 Carboxylic acid −OH stretch
∗
2935 2927 C–H vibrations
∗
2369 2391 O�C�O asymmetric stretch (CO2)
∗
1750 1741 Carboxylic COOH stretching
∗
1654 1659 Carboxylic COOH stretching
∗
1470–1269 1461–1260 C–H bending
∗
1025 1022 C–O stretching of alcoholic OH
∗
565 561 C–H vibration
∗
Not available.

140

120
T (%)

100

80

60
4000 3500 3000 2500 2000 1500 1000 500
Wave number (Cm–1)

DPAC
PPAC
Figure 3: FTIR spectrum of adsorbents: DPAC (red line) and PPAC (black line).

Table 2: The specific surface areas, radii, and pore volumes obtained for DPAC and PPAC.
Sorbent SBET (m2g−1) r (nm) VPtotal (cm3g−1)
DPAC 278.185 53.94 0.485
PPAC 350.22 31.17 0.383
Journal of Chemistry 5

PPAC DPAC
70 70

60 60

50 50
Va/cm3 (STP) g–1

Va/cm3 (STP) g–1

40 40

30 30

20 20

10 10

0 0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
P/P0 P/P0

Figure 4: N2 sorption-desorption isotherms of prepared nanocomposites.

Pb Cd
100 100

90 90
Removal Efficiency (%)

Removal Efficiency (%)

80 80

70 70

60 60

50 50

40 40
2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5 7.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5 7.0
pH values pH values

PPAC PPAC
DPAC DPAC
Figure 5: Effect of pH on the adsorption efficiencies of Pb(II) and Cd(II) on the surfaces of DPAC and PPAC (metal concen-
tration � 100 mg/L, contact time � 90 min, dose of DPAC � 1 g/L, and dose of PPAC � 0.5 g/L).

We observed an obvious increase in removal efficiency metal ions increases [44, 45], and at very high pH values
by gradually increasing pH values. The maximum removal (>8), the metal ions precipitated (Figure 6).
ratio for Pb(II) was 91.1% for PPAC and 88.8% for DPAC at
≡ Cd − OH + OH− ← ⟶ ≡ Cd − O− + H2 O
pH 6. The maximum removal ratio for Cd(II) was 92.5% for (3)
PPAC and 87.3% for DPAC at pH 6.5 (Figure 5). A re- ≡ Pb − OH + OH− ← ⟶ ≡ Pb − O− + H2 O
markable lowering in removal efficiency was observed at
very low pH values (1–3) because of the high protonation Analysis of variance (ANOVA) revealed an insignificant
process, which causes the formation of protonated hydrous difference in the removal efficiencies between the two ad-
oxides besides generating the positive charges that accu- sorbents (r � 0.08 at P > 0.11).
mulate on the adsorbent surface layer, leading to electro-
static repulsion between positive metal ions and the
positively charged adsorbent surface as shown in the fol- 3.2.2. Effect of Contact Time. The effect of contact time on
lowing equations: the adsorption of Pb(II) and Cd(II) onto the surfaces of
DPAC and PPAC was studied over the range of 15–150 min
≡ Cd − OH + H+ ← ⟶ ≡ Cd − OH+2 (Figure 7). The adsorption rates notably increased in the
(2)
≡ Pb − OH + H+ ← ⟶ ≡ Pb − OH+2 beginning of the reaction during the first 30–45 min because
of the high availability of active sites on the adsorbents’
With increasing pH, the hydrous oxides were depro- surfaces. But then the reaction slowed down until reaching
tonated in addition to the decrease of the positive charges, so equilibrium after 90 min, with a maximum adsorption ca-
the sorption sites become available and the adsorption of pacity of 91.1% and 91.2% for Pb(II) and 91.1% and 91.3% for
6 Journal of Chemistry

Sorption sites saturated Sorption sites become Precipitation of Cd(II)

by H+ available and Pb(II)
Pb(OH)2
H+ H+ OH
Cd(OH)2
Cd+2 Pb+2 Pb+2
H+ Cd+2 Cd+2
Cd+2
H+
H+ Na+
PPAC PPAC PPAC

DPAC DPAC Cd+2 Na+

H+ DPAC Cd+2
Pb+2 Pb+2

H+ H+ Na+
Acid Base

0 3 7 12
OH
H+

Figure 6: Effect of pH on the adsorption of Cd(II) and Pb(II) onto PPAC and DPAC at different pH values.

Pb Cd
100 100

90 90
Removal Efficiency (%)

Removal Efficiency (%)

80 80

70 70

60 60

50 50

40 40

30 30
15 30 45 60 75 90 120 150 15 30 45 60 75 90 120 150
Contact time (min) Contact time (min)

PPAC PPAC
DPAC DPAC
Figure 7: Effect of contact time on the adsorption of Pb(II) and Cd(II) onto the surfaces of DPAC and PPAC (pH � 6, metal concen-
tration � 100 mg/L, DPAC dose � 1 g/L, and PPAC dose � 0.5 g/L).

Cd(II) on the surfaces of DPAC and PPAC, respectively. of the great availability of active exchange sites onto the
ANOVA showed no significant difference in the removal adsorbents’ surfaces. The removal capacity reached a max-
efficiencies between the adsorbents (r � 0.15, P > 0.20), but imum of 92.3% for both Pb(II) and Cd(II) at 0.5 g/L of PPAC
there was a significant difference in time intervals (r � 0.82, and remained steady. The removal capacity reached a
P < 0.05) between the adsorbents. maximum of 91% for Pb(II) and Cd(II) at 1 g/L of DPAC.
Our recent data were consistent with the Hilal et al. [46] ANOVA showed a slightly significant difference in ad-
data showing 75 min as the optimum duration for the ad- sorption efficiency between DPAC and PPAC (r � 0.41,
sorption of Cd(II) and Cu(II) onto the surface of DPAC. In P < 0.05). Moghadam et al. [43] and Salmani et al. [44] found
addition, Salmani et al. [44] found that the optimum that 1 g/L was the optimum dose of PPAC for the maximum
equilibrium time was 90 min for the adsorption of Pb(II) removal of Fe(II) and Pb(II) from their aqueous solution. Al-
onto modified PPAC (Table 3). Balushi et al. [47] reported an optimum dose of 1 g/L for
DPAC to reach the maximum removal efficiency for
methylene blue dye from aqueous solutions.
3.2.3. Effect of Dose. To detect the optimum amount of
adsorbent required for the maximum adsorption efficiency,
the adsorbent dose was investigated by varying the quantities 3.2.4. Effect of Initial Metal Concentration. The effect of
of both adsorbents from 0.1 to 1 g/L at pH 6, initial metal ion initial Pb(II) and Cd(II) concentrations on the efficiency of
concentration of 100 mg/L, and a 90 min contact time adsorption was investigated over a concentration range from
(Figure 8). The results showed a gradual increase in ad- 10 to 100 mg/L (Figure 9). The results showed increasing
sorption efficiency by increasing the adsorbent mass because removal rates with increasing Pb(II) and Cd(II)
Journal of Chemistry 7

Table 3: Comparison of the parameters affecting the maximum adsorption efficiencies of different metal ions using different agricultural
precursors between the two AC adsorbents.
Adsorbent Elements pH Dose (g/L) Time (min) qe (mg/g) Kinetics Ref.
Orange peel Cu(II) 5.8 0.5 120 25.8 Pseudo 2nd order [12]
Raw date pits Hg(II) 5 4 90 38.5–52.6 Pseudo 2nd order [48]
Pomegranate peel Pb(II) 6–6.5 1 60 22.5–27.5 Pseudo 2nd order [43]
Cd(II)
Date pits 5.8 1 75 7.4–33.44 Pseudo 2nd order [46]
Cu(II)
Pomegranate peel Pb(II) 6.5 1 80 18.52 Pseudo 1st order [44]
∗
Phragmites australis Cd(II) 6 0.5 30 5.8–7.8 [49]
Plum stone Pb(II) 5.5 0.5 90 48.3–80.6 Pseudo 2nd order [50]
∗
Banana peel Cd(II) 3 30 20 5.7 [51]
∗
Modified orange peel Cu(II) 5 2 180 28.9 [52]
∗
Pomelo peel Cu(II) 4 5 60 34.84 [53]
∗
Mango peel Ni(II) 4–6 2 80 28.21 [54]
Date pits Pb(II) 1
6–6.5 90 53.8–68.6 Pseudo 2nd order Recent data
Pomegranate peel Cd(II) 0.5
∗
Not available.

Pb Cd
100 100

90 90
Removal Efficiency (%)

Removal Efficiency (%)

80 80

70 70

60 60

50 50

40 40
0.1 0.2 0.3 0.4 0.5 0.6 0.8 1.0 0.1 0.2 0.3 0.4 0.5 0.6 0.8 1.0
Adsorbent Dose (g/L) Adsorbent Dose (g/L)

PPAC PPAC
DPAC DPAC
Figure 8: Effect of adsorbent dose on the adsorption of Pb(II) and Cd(II) (pH � 6, metal concentration � 100 mg/L, and contact
time � 90 min).

Pb Cd
100 100

95 95
Removal Efficiency (%)

Removal Efficiency (%)

90 90

85 85

80 80

75 75
10 20 30 40 60 80 100 10 20 30 40 60 80 100
Initial metal concentration (mg/L) Initial metal concentration (mg/L)

PPAC PPAC
DPAC DPAC
Figure 9: Effect of initial metal concentration on the adsorption of Pb(II) and Cd(II) (pH � 6, contact time � 90 min, dose of DPAC � 1 g/L,
and dose of PPAC � 0.5 g/L).
8 Journal of Chemistry

concentrations. The maximum removal efficiencies of Pb(II) model could be applied to both monolayer and multilayer
and Cd(II) were 93.9% and 94.4% for DPAC and 93.1% and adsorption. The Freundlich isotherm model is described by
92.3% for PPAC at 100 mg/L metal ion concentrations, equations (6) and (7) [58].
respectively. Slight variations in the removal efficiency were
observed for both adsorbents. qe � Kf C1/n
e , (6)

1
4. Adsorption Equilibrium Isotherms log qe � log Kf + log Ce , (7)
n
The equilibrium between the adsorbent (solid phase) and where qe is the amount of metal adsorbed by the adsorbent
adsorbate (liquid phase) was described by using adsorption (mg/g), Ce is the equilibrium adsorbate concentration in mg/
isotherm models. The reaction system reached equilibrium L, Kf is the adsorbent capacity, and n is the adsorption
when a balance between the concentrations of the adsorbate intensity determined from the linear plot.
and adsorbent was achieved. The calculated constants of an Figure 11 shows the linear relationship between log qe
adsorption isotherm measured the surface properties’ af- and log Ct at constant temperature. The Freundlich con-
finities of the DPAC and PPAC adsorbents for Pb(II) and stants (Kf , n, and R2) for both adsorbents are presented in
Cd(II) ions. The Langmuir and Freundlich isotherm models Table 4. It is clear that the adsorption process does not follow
were used to illustrate the adsorption process. the Freundlich model because the R2 values are lower than
those corresponding to those for the Langmuir model
(Table 4). The Freundlich intensity parameter (1/n) is a
4.1. Langmuir Isotherm Model. The isotherm models of
function of the strength of adsorption [59], and the values of
Langmuir postulate that adsorption occurred as a homo-
n were <1, which indicated that the adsorption of both metal
geneous monomolecular layer onto the adsorbent’s surface.
ions was a chemical adsorption process [60].
The Langmuir model is expressed by Langmuir equation
as follows [55]:
5. Kinetics Studies
1 1 1 1
� + · , (4)
qe qmax bqmax ce Kinetic adsorption is one of the most important parameters
used to evaluate the adsorption process efficiency in addition
where qmax (mg·g−1) is the maximum uptake of sorbate, qe is to the transferring behavior of adsorbed molecules onto the
the equilibrium concentration of sorbate (mg·g−1), ce adsorbents’ surfaces [61]. Thus, pseudo-first-order and
(mg·L−1) is the metal concentration at equilibrium, and b pseudo-second-order models were applied to investigate the
(L·mg−1) is the Langmuir constant. kinetics of adsorption of Pb(II) and Cd(II) onto the surfaces
The calculated equilibrium constants for the Pb(II) and of DPAC and PPAC.
Cd(II) adsorptions onto the surface of the two adsorbents
showed good fits to the Langmuir isotherm model with
R2 > 0.95 (Table 4, Figure 10), so homogeneous monolayer 5.1. Pseudo-First-Order Model. This model assumed that
adsorptions of Pb(II) and Cd(II) appeared to best explain metal ions uptake is directly proportional to the difference
this adsorption process. Furthermore, the adsorption effi- between saturation levels and is expressed by the Lagergren
ciencies for both Pb(II) and Cd(II) were higher (qmax � 68.6 [62] equation as follows:
and 53.8 mg/g for Pb(II) and Cd(II)) for PPAC than for k1
DPAC (qmax � 34.18 and 32.90 mg/g for Pb(II) and Cd(II)). log qe − qt 􏼁 � log qe 􏼁 − t, (8)
0.203
The Langmuir dimensionless separation constant (RL) that
defines the affinity sorbate-sorbent affinity is an important where qt is the concentration of adsorbed metal ions (mg/g)
feature of the adsorption isotherm. RL is expressed in at time t, qe is the amount of adsorbed metal ions (mg/g) at
equation (5) [56]. equilibrium, and k1 (min−1) is the pseudo-first-order reac-
1 tion constant.
RL � , (5)
1 + bCi
5.2. Pseudo-Second-Order Model. This model supposes that
where Ci is the initial metal ion concentration (mg/L) and b chemical adsorption occurred since chemical bonds were
is the Langmuir constant. RL describes the type of Langmuir formed between the adsorbent surface and adsorbate [63].
isotherm: irreversible if RL � 0, linear if RL � 1, unfavorable The pseudo-second-order model is expressed in equation (9)
if RL > 1, or favorable if 0 < RL < 1 [57]. RL values for Pb(II) as follows:
and Cd(II) adsorption onto the surface of PPAC and DPAC
were found in the range of 0 < RL < 1, so a favorable ad- t 1 1
� 2 + t, (9)
sorption was achieved (Table 4). qt k 2 qe qe

where qt is the concentration of adsorbed metal ions (mg/g)

4.2. Freundlich Isotherm Model. The Freundlich isotherm at time t, qe is the amount of adsorbed metal ions (mg/g) at
model assumed that a heterogeneous adsorption took place equilibrium, and k2 (mg/g·min−1) is the pseudo-second-
on the adsorbent surface by the adsorbate molecules, so this order reaction constant.
Journal of Chemistry 9

Table 4: Constants of Langmuir and Freundlich isotherms for Pb(II) and Cd(II) adsorption by DPAC and PPAC adsorbents.
Langmuir Freundlich
PPAC DPAC PPAC DPAC
b qmax RL R2 b qmax RL R2 Kf n R2 Kf n R2
Pb(II) 0.01 68.60 0.50 0.95 0.01 34.18 0.45 0.98 1.08 0.54 0.82 1.13 0.55 0.91
Cd(II) 0.01 53.80 0.42 0.97 0.01 32.90 0.55 0.98 1.06 0.53 0.97 1.22 0.54 0.90

Pb Cd
1.40 1.40
y = 2.4381x – 0.02925 y = 3.6962x – 0.0303
1.20 R2 = 0.977 1.20 R2 = 0.9766

1.00 1.00
0.80 0.80
1/Qe

1/Qe
0.60 0.60

0.40 0.40
y = 1.3791x – 0.01456
0.20 R2 = 0.948 0.20 y = 1.3563x – 0.0186
R2 = 0.9733
0.00 0.00
0.00 0.20 0.40 0.60 0.80 0.00 0.10 0.20 0.30 0.40 0.50 0.60
1/Ct 1/Ct

PPAC PPAC
DPAC DPAC
Figure 10: Langmuir isotherm plot for adsorption of Pb(II) and Cd(II) ions by the DPAC and PPAC adsorbents.

Pb Cd
1.40 1.40
1.20 1.20
1.00 1.00
0.80 0.80 y = 1.9019x – 0.0271
0.60 0.60 R2 = 0.9774
Log Qe

Log Qe

y = 1.8566x – 0.03431
0.40 R2 = 0.8216 y = 1.8247x – 0.05331 0.40
R2 = 0.9061 y = 1.8672x – 0.0872
0.20 0.20
R2 = 0.8995
0.00 0.00
0.00 0.20 0.40 0.60 0.80 1.00 0.00 0.20 0.40 0.60 0.80 1.00
–0.20 –0.20
Log Ct Log Ct
–0.40 –0.40

PPAC PPAC
DPAC DPAC
Figure 11: Freundlich isotherm plot for adsorption of Pb(II) and Cd(II) ions by the DPAC and PPAC adsorbents.

The linear plots and kinetic constants of the pseudo- Pb(II), and Cu(II) onto the surface of some extremophilic
first- and pseudo-second-order reactions are presented in cyanobacterial mats. In addition, several studies proved
Table 5 and Figures 12 and 13. Notably, all kinetics that the pseudo-second-order kinetic model fit the data
constants were higher for the pseudo-second-order re- well for the adsorption processes of Pb(II), Cd(II), and
action than for the pseudo-first-order reaction, and the Hg onto the surfaces of different adsorbents
recorded qe ranged from 12.0 to 22.37 mg/g, with [27, 35, 41, 65].
R2 � 0.99. Therefore, the Pb(II) and Cd(II) adsorption The proposed adsorption mechanism onto the PPAC
processes followed the pseudo-second-order kinetic and DPAC is demonstrated in Figure 14. Many research
model. Our findings are concordant with those obtained studies have reported that the dominant mechanism is ion
by Al-Qahtani et al. [64] who reported that the pseudo- exchange in the sorption of heavy metals by natural
second-order model reflected the adsorption of Ni(II), materials.
10 Journal of Chemistry

Table 5: Pseudo-first-order and pseudo-second-order reaction constants for adsorption of Pb(II) and Cd(II) onto the surface of PPAC and
DPAC adsorbents.
Pseudo-first-order reaction Pseudo-second-order reaction
PPAC DPAC PPAC DPAC
2
qe K1 R qe K1 R2 qe K2 R 2
qe K2 R2
Pb(II) 6.24 0.029 0.46 12.88 0.035 0.87 20.28 0.003 0.99 13.21 0.001 0.91
Cd(II) 13.15 0.033 0.67 8.50 0.038 0.59 22.37 0.002 0.97 12.00 0.002 0.94

Pb Cd
1.0 1.0
y = –0.0146x + 1.1191
y = –0.0152x + 1.11
R2 = 0.6702
0.5 R2 = 0.8739 0.5

0.0 0.0
In (qe-qt)

In (qe-qt)
0 20 40 60 80 100 120 140 160 0 20 40 60 80 100 120 140 160
t t
–0.5 –0.5

y = –0.0167x + 0.9296
–1.0 –1.0 R2 = 0.5874
y = –0.0128x + 0.7955
–1.5 R2 = 0.4619 –1.5
PPAC PPAC
DPAC DPAC
Figure 12: Pseudo-first-order reaction plots for Pb(II) and Cd(II) adsorption onto DPAC and PPAC.

Pb Cd
18.0 18.0
16.0 16.0
y = 0.0757x + 4.2761 y = 0.0833x + 3.3308
14.0 14.0
R2 = 0.9069 R2 = 0.9498
12.0 12.0
10.0 10.0
t (Qt)

t (Qt)

8.0 8.0
6.0 6.0
4.0 4.0 y = 0.0447x + 1.2848
y = –0.0493x + 0.707
R2 = 0.971
2.0 R2 = 0.9863 2.0
0.0 0.0
0 50 100 150 200 0 20 40 60 80 100 120 140 160
t t
PPAC PPAC
DPAC DPAC
Figure 13: Pseudo-second-order reaction plots for Pb(II) and Cd(II) adsorption onto DPAC and PPAC.
Journal of Chemistry 11

NH+3
NH+3
–OOC –OOC
COO– COO–

PPAC –OOC
PPAC
–OOC
COO– COO–

–OOC
DPAC COO– –OOC
DPAC COO–

OH OH
OH OH
NH+3 NH+3

Figure 14: Schematic diagram illustrating the proposed mechanisms for heavy metals’ adsorption onto DPAC and PPAC.

6. Conclusion University. The authors also thank the Deanship of Scientific

Research and RSSU at King Saud University for their
Removal of different inorganic or organic pollutants by technical support.
adsorption onto the surface of agricultural wastes has the
advantages such as low cost, high efficiency and selectivity,
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