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Adsorption Of Atrazine From Aqueous solution using Unmodified and

Modified Bentonite clays

Article  in  Applied Water Science · October 2018

DOI: 10.1007/s13201-018-0855-y

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Applied Water Science (2018) 8:214
https://doi.org/10.1007/s13201-018-0855-y

ORIGINAL ARTICLE

Adsorption of atrazine from aqueous solution using unmodified

and modified bentonite clays
Oluwaseun Jacob Ajala1 · Friday Onyekwere Nwosu1 · Rasheed Kayode Ahmed1

Received: 12 April 2018 / Accepted: 16 October 2018

© The Author(s) 2018

Abstract
Properties of raw bentonite clay of Afuze in Edo state which are abundant and cheap bentonite mineral in Nigeria as adsor-
bents for the removal of atrazine in aqueous solution were investigated. The bentonite clay-types were characterized using
scanning electron microscopy (SEM), Fourier transform infrared (FTIR) spectrophotometry and X-ray diffraction (XRD).
Batch adsorption experiments were carried out to determine the equilibrium characteristics, thermodynamics and kinet-
ics of the sorption processes. The data obtained were subjected to Langmuir, Freundlich and Temkin isotherm equations,
while pseudo-first-order, pseudo-second-order rate equations, intra-particle diffusion and Elovich models were considered
for kinetics and mechanism. The results showed that the adsorption processes were described by different isotherm models;
they were all spontaneous (∆G ranges from − 938.34 to − 6263.58 kJ/mol) and exothermic (range of ∆H is − 252.73 to
− 1057.08 kJ/mol), and with decreased randomness, ∆S (− 3.110 to − 0.581 J.mol/K). Pseudo-second-order kinetics model
gave the better fit for all the sorption processes which implies physisorption process as the rate limiting step. Thus, bentonite
clay-types can be used to adsorb atrazine.

Keywords  Atrazine · Bentonite clay · Kinetics · Isotherm · Thermodynamics

Introduction 70 countries worldwide (Kauffmann et al. 2000). It has been

in use since 1958 as a pre- and post-emergent herbicide
Frequent usage of herbicides (i.e. atrazine) at the home, to control broad-leaved weeds in production of corn and
farm land, school field, etc., and discharge of its wastewa- sorghum (Jone et al. 1982). Atrazine is a probable human
ter from the producing industries into surface water bod- carcinogen, and its current maximum contaminant level in
ies have become endangered to our ecosystem (i.e. aquatic drinking water established by the environmental protection
organism and human). The major sources of atrazine in sur- agency is 3.0 µg/L.
face and underground water system are industrial effluents, The atrazine pollutants in most wastewater could be
domestic wastewaters, agricultural effluents and spillage treated using advanced oxidation process (AOPs) (Xu et al.
of chemicals from anthropogenic activities (Kolpin et al. 2013); adsorption principles have been found useful for
1997; Miller et al. 2000). Continuous exposure to atrazine removal of atrazine polluted wastewater (Liu et al. 2015).
in water may cause cancer, endocrine disrupter and mam- Among others, selective adsorptions that make use of bio-
mary gland tumour. Humans and living organisms can also logical materials and active carbon have created great inter-
suffer mutagenesis and carcinogenesis as a result of atrazine est among the researchers.
contamination (EPA 1990). Although it has been banned in Active carbon can be used to adsorb organic pollutants
most European countries, it is still one of the most widely because of its large surface but exhibits higher disposal cost
used herbicides in the USA and also registered in more than and usually difficult to prepare and exhibit higher disposal
cost (Burleigh et al. 2002). The economical cost of active
carbon made scientist to search for the development of
* Oluwaseun Jacob Ajala
oluwaseun_ajala81@yahoo.com adsorbents from cheaper raw materials. These include bio-
char prepared from tamarind nut (Nwosu et al. 2017) for the
1
Analytical Environmental Chemistry Unit, Department removal of triazine compounds. Therefore, the preparations
of Industrial Chemistry, Faculty of Physical Sciences, of good adsorbents via clay such as bentonite for removal
University of Ilorin, P.M. B. 1515, Ilorin, Nigeria

13
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 214   Page 2 of 11 Applied Water Science (2018) 8:214

of different concentration of atrazine molecule become morphology (Mullan 2006) of the modified and unmodified
important. clay-types, respectively.
The main aim of this study is to prepare a low cost, con-
stant available and environmentally safe adsorbent from ben- Adsorbate
tonite clay and use for removal of atrazine from wastewater.
Thus, the bentonite clay which is always available without The primary adsorbate in this study is atrazine and its struc-
season effect was converted into adsorbents. Batch adsorp- ture is in fig 1. The International union of Pure and Applied
tion, adsorption data, kinetics studies and thermodynamic Chemistry name of atrazine is 2-chloro-4-(ethylamino)-6-
were carried out. (isopropylamino)-1, 3, 5-triazine. The following are the
physicochemical of atrazine based on their relevant on
environment; melting point: 175–177 °C, density: 1.187 g/
Materials and method cm3 at 20 °C, water solubility: 7 mg/100 ml, log octanol—
water partition coefficient: 2.3, vapour pressure: 40 × 10−6
Adsorbents pa at 20  °C, molar mass: 215.69  g/mol boiling point:
200 °C, appearance: colourless solid, molecular formula:
The bentonite clay was utilized for the preparation of the ­C8H14ClN5. It is usually produced by synthesis but does not
adsorbents. The bentonite clay which was collected from occur naturally (Tomlin 2000)
major deposit of Afuze in Edo state, south -west region
of Nigeria with longitude and latitude of 6°56′24.2″N and Preparation of adsorbate
5°59′07.7″E, respectively.
Working aqueous solutions of different concentrations of
atrazine were prepared by serial dilution using micropipettes
Preparation of adsorbents and standard volumetric flasks from the stock solution of the
atrazine (1000 mg/L) which was prepared by taken 1 g of
Raw bentonite clay was washed with distilled water to atrazine and dissolved in 1 L of distilled water.
remove impurities until its pH reaches 7, and it was further
air-dried, oven-dried and then crushed into small sizes and Adsorption procedure
sieved to < 250 µm to make unmodified (pretreated) ben-
tonite clay type (UBC). While a known quantity (50.0 g) of In each of the factors studied, the atrazine uptake at equi-
unmodified (pretreated) bentonite clay was impregnated with librium qt was calculated using the following expression:
2 M ­H2SO4 and NaOH differently using ratio 1:2 w/v. It was
shaken vigorously using a Uniscope SM 101 shaker water (Co − Cf )v
qt = (1)
bath for 24 h at 30 °C and then washed with distilled water m
to remove the excess acid until its effluent become neutral
where qt is the quantity of atrazine uptake in mg/g, v is vol-
(pH = 7). (Nwosu et al. 2018, Abu-Elella et al. 2015). It was
ume (L), Co and Cf are the initial and final concentrations in
then filtered under vacuum and dried in oven at 376 K for
mg/L, respectively. The sample bottles containing the mix-
8 h. The dried samples were grounded and stored in airtight
ture of various atrazine concentrations and the clay-types
sample bottle (Nwosu et al. 2018, Gómez-Tamayo et al.
were separately removed from the water bath shaker and the
2008) to produce 2 M sulphuric acid modified bentonite clay
solutions centrifuged to remove the adsorbent. The initial
(2-ABC) and 2 M sodium hydroxide modified bentonite clay
(2-BBC), respectively.

Characterization of unmodified and modified

bentonite clay‑types

Chemical and mineralogical compositions were character-

ized by Fourier transform infrared (FTIR) a Perkin Elmer
1600 Series FTIR spectrophotometer model 1615, X-ray dif-
fraction (XRD) model 6000 machine and scanning electron
microscope (SEM) using a Phenom World scanning electron
microscope for functional group (Austin and Hoang 2009),
structure (Ramachandran and Beaudoin 2008) and physical
Fig. 1  Structure of atrazine molecule

13
Applied Water Science (2018) 8:214 Page 3 of 11  214

concentration and residual aqueous concentrations of atra-

zine were determined using UV–visible spectrophotometer
UBC
(DU 640, BECKMAN) at ʎ max = 273. Prior to determi-
nation using UV–visible techniques, the effect of variables
on adsorption capacities of UBC, 2-ABC and 2-BBC was
carried out.

Results and discussion

Adsorbent characterization

Figure 2 represents the FTIR spectra of the three adsor-

bents, respectively. The sharp bands at 3696.17 cm−1 and
3626.39 cm−1 are attributed to the N–H stretching for the
UBC and 2-ABC types as it is the same as the peaks at 3697
and 3620 cm−1 reported by Georges-IVO, (2005). The peaks
at 3436.41 cm−1 in the 2-ABC sample and 3430.21 cm−1
in the UBC are assigned to OH stretching which is close to
3426 cm−1 and 3420 cm−1 reported by Isci et al. (2006) and
Aroke et al. (2013). 2-ABC
The bands 1644.47 cm−1 and 1637.99 cm−1 that pre-
sent UBC and 2-ABC samples are assigned to the H–O–H
bending of water which fit within range reported at peaks
1620 cm−1–1642 cm−1 by Bhasker and Gopalakrishnarao
(2010). The peaks observed at 1042.89 cm−1, 1036.41 cm−1
and 1029.58 cm−1 are assigned to the characteristic bands
of silicate which are greatly related to the stretching vibra-
tions of Si–O. The peaks at 913.08 cm−1, 916.09 cm−1 and
912.55 cm−1 are responsible for Al–Al–OH group defor-
mation and are similar to those of 913 cm−1 and 914 cm−1
reported by Amin et al. (2010). Figure 3 shows the SEM
micrographs at × 500 and × 1000 magnifications for UBC,
2-ABC and 2-BBC, respectively. It clearly indicated the
presence of numerous pores on the surfaces of the modified
clay-types adsorbents but is few on the surface of unmodified
ones. The structures of the modified adsorbents are rough
and irregular shapes which signify a favourable adsorption
(Patel and Sudhakar 2008) compared to unmodified adsor-
bents which has a fine, smooth and regular shape. The XRD 2-BBC
powder analysis for these various clay-types is presented
in Fig. 4. There is a conspicuous peak at 2θ equal 1­ 8o, and
2θ equal ­24o for the 2-ABC and 2-BBC, respectively, and
showed that they are crystalline in nature.

Influence of various factors on amount of atrazine

uptake
Fig. 2  FTIR spectra of various bentonite clay-types
Effect of concentration Fig. 5a shows the effect of the initial
concentration ­(Co mg/L) of atrazine on the adsorption capac-
ities of the prepared UBC, 2-ABC and 2-BBC, respectively. to 227.65 mg/g and 22.3 to 267.85 mg/g as atrazine con-
As indicated in Fig. 5(a), the amount adsorbed of these vari- centration increased from 100 to 1000 mg/L, from 100 to
ous clay-types increased from 23.15 to 138.75 mg/g, 23.7 1500 mg/L and 100 to 1500 mg/L for UBC, 2-ABC and

13
 214   Page 4 of 11 Applied Water Science (2018) 8:214

surface (Hatem et al. 2012). Therefore, the rate of atrazine

UBC
molecules that travels from the bulk solution to the particle
surface increases.
Similar trends have been reportedly observed in the
adsorption of P-nitrophenol using active carbon pro-
duced from different precursors that are known (Nwosu
et al. 2017). Further increase in adsorbate brought a slight
decrease in the amount of adsorbed, and thus, concentra-
tions of 800 mg/L, 1100 mg/L and 1100 mg/L were chosen
as equilibrium concentration for UBC, 2-ABC and 2-BBC,
respectively.
Effect of contact time The effect of contact time of adsor-
2-ABC
bents is important in adsorption processes because it exer-
cises a great deal of influence on the adsorption capacity of
adsorbents. Figure 5b shows the variation in the quantity of
atrazine adsorbed by 0.1 g of UBC, 2-ABC and 2-BBC at
303 K with time. The rate at which adsorption occurred was
rapid initially between 5 and 30 min, and became slower
between 60 and 200 min. This phenomenon may be due to a
large number of available vacant surface sites for adsorption
2-BBC during the initial stage, and after a lapse of time, remain-
ing vacant surface sites were difficult to be occupied due to
repulsive force between solute molecules on the solid and
bulk phases (Ahmed et al. 2007). The high adsorption rate at
the beginning of adsorption process by 0.1 g UBC, 2-ABC
and 2-BBC separately may also be due to the adsorption of
atrazine by exterior surface of the adsorbent. When satura-
tion was reached at the exterior surface, the atrazine mol-
Fig. 3  SEM Micrograph of UBC, 2-ABC and 2-BBC, respectively,
ecules would then enter the pores of adsorbent and become
at × 500 and × 1000 magnifications adsorbed by the interior surface of the particles. This phe-
nomenon takes relatively longer contact time (3 h) to reach
equilibrium (Sathishkumar et al. 2007).
Effect of adsorbent dose Figure 5d shows the adsorbent
dose profile diagram for both adsorbents (UBC, 2-ABC and
2-BBC). The amount of atrazine adsorbed per gram of these
different clay-types decreased with increasing adsorbent
dose. It decreased from 230.2 to 29.73 mg/g, from 283 to
74.37 mg/g and from 263.5 to 50.74 mg/g for UBC, 2-ABC
and 2-BBC, respectively, when adsorbent dose increased
from 0.05 to 0.35 g. Thus, for the remainder of the research,
adsorbent dose of 0.1 g was used as the optimized adsor-
bent dose. This is similar to adsorbent dose reported in the
adsorption process of PNP using active carbon from coconut
husk (Nwosu et al. 2017).
Effect of pH of the solution Adsorption was reported to
be affected by the pH of the adsorbents on atrazine as shown
in Fig. 5(c); the adsorption of atrazine on UBC and 2-ABC
Fig. 4  XRD Spectra of 2-ABC and 2-BBC, respectively
increases from pH 2 to 12, while for 2-BBC it increases
from pH 2 to 7 and reduced from pH 7 to 12. The values of
2-BBC, respectively. This may be due to the increases in the pHpzc for the UBC, 2-ABC and 2-BBC are 6.2, 7.0 and 7.8,
initial concentration of atrazine which can provide an impor- respectively. It has been reported that sorption of cations
tant driving force to overcome all mass transfer resistances is favoured at pH > pHpzc, while the sorption of anion is
of atrazine between adsorbate solution and the adsorbent favoured at pH < pHpzc. The specific adsorption of cations

13
Applied Water Science (2018) 8:214 Page 5 of 11  214

Fig. 5  Effect of adsorption conditions on adsorption capacities of the active carbons. a Initial concentration; b contact time; c pH; d adsorbent
dosage; e temperature

shifts pHpzc towards lower values, whereas the specific the available adsorption sites with atrazine molecule which
adsorption of anion shifts pHpzc towards higher value (Mall cannot compete with them for adsorption site. This could
et al. 2006). The low uptake capacities at low pH values can be partly due to the fact that protons are strong competing
be attributed to the fact that at low pH, the adsorbent surface adsorbate because of their higher concentration. However, at
is completely covered by ­H+ increasing the competition for the high pH value, the surface of the adsorbent is saturated

13
 214   Page 6 of 11 Applied Water Science (2018) 8:214

with negative charge which enhances the adsorption of posi- (a) 0.07
y = 0.1791x + 0.0084
tively charged atrazine onto the surface of the adsorbents 0.06
R² = 0.9697
y = 0.1574x + 0.0091
R² = 0.9883
(Liu et al. 2015). 0.05

1/qe (g/mg)
Effect of temperature Plots of the amount adsorbed at 0.04

equilibrium, qe (mg/g) versus absolute temperature (T K) are 0.03

y = 0.0973x + 0.0133 UBC
shown in Fig. 5e for UBC, 2-ABC and 2-BBC. It can be seen 0.02 R² = 0.9076
2-ABC
from this figure that the amount adsorbed decreases with 0.01
2-BBC
increasing temperature for the three adsorbents, indicating 0
0 0.05 0.1 0.15 0.2 0.25 0.3 0.35
the apparent exothermic nature of the adsorption process. 1/Ce (l/mg)
In the liquid phase, an increase in temperature commonly
increases the solubility of the molecules and their diffusion (b) 2.5
y = 0.4875x + 1.0767
y = 0.3734x + 1.1774
R² = 0.8438
R² = 0.9708
within the pores of the adsorbent materials is hampered, 2

and hence, at higher temperature adsorbed molecules tend 1.5

log qe
to desorb suggesting physisorption (Nwosu et al. 2017, Tang y = 0.5257x + 1.0358
1 R² = 0.9102
et al. 2007). The adsorption capacity of UBC decreased UKC

from 120.25 to 106.1 mg/g, for 2-ABC adsorption capac- 0.5 2-AKC

ity decreased from 122.35 to 107.2 mg/g, and for 2-BBC 0

2-BKC

adsorption capacity decreased from 120.9 to 118 mg/g; the 0.5 0.7 0.9 1.1 1.3 1.5 1.7 1.9 2.1
temperature increases from 308 to 333 k. log Ce

(c) 120

Equilibrium adsorption isotherms modelling 100

y = 26.202x - 19.667 y = 28.273x - 24.595
R² = 0.939 R² = 0.9113
80
qe (mg/g)

The equilibrium experimental data obtained were fitted into

60 y = 18.465x - 2.2534
three adsorption isotherm models, namely Langmuir, Fre- R² = 0.6676
undlich and Temkin, and they all gave varying degree of 40 2-ABC

success. 20 2-BBC
UBC
0
0 1 2 3 4 5
The Langmuir adsorption isotherm model Ln Ce

This is explained supposition of a homogeneous adsorbent Fig. 6  Various adsorption isotherms for the removal of atrazine using
surface with identical adsorption sites (Varank et al. 2012). UBC, 2-ABC and 2-BBC Types. (a) Langmuir; (b) Freundlich; (c)
The linearized form of Langmuir equation is given as: Temkin
( ) ( )( ) ( )
1 1 1 1
= + (2)
qe ce bqmax qmax

The Langmuir plots of 1/qe versus 1/Ce for both adsor- Table 1  Adsorption Isotherm Parameters
bents are depicted in Fig. 6a and the Langmuir parameters Isotherm UBC 2-ABC 2-BBC
obtained from the slope and intercept of the plots are listed
in Table 2. The three adsorbents exhibited high correlation Langmuir
coefficient R2 values of 0.907, 0.969 and 0.988 for UBC, qmax (mg/g) 76.92 125.00 111.11
2-ABC and 2-BBC, respectively. KL 0.1340 0.0447 0.0573
It can be observed from Table 1 that the 2-ABC has an RL 0.0694 0.1828 0.1486
adsorption capacity (125.00 mg/g) higher than that of the R2 0.907 0.969 0.988
2-BBC (111.11 mg/g) and UBC (76.92 mg/g). Furthermore, Freundlich
a dimensionless separation factor RL equation is given in KF (mg/g) 15.031 10.839 11.912
Eq. 3: 1/n 0.373 0.525 0.487
R2 0.843 0.910 0.970
1 Temkin
RL =
1 + KL Ce (3)
B 18.46 28.27 26.20
bT 136.46 89.11 96.11
It expresses the essential characteristic of the Langmuir
AT (L/mg) 0.8851 0.4190 0.4722
equation and indicates the nature of adsorption process,
R2 0.667 0.911 0.939
and its value was found to be in between 0 and 1 as listed

13
Applied Water Science (2018) 8:214 Page 7 of 11  214

Table 2  Kinetic Parameters of Adsorption of Atrazine (KF = 15.031 mg/g) of UBC is larger than that obtained
Kinetic model UBC 2-ABC 2-BBC of 2-BBC (KF = 11.912 mg/g), while 2-BBC is also larger
than of 2-ABC (Kf = 10.839 mg/g). The results indicated that
Pseudo-first 2-BBC has higher adsorption affinity towards atrazine than
k1 ­(min−1) 0.0253 0.0253 0.000 UBC and 2-ABC. The value of 1/n indicates a favourable
qe (mg/g) 14.06 0.05 8.26 adsorption when 0 < 1/n < 1 (Halif et al. 2007). The adsorp-
R2 0.848 0.895 0.917 tion intensity 1/n is found to be 0.373, 0.525 and 0.487 for
Pseudo-second UBC, 2-ABC and 2-BBC, respectively. It is observed that all
k2 ­(gmg−1 min−1) 0.0162 3.200 0.000 the three adsorbents satisfy the conditions of heterogeneity.
qe (mg/g) 111.11 125.00 111.11
R2 0.999 1.00 1.00
Intra-particle diffusion Temkin adsorption isotherm
ki (mg/gmin1/2) 1.471 0.003 0.146
C 100.6 124.9 104.6 It suggests that the heat of adsorption of all the molecules
R2 0.896 0.799 0.873 in the layer is inversely proportional to coverage of the
Elovich adsorbent surface which might be attributed to adsorbate
Α 3.95 × 1012 1.93 × 1052 6.58 × 1044 species—adsorbent interactions. A uniform distribution of
Β 0.287 90.91 3.676 binding energies up to some maximum binding energy is the
R2 0.955 0.881 0.780 characteristics of Temkin adsorption (Tempkin and Pyzhev
1940). The linear form of the Temkin isotherm is repre-
sented in Eq. (5):
in Table 1. This confirms that the adsorption of atrazine is ( )
RT RT
favourable on the three adsorbents. These are the reasons: qe = ln AT + ln Ce (5)
bT bT
on the surface of the adsorbent, monolayer was formed with
minimal interaction among molecules of adsorbate, immo- and
bile and localized adsorption and all the sites having equal
adsorption energies (Li et al. 2011). RT
B=
bT (6)

Freundlich adsorption isotherm model Figure  6c depicts the Temkin isotherm plots for the
atrazine uptake onto the UBC, 2-ABC and 2-BBC from
This model suggests neither homogeneous site energies which the relevant Temkin adsorption isotherm values are
nor limited levels of adsorption which implies that it can obtained and are shown with values of correlation coeffi-
describe the experimental data of adsorption isotherm cients in Table 1. The BT values indicate the heat of adsorp-
whether adsorption occurs on homogeneous or heterogene- tion obtained as 136.46, 89.11 and 96.15 for UBC, 2-ABC
ous sites and it is not controlled by the formation of the and 2-BBC, respectively, while AT representing the equi-
monolayer (Halif et al. 2007). The linearized Freundlich librium binding energy are 0.8851 (L/mg), 0.4190 (L/mg)
equation is given as: and 0.4722 (L/mg) for UBC, 2-ABC and 2-BBC, respec-
x 1 tively. Thus, these values imply that the atrazine is more
log = log K + log Ce (4) strongly adsorbed on the UBC surface than that of 2-ABC
m n
and 2-BBC, indicating that there is a stronger interaction
From the slope and intercept of the linear plots of ln ­qe between atrazine and the respective bentonite clays. Similar
versus ln Ce, Fig. 5b, Freundlich parameters KF and 1/n indi- results have been reported as per the adsorption of N-nitro-
cating the measures of adsorption capacity of UBC, 2-ABC phenol using Pili nut shell-derived active carbon (Nwosu
and 2-BBC and its intensity of adsorption, respectively, were et al. 2017). They reported BT value of 24.292 and AT value
obtained and listed with the correlation coefficient value, R2 of 0.162.
(Table 1).
The results revealed that the adsorption of atrazine on
UBC, 2-ABC and 2-BBC obeys both Freundlich and Lang- Adsorption kinetics studies
muir adsorption isotherms, as indicated by high R ­ 2 Val-
ues (> 0.9) except of Freundlich isotherm of UBC with The kinetic experimental data obtained for the adsorption
a fair R2 value (0.84). Moreover, the Freundlich constant of atrazine on UBC, 2-ABC and 2-BBC were interpreted
by means of pseudo-first-order, pseudo-second-order,

13
 214   Page 8 of 11 Applied Water Science (2018) 8:214

intra-particle diffusion and Elovich kinetic models  in features of an initial step linear portion and plateau are
figure 7. attributed to the bulk diffusion; intra-particle diffusion and
the plateau portion represent the equilibrium. The magni-
Pseudo‑first‑order and pseudo‑second‑order kinetic tudes of kid, C and the corresponding regression coefficients
models of the three adsorption system are listed in Table 3. The
pore diffusion rate constant kid values: 1.377 mg/g min1/2,
The linear forms of pseudo-first-order and pseudo-second- 0.003 mg/g min1/2 and 0.146 mg/g min1/2, indicated substan-
order kinetic model equations are given in Eqs. 7 and 8. tial diffusion of atrazine onto UBC , 2-ABC, and 2-BBC,
respectively.
k t
log qe − qt = log qe − 1 (7) The existence of linear relationship between amount qe
( )
2.303 against t1/2 indicates that intra-particle diffusion participated
during the adsorption process. If the straight line of the plot
t 1 1
= + (8) of qe against t1/2 passes through the origin, then intra-particle
q k2 q2e qe
diffusion becomes the controlling step. The pore diffusion
The plot of linearized form of the equation is shown in rate constants of 0.46 mg/g min1/2 and 0.161 mg/g min1/2
Fig. 6a. The pseudo-first-order rate constant k1, amount of in the adsorption of P-nitrophenol with zeolite and benton-
atrazine adsorbed at equilibrium qe and correlation coeffi- ite have been obtained (Varank et al. 2012). This is simi-
cients are shown in Table 2. The results showed that their lar to the adsorption of Direct Red Dye 81 with bamboo
correlation coefficients R2 obtained for UBC, 2-ABC and sawdust and treated bamboo sawdust where kid values of
2-BBC for pseudo-first-order kinetics model are 0.848, 0895 0.32 mg/g min1/2 and 0.62 mg/g min1/2 were obtained.
and 0.917, respectively, which are lower than their corre- Moreover, kid value of 3.2479  mg/g  min1/2 has been
sponding pseudo-second-order kinetics model (R2 = 0.999, obtained in the adsorption of phenol using active carbon
1.000 and 1.000). Therefore, adsorption of atrazine onto from olive stones (Bohli et al. 2013). The adsorption of
these various bentonite clay-types revealed that pseudo- P-nitrophenol using active carbon fibre and granular active
second-order kinetic model is better to explain the kinetic carbon gave similar result obtained in this study with kid val-
adsorption process than pseudo-first-order kinetic model. ues of 8.924 mg/g min1/2 and 11.91 mg/g min1/2, respectively
This may be due to the fact the adsorption rate of atrazine (Nwosu et al. 2017).
onto the three clay adsorbents depends on the behaviour over The adsorption data could also be treated using Elovich
a whole range of adsorption process. Figure 6(b) shows the equation that is shown in Eq. 10 (Varank et al. 2012):
plots of t/q against t, and the resulting kinetic parameters are dqt
presented in Table 2. The calculated values of qe were closer = 𝛼e𝛽qt (10)
dt
to the experimental qe values for UBC, 2-ABC and 2-BBC.
The transfer of solute molecules on to solid surface par- This on linearizing and simplifying can be written as:
ticulates from the aqueous phase, and then, diffusion of the 1 1
solute molecules into the pore interiors could be described qt = ln (𝛼𝛽) + ln (t) (11)
𝛽 𝛽
by the intra-particle diffusion rate equation and is given as
(Bohli et al. 2013). where α (mg/g min) and β (g/mg) are the initial adsorp-
tion rate constant and desorption rate constant, respectively.
1
qt = kid t ∕2 + C (9) Kinetics of adsorption of atrazine with UBC, 2-ABC and
2-BBC also followed Elovich equation with the plots of qt
where kid and C are the intra-particle diffusion rate constant against ln t giving straight lines with fairly high correlation
and boundary layer thickness, respectively. The plotting qt coefficient (Fig. 6d). The Elovich constants α, β computed
against t1/2 as shown in Fig. 6(c) indicates the effect of either from the plots are 3.95 × 1012 mg/g min, 0.287 g/mg for
film pore diffusion or intra-particle diffusion. The general UBC, 1.926 × 1052 mg/g min, 90.91 g/mg for 2-ABC and

Table 3  Thermodynamics Adsorbent ∆H (kJ/mol) ∆S (J/mol) ∆G (kJ/mol)

Parameters temp (K)
308 313 318 323 328 333

UBC − 760.02 − 2.215 − 4724.9 − 4717.4 − 4279.7 − 3445.8 − 2322.3 − 938.3

2-ABC − 1057.08 − 3.110 − 6263.6 − 6218.8 − 4449.1 − 4252.9 − 2322.3 − 1132.9
2-BBC − 252.73 − 0.581 − 5115.5 − 4717.4 − 4655.7 − 4544.5 − 4318.7 − 3982.5

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Applied Water Science (2018) 8:214 Page 9 of 11  214

6.58 × 1044 mg/g min, 3.676 g/mg for 2-BBC as given in with the highest correlation coefficient values (Table 2,
Table 2. These values might also explain why the adsorption Fig 7).
process took longer time to reach equilibrium.
The comparison of correlation coefficients obtained Thermodynamics studies
for pseudo-second-order kinetic model (R2 = 0.999, 1.000
and 1.000) explained the adsorption process better than Thermodynamic parameters can provide useful and strong
Elovich model (R 2 = 0.955, 0.881 and 0.780). However, information about the mechanism involved in the adsorp-
in overall, the pseudo-second-order kinetic model still tion process. The characterization of equilibrium system like
appears to be the rate determining model as it is the model the adsorption system in this study is described by ther-
modynamic parameters such as free energy (∆G), enthalpy
(∆H) and entropy (∆S) changes which were calculated using
Eqs. 12–14.
ΔH ΔS
ln K = − + (12)
RT R

ΔG = −RT ln K (13)
Ci − Cf
K= (14)
Ci

where R is gas constant (8.314  J­ mol−1 K−1), T is absolute

temperature in K, Ci is initial concentration before adsorp-
tion, and Cf is concentration left in solution after adsorption.
The thermodynamic plots obtained from Eqs. 12 to 14 are
depicted in Fig. 8, while the values of ∆G, ∆H and ∆S for
the three adsorbents are listed in Table 3.
As seen from Table 3, the negative values of the enthalpy,
entropy and free energy changes indicate exothermic nature
of the processes, decrease in disorderliness and that the
adsorption processes are spontaneous and feasible.
Moreover, the ∆H values of adsorption of atrazine with
UBC (− 760.02 kJ/mol), 2-ABC (− 1057.08 kJ/mol) as well
as 2-BBC (− 252.73 kJ/mol) suggest that the process is exo-
thermic nature. Furthermore, 2-BBC shows higher adsorp-
tion enthalpy changes than the 2-ABC and UBC, which
signifies that 2-BBC has a stronger affinity for atrazine than
2-ABC and UBC.

Fig. 7  Kinetic models fit of adsorption of atrazine molecule with the

UBC, 2-ABC and 2-BBC. a Pseudo-first; b pseudo-second; c intra- Fig. 8  Thermodynamic plot of adsorption of atrazine with the clay-
particle; d Elovich types

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 214   Page 10 of 11 Applied Water Science (2018) 8:214

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