Journal of Advanced Research 14 (2018) 1–9

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Journal of Advanced Research

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Original Article

Detachment of Cu (II) and Co (II) ions from synthetic wastewater via

adsorption on Lates niloticus fish bones using LIBS and XRF
R.A. Rezk a, A.H. Galmed b, M. Abdelkreem a, N.A. Abdel Ghany c, M.A. Harith b,⇑
a
Higher Technological Institute, 10th of Ramadan City, 6th of October Branch, Egypt
b
National Institute of Laser Enhanced Science (NILES), Cairo University, Egypt
c
National Research Centre, Physical Chemistry Department, Cairo, Egypt

g r a p h i c a l a b s t r a c t

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

Article history: Natural fish bones, that are known to have unique adsorption capacity, have been used in the present
Received 29 November 2017 work for removal of heavy metals, copper, and cobalt, from wastewater. It has been found that sorption
Revised 26 April 2018 process depends on the initial metal concentration and on the contact time. Laser-induced breakdown
Accepted 1 May 2018
spectroscopy (LIBS) as a spectrochemical analytical technique was used for qualitative and quantitative
Available online 4 May 2018
analysis of the water samples. X-ray Fluorescence (XRF), as another spectrochemical analytical method,
was exploited to characterize the remediation of wastewater. The optimum contact time values for the
Keywords:
removal of Cu (II) and Co (II) were 270 and 300 min, respectively. Furthermore, the percentages of
Co and Cu ions
Adsorption
adsorbed Cu (II) and Co (II) were high for low initial concentrations and decreased with increasing the
Fishbones heavy metal initial concentrations. The Langmuir and Freundlich isotherm models were used to analyze
Spectrochemical techniques the equilibrium adsorption data and Freundlich isotherm was found to represent the experimental
Isotherm models results well with a correlation factor close to one. However, the pseudo-second-order kinetic model pro-
vided the best fit to the experimental data for the adsorption of heavy metals using fish bones compared
to the pseudo-first-order model. The obtained results demonstrate the potential of using both LIBS and
XRF in the analysis of contaminant wastewater effectively.
Ó 2018 Production and hosting by Elsevier B.V. on behalf of Cairo University. This is an open access article
under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

Introduction

Contamination of water by heavy metals poses serious ecologi-

Peer review under responsibility of Cairo University. cal problems because of their pernicious effects on human, ani-
⇑ Corresponding author at: National Institute of Laser Enhanced Science, Cairo
mals, and plants [1,2]. Heavy metals such as copper and cobalt
University, Giza 12613, Egypt.
E-mail address: mharithm@niles.edu.eg (M.A. Harith).
find their way to aquatic environment as a result of the rapid

https://doi.org/10.1016/j.jare.2018.05.002
2090-1232/Ó 2018 Production and hosting by Elsevier B.V. on behalf of Cairo University.
This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
2 R.A. Rezk et al. / Journal of Advanced Research 14 (2018) 1–9
industrial development. Textile, mining, automotive metal-
finishing, as well as metallurgical industries, release different
heavy metals in nearby water drains [1–5]. Because of the high
toxicity of these contaminants, extensive efforts have been exerted
to remediate polluted wastewater. Conventional physical and
chemical treatment techniques, including chemical precipitation,
reverse osmosis, membrane filtration, ion exchange, and
oxidation-reduction have been exploited to remove heavy metals
from the wastewater [6]. Among these techniques, adsorption
can be counted upon as an effective economic technique for the
removal of heavy metals from wastewater due to its efficiency, ver-
satility, and ease of operation [7]. More recently, biogenic hydrox-
yapatite (HAP) of different origins, such as fish and animal bones,
bone chars, and food waste, has been used as sorbent materials
for remediation of wastewater [8–11]. Fishbones as a distinctive
material of low cost and natural abundance have proven to be
one of the most effective heavy metal sorbents used in industrial
applications [12]. The adsorption efficiency of fish bones is due
to the presence of hydroxyapatite (Ca10(PO4)6(OH)2) structure, that
dependence on the exchange reaction with calcium ions with
heavy metals [12–16].
Spectrochemical analytical techniques, such as Laser-Induced
Breakdown Spectroscopy (LIBS) and X-ray Fluorescence (XRF)
could be used effectively to follow up the adsorption procedure.
LIBS uses laser-generated plasma as a source of material vaporiza-
tion, atomization, and excitation. This technique has been success-
fully applied to analyze solid, liquid, and gaseous samples. LIBS
also offers attractive features for real-time multi-elemental analy-
sis at atmospheric pressure, including remote applications with no
or minimal sample preparation in addition of being noninvasive
and quasi-nondestructive. This laser spectroscopic technique has
the capability for qualitative and semi-quantitative elemental
analysis, with detection of most existing species such as major
components and/or trace elements with low and high Z-number.
It is also possible to use LIBS in situ with portable systems because
of its simplicity and compactness of the required equipment con-
trary to other techniques such as Atomic Absorption Spectroscopy
or Inductively Coupled Plasma Optical Emission Spectroscopy. LIBS
has significant potential in the environmental applications, for
tracing pollutants and for the detection of heavy metals contami-
nation [17–19]. On the other hand, XRF as a well-established spec-
trochemical analytical technique offers some unique advantages as
being fully non-destructive, requiring minimal sample preparation,
simple and suitable for in situ use with portable equipment.
Because of the simplicity of XRF analysis, it has been widely used
for numerous environmental applications [20]. The limit of detec-
tion of both LIBS and XRF for metals is typically in the ppm range
[19–21]. The main goal of this research work is to confirm the
adsorption efficiency of fish bones for heavy metals. The variation
of initial metals concentrations and contact times as adsorption
parameters were examined. The LIBS results were validated by
the XRF technique measurements. Adsorption isotherms and kinet-
ics studies were reported to account for fish bones as an effective
adsorbent of copper and cobalt from wastewater. Our resultsRefer-
ence has been inserted in the text differ from the previously pub-
lished research [19] mainly by focusing on the kinetics of the
adsorption process and demonstrating the potential of LIBS tech-
nique as an environmental diagnostic technique by following up
the concentration of the adsorbed copper and cobalt on fish bone.
Experimental
Preparation of sorbent
Lates niloticus fish bones (Egyptian Nile Perch) as a basic sorbent
have been obtained from local markets in the vicinity of Cairo
University. Fish bones were washed several times with hot distilled
water after removal of fats and solid residues. Bones dried at 40 °C
for 24 h were then ground and sieved down to about 300 mm size.
Preparation of synthetic wastewater
Standard synthetic wastewater stocks (1000 mg L
1) of copper
ion (Cu II) and cobalt ion (Co II) solutions were prepared by dissolv-
ing individually 3.93 g of crystalline copper sulfate ‘‘CuSO45H2O”
and 4.036 g of crystalline cobalt chloride (CoCl2) salt in 1-liter dis-
tilled water. The standard solutions of both Cu (II) and Co (II) were
diluted to outfit different concentrations (50, 100, 150, 200, 250,
and 300 mg L
1) required in the experimental measurements.
Adsorption studies
The sorption experiments were carried out in 500 mL Erlen-
meyer flasks by mixing 300 mL metal solution with 2.0 g dry
weight of fish bones sorbent material. Mixtures have been stirred
for predetermined time intervals, from 30 min until 6 h, at room
temperature (25 ± 2 °C) on a magnetic stirrer at 200 rpm with an
initial pH of (6.6 ± 0.1). Thereafter, the solutions have been filtered
after 30 min in each case with 0.7 mm filter paper (Whatman, Cat
No. 1001 125). The fish bones filtrates were then collected and
dried, and the treated wastewater has been collected and stored
in glass bottles.
LIBS setup
All experiments were carried out using a typical single pulse
LIBS setup that employs a Q-switched, Nd: YAG laser (BRIO, Quan-
tel, France) operating at a wavelength of 1064 nm. The laser pulse
energy was 96 mJ, at 5 ns pulse duration and 10 Hz repetition rate.
The measurements were performed in air at ambient atmospheric
pressure. The laser was focused by a 10 cm focal length plano-
convex quartz lens onto the target surface. A 2 m length optical
fiber of 600 mm diameter has been mounted at a 45-degree angle
with respect to the target surface to collect the emission from
the plasma plum then fed it to the entrance slit of an echelle spec-
trometer (Mechelle 7500, multichannel, Sweden), covering the
spectral wavelength range of 200–1000 nm (displayable in a single
spectrum). An intensified CCD camera (DiCAM-PRO, PCO-computer
optics, Germany) detects the spectra of the plasma emission. LIBS++
software has been used for the analysis and identification of the
obtained LIBS spectral lines. Each LIBS spectrum represents the
average of 25 spectra taken as 5 spectra at 5 different positions
on each fish bone sample target [16]. Detailed study of the exper-
imental parameters of the present setup can be found in our previ-
ous work [19]. The optimum experimental conditions for LIBS
analysis such as delay time (td) which is the time interval between
firing the laser and triggering the detector (ICCD camera), and gate
width (Dt) which is the time during which the detector is sensitive,
were 1500 ns, and 2500 ns, respectively. These conditions provided
very good spectral signal-to-noise ratio. For quantitative analysis
using LIBS, the laser-induced plasma should satisfy the conditions
of local thermodynamic equilibrium (LTE) [22]. Under the present
experimental conditions, the plasma temperature Te ranges from
6267 to 10676 K and the values of electron density Ne (cm
3) is
greater than 1016 which fulfills McWhirter criterion (Te > 5000 K,
Ne > 1016).
XRF setup
As mentioned above, the samples have been also analyzed via
the XRF technique. An XRF spectrometer (Portable XRF, Thermo
Scientific, NITON/XLt 8138, 592 GKV, USA) having a 40 kV X-ray
 R.A. Rezk et al. / Journal of Advanced Research 14 (2018) 1–9 3

tube with a gold anode excitation source. The detection range of
this spectrometer expands from sulfur to uranium with a low limit
of detection for high-Z elements. The advanced NITON software
has been used for the analysis of the obtained XRF spectra [23].
Scanning electron microscopy (SEM)
Scanning electron microscopy (SEM, FEI Quanta FEG 250 series,
Japan) [24] investigations were performed at magnifications of
10 to 10,000. It has been used for the morphological character-
ization of the samples to elucidate the porous properties of the
biosorbents. For cross-sectional inspection, the fragmented sam-
ples were embedded in carbon tab.
Results and discussion
Scanning electron microscope (SEM) analysis
To show clearly the adsorption effect on the bones surface mor-
phology, the physical morphology of fish bones surface is shown in
Fig. 1. The SEM micrographs depict the surface morphology before
and after adsorption processes at the highest concentration of 300
mg L
1 for 270 min at initial pH (6.6 ± 0.1).
For comparison studies, all images have had the same 2000
magnification. Analysis of SEM image presented in Fig. 1(a)
revealed that the dried pure fish bones have numerous small pores
on the surface which are responsible for increasing the surface area

Fig. 1. SEM images of fish bones (a) before adsorption (b) after adsorption of Cu (II) (c) after adsorption of Co (II) [in 300 mg L
1 concentration after 270 min with initial pH
(6.6 ± 0.1)].
4 R.A. Rezk et al. / Journal of Advanced Research 14 (2018) 1–9

and consequently the increase of adsorption capacity and effi-
ciency [25]. Fig. 1(b) and (c) displays a comparison between the
adsorption processes of both Cu (II) and Co (II) on fish bones sur-
face. Fig. 1(b) indicates that all pores appearing on the adsorbent
surface are almost completely covered by Co (II) ions. On the other
hand, Fig. 1(c) apparently shows that fish bones surface is partially
covered by Co (II) ions.
Influence of contact time and metal ions initial concentration on
removal process
Fig. 2(a), (c) depicts the effect of contact time on adsorption
uptake of Cu (II) and Co (II) onto fish bones from synthetic wastew-
ater at different concentrations using LIBS analysis, respectively.
The results indicate that both LIBS intensity and adsorption uptake
increase with increasing contact time until reaching the equilib-
rium point of 270 min for Cu (II) and 300 min for Co (II). The effect
of contact time on adsorption uptake of Cu (II) and Co (II) onto fish
bones is accentuated by making use of XRF analysis at the same
experimental conditions as shown in Fig. 2(b), (d). The trend of
the XRF curves indicates a significant consistency; that lends con-
fidence to the LIBS results.
Fig. 3(a), (b) shows the effect of contact time on removing
Cu (II) and Co (II) respectively from the synthetic wastewater
by means of XRF analysis with same initial concentrations. In
Fig. 3(a) it is clear that the reduction in the -intensities arises
as a consequence of increasing the contact time. By repeating
the experiment for Co (II), Fig. 3(b) demonstrates similar trend
of decreasing intensities; which shows the increase in the
removed amount of Co (II) from synthetic wastewater with
longer contact time for the same initial concentrations mea-
sured for Cu (II).
It should be noted that the metal cations adsorption on the fish
bones is higher in the beginning due to the availability of a large
surface area with specific sites of the adsorbent. Reaching satura-
tion means that all active sites in the adsorbent are occupied
[26,27].
Adsorption isotherm
The adsorption percentage efficiency of metal ion removal E has
been calculated by the following equation:
E ¼ ðci
ce Þ=ci  100 ð1Þ

300 ppm (a) 300 ppm

250 ppm (b)
80 Cu I (327.4 nm) 35 250 ppm
200 ppm 200 ppm Cu (II)
150 ppm 150 ppm
70 100 ppm 30 100 ppm
50 ppm 50 ppm
Normalized intensity

25
Intensity (a. u.)

60

20
50

15
40

10
30
5

60 120 180 240 300 360 60 120 180 240 300 360

Contact time (min) Contact time (min)

35 300 ppm (c) 8

300 ppm (b)
250 ppm 250 ppm
Co I (340.5 nm) 200 ppm Co (II)
200 ppm
30 7 150 ppm
150 ppm
100 ppm
100 ppm
50 ppm
50 ppm
25
Normalized intensity

6
Intensity (a. u.)

20 5

15
4

10
3

5
2

60 120 180 240 300 360 60 120 180 240 300 360
Contact time (min) Contact time (min)

Fig. 2. Effect of contact time on adsorption of Cu (II) and Co (II) on fish bones for different concentrations using LIBS (a, c) and XRF (b, d).
 R.A. Rezk et al. / Journal of Advanced Research 14 (2018) 1–9 5

2.0 (a) 300 ppm Cu (II)

250 ppm 40 Co (II)
Cu (II) 200 ppm
150 ppm 35
1.6 100 ppm
50 ppm 30

Removal efficiency %
Intensity (a. u.)

25
1.2

20

0.8 15

10

0.4 5

0
60 120 180 240 300 360 50 100 150 200 250 300
Contact time (min) Concentrations (ppm)

Fig. 4. Effect of initial metal concentration on the percentage removal efficiency of

300 ppm Cu (II) and Co (II). The error bars represent the standard deviation of the
0.8 (b) 250 ppm experimental data.
200 ppm
Co (II)
0.7 150 ppm
100 ppm
Langmuir isotherm
50 ppm
0.6
This model assumes that adsorbent has sites with uniform
Intensity (a. u.)

0.5 energy for adsorption of adsorbate providing a monolayer homoge-

neous adsorption [30,31]. The linear form of Langmuir isotherm is
0.4 presented as follows [32]:

0.3
0.2
0.1
60 120 180 240 300
Contact time (min)
Fig. 3. Effect of contact time on removal of (a) Cu (II) and (b) Co (II) from synthetic
wastewater for different concentrations using XRF.
where ci is the initial metal ion concentration (mg L
1), and ce is the
equilibrium metal ion concentration (mg L
1). The calculations are
performed at a fixed contact time of 30 min with initial pH (6.6 ±
0.1) and temperature (25 ± 2 °C).
Fig. 4 shows the percentage removal efficiency calculated by Eq.
(1) versus different initial metal concentrations, under the previ-
ously specified conditions. These results assure that the removal
efficiency for copper is higher than that of cobalt at all concentra-
tions. The difference in ion exchange capacity on the adsorbent
surface for the two elements could justify this difference in
removal efficiency [28]. However, the dependence on charge den-
sity of each element, extent of hydrolysis, and solubility of hydro-
lyzed metal ions in the solution can also be taken into
consideration in this issue [29].
1 1 1
¼ þ ð2Þ
qe bce qmax qmax
qe (mg g
1) is the amount of metal ion adsorbed at specified equilib-
rium, qmax (mg g
1) is the maximum amount of the metal ion per
unit weight of sorbent and b (L mg
1) is Langmuir adsorption equi-
librium constant related to the energy of adsorption.
360
Fig. 5(a), (b) shows the Langmuir adsorption isotherm plot of
1=ce versus 1=qe for Cu (II) and Co (II), respectively. The values of
Langmuir constants, qmax and b, are calculated from the intercept
is equal to 1=qmax and the slope is equal to 1=bqmax through linear
regression. Usually, high correlation coefficient, 0.8888 and
0.8623 respectively, indicates that the application of the Langmuir
equation supports monolayer formation on the surface of the
adsorbent.
The Langmuir isotherm constants for the adsorption of copper
and cobalt ions are given on the corresponding figures. The
obtained values of b and qmax are 0.25 and 35.12 for Cu (II) and
0.06 and 23.46 for Co (II), which prove that the adsorption process
depends on both the concentration and contact time.
Langmuir isotherm can be described by a dimensionless con-
stant known as the separation factor or the equilibrium factor RL ,
given by [28,33,34]:
1
RL ¼ ð3Þ
1 þ bco

b is Langmuir constant (L mg
1) and co is the initial concentration

Adsorption isotherm models
At a fixed temperature, the adsorbate quantity adsorbed to that
remaining in the solution is called adsorption isotherm and it
describes the equilibrium relation between the concentrations in
both adsorbent and solution phases [29]. Langmuir and Freundlich
isotherm models are the most widely adsorption isotherm models
that are used to quantify the sorption capacity of adsorbate.
(mg L
1). RL is used to predict the shape of the isotherms, which
gives information about the favorability of the adsorption of metal
ions on the adsorbent. According to equation (3), the values of the
separation factor (RL ) for all selected concentrations (50–300 mg
L
1) of metal ions are found to be less than 1, which indicates the
favorable biosorption conditions. Fig. 6 provides the relation t
between co (mg L
1) and RL values which shows that by increasing
the concentration the RL values decrease exponentially in the range
6 R.A. Rezk et al. / Journal of Advanced Research 14 (2018) 1–9

0.16 of 0 < RL < 1. This consequently assures that the adsorption of Cu (II)
(a) and Co (II) is still favorable even at higher concentrations.
0.14
Cu (II)
Freundlich isotherm
0.12
Freundlich model [35] is an empirical expression used to
describe both the heterogeneous surfaces and multilayer sorption.
0.10
1/qe

The mathematical form of Freundlich adsorption isotherm is repre-

sented by the following equation:
0.08
1
ln qe ¼ ln kf þ ln ce ð4Þ
0.06
2
R = 0.8888 n
slope = 0.11382
where kf and n are constants, being indicative of the extent of
Intercept = 0.02847
0.04 adsorption and the degree of non-linearity between solution and
adsorbent, respectively. The coefficient kf (mg1
1/n g
1 L1/n) is a
0.02 measure of the adsorption capacity; the greater is the surface acces-
0.0 0.2 0.4 0.6 0.8 1.0 1.2 sible for adsorbate particles, the greater is the value of kf [5]. Plot-
1/ce ting ln ce versus ln qe will yield an intercept of ln kf and a slope of
1=n.
0.16 Fig. 7(a), (b) shows the fitting plot of Freundlich isotherm for
(b) Cu (II) and Co (II), respectively. The constant values obtained
from Freundlich adsorption isotherm and its correlation coeffi-
0.14 Co (II)
cient R2 are summarized in the figures. Regression values of
0.992 for Cu (II) and 0.981 for Co (II) are acceptable to describe
0.12
the adsorption of both heavy metals on fish bones. The con-
stants obtained from ð1=nÞ are 0.689 for Cu (II) and 0.561 for
1/q e

0.10

2.6 (a)
0.08
2 2.4
Cu (II)
R = 0.86232
slope = 0.66701
0.06
Intercept = 0.04263 2.2

0.04 2.0
ln qe

0.00 0.03 0.06 0.09 0.12 0.15 0.18

1.8
1/c e
1.6 2
Fig. 5. Langmuir adsorption isotherm for the adsorption of (a) Cu (II) and (b) Co (II) R = 0.992
by fish bones. 1.4 1/n = 0.689
kf = 3.022
1.2

3.5 4.0 4.5 5.0 5.5

0.25 ln ce
Cu (II)
3.0
Co (II)
(b)
0.20 2.8 Co (II)

2.6
0.15
2.4
RL

ln qe

2.2
0.10

2.0
2
R = 0.981
0.05 1.8 1/n = 0.561
kf = 1.046
1.6
0.00
50 100 150 200 250 300 1.4
C0 (mg/L) 3.0 3.5 4.0 4.5 5.0 5.5
ln ce
Fig. 6. The calculated separation factor RL versus the initial concentrations of Cu (II)
and Co (II). Fig. 7. Freundlich adsorption isotherm of (a) Cu (II) and (b) Co (II) by fish bones.
 R.A. Rezk et al. / Journal of Advanced Research 14 (2018) 1–9 7

Co (II) indicate favorable and high-affinity adsorption of fish order kinetic models were tested to interpret the experimental
bones for metallic ions. data.
Finally, from all parameters of both isotherms, it has been found
that the equilibrium data are well-fitted to Freundlich isotherm. Pseudo-first order kinetic model
This assumes that it is applicable for non-ideal adsorption on
heterogeneous adsorbent surfaces. The pseudo-first-order equation of Lagergren is generally
expressed as [36]:
Adsorption kinetic model
dq
¼ qe ð1
e
k1 t Þ ð5Þ
dt
To evaluate the kinetics of the adsorption of the Cu (II) and Co
(II) from wastewater, the pseudo-first-order, and pseudo-second- where dq
dt
is the adsorption capacity at time t, qe (mg g
1) is the equi-
librium adsorption capacity, and k1 (min
1) is the rate constant of
4
300 ppm
(a) 30 (a)
3 250 ppm
Cu (II) 200 ppm Cu (II)
150 ppm
2
25 100 ppm
50 ppm
1
ln (qe - qt)

20
0

-1

t/q t
15
-2
300 ppm 10
-3 250 ppm
200 ppm
-4 150 ppm
100 ppm 5
-5 50 ppm

30 60 90 120 150 180 210 0

30 60 90 120 150 180 210
time (min)
time (min)

3.2
40
(b) 300 ppm
2.8 250 ppm (b)
Co (II) 35 200 ppm
2.4 150 ppm Co (II)
100 ppm
2.0 30 50 ppm

1.6 25
ln (qe - qt)

1.2
t/q t

20
0.8

0.4 15
300 ppm
0.0 250 ppm 10
200 ppm
-0.4 150 ppm
100 ppm 5
-0.8 50 ppm

0
30 60 90 120 150 180 210
30 60 90 120 150 180 210
time (min) time (min)

Fig. 8. The linear pseudo first-order kinetic sorption data for (a) Cu (II) and (b) Co Fig. 9. The linear pseudo second-order kinetic sorption data for (a) Cu (II) and (b) Co
(II) at different concentrations. (II) at different concentrations.

Table 1
Pseudo-first order kinetic model parameters for different initial concentrations of Cu (II) and Co (II).

Initial metal concentration (mg L
1) K1 (min
1)  10
3 R2 qe (cal.) qe (exp.)

Cu (II) Co (II) Cu (II) Co (II) Cu (II) Co (II) Cu (II) Co (II)
50 15.53 7.36 0.867 0.973 4.542 4.074 7.3 6.6
100 19.58 16.61 0.933 0.979 22.471 17.898 14.4 12.2
150 19.2 16.06 0.815 0.948 38.477 18.667 20.9 14.4
200 22.28 8.85 0.917 0.962 83.386 14.366 27.6 18.3
250 12.25 7.7 0.983 0.985 37.156 13.762 32.6 22.2
300 10.58 10.99 0.939 0.907 39.636 26.731 36.4 24.8
8 R.A. Rezk et al. / Journal of Advanced Research 14 (2018) 1–9

Table 2
Kinetic parameters for the adsorption of Cu (II) ion and Co (II) ion onto fish bones based on the pseudo-second-order kinetic model.

Initial metal concentration (mg L
1) K2 (min
1)  10
3 R2 qe (cal.) qe (exp.)

Cu (II) Co (II) Cu (II) Co (II) Cu (II) Co (II) Cu (II) Co (II)
50 0.688 1.32 0.985 0.984 9.634 6.590 7.3 6.6
100 0.490 3.95 0.998 0.936 19.360 15.045 14.4 12.2
150 0.355 1.02 0.997 0.987 27.787 16.392 20.9 14.4
200 0.366 1.42 0.986 0.974 36.405 17.293 27.6 18.3
250 0.493 2.06 0.968 0.996 39.186 23.186 32.6 22.2
300 1.62 1.03 0.946 0.948 39.038 23.946 36.4 24.8

pseudo-first order adsorption. Integrating and applying boundary
conditions, qt ¼ 0 at initial time ðt ¼ 0Þ and q ¼ qt at a given time
ðt ¼ tÞ, equation (5) takes the form:
lnðqe
qt Þ ¼ ln qe
k1 t
Fig. 8(a), (b) shows the plot of lnðqe
qt Þ versus t for different
metal concentrations to obtain the rate constant k1 from the slope
and qe from the intercept.
Table 1 shows the parameters from the pseudo-first-order
model for both Cu (II) and Co (II). By comparing the presented
results, it is clear that the rate of cobalt adsorption on fish bones
is less than that of copper for all concentrations. Therefore, the
adsorption of Cu (II) onto fish bones is much higher than that of
Co (II). On the other hand, there is an observable difference
between calculated adsorption capacities and the experimental
values for both metallic ions.
Pseudo-second order kinetic model
The pseudo-second-order equation is also based on the sorption
capacity of the solid phase and is expressed as [37]:
dqt
¼ k2 ðqe
qt Þ2
dt
where qt is the adsorption capacity at time t and k2 (g mg
1 min
1)
represents the pseudo-second-order rate constant.
After integration and application of the boundary conditions qt
= 0 at t = 0 and qt = qt at t = t, the integrated form becomes:
t 1 t subjects.
¼ þ
qt k2 q2e qe
Fig. 9(a), (b) depicts a linear relationship between
according to Eq. (8), regarding both metallic ions measurements
for their different concentrations.
The kinetic parameters given in Table 2 for the pseudo-second-
order model were determined from the slopes and intercepts of the
lines in Fig. 9(a), (b) for different concentrations Cu (II) and Co (II),
respectively.
The best fitting of adsorption data was obtained for the pseudo-
second-order kinetic model as shown in Fig. 9(a), (b). This model
assumes that a chemisorption mechanism is involved in the
adsorption process and the rate of the site is proportional to the
square of the number of unoccupied sites. The adsorption kinetics
of Cu (II) and Co (II) ions onto fish bones, suggests that the rate-
limiting step could be chemical sorption or ion exchange [37,38].
Conclusions
In the present work, Lates niloticus fish bones (Egyptian Nile
Perch) that dried and ground to 300 mm size have been used as a
sorbent for the removal of the toxic heavy metals (Cu (II) and Co
(II)) from wastewater. LIBS and XRF as well-established spectro-
chemical analytical techniques were applied for the qualitative
and quantitative monitoring of the heavy metals removal. The effi-
ciency of fish bones in adsorption of heavy metals, is mainly due to
its content of the natural hydroxyapatite (HAP) that depend on the
ion exchange reaction with calcium ions on the bone surface. The
ð6Þ
obtained optimum contact time values for the heavy metal ion
removal of Cu (II) and Co (II) were 270 and 300 min, respectively.
Furthermore, the highest percentage values of adsorbed Cu (II)
and Co (II) were found at the low initial ion concentrations. Based
on correlation coefficients, the best fit model is the Freundlich iso-
therm that was found to provide the best correlation of Cu (II) and
Co (II) adsorption onto fish bones. The kinetic studies revealed that
the adsorption process of both ions followed well the pseudo-
second-order kinetic model. These experimental studies accentu-
ate the potential of using LIBS and XRF as powerful spectrochemi-
cal analytical techniques for environmental analysis, which
develop an appropriate technology regarding the removal of heavy
metals from contaminated industrial effluents. However, the
results obtained are preliminary and further studies are planned
in future work on real wastewater samples and highly optimized
experimental conditions.
Conflict of interest
ð7Þ
The authors have declared no conflict of interest.
Compliance with Ethics Requirements
This article does not contain any studies with human or animal
ð8Þ
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