Ecological Engineering 95 (2016) 743–752

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Ecological Engineering
journal homepage: www.elsevier.com/locate/ecoleng

Environmental approach and artificial intelligence for Ni(II) and Cd(II)

biosorption from aqueous solution using Typha domingensis biomass
Manal Fawzy a , Mahmoud Nasr b,∗ , Samar Adel c , Heba Nagy c , Shacker Helmi c
a
Department of Environmental Sciences, Faculty of Science, Alexandria University, 21511 Alexandria, Egypt
b
Department of Sanitary Engineering, Faculty of Engineering, Alexandria University, 21544 Alexandria, Egypt
c
Department of Environmental Studies, Institute of Graduate Studies and Research, Alexandria University, 21526 Alexandria, Egypt

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

Article history: This study was carried out to examine the Typha domingensis as a biosorbent for the removal of Ni(II)
Received 17 May 2016 and Cd(II) ions from aqueous solution, and to determine the experimental parameter that mostly influ-
Received in revised form 24 June 2016 enced the biosorption process. The sorption mechanism was discussed in combination with the results
Accepted 19 July 2016
obtained from Fourier-transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), and
energy-dispersive X-ray spectroscopy (EDX). Results revealed that, at initial metal-ions concentration:
Keywords:
50 mg L−1 , biosorbent dosage: 10.0 g L−1 and particle-size: 0.5 mm, the highest Ni(II) removal efficiency of
Artificial modeling
31.0% was obtained at pH: 6.0 within 30 min, whereas the maximum Cd(II) removal efficiency was 78.1%
Biosorption
Isotherms and kinetics
at pH: 7.0 within 15 min. The adsorption equilibrium data of Ni(II) fitted well to the Freundlich isotherm
Ni(II) and Cd(II) (r2 : 0.9202), while Cd(II) adsorption was described well with both isotherms of Langmuir (r2 : 0.9504) and
Typha domingensis characterization Freundlich (r2 : 0.9480). Kinetic studies showed that pseudo-second order described well the biosorption
experimental data (r2 > 0.98). Furthermore, through modeling of an adaptive neuro-fuzzy inference sys-
tem (ANFIS), the sequence of experimental parameters affecting metal-ions removal efficiency for Ni(II)
ions was: Ni(II) concentration > contact time > pH > biosorbent dosage > particle-size, while for Cd(II) ions,
the sequence was: pH > Cd(II) concentration > contact time > particle-size > biosorbent dosage.
© 2016 Elsevier B.V. All rights reserved.

1. Introduction removal of Ni and Cd from wastewater still remains a major topic

Heavy metals, entering an aquatic environment from industrial
wastewater discharges, cause severe toxicity to living organisms
due to their non-biodegradable and bioaccumulation properties
(Zheng et al., 2010). Moreover, uptake of heavy metals by plants
and their subsequent introduction into the food chain poses seri-
ous threats to all forms of life (Godt et al., 2006). Nickel (Ni) and
cadmium (Cd) are the most common causes of heavy metals poison-
ing, and they have carcinogenic, teratogenic and mutagenic effects
(Järup, 2003). Long-term exposure to Ni can cause cancer and lung
fibrosis, as well as dermatitis (eczema) upon exposure to the skin
(Järup, 2003; Guo et al., 2015). Additionally, long-time exposure to
Cd may cause kidney damage, which occurs at Cd concentration of
200 mg (kg kidney cortex)−1 (Piscator, 1985). Therefore, effective
∗ Corresponding author at: Sanitary Engineering Department, Faculty of Engineer-
ing, Alexandria University, P.O. Box 21544, Alexandria, Egypt.
E-mail addresses: mahmmoudsaid@gmail.com, mahmoud.said@ejust.edu.eg
(M. Nasr).
of present research.
During the 20th century, production of divalent nickel “Ni(II)”
and divalent Cadmium “Cd(II)” has been dramatically increased
worldwide (Zheng et al., 2010). The hazardous nature of the heavy
metals has made the governments to impose stringent standards.
For example, the permissible limits of Ni(II) and Cd(II) in drinking
water as set by the world Health organization (WHO, 2006) are
0.5 and 0.005 mg L−1 , respectively. Ni(II) presents in wastewater
from alloy manufacturing, mining and refining industries, whereas
Cd(II) is released into the environment from chemical, petrochemi-
cal, textile and cement industries (Fawzy et al., 2016). Additionally,
Cd(II) can be used as color pigments, stabilizers in PVC products
and anticorrosive agents. As a result, the total global emission of
Cd(II) amounts to 7000 tons per year (Godt et al., 2006).
The most widely proposed methods for the removal of heavy
metals from industrial effluents include ion exchange, chemical
precipitation, membrane filtration, reverse osmosis and adsorption
(Alimohammadi et al., 2013). However, the process of adsorption
has a number of advantages over other treatment methods, such
as low operating cost, short reaction time, minimization of chem-
ical addition and/or sludge generation, no nutrient requirements,

http://dx.doi.org/10.1016/j.ecoleng.2016.07.007
0925-8574/© 2016 Elsevier B.V. All rights reserved.
744 M. Fawzy et al. / Ecological Engineering 95 (2016) 743–752
regeneration of the biosorbent and possibility of metal recovery
(Reddad et al., 2002; Öztürk et al., 2004; Saleem et al., 2016). Dur-
ing adsorption, metal species (namely adsorbate) contained in an
aqueous phase (such as wastewater) are sorbed onto a solid phase,
known as sorbent, adsorbent or biosorbent (Alimohammadi et al.,
2013). Adsorption envolves several physico-chemical mechanisms
as absorption, adsorption, ion exchange, surface complexation and
precipitation (Iqbal et al., 2009; Hokkanen et al., 2013). Growing
attention has been driven toward adsorption as an economic and
effective method for the removal of heavy metals from industrial
wastewater (Sari and Tuzen, 2008).
The term “Biosorption” refers to an eco-friendly adsorption pro-
cess using living or dead biomasses to reduce toxic heavy metals
from aqueous solution (Nasr et al., 2015). Plant species are effec-
tive and affordable biomaterials for the adsorption process due to
their unique chemical composition (Iqbal et al., 2009). Plant bioma-
terials are composed of different types of functional groups, such
as hydroxyl ( OH), carbonyl (C O), amino ( NH2 ) and carboxylic
( COOH) groups, allowing the sorption of metal-ions by strong
coordination (Yoonaiwong et al., 2011). Biosorbent aquatic plants
include agrowastes of wheat bran, wheat husk, rice bran, rice husk,
black gram husk, cassia fistula leaves and apple, banana and orange
peels (Öztürk et al., 2004; Saleem et al., 2016).
Biosorption process is generally affected by several experi-
mental parameters, such as pH, biosorbent dosage, metal-ions
concentration, etc. Artificial intelligence, such as artificial neural
network (ANN), fuzzy inference system (FIS) and adaptive neuro-
fuzzy inference system (ANFIS) can be used to describe the effect
of these parameters on biosorption (Fawzy et al., 2016). ANN is
an interconnected assembly of nodes (units) known as artificial
neurons (Nasr et al., 2012). During training, ANN can learn how to
do tasks based on the data given for training or initial experience
(Nasr et al., 2016). Additionally, ANN can create its own organi-
zation of the information it receives during learning time (Nasr
et al., 2015). FIS is particularly well-suited for dealing with the prob-
lem of knowledge representation in an environment of uncertainty
and imprecision. FIS can interpret relationship between inputs-
outputs by human knowledge in the form of “if-then” rules (Nasr
et al., 2014). ANFIS is an effective method developed to com-
bine the learning and connectionist structure of neural networks
with the humanlike reasoning style of fuzzy systems (Azar, 2011).
Additionally, ANFIS requires fewer adjustable parameters than
those required in other ANN structures. Thus, ANFIS comprises the
advantages of both ANN (e.g. parallelism, adaptive processing, self-
organization, universal approximation and ability of tackling highly
nonlinear problems) and FIS (e.g. modeling uncertainty, approx-
imate reasoning and qualitative knowledge), leading to improve
the accuracy of the resulting fuzzy model (Jang, 1993 Wang, 1994).
The biomaterial of Typha domingensis was chosen in this study
as a biosorbent due to its abundance in Egypt. Practically, the Typha
domingensis creates waste management problems, since it has no
uses till now. This work can be divided into two parts. The first part
studied the biosorption process of Ni(II) and Cd(II) ions onto the
indigenous plant of Typha domingensis. This part was carried out
by: (1) investigating the effects of experimental parameters (i.e.
initial pH, biomass dosage, initial metal-ions concentration, con-
tact time and particle size) on the biosorption process, (2) fitting the
experimental data to isotherm model (Langmuir and Freundlich),
and biosorption kinetics (pseudo-first-order and pseudo-second
order), and (3) determining the biomass properties, before and
after adsorption, by Fourier transform infrared spectroscopy (FTIR),
scanning electron microscopy (SEM), and energy dispersive X-
ray spectroscopy (EDX). The second part was developed to select
the experimental parameter that mostly influenced the sorption
process. This step was implemented by applying the artificial intel-
ligence modeling of ANFIS.
2. Materials and methods
2.1. Preparation of plant based biosorbents
Plant samples were collected from an agro-ecosystem of Abu
Hommos town, located in Northern Egypt (Latitude: 31.0833 and
Longitude: 30.3167). The harvested plant was thoroughly rinsed
with distilled water to remove dust and any particles stick to plant
parts. Further, the samples were oven-dried at 70–80 ◦ C for 48 h.
The dried weight was crushed by a stainless steel grinder (Monuliex
DEPOSE, France: 50/60 hz, 700 w) and sieved by standard sieves
(Dual Manufacturing Co., USA) to obtain biosorbent with known
particle-size. The resultant biomaterial was stored in plastic bottles
for further experiments.
2.2. Preparation of adsorbate
For Ni(II) ions, a stock solution of 1000 mg L−1 was prepared
by dissolving 4.479 g of ultra-pure nickel sulphate (NiSO4 ·6H2 O)
in double distilled water. Moreover, a stock solution of Cd(II) was
prepared by dissolving 2.282 g of 3CdSO4 ·8H2 O in double distilled
water; 1 mL = 1 mg Cd (1000 mg L−1 ). Different concentrations of
Ni(II) and Cd(II) were prepared by appropriate dilutions of the stock
standards with suitable volumes of distilled water.
2.3. Experimental setup
In this study, main experiments can be divided into two parts,
as follows:
In the first part, batch experiments were conducted to inves-
tigate the effects of experimental parameters on biosorption
of Ni(II) and Cd(II) using Typha domingensis. Those parameters
were, initial pH: 2–8, biosorbent dosage: 2.5–40.0 g L−1 , initial
metal-ions concentration: 25–300 mg L−1 , contact time: 5–150 min
and biosorbent particle-size: 0.25–1.0 mm. All experiments were
conducted in triplicate using agitation speed: 2.5 Hz at room tem-
perature: 25 ± 3 ◦ C.
In the second part, ANFIS modeling was performed to determine
the experimental parameter that mostly influenced the biosorption
process. This step was achieved by creating a software program
using MATLAB R2014a, as presented in the Supplementary file (S1).
2.4. Analytical analysis
The concentrations of heavy metals were determined by Atomic
Absorption spectrophotometer (PerkinElmer AAnalyst 100, USA). A
pH/mV hand-held meter (CRISON, pH 25+, Spain) calibrated with
standard buffer solutions was employed for measuring pH values
in the aqueous phase. The pH of each solution was adjusted to a
predetermined value with 1 N HCl and/or 1 N NaOH. All chemicals
used in this study were of analytical reagent grade. Measurements
were conducted according to Eaton et al. (1995).
FTIR spectroscopy (Bruker Tensor 37, USA) was used to identify
the chemical functional groups and absorption bands of the studied
biomass (Alslaibi et al., 2013). About 1–2 g of plant biomass were
ground to fine powder and mixed with potassium bromide (KBr)
powder in order to form samples that were transparent to FTIR.
Solid samples were examined as translucent KBr pellets. The sam-
ples were then inserted into FTIR spectroscopy, and spectra were
recorded over the range of 400–4000 cm−1 . Frequency calibration
was done by a polystyrene film.
The surface structure of biomass was analyzed by SEM (JEOL
JSM-5300 SEM, USA). For SEM analysis, dried samples were
 M. Fawzy et al. / Ecological Engineering 95 (2016) 743–752 745

Table 1
Function of each layer in the ANFIS architecture that has a total of five layers.

Layer number Function

Layer 1 Input parameters to input membership functions

Layer 2 Input membership function to rules
Layer 3 Rules to a set of output characteristics
Layer 4 Output characteristics to output membership functions
Layer 5 The output membership function to a single-valued output

to “premise parameters”. The membership functions of Ai and Bi-2

are given by Eq. (3) and Eq. (4), respectively.

Fig. 1. Basic structure of ANFIS for two-input and one-output Sugeno-type fuzzy O1,i = Ai (x) i = 1, 2 (3)
inference system.

O1,i = Bi−2 (y) i = 3, 4 (4)

mounted on stubs with double-sided adhesive tape, followed by
coating the samples with a 30 nm layer of gold. The EDX in con- Layer 2 (Rule nodes): In the second layer, the rule operator
junction with SEM was used to evaluate the binding characteristics “and/or” is used to get one output that represents the results of the
of biomaterial with metal-ions (Fawzy et al., 2016). antecedent for the fuzzy “if–then” rule. The outputs of this layer,
known as firing strengths O2,i , are calculated by cross multiplying
the incoming signals obtained from layer 1, Eq. (5).
2.5. Calculation of biosorption efficiency
O2,i = wi = Ai (x) Bi (y) i = 1, 2 (5)
The percentage of metal-ions removed due to adsorption was
calculated by Eq. (1).
Layer 3 (Average nodes): Outputs of this layer are called “nor-
  malized firing strengths”. As expressed by Eq. (6), the ith node
Ci − Cf
R= × 100 (1) calculates the ratio of the ith rule’s firing strength to the sum of
Ci
all rules’ firing strengths.
Where,
w
R is the metal-ions removal efficiency (%); Ci and Cf are the initial O3,i = wi = i i = 1, 2 (6)
and final concentration of metal-ions (mg L−1 ) i
wi
Adsorption capacity, which is the amount of metal-ions
Layer 4 (Consequent nodes): In the fourth layer, every node i is
adsorbed onto a biosorbent, was calculated using Eq. (2):
an adaptive node with a node function. The output of each node,
 
Ci − Cf · V as expressed by Eq. (7), is basically the product of the normalized
q= (2) firing strength and a first order polynomial (for a first-order Sugeno
w
model).
Where,
q is the quantity of solute adsorbed per unit mass of biosor- O4,i = wi fi = wi (pi x + qi y + ri ) i = 1, 2 (7)
bent (mg g−1 ); V is the volume of solution (L); and w is the mass of
biosorbent (g) Where wi is the output of layer 3.
Layer 5 (Output nodes):
 In the fifth layer, there is only one single
2.6. Architecture of ANFIS fixed node labeled with , which computes the overall output as
the summation of all incoming signals. Thus, the overall output of
Based on a first-order Sugeno fuzzy model, a typical rule set with the model is calculated by Eq. (8).
two fuzzy “if–then” rules can be developed to express the ANFIS 
architecture (Azar, 2011). Fig. 1 shows the ANFIS under considera-  wf
O5,i = wf =
i i i
i i i i = 1, 2 (8)
tion that has two inputs with two rules, and consists of five layers. wi
i
The “if–then” rules are:

Rule 1 : If x is A1 and y is B1 then f1 = p1 x + q1 y + r1 2.7. Application of ANFIS

The function “exhsrch” in MATLAB software is used to run an

Rule 2 : If x is A2 and y is B2 then f2 = p2 x + q2 y + r2
Where,
x and y are the crisp inputs to the node i; Ai and Bi are the lin-
guistic labels (low, medium, high, etc.) related to this node; fi are
the outputs within the fuzzy region specified by the fuzzy rule; {pi ,
qi , ri } are the coefficients of a linear combination in the Sugeno
inference system (referred to as consequent parameters, i = 1 or 2).
The function of each layer can be summarized in Table 1, as
follows (Jang, 1993):
Layer 1 (Input node): Nodes of this layer generate fuzzy mem-
bership grades of the crisp inputs. The membership grades belong
to each of the convenient fuzzy sets using membership functions.
The parameters of membership function in this layer are referred
exhaustive search within the available inputs to select the input
that mostly influences the desired output. Basically, this function
builds an ANFIS model for each input combination, trains it for one
epoch and reports the performance achieved (Takagi and Sugeno,
1985). The function “exhsrch” launches C(M, N) ANFIS modeling
processes for selecting N inputs from M candidates.
In the current study, there were five input candidates, namely,
pH, biosorbent dosage, metal-ions concentration, contact time and
particle size, and the output to be expected was metal-ions removal
efficiency. Accordingly, the number of ANFIS models was C(5, 1) = 5
(i.e. select one input from five candidates). The ANFIS structure con-
tained one-epoch training of five ANFIS models, and the number of
membership function for each input was 2.
746 M. Fawzy et al. / Ecological Engineering 95 (2016) 743–752
3. Results and discussion
3.1. Effect of initial pH
The effect of initial pH on metal-ions biosorption was performed
under the experimental condition: 50 mg L−1 initial metal-ions
concentration, 10 g L−1 biosorbent dosage, 0.5 mm biosorbent
particle-size and 150 min contact time.
As shown in Fig. 2a, the removal efficiency of Ni(II) significantly
increased from 17.3% to 30.4% when pH was increased from 2.0 to
6.0, respectively (r: 0.9633, p: 0.0367). However, the removal rate of
Ni(II) declined when the pH levels were higher than 6.0 (r: −0.9937,
p: 0.0714). The effect of pH on Cd(II) biosorption was also notice-
able, where Cd(II) removal efficiency elevated from 2.0% at pH 2.0
to 73.5% at pH 4.0. However, an increased value of pH above 4.0
lead to a slight increase in the Cd(II) removal efficiency (r: 0.6230,
p: 0.2616). These results indicated that the maximum sorption effi-
ciency of Ni(II) was achieved at pH 6, while it decreased by either
raising or lowering pH under the present range of the experimental
condition. Additionally, the removal efficiency of Cd(II) was higher
than Ni(II), and could be obtained at a wider pH range of 4–8.
At low pH values, H+ ions occupy most of the biosorption sites
on the biosorbent surface (i.e. the lower the pH the higher the
H+ ions). Under this condition, the adsorption of metal-ions was
inhibited, possibly due to the electrostatic repulsion between pro-
tons (H+ ions) and metal cations (e.g. Ni2+ or Cd2+ ) occupying the
biosorption sites (Alimohammadi et al., 2013). However, increas-
ing the initial pH values results in deprotonation of the functional
groups, and thus the biosorbent surface becomes more negatively
charged (Alslaibi et al., 2013). Under this environment, the neg-
atively charge sites attract the positively charged metal cations,
leading to increase the adsorption capacity. On the contrary, when
initial pH exceeds the optimum value, no remarkable enhancement
in the adsorption of metal-ions could be attained. This could be due
to the formation of soluble hydroxyl complexes of metal-ions that
compete with the active sites (Farinella et al., 2008).
Our results were in agreement with previous studies. For exam-
ple, Salem and Awwad (2014) found that the biosorption of Ni(II)
ions onto modified loquat bark waste increased with pH, and
reached equilibrium at pH 6.0. Moreover, Zheng et al. (2010) noted
that more than 90% of Cd(II) removal was performed at pH range of
3–7, when studying Cd(II) adsorption from aqueous solution onto
corn stalk graft copolymers.
3.2. Effect of biosorbent dosage
The effect of biomass dosage on the biosorption of metal-ions
was undertaken at pH 6.0 for Ni(II) and 7.0 for Cd(II), initial metal-
ions 50 mg L−1 and particle size 0.5 mm for 150 min.
As displayed in Fig. 2b, the Ni(II) removal efficiency increased
from 22.6% to 31.1% with elevating the biosorbent dosage from 2.5
to 15.0 g L−1 , respectively (r: 0.9695, p: 0.0305). However, it was
pronounced that the removal efficiency of Ni(II) remained approx-
imately unchanged along with an increase in the biosorbent dosage
from 15.0 to 40.0 g L−1 (r: 0.2549, p: 0.7451). Moreover, the Cd(II)
removal efficiency significantly increased from 67.7% at 2.5 g L−1 to
79.3% at 10.0 g L−1 (r: 0.9980, p: 0.0402), and then declined with ris-
ing the biomass concentration from 10.0 to 40.0 g L−1 (r: −0.9852,
p: 0.0022).
It was clear that the removal efficiency of Cd(II) was higher than
Ni(II) at the same biosorbent dosage. Biosorbent dosage is also an
important parameter affecting the adsorption process, since it cor-
responds to the amount of surface available for metal uptake. The
improvement in removal efficiency of metal-ions with increasing
the biosorbent dosage could be elucidated by the availability of
more active sites (Zheng et al., 2010). However, at increasing the
biosorbent dosage higher than the optimum value, the removal
percentage of metal-ions tended to be almost same or slightly
decreased. This trend can be illustrated by the formation of par-
tial aggregation (agglomeration) of biomass and/or interference
between the metal-binding sites, leading to reduce the effective
surface area of the biosorbent (Samuel et al., 2015).
3.3. Effect of initial metal-ions concentration
The influence of initial metal-ions concentration on the sorption
process was investigated at pH 6.0 for Ni(II) and 7.0 for Cd(II) with
10 g L−1 biosorbent dosage for a contact time of 150 min.
As shown in Fig. 2c, the Ni(II) removal efficiency was seen to
significantly decrease from 41.6% to 12.7% when increasing the
initial Ni(II) concentration from 25 to 300 mg L−1 , respectively (r:
−0.8075, p: 0.0520). This trend was similar to that occurred for
Cd(II) removal efficiency, which significantly dropped after an ini-
tial Cd(II) concentration of 25 mg L−1 (r: −0.8761, p: 0.0514).
From the experimental results, it was clear that an increase
in the initial metal-ions concentration caused a decrease in the
removal percentage. At low metal-ions concentration, the amount
of ions competing for the available active sites in the biomass is
low, and thus there exists sufficient surface area to uptake the ions
available in the liquid phase (Ju et al., 2012). On the conrary, at
higher concentrations of metal-ions, the available sites for sorp-
tion become fewer compared to the moles of metal-ions present
(Fawzy et al., 2016). This behavior results in saturation of adsorp-
tion sites and/or a collision between the metal-ions and sorbents;
and thus no considerable enhancement can be achieved (Salem and
Awwad, 2014).
3.4. Effect of contact time
The impact of contact time on metal-ions biosorption was per-
formed at pH 6.0 for Ni(II) and 7.0 for Cd(II) with 50 mg L−1 initial
metal-ions concentration, 10 g L−1 biosorbent dosage and 0.5 mm
particle-size (Fig. 2d).
The Ni(II) removal efficiency elevated from 21.9% to 31.0% with
an increase in contact time from 5 to 30 min, respectively (r:
0.9481, p: 0.0141). However, further increase in reaction time over
30 min witnessed a slight enhancement in Ni(II) removal efficiency
(i.e. from 31.0% to 34.3%). Similarly, the Cd(II) removal efficiency
increased with time and reached 78.1% at 15 min (r: 0.9884, p:
0.0116), after which it remained relatively constant with further
increasing contact time to 150 min (r: 0.0329, p: 0.9507).
It was found that the adsorption of metal-ions was enhanced
with prolonging the contact time until attaining an equilibrium
value after 30 min for Ni(II) and 15 min for Cd(II). In the initial stage,
the metal-ions removal efficiency was high, since there were large
number of vacant active binding sites on the biosorbent surface
(Uluozlu et al., 2008). However, as time increased, the uptake of
cations decreased, probably due to the gradual occupancy of the
active binding sites until they became saturated (Ju et al., 2012).
In a similar study by Salem and Awwad (2014), the biosorption
of Ni(II) onto modified loquat bark was rapid for the first 20 min
and equilibrium was nearly reached after 30 min for initial Ni(II)
concentration 10–100 mg L−1 and at pH 6.0. Their study noted that
any further increase in the contact time has a negligible effect on
the sorption capacity of Ni(II) adsorption (Salem and Awwad, 2014).
Additionally, Iqbal et al. (2009) estimated that the contact time of
60 min was required for reaching the equilibrium condition of Cd(II)
adsorption using mango peel waste.
 M. Fawzy et al. / Ecological Engineering 95 (2016) 743–752 747

a) 90 b) 90

Metal-ion removal efficiency (%)

Metal-ion removal efficiency (%)

80 80
70 70
60 y = -4.2633x2 + 53.502x - 84.182 60 y = -0.0209x2 + 0.8253x + 68.01
r²: 0.9458 r²: 0.5762
50 50
40 40
30 30
20 20 y = -0.0148x2 + 0.8792x + 20.491
y = -0.7706x2 + 8.7044x + 2.549 r²: 0.9351
10 10
r²: 0.8017
0 0
2 3 4 5 6 7 8 0 10 20 30 40
Initial pH Biosorbent dosage (g L-1)

Ni(II) Cd(II) Poly. (Ni(II)) Poly. (Cd(II)) Ni(II) Cd(II) Poly. (Ni(II)) Poly. (Cd(II))

c) 100 d) 90
Metal-ion removal efficiency (%)

Metal-ion removal efficiency (%)

y = 0.0005x2 - 0.223x + 88.879 80
80 70
r²: 0.9298 y = -0.0008x2 + 0.1574x + 73.159
60 r²: 0.6372
60
50
40 40
y = 0.0007x2 - 0.3191x + 48.546
30
r²: 0.8247 y = -0.0009x2 + 0.2014x + 23.554
20 20
r²: 0.8577
10
0 0
0 50 100 150 200 250 300 0 25 50 75 100 125 150
Initial metal-ion concentration (mg L-1) Contact time (min)

Ni(II) Cd(II) Poly. (Ni(II)) Poly. (Cd(II)) Ni(II) Cd(II) Poly. (Ni(II)) Poly. (Cd(II))

e) 100
Metal-ion removal efficiency (%)

80
y = -0.3387x2 - 9.766x + 84.294
60 r²: 1
40

20 y = 0.8889x2 - 18x + 40.311

r²: 1
0
0.00 0.25 0.50 0.75 1.00 1.25
Average particle size (mm)

Ni(II) Cd(II) Poly. (Ni(II)) Poly. (Cd(II))

Fig. 2. Effect of experimental parameters on the biosorption of Ni(II) and Cd(II): (a) pH, (b) biosorbent dosage, (c) initial metal-ion concentration, (d) contact time, and (e)
biosorbent particle size.

3.5. Effect of biosorbent particle size 3.6.1. Langmuir isotherm

Langmuir isotherm refers to the homogeneous adsorption
The influence of biomass particle size on metal biosorption was mechanism, where each molecule owns its enthalpy and activation
investigated at pH 6.0 for Ni(II) and 7.0 for Cd(II), under 50 mg L−1 energy at the same time. Langmuir presumes (Langmuir, 1918): (1)
initial metal-ions concentration with 10 g L−1 biosorbent dosage for adsorption energy is constant over all sites, (2) adsorption can only
150 min (Fig. 2e). occur at a fixed number of localized sites, (3) each active site can
When particle-size was increased from 0.25 to 1.00 mm, the accommodate only one molecule or atom (i.e. Once a site is filled,
Ni(II) removal efficiency decreased from 35.9% to 23.2% (r: −0.9999, no further sorption can take place at that site), and (4) there is no
p: 0.0093), whereas the Cd(II) removal declined from 81.8% to 74.2%, interaction between the adsorbed species.
respectively (r: −0.999, p: 0.0031). As described in Eq. (9), the linear plot of Ce /qe versus Ce gives a
It was obvious that the smaller the particle size of the studied slope 1/qm and an intercept 1/(qm KL ).
biomass the higher the cations sorption characteristics. This could
Ce 1 Ce
be explained by the fact that a biosorbent composed of smaller = + (9)
particle-size tends to provide larger specific surface area and bind- qe qm · KL qm
ing sites for metal uptake (Cataldo et al., 2013; Fawzy et al., 2016). Where,
Ce is the equilibrium concentration of metal-ions remained in
the solution (mg L−1 ); qe is the equilibrium metal-ions concentra-
tion on the biosorbent (mg g−1 ); qm is the monolayer adsorption
3.6. Isotherm studies capacity of the biosorbent (mg g−1 ); and KL is the Langmuir adsorp-
tion constant related to the free energy of biosorption (L mg−1 ).
The capacity of Typha domingensis biomaterial to uptake metal- As listed in Table 2, the coefficients of determination (r2 -values)
ions can be described by equilibrium sorption isotherms, namely were found to be 0.7964 and 0.9504 for Ni(II) and Cd(II), respec-
Langmuir and Freundlich models. tively, indicating that the biosorption of Cd(II) ions fitted better
748 M. Fawzy et al. / Ecological Engineering 95 (2016) 743–752
Table 2
Estimated parameters of the isotherm study (Langmuir and Freundlich models).
Linear equation
Langmuir isotherm Ni(II)
Cd(II)
Freundlich isotherm Ni(II)
Cd(II)
with the Langmuir model. The applicability of Langmuir isotherm
implied that the adsorption of Cd(II) ions, occurring at the binding
sites on the biosorbent surface, was regarded as monolayer cover-
age. This means that the adsorbed layer performs in one molecule
in thickness (Samuel et al., 2015). The values of qm were about
4.51 mg g−1 for Ni(II) and 28.49 mg g−1 for Cd(II). This indicated that
the maximum amount of Cd(II) ions that form a complete mono-
layer onto the surface of Typha domingensis was higher than that of
Ni(II).
The monolayer sorption capacity was higher than that obtained
from a study by Alslaibi et al. (2013), which recorded qm of
11.72 mg g−1 for Cd(II) removal from aqueous solution using
microwaved olive stone activated carbon. On the contrary, a study
by Sari and Tuzen (2008) exhibited higher monolayer biosorption
capacity of 29.2 mg g−1 for Cd(II) biosorption using green alga (Ulva
lactuca) biomass.
3.6.2. Freundlich isotherm
The Freundlich isotherm model stipulates a monolayer sorption
with a heterogeneous energetic distribution of active sites, accom-
panied by interactions between sorbed molecules (Freundlich,
1906). This model gives the information regarding non-ideal and
reversible adsorption processes (Cataldo et al., 2013).
As formulated in Eq. (10), a linear plot of ln(qe ) versus ln(Ce )
gives a slope 1/n and an intercept ln(KF ) (Freundlich, 1906).
1 (12). The values of t/qt were calculated from the kinetic data and
ln (qe ) = ln (KF ) + ln (Ce )
n plotted against time. A linear fit to the experimental data should
Where,
KF is a Freundlich constant relating the adsorption capacity, and
1/n is an empirical parameter relating the biosorption intensity,
which varies with the heterogeneity of the adsorbent.
The r2 -values of Ni(II) and Cd(II) sorption were 0.9202 and
0.9480, respectively, suggesting that the Freundlich model was
able to describe the relationship between the amount of metal-
ions adsorbed by the biomass and its equilibrium concentration in
the solution. The values of KF for Ni(II) and Cd(II) were 0.18 and
0.98 mg g−1 , respectively, indicating that Typha domingensis had
a better ability to adsorb the Cd(II) ion. The results of 1/n were
found to be 0.57 L g−1 for Ni(II) and 0.59 L g−1 for Cd(II). The 1/n
value between 0 and 1 indicates that the biosorption of metal-
ions onto the biomass was favourable at the studied conditions
(Öztürk et al., 2004; Gregory et al., 2005). According to Gregory
et al. (2005), a more homogeneous system would have 1/n value
closer to unity, while a more heterogeneous system would have
1/n value approaching zero.
Our results were in agreement with a study by Öztürk et al.
(2004), which found that the Freundlich isotherm obtained an
excellent fit for the Ni(II) adsorption with r2 -value of 0.99
(KF = 0.08 mg g−1 and 1/n = 0.98). However, when the Langmuir
isotherm model was applied to the adsorption data of Ni(II) ions, a
poor fit (r2 0.80) was obtained. In another study, Yoonaiwong et al.
(2011) estimated Freundlich parameters of KF 2.24 and 1/n 0.74
with r2 -value = 0.8176, when studying Cd(II) sorption by means of
U. aurea biomass.
Coefficients r2
y = 0.2218x + 14.263 qm = 4.51 mg g−1 KL = 0.016 L mg−1 0.7964
y = 0.0351x + 2.3151 qm = 28.49 mg g−1 KL = 0.015 L mg−1 0.9504
y = 0.5681x − 1.7027 1/n = 0.57 L g−1 KF = 0.18 mg g−1 0.9202
y = 0.589x − 0.0246 1/n = 0.59 L g−1 KF = 0.98 mg g−1 0.9480
3.7. Biosorption kinetics
Biosorption kinetics were analyzed based on the models of
pseudo-first-order and the pseudo-second-order.
3.7.1. The pseudo-first-order kinetic model
Pseudo-first-order model can be expressed by Eq. (11). The val-
ues of log(qe –qt ) were calculated from the kinetic data and plotted
against time. A linear fit to the experimental data gives a straight
line with a slope k1 /2.303 and an intercept log(qe ) (Lagergren,
1898).
k1
log (qe − qt ) = log (qe ) − t (11)
2.303
Where,
qt is the amount of metal-ions adsorbed at time t (mg g−1 ), and
k1 is the rate constant of pseudo-first-order in mg g−1 min−1 .
As listed in Table 3, the calculated equilibrium metal-ions con-
centration (qe,cal ) from the pseudo-first-order kinetic model (i.e.
0.70 and 1.20 mg g−1 for Ni(II) and Cd(II), respectively) were found
to be far less than the experimental data (qe,exp for Ni(II) and Cd(II)
of 1.41 and 3.90 mg g−1 , respectively). Accordingly, the pseudo-
first order model was not considered appropriate for describing
the biosorption kinetics of metal-ions by the Typha domingensis.
3.7.2. The pseudo-second-order model
The amount of metal-ions sorbed at equilibrium can be calcu-
lated from the pseudo-second-order equation, as expressed by Eq.
(10)
provide a straight line with a slope 1/qe and an intercept 1/(k2 qe 2 )
(Ho and McKay, 1999).
t 1 t
= + (12)
qt k2 · q2e qe
Where,
k2 is the rate constant of pseudo-second-order in g mg−1 min−1 .
According to pseudo-second-order model, the qe,exp values
for the experimental data were very close to the calculated
results of qe,cal 1.40 and 3.94 mg g−1 for Ni(II) and Cd(II), respec-
tively (Table 3). Additionally, results showed r2 -value close to
unity, suggesting that metal-ions biosorption followed the pseudo-
second-order kinetics under the tested condition.
The applicability of pseudo-second-order model indicated
that the mechanism of adsorption was chemical interaction (i.e.
chemisorption) (Atkins, 1995). The pseudo-second-order kinetics
also suggests that the key interaction between the metal-ions and
the biosorbent involves their sharing of valence electrons (Saleem
et al., 2016).
In a similar study, Saleem et al. (2016) observed that the pseudo-
second-order kinetics can be used to describe the biosorption of
Ni(II) onto coconut copra meal (r2 1.00). At initial Ni(II) concen-
tration of 100 mg L−1 and pH 5.0, the estimated qe,cal and k2 were
2.536 mg g−1 and 0.061 g mg−1 min−1 , respectively (Saleem et al.,
2016). In another study, Ju et al. (2012) studied the biosorption
of Cd(II) from aqueous solutions using red mud granulated with
cement. They also revealed that a pseudo-second-order matched
the kinetics of adsorption well, and the estimated qe,cal was
 M. Fawzy et al. / Ecological Engineering 95 (2016) 743–752 749

Table 3
Estimated parameters of the reaction kinetics (Pseudo 1st-order and Pseudo 2nd-order).

Linear equation Coefficients r2

Pseudo-first-order Ni(II) y = −0.0428x − 0.1535 k1 = 0.10 mg g−1 min−1 qe,cal = 0.70 mg g−1 qe,exp = 1.41 mg g−1 0.9215
Cd(II) y = −0.0759x + 0.0793 k1 = 0.17 mg g−1 min−1 qe,cal = 1.20 mg g−1 qe,exp = 3.90 mg g−1 0.9883
Pseudo-second-order Ni(II) y = 0.7158x + 0.4801 k2 = 1.07 g mg−1 min−1 qe,cal = 1.40 mg g−1 qe,exp = 1.41 mg g−1 0.9852
Cd(II) y = 0.254x + 0.097 k2 = 0.67 g mg−1 min−1 qe,cal = 3.94 mg g−1 qe,exp = 3.90 mg g−1 0.9981

a) the metal-ions and the bounded hydroxyl group (–OH) occurred

80 - on the biomass surface (Uluozlu et al., 2008). Additionally, a shift
from 2923.3 cm−1 to 2921.9 and 2920.2 cm−1 for Ni(II) and Cd(II),
75 -
respectively, demonstrating that the C H group contributed to
Transmittance (%)

70 - the metal ions adsorption (Li et al., 2007). Moreover, the peak at
1738.4 cm−1 was disappeared after absorption, suggesting that the
65 -
C O group was reacted with Ni(II) and Cd(II) ions. Furthermore,
60 - the spectra witnessed a shifted band from 1637.6 cm−1 to 1633.2
and 1633.3 cm−1 for Ni(II) and Cd(II), respectively, which could
55 - be assigned to stretching vibration of the carboxyl group ( C O)
(Iqbal et al., 2009). Likewise, an observed shift from 1457.3 cm−1 to
- 3437.76

2923.35
3729.54

1635.99
1738.94

- 1457.30
1378.52

1164.72
1056.56
50 -

617.98
1430.9 cm−1 for Ni(II) and to 1429.8 cm−1 for Cd(II) suggested that
-

-
3500 3000 2500 2000 1500 1000 500 the carboxylate group (–COO–) symmetric stretching was respon-
Wavenumber (cm-1) sible for the sorption of metal-ions (Farinella et al., 2008). These
results revealed that the mentioned functional groups (i.e. OH,
C H, C O and COO ) participated to the adsorption process of
b)
80 - metal-ions onto the Typha domingensis.
Transmittance (%)

75 -
3.9. SEM/EDX
70 -
Results obtained from SEM revealed that the surface texture of
native Typha domingensis was smooth and entire (Fig. 4a). However,
65 -
after biosorption of Ni(II) (Fig. 4b) and Cd(II) (Fig. 4c), the surface
texture was found to be rough and irregular, indicating that the
60 -
biomaterial captured large amounts of metal-ions.
- 3433.27

2921.92

1633.17
- 1430.99

1056.14
1251.02
1376.80

1164.05

590.03

The EDX spectrum of metal-unloaded biomass is displayed

55 -
in Fig. 5a. After metal-ions adsorption, the EDX spectrum dis-
-

3500 3000 2500 2000 1500 1000 500 played signals at 7.5 keV (Fig. 5b) for Ni(II) and 3.0 keV (Fig. 5c)
Wavenumber (cm-1)
for Cd(II), with relative concentrations of 6.4% and 9.8%, respec-
tively. Before biosorption, the relative concentration of K+ ions was
c) 18.6%, whereas, after biosorption it decreased to 5.8% and 1.2% for
85 - Ni(II) and Cd(II), respectively. Additionally, the relative concentra-
80 -
tion of Mg2+ ions was 5.6% for the native Typha domingensis, which
Transmittance (%)

was totally disappeared after the biosorption of metal-ions. This

75 - indicated that the uptake of Ni(II) and Cd(II) ions concomitantly
occurred with the release of cations from the Typha domingen-
70 - sis biomass. The interchange between metal-ions in the solution
and another ion on the biomass indicates that ion-exchange, both
65 -
surface and inner of the biomass, playes an important role during
60 - the adsorption process (Cataldo et al., 2013). Similar phenomenon
- 3435.03

2920.20

1255.17
3727.51

1633.27
- 1514.43

1055.76
1379.30

1164.72

was documented in an earlier study by Kadirvelu et al. (2000),

617.01
- 419.31

55 - which indicated that the adsorption of Ni(II) onto the adsorbent

-

3500 3000 2500 2000 1500 1000 500 of activated carbon cloths was due to the ion-exchange process.
Wavenumber (cm-1) Additionally, Cataldo et al. (2013) observed that ion-exchange was
the major mechanism governing the sorption of Cd(II) ions from an
Fig. 3. Fourier transform infrared spectra of Typha domingensis: (a) before metal-ion
aqueous solution using mixed alginate/pectin gel beads.
biosorption, (b) after Ni(II) biosorption, and (c) after Cd(II) biosorption.
Our results also observed that, after adsorption, the relative con-
centrations of Ni(II) on the Typha domingensis surface was lower
7.8235 mg g−1 , at initial Cd(II) concentration 10 mg L−1 and pH of than that of Cd(II) (Fig. 5b & c). Simultaneously, the Typha domingen-
6.5 (Ju et al., 2012). sis released/replaced more cations (such as K+ ) during the uptake
of Cd(II). This indicated that there was a preference of the Typha
3.8. FTIR domingensis biomaterial towards the displacement of Cd(II) ions
over Ni(II) ions by the exchanging surface. Previous studies indi-
Fig. 3 depicts the FTIR spectra before and after sorption of cated that the difference in percentage removal of Ni(II) and Cd(II)
metal ions onto the Typha domingensis. Bands were shifted from ions could be attributed to varying degrees of their chemical affinity
3437.8 cm−1 to 3433.3 and 3435.0 cm−1 for Ni(II) and Cd(II), respec- and ion-exchange capacity with respect to the chemical functional
tively, which could be attributed to a chemical interaction between group on the biomass surface. For example, Reddad et al. (2002)
750 M. Fawzy et al. / Ecological Engineering 95 (2016) 743–752

a)
Cl
600

Counts
400

K
200
Mg S Ca
P Cu Zn
Na Al
0
0 5 10 15 20
Energy (keV)

b)
Ca
Ca

1000
1000

800
800

Counts
600
600

400 Cl K Cu
400
PSSCl K Cu
Zn
Zn
Si P
Si
AlAl Fe Ni
Ni
200
200 Fe

00
00 55 10
10 15
15 20
20
Energy (keV)

c)
600
Al

400
Counts

Fig. 4. Surface morphology of Typha domingensis observed by scanning electron Cd

200 S
microscopy: (a) before metal-ion biosorption, (b) after Ni(II) biosorption, and (c) P K Cu
after Cd(II) biosorption. Ca
Zn

found that the affinity order of Cd(II) was higher than Ni(II) when 0
studying the adsorption of heavy metals from aqueous solutions 0 5 10 15 20
onto sugar beet pulp. Similarly, Sheng et al. (2004) revealed that the Energy (keV)
affinity sequence of Cd(II) was higher than Ni(II) for the removal of
Fig. 5. Energy dispersive X-ray spectrum of Typha domingensis: (a) before metal-ion
heavy metals from dilute aqueous solutions using the marine algae
biosorption, (b) after Ni(II) biosorption, and (c) after Cd(II) biosorption. Note: after
Sargassum species and Padina species. Guo et al. (2015) used the biosorption, signals displayed at 7.5 and 3.5 keV corresponded to Ni(II) and Cd(II),
biosorbent succinylated maize straw treated with Na2 CO3 (NaS- respectively.
MS) to recover Ni(II) and Cd(II) ions from a binary mixture. Their
study indicated that NaS-MS was more selective to Cd(II) than to
Ni(II). Their work explained this phenomenon as follow (Guo et al.,
2015).
The metal physico-chemical properties, such as hydration num- Table 4
ber (N) and hydrated radius (RH) were considered to elucidate the The physico-chemical properties of Ni(II) and Cd(II) ions (Guo et al., 2015).

metal affinity of adsorbents (Hokkanen et al., 2013). Metals that Properties Ni(II) Cd(II)
have low N/RH ratios promote high Coulombic forces toward amor- Electronegativity (Xm ) 1.91 1.61
phous oxide surfaces (Trivedi and Axe, 2001). As listed in Table 4, Ionic radium, A (r) 0.69 0.97
the N/RH of Cd(II) is lower than that of Ni(II), and thus, Cd(II) ions Hydration number (N) 6.6 6.0
could exhibit a higher affinity to the biomaterial surface. Hydrated radium (RH ) 2.06 2.28
Another explanation of this trend could be linked with the cova-
lent index (Eq. (13)) developed by Nieboer and McBryde, (1973).
 M. Fawzy et al. / Ecological Engineering 95 (2016) 743–752 751

From the physico-chemical properties of metal-ions in Table 4, it a) Training (Circles) and Checking (Asterisks) Errors
can be observed that the covalent index value of Cd(II) is higher than
that of Ni(II). Since the metal-ions adsorption capacity increases 8
with the covalent index (Jing et al., 2009), the affinity of Cd(II) to the 7
biosorbent could be higher than that of Ni(II). These observations

Root mean square error

6
further confirm our previous results that at the same experimental
condition, the removal efficiency of Cd(II) was higher than that of 5
Ni(II). 4

3
Covalent index = Xm 2 × r (13)
2

1
Where,
Xm represents the electronegativity of the metal-ions, and r is 0

particle size
time

Biosorbent
Contact

Biosorbent
pH

dosage
Initial Ni(II)
concentration
the cationic crystal radius.

3.10. Results from ANFIS

In the current study, the experimental data were quantified

b) Training (Circles) and Checking (Asterisks) Errors
and fed to the ANFIS-based algorithm by using the function “exh-
srch”. The data were arranged as: the first five columns contained 18
input candidates (pH, biosorbent dosage, metal-ions concentration, 16
contact time and particle size), and the final column contained 14

Root mean square error

output data (metal-ions removal efficiency). During training, the
12
membership function parameters were adjusted using hybrid
10
learning methodology, which consisted of a combination of the
least-squares method and the backpropagation gradient descent 8
method. The checking data were used to cross-validate the fuzzy 6
inference model for the detection and prevention of model overfit- 4
ting. The hold-out cross-validation method was adopted for ANFIS 2
because of its accuracy, relative stability and low computational
0
time requirements (Azar, 2011). To validate the ANFIS model, the
pH

Initial Cd(II)

dosage
Contact
time

particle size
Biosorbent

training and checking data errors were calculated in the form of
root mean square error. The training process terminated when both
training and checking data were associated with the training epoch
that has a minimum checking error. The computation time con-
sumed to complete the training progress was 0:00:11 using PC
memory: 2.00 GB RAM.
The left-most input variable in Fig. 6 had the least root mean
Biosorbent
concentration
Fig. 6. Adaptive neuro-fuzzy inference system for determining the order of oper-
ating parameters affecting the removal efficiencies of (a) Ni(II), and (b) Cd(II),
respectively. Note: the left-most input variable has the least error or in other words,
the most relevance with respect to the output.

square error or in other words, the most relevance with respect

to the output. As shown in Fig. 6a, the ANFIS of Ni(II) biosorp-
tion process indicated training errors of 7.80, 7.90, 5.53, 7.48
and 8.04, as well as checking errors of 8.18, 8.45, 5.87, 8.11 and
8.56 for pH, biosorbent dosage, initial Ni(II) concentration, contact
time and biosorbent particle-size, respectively. Accordingly, results
from the ANFIS model revealed that the order of experimental
parameters affecting the Ni(II) removal efficiency was: initial Ni(II)
concentration > contact time > pH > biosorbent dosage > biosorbent
particle-size.
Additionally, ANFIS of the Cd(II) sorption process revealed train-
ing root mean square errors of 12.17, 16.58, 13.25, 16.05 and 16.46,
as well as checking errors of 10.40, 19.07, 17.80, 18.50 and 19.18
for pH, biosorbent dosage, initial Cd(II) concentration, contact time
and biosorbent particle-size, respectively (Fig. 6b). Thus, the results
from ANFIS indicated that the sequence of experimental parame-
ters affecting the Cd(II) removal efficiency was: pH > initial Cd(II)
concentration > contact time > particle size > biosorbent dosage.
Those results clearly indicated that the parameters “initial Ni(II)
concentration” and “pH” were the most influential inputs on the
removal efficiencies of Ni(II) and Cd(II), respectively. As previously
mentioned in Section 3.1, the maximum Cd(II) removal efficiency
was observed at an initial pH of 7.0, and the adsorption capacity was
decreased about 39 times by lowering the initial pH from 7.0 to 2.0.
Thus, in accordance with ANFIS results, the removal efficiency of
Cd(II) was mainly pH-dependent.
Reed and Matsumoto (1993) reported that the principal species
of Cd2+ are formed according to the following reactions:
Cd2 + H2 O ⇔ Cd(OH)+ + H+ pK1 = 9.0
Cd2 + 2H2 O ⇔ Cd(OH)2 + 2H+ pK2 = 19.1
Cd2 + 3H2 O ⇔ Cd(OH)3 − + 3H+ pK3 = 30.3
Cd2 + 2H2 O ⇔ Cd(OH)2 (s) + 2H+ pKs = 30.3
Leyva-Ramos et al. (2005) noted that at pH below 7.0, the Cd2+
ion predominates and at pH values just below 9.0, cadmium starts
to precipitate out as Cd(OH)2 . At pH equals to 8.0, the species dis-
tribution is about 90% Cd2+ and 10% Cd(OH)+ . This indicates that all
the species arising at pH values ≤ 8.0 could carry a positive charge
either as Cd2+ or Cd(OH)+ .
Similar hypothesis were observed when applying ANFIS model-
ing for Cd(II) biosorption using rice straw (Nasr et al., 2015), as well
as biosorption of Cr(VI) from aqueous solution by date-palm-leaves
and broad-bean-shoots (Fawzy et al., 2016).
752 M. Fawzy et al. / Ecological Engineering 95 (2016) 743–752
4. Conclusions
This work succeeded to study the biosorption efficiency of Ni(II)
and Cd(II) ions from aqueous solution onto the Typha domingen-
sis biomass. Adsorption data of Ni(II) fitted well to Freundlich
isotherm, while Cd(II) adsorption was described by both Lang-
muir and Freundlich isotherms. Biosorption capacity of Ni(II) was
maximum at pH of 6.0, while the removal efficiency of Cd(II)
was higher than Ni(II), and could be obtained at a wider pH
range of 4–8. Results from ANFIS indicated that the adsorption of
Ni(II) was mainly affected by the initial metal-ions concentration,
whereas the adsorption of Cd(II) was mostly pH-dependent. This
study demonstrated that the Typha domingensis could be used as a
promising sorbent biomaterial for the removal of metal-ions from
aqueous solution.
Acknowledgements
The authors would like to thank the chemist Shaimaa Fadly
and members of the Electron Microscopy Unit, Faculty of Science,
Alexandria University for their assistance during the development
of the experimental protocol.
This work was funded by the Environmental biology lab of
Environmental Sciences department, Faculty of Science, Alexandria
University, Alexandria, Egypt.
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.ecoleng.2016.07.
007.
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