Egyptian Journal of Aquatic Research xxx (2018) xxx–xxx

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Egyptian Journal of Aquatic Research

journal homepage: www.sciencedirect.com/locate/ejar

Adsorption study of heavy metal ions from aqueous solution by

nanoparticle of wild herbs
Ghadah M. Al-Senani ⇑, Foziah F. Al-Fawzan
Department of Chemistry, College of Science, Princess Nourah bint Abdulrahman University, Riyadh, Saudi Arabia

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

Article history: Wild herbs (Equisetum, EH and Teucrium, TH) were used as environment friendly adsorbents in the pre-
Received 27 March 2018 sent study. This study focuses on the investigation of the adsorption ability of Co, Cd and Li from aqueous
Revised 24 July 2018 solution. The adsorption of heavy metals onto EH and TH was dependent on particle size, dose, solution
Accepted 26 July 2018
pH, contact time, and temperature. Kinetic data were tested using pseudo-first-order and pseudo-second-
Available online xxxx
order kinetic models. The best fit was obtained with the pseudo-second-order kinetic model. Langmuir
and Freundlich models have been applied to calculate adsorption data and the thermodynamic parame-
Keywords:
ters; entropy, DS°, enthalpy, DH°, and the Gibbs free energy, DG°; were determined. The results suggests
Wild herbs
Heavy metal
that the adsorption of heavy metals by the wild herbs are endothermic and a spontaneous process. Thus,
Equisetum it was concluded that EH and TH are promising adsorbents for the adsorption of heavy metals from aque-
Teucrium ous solutions.
Adsorption Ó 2018 National Institute of Oceanography and Fisheries. Hosting by Elsevier B.V. This is an open access
article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

Contents

Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Experimental . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Preparation of the adsorbents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Characterization of the adsorbents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Results and discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Characterization of the adsorbents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Effect of particles sizes of adsorbent . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Effect of initial metal ion concentration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Effect of adsorbent dosage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Effect of contact time . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Effect of pH . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Effect of temperature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Adsorption kinetic model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Pseudo first order kinetic model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Pseudo second order kinetic model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Adsorption isotherm . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Thermodynamic parameters. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Acknowledgment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00

Peer review under responsibility of National Institute of Oceanography and Fisheries.

⇑ Corresponding author.
E-mail address: gmalsnany@pnu.edu.sa (G.M. Al-Senani).

https://doi.org/10.1016/j.ejar.2018.07.006
1687-4285/Ó 2018 National Institute of Oceanography and Fisheries. Hosting by Elsevier B.V.
This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

Please cite this article in press as: Al-Senani, G.M., Al-Fawzan, F.F. Adsorption study of heavy metal ions from aqueous solution by nanoparticle of wild
herbs. Egyptian Journal of Aquatic Research (2018), https://doi.org/10.1016/j.ejar.2018.07.006
2 G.M. Al-Senani, F.F. Al-Fawzan / Egyptian Journal of Aquatic Research xxx (2018) xxx–xxx
Introduction
The adsorption of toxic substances resulting from the accumu-
lation of industrial wastes is important and one of the most dan-
gerous challenges facing the environment and society todays.
One of the most significant contaminants affecting water resources
is heavy metals. These metal ions present a significant risk to ani-
mals and humans, because of their high toxicity at both low and
high concentrations in soil and water. The search for new tech-
niques to remove these contaminants has involved both chemical
and biological methods.
Contaminating materials have become increasingly dangerous
with increasing technological development and the need for
diverse heavy metals, for example, in ore processing and other
modern industries, prompted the organizations concerned with
the preservation of the environment to develop restrictions and
laws for laboratories and concerning the treatment industrial
waste before its release into the environment so that toxic materi-
als do not exceed the allowable limits. Researchers have, thus,
devoted efforts to find effective methods for the adsorption of con-
taminants from waste, but, these processes are often economically
expensive; therefore, we must find ways to bypass conventional,
high-cost advanced adsorption technologies.
The adsorption of contaminants on the surfaces of solids an
effective method for heavy metals remediation. Activated carbon
is considered to be an efficient, competitive materials for this task.
However, the cost of production is still high; thus, many research-
ers have begun to search for alternative adsorbents made from
local natural materials. Plants are one type of alternative material
that can be used to adsorbate heavy metals from water systems
and soil.
The current proliferation of technology and development of
science have been an enormous boon for humans. They have
become dependent on technology and scientific development in
various aspects such as daily activities, trade, industry, and work.
Heavy metals are structural elements such as lead, zinc, arsenic,
cadmium, copper, titanium, cobalt, lithium, aluminum and mer-
cury, and can be in the form of metals or dissolved salts.
These metals are present in the environment in air, water, and
soil. For example, factory chimneys release metal oxides into the
air, thus transmitting heavy metal pollution to humans, animals
and plants. In addition, car exhausts release lead oxides, resulting
from the combustion of tetraethyl lead, into the atmosphere and
this is one of the most widespread routes to leading contamination
of marine organisms with metals, and the transit these contami-
nants via sea fishing to humans and animals. Furthermore, agricul-
tural soil is one of the most important sources of food polluted by
heavy metals, which arises through the irrigation of crops with pol-
luted water or the use of pesticides. In this situation, the metals are
transmitted through the vascular system of plants and fruits.
Fig. 1. Equisetum (EH) and Teucrium (TH).
Please cite this article in press as: Al-Senani, G.M., Al-Fawzan, F.F. Adsorption study of heavy metal ions from aqueous solution by nanoparticle of wild
herbs. Egyptian Journal of Aquatic Research (2018), https://doi.org/10.1016/j.ejar.2018.07.006
Therefore, field crops irrigated with drainage water contaminated
by heavy metal ions are one of the most important and most dan-
gerous sources for the entry of poisonous heavy metals into the
human body (Al-Qahtani, 2015).
There are many methods adsorption of heavy metals from the
environment, both chemical and physical. However, some of these
are not economically feasible. Therefore, it is necessary to investi-
gate low-cost effective alternatives. The adsorption of heavy met-
als by adsorption technology is a good alternative, and it is used
in the treatment of wastewater and soil. To compare, the adsorbent
substances, the cost, as well as effectiveness, must be considered.
Activated carbon is a highly effective adsorption substance of
heavy metals from wastewater, but it is soluble under extremely
acidic conditions (Wasewar, 2010).
Consequently, there is an increased interest from researchers
into low-cost, effective alternatives adsorbents. Many natural
materials used in the adsorption of heavy metals (cadmium, cop-
per, chromium, lead, nickel, cobalt, and lithium), have been discov-
ered, such as diplotaxis harra, glebionis coronaria, coffee grounds,
banana Peel, fruit and vegetable peels, cactus, rice straw, wheat
straw, and salvinia plant (Tounsadi et al., 2015; Seniunait et al.,
2014; Hossain et al., 2012; Jain, 2015; Derbe et al., 2015).
The aim of this work is to study the adsorption of heavy metals
from water using nanoparticle of abundant wild herbs, which are
considered environmentally safe and low-cost. The particle size,
dose, solution pH, contact time, and temperature were investigated.
Thermodynamic parameters, kinetic, equilibrium and adsorption
isotherms were determined to analysis of the adsorption behavior.
Experimental
Materials
All the chemicals used in this study were analytical grade. Cd
(Cl)2
4H2O (98), Co(Cl)2
6H2O (98), and LiCl (99)%. were purchased
from Sigma–Aldrich (Germany).
Preparation of the adsorbents
Equisetum (EH – Fig. 1), the horsetail, is an herbaceous perennial
horsetail native that has fertile spore-bearing stems growing from
a perennial underground rhizomatous and non-reproductive, and
growing throughout arctic and temperate regions of the northern
hemisphere. It contains several substances that can be used medic-
inally (Jump up, 2015).
Teucrium (TH – Fig. 1) is a genus of perennial and annual plants.
There are many species, including herbs, shrubs, and sub-shrubs.
They are found all over the world but are more common in the
Mediterranean climates (Jump up, 2011).
 G.M. Al-Senani, F.F. Al-Fawzan / Egyptian Journal of Aquatic Research xxx (2018) xxx–xxx
The wild herbs used in this study were purchased from a per-
fumer. The dried herbs were then cut into small pieces, and milled
to a powder using laboratory planetary ball mill (DECO-PBM-V-
0.4L). The powders were sieved into particles 50, 100, 200, 300,
and 400 lm using an Octagon D200 Digital Sieve Shaker. The
adsorbents were stored in glass bottles for further use without
any pre-treatment.
Methods
For the study of adsorption, distilled water was used to prepare
the desired concentrations from stock solution. The experiments of
adsorption were performed in a series of flasks containing 100 mL
solutions of metal ions at desired concentration and mass of adsor-
bent herbs. The mixtures were shaken for 16 h at 120 rpm using a
shaker (‘‘Rotaterm” Orbital and linear shaker). The mixtures were
filtered, and determined the concentrations of heavy metals by
inductively coupled plasma (ICP) mass spectrometry. The effect
of adsorbent doses from 0.1 to 2 g on the metal adsorption was
studied. The initial concentration used was 100 mg/L. The effect
of pH on the process of heavy metal adsorption was investigated
at pH values from 3 to 12, adjusted either with 1 M HCl or 1 M
NaOH using a pH meter, to monitor the change. In addition, the
effect of the adsorbent particle size was investigated from 400 to
less than 50 lm, and the contact time was varied between 1 and
6 h. The effect of temperature was studied from 25° to 60 °C for
2 h using 0.5 g of the adsorbent at an initial metal concentration
of 100 mg/L.
The adsorption equilibrium was investigated for different metal
concentrations between 10 and 500 mg/L. In addition, kinetics
experiments were conducted with 100 mg/L metal and 0.5 g of
adsorbent at room temperature with stirring at 120 rpm for 6 h.
At equilibrium, the adsorption, qe (mg/g), was calculated by
Eq. (1):
ðC 0  C e ÞV
qe ¼
m
where C0 and Ce (mg/L) are the concentrations of heavy metals at
initially and at equilibrium, respectively. V is the solution volume
(L) and m is the dry adsorbent mass (g).
The heavy metal adsorption percentage (AdsHM %) from the
solution was calculated as follows Eq. (2):
ðC 0  C e Þ
AdsHM % ¼  100
C0
For describing the adsorbent behavior, the pseudo first and sec-
ond order adsorption Kinetic models were applied.
The equilibrium data were then fitted using the Langmuir and
Freundlich isotherm models.
The thermodynamic parameters, including the changes in
enthalpy (DH°), entropy (DS°) and free energy (DG°), were calcu-
lated to describe the adsorption process onto EH and TH.
Fig. 2. FT-IR spectra of the functional groups in Equisetum, EH and Teucrium, TH.
Please cite this article in press as: Al-Senani, G.M., Al-Fawzan, F.F. Adsorption study of heavy metal ions from aqueous solution by nanoparticle of wild
herbs. Egyptian Journal of Aquatic Research (2018), https://doi.org/10.1016/j.ejar.2018.07.006
3
Characterization of the adsorbents
The functional groups in the adsorbents were determined by
Fourier transform FT-IR analysis.
The particle size of adsorbents was measured using an XRD. The
initial metals concentrations of the adsorbents were determined
for Co, Ni, Cu, Li, Cd, and Ba from ICP measurements.
Results and discussion
Characterization of the adsorbents
Fig. 2 shows the FTIR absorption bands of the adsorbent. The
peaks indicate the presence of functional groups containing O–H
and N–H at 3298 cm1, and carboxylic acid (–COOH) groups at
1610 cm1 and 1051 cm1 wavelength, which have a significant
effect in the process of adsorption and efficiency of adsorbing
metal ions via ion exchange (Nacke et al., 2016).
The mineral composition of biomass ash commonly shows a
high amount of Cu, Ni, Co and Ba in EH, as does TH (except Co).
The lowest amounts of Li and Cd were found (Fig. 3), so Li, Cd
and Co were selected for further study.
The smallest size obtained after milling the wild herbs was
50 lm. Fig. 4 shows the size of adsorbent particles, that had been
ground to less than 50 lm. The diameter of the particle is
282.8 nm, which is smaller than the size reached by milling, and
smaller particles can increase the effectiveness of adsorption.
The small particle size was characterized by fine porosity and a
large internal surface area, while the powder form has larger diam-
eter pores and smaller internal surface area. A smaller pore size
results in stronger and greater adsorption capacity because the
small adsorbent particle size reduces the pathway for both mass
transport and internal diffusion of the adsorbent inside the adsor-
bents (Al-Anber, 2011).
ð1Þ Effect of particles sizes of adsorbent
The experimental effect of particles on metal adsorption was
investigated for five sizes (400 to less than 50 lm) at room temper-
ature and initial pH (6.5 for Cd, Co, and 9 for Li). Fig. 5 indicates that
ð2Þ
Fig. 3. Concentration of heavy metals in adsorbent.
4 G.M. Al-Senani, F.F. Al-Fawzan / Egyptian Journal of Aquatic Research xxx (2018) xxx–xxx

Fig. 4. XRD of the particle size of adsorbents.

Fig. 5. The particle size effect on the metal ions adsorption by EH and TH.

metal removal increased with decreasing particle size for TH,
but decreased with EH. This behavior can be attributed to
the increased internal surface area with decreasing particle size
(Al-Anber, 2011).
This behavior arises because most of the internal particles sur-
face can be used for adsorption, and the smaller particle size gives
high rates of adsorption, due to transfer the metal ions through a
short path inside the adsorbent particle pores (Al-Anber, 2010).
However, one can expect that as the particle size increases, the
number of small pores increases. The particle dimensions deter-
mine the propagation distance, because the dimensions of the
adsorbent particles obtained by standard sieves depend on the par-
ticle length and width; thus, this explains the decreased adsorption
of metals with increasing adsorbent particle size (Osu Charles
et al., 2010).
Effect of initial metal ion concentration
The initial concentration of metal ions in aqueous solutions
affected on metal adsorption. In the present study, the initial metal
concentrations from 10 to 500 mg/L have affected on all of the
adsorbent metals, but, with EH; the initial concentration of Li
had no effect on the percentage of Li adsorption. Fig. 6 shows that
when the initial metal concentration increased, the percentage
adsorption of heavy metals decreased. This could be attributed to
the metal particle size (50 lm) used in the experiment, and the
lowest adsorption of metals was observed with a high initial con-
centration of metals. At high concentrations, the competitive dis-
persion of metal ions has increased at the sites available
adsorbent surface; these pores are closed and metal ions are pre-
vented from passing deep into the absorbent pores, which means
that adsorption occurs only on the surface (Wasewar, 2010).
Effect of adsorbent dosage
The effect of the adsorbent doses on heavy metal adsorption by
EH and TH was studied. As shown in Fig. 7 the increased of adsorp-
tion percentage of Co, Li and Cd with increasing of adsorbent doses.
The increase in adsorption percentage with increasing adsorbent
dose arises because of the increased availability of surface area
or exchange sites at higher concentrations of adsorbents (Al-
Qahtani, 2016). Similar behavior has been observed in previous
studies and arises from the effect of interactions between mineral
ions and adsorbent. The increased dose is consistent with the
greater area and larger number of desorption sites (Samindika,
2013).

Fig. 6. The concentration effect on the metal ions adsorption by EH and TH.

Please cite this article in press as: Al-Senani, G.M., Al-Fawzan, F.F. Adsorption study of heavy metal ions from aqueous solution by nanoparticle of wild
herbs. Egyptian Journal of Aquatic Research (2018), https://doi.org/10.1016/j.ejar.2018.07.006
 G.M. Al-Senani, F.F. Al-Fawzan / Egyptian Journal of Aquatic Research xxx (2018) xxx–xxx 5

Fig. 7. The dosage effect on the metal ions adsorption by EH and TH.

Fig. 8. The contact time effect on the metal ions adsorption by EH and TH.

Effect of contact time
Adsorption equilibrium studies were performed for 2–6 h. Fig. 8
shows that the ratio of adsorption of heavy metals is approximately
constant with time, meaning that the equilibrium was reached
before 2 h. This is due to the decrease in the number of active sites
after this time (Al-Anber, 2010; Samindika, 2013), and this result is
consistent with the results obtained by Al-Tohami et al. (2013) con-
cerning the attainment of equilibrium within 1–2 h.
Effect of pH
stabilized until reaching pH 9; after that, the adsorption increased
to 98% for both adsorbents. This is due to the adsorbents surface hav-
ing functional groups of carboxyl, hydroxyl and amine, which are
involved in binding mechanisms, and the affinity of ionic species
toward it is strongly affected by pH value. Generally, metals adsorp-
tion increases with pH increase, this means that at low pH the hydro-
gen ions become more effective. In contrast, the percent adsorption
of Li remained constant and was not affected by the increase in pH.
This might be caused by the stability of Li adsorption ratio with
the increase in pH due to the decrease of electronegativity and the
increase of the ionic radius (Al-Qahtani, 2016; Tounsadi et al., 2015).

As shown in Fig. 9, there was a slight increase in the percentage Effect of temperature
adsorption of Co from pH 3 to 9, and adsorption increased signifi-
cantly above pH 9 for both adsorbents TH and EH. The percent The obtained results showed that the temperature had a slight
adsorption of Cd increased with increasing pH from 3 to 5, then effect on metal adsorption in the range of 25–60 °C (Fig. 10). This

Fig. 9. The pH effect on the metal ions adsorption by EH and TH.

Fig. 10. The temperature effect on the metal ions adsorption by EH and TH.

Please cite this article in press as: Al-Senani, G.M., Al-Fawzan, F.F. Adsorption study of heavy metal ions from aqueous solution by nanoparticle of wild
herbs. Egyptian Journal of Aquatic Research (2018), https://doi.org/10.1016/j.ejar.2018.07.006
6 G.M. Al-Senani, F.F. Al-Fawzan / Egyptian Journal of Aquatic Research xxx (2018) xxx–xxx

Fig. 11. Plot of pseudo first order and pseudo second order for the metal ions adsorption onto EH and TH.

Table 1
Kinetic model parameters for the metal ions adsorption onto EH and TH.

Kinetic Model Parameter Adsorbent (EH) Adsorbent (TH)

Co Li Cd Co Li Cd
Pseudo first order qe,exp (mg/g) 15.56 11.16 17.28 16.60 12.07 18.17
qe,calc (mg/g) 16.35 16.12 7.60 6.68 18.19 7.37
K1  103(min1) 3.35 4.42 6.21 3.17 3.47 8.80
R2 0.996 0.987 0.968 0.909 0.992 0.959
Pseudo second order qe,calc (mg/g) 15.75 11.51 16.50 15.90 12.36 17.06
K2  103 (g/mg min) 12.60 7.90 5.30 14.33 11.64 3.35
h (mg/g min) 3.12 1.05 1.44 3.62 1.78 0.98
t½ (min) 5.04 10.99 11.45 4.39 6.95 17.47
R2 0.999 0.998 0.997 0.999 0.999 0.996

can be explained by the nature of the adsorbent molecules
(Tounsadi et al., 2015). The increase of adsorption with increased
temperature indicated that the adsorption of heavy metal ions by
adsorbent may involve not only physical but also chemical adsorp-
tion. This effect may be due to higher temperature, thus an increase
in active sites occurs due to bond rupture (Wasewar, 2010).
Adsorption kinetic model
To understand the rate and type of adsorption on adsorbents,
we studied several kinetic models.
Pseudo first order kinetic model
The pseudo first order model is expressed by Eq. (3):
K1t
logðqe  qt Þ ¼ logqe 
2:303
where qe and qt represent the amount of metal ions adsorbed at
equilibrium and at time, t, respectively, K1 is pseudo first order rate
constant.
As shown in Fig. 11 and Table 1, the regression coefficient (R2 
0.91) indicates that the experimental data of the adsorption kinetics
of metal ions is accurately supported with the first order model.
However, we found that the typical values of qm are lower than
the experimental values. This indicates the participation of both
metal ions and adsorbent in the adsorption process (Arshadi et al.,
2014). Therefore, the first order model may not be suitable for
explaining the adsorption kinetics of ions on the adsorbents. Similar
results were obtained for the kinetics of adsorption of different
metal ions on other adsorbents (Meitei et al., 2014; Arshadi et al.,
2014; Caźon et al., 2013).
Pseudo second order kinetic model
where K2 is pseudo second order rate constant.
The experimental data showed the best fit with the highest cor-
relation coefficients (R2 = 0.998) for pseudo second order model for
each of the metal ions. In addition, the experimental values were
well matched with the calculated data (Table 1). Therefore, the
experimental data of the adsorption kinetics of metal ions are
accurately supported with the second order model.
This finding indicates that the rate-limiting step was not the
resistance of the boundary layer (Tounsadi et al., 2015). Thus, the
rate-limiting step is chemisorption involving exchange of the
metal ions with functional groups in the adsorbent during valence
forces (Rahman et al., 2015). This is consistent with the observed
rapid adsorption.
As shown in Fig. 11, the kinetics analysis of metal ions adsorp-
tion on the catalysts revealed two steps: the rate of adsorption dur-
ing the first hour is rapid, but this is followed by a slower
ð3Þ absorption rate that ends in the equilibrium state (ca. 140 min).
Similar results have been obtained previously (Meitei et al.,
2014; Arshadi et al., 2014). This phenomenon indicates that prop-
agation is the dominant step affecting the rate of adsorption
(Caźon et al., 2013). The adsorption half-time of t½ the time for
the adsorption of half the metal ions in minutes was between 4.4
and 17.5 min, indicating the significant affinity of the adsorbent
molecules for the adsorbate (Tounsadi et al., 2015).
Adsorption isotherm
To understand the mechanism of metal ion adsorption from an
aqueous solution by the adsorbents, we tested several adsorption
isotherm models. The Langmuir adsorption model was applied in
accordance to Eq. (5):
Ce 1 Ce
¼ þ ð5Þ
qe K L qm qm

The pseudo second order model is expressed by Eq. (4): where Ce is the adsorbate equilibrium concentration, qe is the
observed adsorption capacity at equilibrium, qm is the maximum
t 1 t
¼ þ ð4Þ adsorption capacity, KL is the adsorption equilibrium constant.
qt K 2 qe 2 qe
The Langmuir isotherm showed a linear relationship between

Please cite this article in press as: Al-Senani, G.M., Al-Fawzan, F.F. Adsorption study of heavy metal ions from aqueous solution by nanoparticle of wild
herbs. Egyptian Journal of Aquatic Research (2018), https://doi.org/10.1016/j.ejar.2018.07.006
 G.M. Al-Senani, F.F. Al-Fawzan / Egyptian Journal of Aquatic Research xxx (2018) xxx–xxx 7

Fig. 12. Langmuir and Freundlich isotherms for the metal ions adsorption onto EH and TH.

Table 2
Adsorption isotherm parameters for the metal ions adsorption onto EH and TH.

Adsorption isotherm Parameter Adsorbent (EH) Adsorbent (TH)

Co Li Cd Co Li Cd
Langmuir qm (mg/g) 40.82 181.82 52.91 39.06 120.48 56.82
KL  103 (L/mg) 18.59 1.71 45.51 41.63 3.41 87.61
RL 0.35 0.85 0.18 0.19 0.75 0.10
R2 0.963 0.979 0.976 0.999 0.975 0.993
Freundlich KF (mg(11/n) g1 L1/n) 1.54 0.37 4.49 1.10 0.55 7.55
n 1.71 1.09 2.16 1.96 1.16 2.55
R2 0.914 0.998 0.980 0.936 0.997 0.993

Ce/qe and Ce for the adsorption of metals on EH and TH (Fig. 12), and Thermodynamic parameters
the slope and R2 presented in Table 2. The plot exhibited good
correlation coefficient and linearity. The R2 values are very close For understanding the adsorption nature, the thermodynamic
to unit, indicating strong correlation with the Langmuir isotherm. parameters, entropy, DS°, enthalpy, DH°, and the Gibbs free energy,
The maximum capacity of adsorption for the adsorbent, qm (mg/g), DG°, were calculated using the following Eqs. (9) and (10):
for metal ions is high, which can be explained by their non-
^  DH A
DSA ^
covalent interaction with ions. Another reason may be the presence lnK eq ¼  ð8Þ
of carboxylic-acid-containing sugars in the herbs, which bond the R RT
metal ions (Lasheen et al., 2012). So the values of RL were calculated
from the following Eq. (6): ^  ¼ DH A
DGA ^   T DSA
^ ð9Þ

1 The thermodynamic parameters values are shown in Table 3.

RL ¼ logC e ð6Þ The Van’t Hoff plots of ln Keq against 1/T are shown in Fig. 13.
1 þ K L qm
The values of DH° and DS° were determined from the intercept
RL  1, indicating that the Langmuir adsorption is appropriate and slope of the linear plot.
for adsorption process. For a single adsorption system, C0 is usually The values of DH° and DS° indicate that the adsorption process
the highest concentration of the liquid-phase encountered (Yalcin, is endothermic and spontaneous. The positive value of (DS°) indi-
2014). cate that the degrees of unrestraint of the adsorbed species for
Freundlich adsorption model is given by Eq. (7):

1
logqe ¼ logK F þ logC e ð7Þ
n

where n is Freundlich equilibrium coefficient. Values of log qe are

plotted against log Ce (Fig. 12). The slope and R2 data are presented
in Table 2. Values of 1/n < 1 indicate the convenient adsorption of all
heavy metals, and n values in the range 1–10 represent good
adsorption and a favorable physical process. Higher values of KF
indicate a high adsorption intensity (Tofan et al., 2016).
From the Langmuir and Freundlich isotherms, it is clear the
metals ions were strongly adsorbed in the pores of the herbs. Fig. 13. Van’t Hoff plots for the metal ions adsorption onto EH and TH.

Table 3
Thermodynamic parameters for the metal ions adsorption onto EH and TH.

Parameter Adsorbent (EH) Adsorbent (TH)

Co Li Cd Co Li Cd
DH° (J/mol) 491.47 556.22 597.86 1615.91 609.74 2656.91
DS° (J/mol K) 1.69 9.14 3.99 5.75 7.87 12.06
DG° (kJ/mol) at 298 K 0.01 3.28 0.59 0.10 2.95 0.94
R2 0.997 0.949 0.977 0.975 0.912 0.972

Please cite this article in press as: Al-Senani, G.M., Al-Fawzan, F.F. Adsorption study of heavy metal ions from aqueous solution by nanoparticle of wild
herbs. Egyptian Journal of Aquatic Research (2018), https://doi.org/10.1016/j.ejar.2018.07.006
8 G.M. Al-Senani, F.F. Al-Fawzan / Egyptian Journal of Aquatic Research xxx (2018) xxx–xxx
Co and Cd ions were increased. In contrast, for Li ions, the adsorp-
tion process is exothermic and unspontaneous.
The values of DG° were negative for Co and Cd ions, indicate that
the adsorption process was spontaneous, but it was a positive
value for Li ion and thus, is not spontaneous (Tounsadi et al.,
2015). Further, the increased temperature causes increase in the
negative DG° values, and an increased probability of adsorption
at higher temperatures, which is consistent with an earlier report
(Massocatto et al., 2013).
Conclusion
In this study, the adsorption of Co, Li and Cd onto EH and TH was
investigated with respect to particle size, initial concentration, the
dosage of the adsorbent, contact time, pH and temperature. Char-
acterization of the adsorbents revealed the presence of carboxylic,
O–H and N–H groups that were involved in the adsorption of the
heavy metal ions. Adsorption was maximum with 50 lm particles
size and 0.5 g of the adsorbent. Metal ion adsorption onto wild
herbs follows the pseudo second order model. The adsorption of
the Co and Cd ions fit well with Langmuir model. However, the Li
adsorption correlated better with the Freundlich model. The values
of DH°, DS°, and DG° indicate that the adsorption process are spon-
taneous, and endothermic in nature for Co and Cd. Hence, the wild
herbs can be used as adsorbent for the removal of heavy metal ions
from aqueous solutions. In addition, further study is needed to
assess the adsorbents efficiency in the removal of heavy metals
from aqueous solutions.
Acknowledgment
The researchers would like to thank the Deanship of Scientific
Research at Princess Nourah bint Abdulrahman University for pro-
viding the funding for this study under project number 216 – ‫– ﺹ‬
38.
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