Environ Monit Assess (2013) 185:10365–10375

DOI 10.1007/s10661-013-3338-5

Removal of 8-quinolinecarboxylic acid pesticide

from aqueous solution by adsorption on activated
montmorillonites
M. Mekhloufi & A. Zehhaf & A. Benyoucef &
C. Quijada & E. Morallon

Received: 4 May 2013 / Accepted: 2 July 2013 / Published online: 8 August 2013
# Springer Science+Business Media Dordrecht 2013

Abstract Sodium montmorillonite (Na-M), acidic Keywords Adsorption isotherms . 8-Quinolinecarboxylic

montmorillonite (H-M), and organo-acidic montmoril- acid . Activated montmorillonite . Kinetics .
lonite (Org-H-M) were applied to remove the herbicide Thermodynamic data
8-quinolinecarboxylic acid (8-QCA). The montmoril-
lonites containing adsorbed 8-QCA were investigated
by transmission electron microscopy, FT-IR spectrosco-
Introduction
py, X-ray diffraction analysis, X-ray fluorescence
thermogravimetric analysis, and physical adsorption of
Water pollution is any human-caused contamination of
gases. Experiments showed that the amount of adsorbed
water that reduces its usefulness to humans and other
8-QCA increased at lower pH, reaching a maximum at
organisms in nature. Pollutants such as pesticides, fertil-
pH 2. The adsorption kinetics was found to follow the
izers, and hazardous chemicals often find their way into
pseudo-second-order kinetic model. The Langmuir
water channels. When water supply is contaminated, it
model provided the best correlation of experimental data
posed a great threat to humans, animals, and plants’ health
for adsorption equilibria. The adsorption of 8-QCA
unless it goes through a costly purification procedure.
decreased in the order Org-H-M > H-M > Na-M. Iso-
Water pollution can be considered in a number of ways,
therms were also used to obtain the thermodynamic
but in simple terms, it is an addition of an array of
parameters. The negative values of ΔG indicated the
unwanted contaminant elements to it (Forster 2003). Pol-
spontaneous nature of the adsorption process.
lution of surface water and groundwater causes a risk to
human health because of the potential health hazards of
their contents of inorganic and organic compounds. Pesti-
M. Mekhloufi : A. Zehhaf : A. Benyoucef (*) cides are a group of hazardous compounds that may
Laboratoire de Chimie Organique, Macromoléculaire et des
pollute water due to their extensive application in agricul-
Matériaux, Université de Mascara,
Bp 763, Mascara 29000, Algeria ture (Ayranci and Hoda 2005; Daneshvar et al. 2007;
e-mail: ghani29000@yahoo.fr Gupta et al. 2006).
Substituted quinolinecarboxylic acids are a class of
C. Quijada
highly selective auxin herbicides that effectively controls
Departamento de Ingeniería Textil y Papelera,
Universitat Politècnica de València, important dicotyledonous weeds, such as cleavers
Pza Ferrandiz i Carbonel, 03801 Alcoy, Alicante, Spain (Galium aparine L.) in sugar beet, oilseed rape, and
wheat (Grossmann and Scheltrup 1998; Sotelo et al.
E. Morallon
2002). Their action mechanism involves the interference
Departamento de Química Física e Instituto Universitario de
Materiales, Universidad de Alicante, with nucleic acid synthesis, which affects the DNA reg-
Apartado 99, 03080 Alicante, Spain ulation during the RNA formation by depression of a
10366
gene or activation of RNA polymerase, simply affecting
RNA message to proteins.
8-Quinolinecarboxylic acid (8-QCA) is a typical per-
sistent organic pollutant. Because of its persistence, low
volatility, bioaccumulation potential, and high toxicity, it
is a major environmental issue, drawing much scientific
and public attention. The 8-QCA can be transferred
throughout the food chain and pollute the entire ecolog-
ical environment, also posing problems to human health.
For soils that are contaminated by organic pollutants,
there are usually two kinds of remediation technologies
available, namely, in situ and ex situ remediations. Ex
situ remediation may gradually be replaced by in situ
remediation (Sui et al. 2003). Among the many in situ
remediation technologies, remediation of contaminated
soils and groundwaters by organoclays has been a topic
under development (Hermosín et al. 2006; Nzengung
et al. 1996; Oyanedel-Craver et al. 2006; Özcan et al.
2006; Pernyeszi et al. 2006; Wang et al. 1997; Zhou et al
2006). Organoclays are synthesized by exchanging the
naturally occurring inorganic cations with organic cat-
ions. By exchanging organic cations on the surface of
clay minerals, a material with radically different physi-
cal and chemical properties is produced (Jaynes and
Boyd 1991; Seki and Yurdakoc 2005). Modification of
clay minerals by ion exchange with organic cations has
been shown to have a significant impact on their
sorptivity (Klumpp et al. 2004; Richard et al. 2001;
Wiles et al. 2005).
In this study, Na montmorillonite was used as an
original clay mineral. Synthesized organoclays are
organophilic rather than hydrophilic and are able to sorb
nonpolar organic contaminants, unlike unmodified clays,
which are poor sorbents for these compounds (Seki and
Yurdakoc 2005; Redding et al. 2002; Yasser and Jamal
2004). Because the naturally occurring inorganic cations
in the interlamellar spaces and on the surface of clays are
not part of the inter-clay structure, they can easily be
replaced by organic cations (Smith and Galan 1995).
Sorption of hydrophobic organic contaminants by
organoclays can occur via different mechanisms and to
different degrees depending on the type of organic cat-
ions used, the type of original clay and its cation ex-
change capacity (CEC), the proportion of CEC satisfied
by organic cations, and characteristics of sorbate, such as
size, shape, solubility, and hydrophobicity (Redding et al.
2002; Richard et al. 2001; Yasser and Jamal 2004).
The aim of this work is to study the adsorption
of 8-QCA on Na montmorillonite, acid-activated
Environ Monit Assess (2013) 185:10365–10375
montmorillonite, and organo-montmorillonite from aque-
ous solutions. This adsorption study has not been report-
ed in the literature. We have been interested in the Na
montmorillonite and acid-activated montmorillonite in-
tercalated with ammonium acetate via ion exchange. As
the montmorillonite is progressively intercalated by this
modification, the surface properties of the clay mineral
change considerably, and so does the ability of organo-
montmorillonites to remove organic contaminants from
water. To understand the adsorption mechanism, the cor-
responding kinetics, isotherm, thermodynamic, pH influ-
ence on adsorption, and equilibrium models were stud-
ied. UV adsorption spectroscopy was used to analyze the
concentration of 8-QCA before and after adsorption onto
the original and modified clay minerals.
Materials and methods
Reagents
All reagents used in the present study were of analyt-
ical grade. 8-QCA of 98 % purity was obtained from
Sigma-Aldrich Chemicals. Ammonium acetate of
98 % purity was obtained from Fluka Ltd. The water
employed for the preparation of these pesticide solu-
tions was double-distilled water. The chemical struc-
ture of 8-QCA used is shown in Fig. 1. All other
reactants were also purchased from Sigma-Aldrich
Chemicals. The raw Na montmorillonite (named as
maghnite) used in this study was from Tlemcen (West
Algeria).
Clay adsorbents
The clay mineral sample was washed with distilled
water to remove impurities; the raw montmorillonite
(20 g) was crushed for 20 min using the Prolabo
Fig. 1 Structure of herbicide 8-quinolinecarboxylic acid
Environ Monit Assess (2013) 185:10365–10375 10367

ceramic balls grinder. Then, it was dried at 423 K for
2 h and stored in tightly stoppered glass bottles for later
use (samples of sodium montmorillonite (Na-M)). The
Na-M sample was activated in acid as acidic montmo-
rillonite (H-M) by the procedure of Belbachir and
Bensaoula (2001). Briefly, this procedure consists on
refluxing 20 g of Na-M in 200 mL of 0.25 M H2SO4 for
3 h. The resulting acidic activated clay was centrifuged
and washed with water several times until it was
free of SO42−, and the pH of the washing was 6.8.
Finally, the sample was dried at 378 K in air until
constant weight. This acid activation also removes
sodium from its composition (Salavagione et al.
2008; Zehhaf et al. 2012). The organo-acidic
montmorillonite (Org-H-M) was prepared by the
addition of 5 mmol of the solid ammonium acetate
salt to 1 L of a 1 % (w/v) aqueous dispersion of
acid-activated montmorillonite under stirring which
was continued for 24 h. The Org-H-M was separated by
centrifugation (4 g, 30 min). The sediments were
washed three times with distilled water. The chemical
composition of the three different clay minerals is in-
cluded in Table 1.
Characterization of the clay adsorbent
The porous texture of all samples was determined by
physical adsorption of gases (N2 at 77 K and CO2 at
273 K) using an automatic adsorption system
(Autosorb-6, Quantrachrome Corporation) after sam-
ple outgassing at 383 K under vacuum for 4 h. Nitro-
gen adsorption at 77 K was used for determining the
total volume of micropores (VDR (N2)) (pore size
smaller than 2 nm) by applying the Dubinin–
Radushkevich (DR) equation (range of relative pres-
sures used for the DR analysis was 0.005<P/P0<0.17)
and for determining the specific surface area by the
Brunauer–Emmett–Teller (BET) equation (SBET),
whereas the adsorption of CO2 at 273 K was used to
assess the narrowest micropores (VDR (CO2)) (pore
size smaller than around 0.7 nm) also by application
of the Dubinin–Radushkevich equation at relative
pressures below 0.025 (Cazorla et al. 1996, 1998;
Lozano et al. 2009).
For transmission electron microscopy (TEM) obser-
vations, the samples were dispersed in water and sup-
ported on TEM grids. The images were collected using
the JEOL (JEM-2010) microscope, working at an op-
eration voltage of 200 kV.
The X-ray diffraction of the powder nanocompos-
ites was taken using the Bruker CCD-Apex equipment
with an X-ray generator (Cu Kα and Ni filter) operated
at 40 kV and 40 mA.
X-ray fluorescence spectroscopy of the powder
samples was made using the Philips PW1480
equipment with the UniQuant II software to deter-
mine element concentration in a semiquantitative
way.
The thermogravimetric analysis was carried out
using the Mettler Toledo 851E/1600/LG equipment in
nitrogen atmosphere at heating rate of 10 °C/min.
Herbicide (8-QCA) adsorption studies
The clay mineral samples were dried at 80 °C
under vacuum for 24 h before adsorption. Then,
0.5 g of adsorbent was put in contact with 50 mL
of an aqueous solution of 8-QCA with concentra-
tion ranging from 1 to 1,500 mg L−1 at 25 °C and
for 24 h. Each adsorption experiment was run in
duplicate. The pH of the 8-QCA initial solution
ranged from 2 to 9.0.
The same adsorption experiments were repeated at
298, 308, and 318 K. The equilibrium concentrations
were measured by using the Unicam UV2-100 Double
Beam Scanning UV–Visible Spectrometer λ=312 nm for
8-QCA. The adsorbed amount of herbicide was calcu-
lated by a difference between the initial concentration

Table 1 Composition (in weight percent) of Na-montmorillonite (Na-M), acidic montmorillonite (H-M), and organo-acidic montmo-
rillonite (Org-H-M)

Composition SiO2 Al2O3 MgO Fe2O3 K2O TiO2 Rb2O ZrO2 SO3 ZnO CaO Na2O P2O5 MnO SrO

Na-M 68.01 18.31 3.56 3.19 1.89 0.08 0.02 0.01 0.16 0.02 0.02 4.58 0.02 0.11 0.02
H-M 72.93 20.66 1.46 2.28 2.46 0.18 0.01 – – – – – 0.01 – –
Org-H-M 72.27 20.42 1.56 2.78 2.67 0.27 0.01 – – – – – 0.01 – –
10368
and that after a time, according to the following
equation:
ðc0 −ct ÞV
qt ðmg=gÞ ¼ ð1Þ
1; 000W
where qt (in milligram per gram) is the amount of
organic pollutant adsorbed on the adsorbent at time t,
c0 is the initial concentration (in milligram per liter), ct
is the concentration of organic pollutant in solution at
time t (in milligram per liter), V is the volume of the
solution used (in milliliter), and W is the weight of the
adsorbent used (in gram).
In order to analyze the experimental data of
organic adsorption from aqueous solutions, the
linear form of well-known Langmuir isotherm
equation applicable to adsorption up to monolayer
levels on a homogeneous surface with no interac-
tion between adsorbed molecules was chosen as
follows:
ce 1 ce
¼ þ ð2Þ
qe K l c m qm
where qe is the amount adsorbed (in milligram per
gram), ce is the equilibrium concentration of the
adsorbate (in milligram per liter), and qm (in mil-
ligram per gram) and Kl (in liter per milligram) are
Langmuir constants, with qm being the maximum
adsorption capacity of adsorbent in a monolayer,
and Kl is related to the free energy of adsorption
(Gu et al. 1995).
The essential characteristics of the Langmuir iso-
therm can be expressed in terms of a dimensionless
constant separation factor Rl as follows:
1 dqt
Rl ¼ ð3Þ
1 þ K l C0
where Co (in milligram per liter) is the highest initial
concentration of adsorbate, and Kl (in liter per milli-
gram) is Langmuir constant.
The essential characteristics of the Langmuir iso-
therm can be expressed in terms of a dimensionless
constant separation factor Rl. The value of Rl indicates
the shape of the isotherm to be either unfavorable
(Rl >1), linear (Rl =1), favorable (0 < Rl < 1), or irre-
versible (Rl = 0) (Salman and Hameed 2010).
The Freundlich isotherm is an empirical equa-
tion based on adsorption on a heterogeneous
Environ Monit Assess (2013) 185:10365–10375
surface. The equation is commonly represented
by the following:
1
lnqe ¼ lnK f þ lnce ð4Þ
n
where qe is the amount adsorbed (in milligram per
gram), ce is the equilibrium concentration of the
adsorbate (in milligram per liter), and Kf (in mil-
ligram1−1/n per liter1/n per gram) and n are the
Freundlich constants characteristics of the system,
corresponding to the adsorption capacity and the
strength of adsorption, respectively.
In order to determine the adsorption kinetics of 8-
QCA herbicide, first- and second-order kinetic models
were checked. The first-order rate expression (Kul and
Koyunchu 2010) is expressed as follows:
dqt
¼ k 1 ðqe −qt Þ ð5Þ
dt
where qe and qt are the amounts of 8-QCA adsorbed
onto the montmorillonite (in milligram per gram), re-
spectively, at equilibrium and at time t, and k1 is the
first-order rate constant (per minute). After integration
from t=0 to t and from qt=0 to qe, it becomes the
Lagergren rate equation as follows:
k1
logðqe −qt Þ ¼ logqe − t: ð6Þ
2:303
In most cases, the first-order equation of Lagergren
does not apply well throughout the whole range of
contact times and is generally applicable over the ini-
tial 20–30 min of the adsorption process.
A pseudo-second-order rate law expression was also
used; the kinetic rate equation is expressed as (Ho and
McKay 1999) follows:
¼ k 2 ðqe −qt Þ2 ð7Þ
dt
where k2 is the second-order rate constant (in gram per
milligram per minute). At boundary conditions from t=0 to
t and from qt = 0 to qe, the rate law becomes the following:
t 1 1
¼ þ t: ð8Þ
qt k 2 q2e qe
Adsorption thermodynamics
The thermodynamic parameters of the adsorption, i.e.,
the standard enthalpy ΔH°, Gibbs free energy ΔG°,
Environ Monit Assess (2013) 185:10365–10375
and entropy ΔS° were calculated using the following
equations:
ΔG ¼ −RT lnK l ð9Þ
ΔS  ΔH 
lnK l ¼ − ð10Þ
R RT
ΔG ¼ ΔH  −T :ΔS  ð11Þ
where R is the ideal gas constant (in joule per mole per
Kelvin), Kl is the equilibrium constant, and T is
the temperature (in Kelvin); ΔH° and ΔS° values
can be obtained from the slope and intercept,
respectively, of van’t Hoff plots of Kl obtained
from the Langmuir isotherm versus 1/T.
Results and discussion
Characterization of the adsorbents
The nitrogen adsorption/desorption isotherms at 77 K for
natural and acidic activated samples (not shown) exhibit a
shape similar to the type II isotherms, with a hysteresis
loop of the H3 type according to IUPAC (Sing et al.
1985). This shape indicates that the samples are mainly
mesoporous solids but also contain some micropores. The
hysteresis loop appears in porous materials with slit-
shaped pores or pores with narrow necks and wide bodies,
and then, they can be associated with capillary condensa-
tion of liquid nitrogen in mesopores. The hysteresis phe-
nomenon becomes more prominent after acidic and or-
ganic activation because the amount of mesopores
increases by the structural deformation and reflects a
change from the laminar structure of the Na montmoril-
lonite to a delaminated structure (Temuulin et al. 2004).
Figure 2 contains the TEM images of the Na-M (Fig. 2a)
and H-M (Fig. 2b) samples which show a laminar
Fig. 2 TEM images of a Na-montmorillonite, b acidic montmorillonite, and c organo-acidic montmorillonite
10369
structure. In the case of Na-M clay, it is possible to
determine the separation between layers being around
3.6 Å. However, clear differences can be observed differ-
ences in the morphology of both samples with respect to
that observed for Org-H-M clay (Fig. 2c). This latter clay
mineral shows a largely exfoliated morphology in agree-
ment with the nitrogen isotherms. The specific surface
area of the samples was obtained from the BET method
by using the adsorption data. Table 2 includes the porous
texture characterization data of the three samples. It can be
observed that the specific surface area increases from
32 m2 g−1 for the Na-M sample to 140 m2 g−1 for the
H-M and to 161 m2 g−1 for Org-H-M sample. The micro-
pore and mesopore volumes also increase in the Org-H-M
> H-M > Na-M samples, possibly as a consequence of the
dissolution of the exchangeable cations like sodium and
the partial dissolution of the structural cations like Fe3+
and Mg2+ (Table 1) (Noyan et al. 2007).
The TG experiments (not shown) contain the
typical features for montmorillonites, namely, two
main processes at around 85 and 450 °C. The
first one corresponds to the evolution of weakly
bonded water molecules with a loss between 0.5
and 2 % by weight, due to the loss of interlayer
water. The second one can be associated with
dehydroxylation of the octahedral sheet (Huang
et al. 2004). Above 650 °C, the clay minerals
are completely calcined.
Herbicide (8-QCA) adsorption
Figure 3 shows the adsorption isotherms of herbicide
(8-QCA) on the different bentonites in solutions of
initial pH=2. The modified clay minerals, Org-H-M
and H-M, displayed a higher adsorbed amount than
Na-M. The adsorption isotherms on both Org-H-M and
H-M had an L-type profile. This profile of isotherms
suggests that the adsorption is driven by the affinity
10370 Environ Monit Assess (2013) 185:10365–10375

Table 2 Textural characterization of Na montmorillonite adsorbed amounts and correspond to the adsorption
(Na-M), acidic montmorillonite (H-M), and organo-acidic
isotherms plateaus. The 8-QCA isotherms exhibited
montmorillonite (Org-H-M)
classical type I characteristics and, as such, obeyed
Samples SBET VDR (N2) VDR (CO2) Vmeso the Langmuir equation. The high levels of adsorption
m2 g−1 cm3 g−1 cm3 g−1 cm3 g−1 indicate that the 8-QCA is attracted sufficiently to the
Na-M 32 0.09 0.01 0.16
hydrophobic surfaces of organo-montmorillonites, and
eventually, it must have penetrated into interlayer
H-M 140 0.19 0.02 0.69
spaces (Yapar et al. 2005).
Org-H-M 161 0.22 0.03 0.70
There are two types of interaction between polar organ-
ic compounds and organoclays: adsorption and partition.
between the 8-QCA molecules and the hydrophobic Surface adsorption may include ion exchange, protonation,
interlayer space (Celis et al. 2007) due to the interca- hydrogen bonding, and coordination/ion–dipole reactions
lation of ammonium acetate and acid-activated mont- with clays (Bleam 1990; Sing et al. 1985). Partition in-
morillonite. In comparison, the adsorption by Na-M, volves interactions between organic matter and nonionic
although noticeable, was lower than that by the mod- organic compounds. When a large organic molecule, for
ified montmorillonites. The maximum adsorption ca- example, ammonium acetate, interacts with clay minerals,
pacity decreases in the order Org-H-M > H-M > Na-M. the partition process plays an important role. For this
The Org-H-M shows the highest adsorption capacity in mechanism, the adsorption of organic contaminants is
agreement with the increase in the BET surface area functionally and conceptually similar to the dissolution of
values. organic contaminants in a bulk-phase organic solvent. This
The Langmuir and Freundlich isotherms were used mechanism results from the change of surface properties
to describe the experimental results. From the linear from hydrophilic to hydrophobic because the long tails of
plot of specific adsorption (Ce/qe) against the equilib- organic molecules form a hydrophobic phase in the
rium concentration (Ce) (figures not shown), the Lang- interlayer of the organoclays (Boyd et al. 1988; Smith
muir constants qm and Kl were determined from the et al. 1990).
slope and intercept and are listed in Table 3. It showed The dimensionless separation factors calculated for
that the model which gives a good fit to the experi- 8-QCA adsorption at 20 °C (Eq. 3) are as follows:
mental data is the Langmuir model. The values of Rl=0.19 for adsorption of 8-QCA on Na-M, Rl=0.16
maximum adsorption capacity determined using Lang- for adsorption of 8-QCA on H-M, and Rl=0.08 for
muir expression are higher than the experimental adsorption of 8-QCA on Org-H-M. Rl values were less

Fig. 3 The isotherms of 8-

QCA adsorption from aque-
ous solutions on the mont-
morillonites (Na-M, H-M,
and Org-H-M) after equilib-
rium time 24 h at 25 °C
Environ Monit Assess (2013) 185:10365–10375 10371

Table 3 Freundlich and Lang-

muir coefficients obtained from Isotherms Adsorbents Coefficients
the adsorption isotherms of 8-
QCA on the montmorillonite Freundlich Kf (mg1−1/nL1/ng−1) n R2
samples at 298 K and pH 2 Na-M 2.40 2.09 0.87
H-M 3.87 2.33 0.96
Org-H-M 8.79 2.98 0.93
Langmuir qm (mg g−1) Kl (L mg−1)×10−3 R2
Na-M 65.4 0.47 0.98
H-M 67.6 0.73 0.98
Org-H-M 75.9 1.71 0.99

than 1 and greater than 0, indicating favorable adsorp-

tion for the three processes.
Figure 4 shows XRD diffraction patterns of all
samples used (before and after adsorption of herbi-
cide). The intercalation of Na montmorillonite by pro-
ton cations (H-M) and, subsequently, by ammonium
acetate (Org-H-M) changes the basal spacing from
d(001)=13.10 to 15.58Ǻ and to 13.02Ǻ, respectively.
A new change to basal spacing for Na-M/8-QCA, H-
M/8-QCA, and Org-H-M/8-QCA was observed after
adsorption of herbicide (Table 4). These results con-
firm that all interlayer spaces were expanded by herbi-
cide 8-QCA.
The infrared spectra of pure 8-QCA, H-M, Org-H-M,
and the herbicide 8-QCA intercalated in Org-H-M are
shown in Fig. 5. The common features to all the clay
minerals are the band at 3,625 cm−1, the broad band at
3,380 cm−1, the intense band at 1,008 cm−1, and the
sharp bands at 798 and 515 cm−1. All these features
correspond to characteristic vibrational modes of the
octahedral and tetrahedral sheets in a montmorillonite

Table 4 Peak maximum and d spacing of modified montmoril-

lonites before and after adsorption of 8-QCA herbicide

Samples Peak maximum, Basal spacing,

2θmax (°) d(001) (Å)

Before
Na-M 6.65 13.10
H-M 5.59 15.58
Org-H-M 6.69 13.02
After
Na-M/8-QCA 5.66 15.39
H-M/8-QCA 5.79 15.05
Fig. 4 XRD diffraction patterns of montmorillonites Na-M, H-M, Org-H-M/8-QCA 5.65 15.42
and Org-H-M before and after adsorption of 8-QCA herbicide
10372 Environ Monit Assess (2013) 185:10365–10375

and ν(Si–O–(Mg)Al) modes (515 cm−1) (Dixon et al.

1977; do Nascimento et al. 2004; Lee et al. 2003; Wu
et al. 2008). The intensity of the bands at 3,380 and
1,631 cm−1 indicated a relatively high water content,
suggesting that the replacement of the original interlayer
inorganic cations of the clay and their hydration occurred
to a great extent. The spectrum of Org-H-M shows an
additional absorption the two N–H-bound vibrations at
1,443 cm−1 (N–H bending) and from 2,920 to 2,840 cm−1
(N–H stretching). The spectrum of Org-H-M/8-QCA
shows the increase in band intensity in the region between
1,615 and 1,650 cm−1 assigned to stretching of C=N
bonds and adsorbed water molecules and the band at
2,920 cm−1 related to N–H stretching. One singular band
around 1,548 cm−1 can be observed in spectra of mont-
morillonite with herbicide. These bands corroborate the
protonation of the nitrogen atoms of the herbicide,
confirming the interaction between herbicide 8-QCA
and montmorillonites.

Effect of the solution pH

To study the influence of the pH on the adsorption

Fig. 5 FT-IR spectra of H-M, Org-H-M, Org-H-M/8-QCA, and
pure 8-QCA herbicide
layer: ν(OH) from structural OH groups in
dioctahedral smectite sheets (3,625 cm−1), ν(Si–O)
modes (1,008 cm−1), ν(Al(Mg–O–)) mode (798 cm−1),
capacity of Na-M, H-M, and Org-H-M, experiments
were run at various pHs ranging from 1 to 9. At first,
the uptake of 8-QCA increased slowly with the increas-
ing pH, reaching a maximum for pH 2 and decreased
again at higher pHs (Fig. 6). It was observed that the
adsorption is highly dependent on the pH of the solu-
tion, which affects the surface charge of the adsorbent

Fig. 6 Effect of pH on 8-
QCA adsorption on Na-M,
H-M, and Org-H-M. Initial
concentration of 8-
QCA=1,500 mg L−1, ad-
sorption time=24 h
Environ Monit Assess (2013) 185:10365–10375 10373

Table 5 Comparison of the first- and second-order adsorption rate constants, for calculated (qe, cal) and experimental (qe, exp) values at 8-
QCA of concentration 1,500 mg L−1 and pH 2

Adsorbent qe, exp First-order kinetic model Second-order kinetic model

mg g−1 k1 qe, cal R2 k2, ads qe, cal R2

min−1 mg g−1 g mg−1 min−1 mg g−1

Na-M 54.7 0.019 85.9 0.90 0.0089 60.9 0.97

H-M 59.5 0.019 91.2 0.91 0.0085 66.2 0.97
Org-H-M 69.9 0.014 87.9 0.95 0.0071 77.5 0.97

and the degree of ionization and speciation of the
adsorbate.
This was due to the chemical characteristics of the Na-
M, H-M, and Org-H-M with acidic pHpzc of 2.9, 3.7, and
4.5, respectively. At a solution pH lower than the pHpzc,
the total surface charge would be on average positive,
whereas at a higher solution pH, it would be negative.
The 8-QCA uptake was the highest at lower pH where
the pH was below the pKa of 8-QCA (8-QCA shows two
pKa values, 2.4 and 6.8). The first one, corresponding to
the deprotonation of the carboxylic group, is comparable
with that observed in picolinic acid. The value of 6.8 is
due to the dissociation of the NH+ quinoline group
(Garribba et al. 2003; Kiss et al. 2000). At acidic pH,
the herbicide was undissociated, and the dispersion inter-
actions predominated (Hamdaoui and Naffrechoux
2007). At basic pH, however, the lower adsorption is
due to the repulsion between the negatively charged
surface of montmorillonite samples and the anions of
8-QCA.
Adsorption kinetics
The kinetics of the herbicide 8-QCA batch adsorption on
the three samples used in this work was examined in terms
of pseudo-first-order and pseudo-second-order kinetics.
Table 5 includes the relevant kinetic parameters, together
with the correlation factor R2 for different 8-QCA concen-
trations, obtained after applying the above mentioned
models to the experimental data. It can be observed that
the second-order model fits better the experimental data in
the whole range of 8-QCA concentrations used (from 1 to
1,500 mg L−1).
The second-order model is based on the assumption
that the rate-limiting step may be a chemical adsorption
involving valence forces through sharing or exchange
of electrons between adsorbent and adsorbate (Brigatti
et al. 2000).
Thermodynamic studies
The effect of temperature on adsorption capacity of Na-
M, H-M, and Org-H-M was studied by carrying out a
series of isotherms at 298, 308, and 318 K using an
initial 8-QCA concentration 1,500 mg L−1 at pH 2. The
effect of temperature on the equilibrium adsorption ca-
pacity of clay mineral samples is presented in Table 6.
The negative value for the Gibbs free energy for 8-QCA
adsorption on the three clay minerals shows that the
adsorption process is spontaneous and that the degree
of spontaneity of the reaction increases with increasing
temperature. The overall adsorption process seems to be
endothermic (ΔH°Na-M=19.88 kJ mol−1, ΔH°H-
−1 −1
M=14.56 kJ mol , and ΔH°Org-H-M=15.73 kJ mol ).

Table 6 Thermodynamic constants for the adsorption of 8-QCA on Na-M, H-M and Org-H-M montmorillonites at various tempera-
tures, (initial 8-QCA concentration 1,500 mg L−1 and pH 2)

Adsorbents Na-M H-M Org-H-M

T (K) 298 308 318 298 308 318 298 308 318
−1
ΔG (kJ mol ) −4.34 −5.15 −5.96 −3.81 −4.43 −5.05 −2.89 −3.52 −4.14
ΔH (kJ mol−1) 19.88 14.56 15.73
ΔS (J mol−1 K−1) 81.27 61.65 62.49
10374
Although not very high, these values of ΔH° can be
interpreted on the basis of a considerably strong inter-
action between 8-QCA and montmorillonite surface.
Table 6 also shows that the ΔS° value was positive.
This occurs as a result of redistribution of energy be-
tween the adsorbate and the adsorbent. Adsorption is
thus likely to occur spontaneously at normal and high
temperatures because ΔH>0 and ΔS>0.
Conclusion
It has been demonstrated here that Na montmorillonite
modified by the addition of the ammonium acetate
exhibits interesting adsorption properties with regard
to 8-QCA herbicide. The organic compound surfactant
has a dual effect. First, it increases the affinity of the
microporous interlayer adsorption sites. In the case of
8-QCA adsorption, this improved affinity allows ad-
sorption to occur much more efficiently than in the case
of conventional Na montmorillonite and acid-activated
montmorillonite. Second, surfactant molecules create
new adsorption sites on the external surfaces of the
clay layers. These surface chemical effects may be very
useful in designing a viable adsorbent for future
groundwater treatment applications.
Acknowledgments This work was supported by the National
Agency for the Development of University Research (CRSTRA)
and the Directorate General of Scientific Research and Techno-
logical Development of Algeria. The Ministerio de Economía y
Competitividad (MAT2010-15273 project) and FEDER are also
acknowledged.
References
Ayranci, E., & Hoda, N. (2005). Adsorption kinetics and iso-
therms of pesticides onto activated carbon-cloth.
Chemosphere, 60, 1600–1607.
Belbachir, M., Bensaoula, A. (2001). US Patent no. 6, 274, 527
B1.
Bleam, W. F. (1990). The nature of cation-substitution sites in
phyllosilicates. Clays and Clay Minerals, 38, 527–536.
Boyd, S. A., Mortland, M. M., & Chiou, C. T. (1988).
Sorption characteristics of organic compounds on
hexadecyltrimethylammonium-smectite. J Soil Sci Soc
Am, 52, 652–657.
Brigatti, M. F., Lugli, C., & Poppi, L. (2000). Kinetics of
heavy-metal removal and recovery in sepiolite. Applied
Clay Science, 16, 45–57.
Environ Monit Assess (2013) 185:10365–10375
Cazorla, A. D., Alcañiz, M. J., & Linares, S. A. (1996). Charac-
terization of activated carbon fibers by CO2 adsorption.
Langmuir, 12, 2820–2824.
Cazorla, A. D., Alcañiz, M. J., De la Casa, L. M. A., & Linares,
S. A. (1998). CO2 as an adsorptive to characterize carbon
molecular sieves and activated carbons. Langmuir, 14,
4589–4596.
Celis, R., Trigo, C., Facenda, G., Hermosín, M. C., & Cornejo, J.
(2007). Selective modification of clay minerals for the
adsorption of herbicides widely used in olive groves. Jour-
nal of Agricultural and Food Chemistry, 55, 6650–6658.
Daneshvar, N., Aber, S., Khani, A., & Rasoulifard, M. H. (2007).
Investigation of adsorption kinetics and isotherms of
imidacloprid as a pollutant from aqueous solution by ad-
sorption onto industrial granular activated carbon. Journal
of Food Agriculture and Environment, 5, 425–429.
Dixon, J. B., Weed, S. B., & Dinauer, R. C. (1977). Minerals in
soil environments. Berkeley: Soil Science Society of
America.
Do-Nascimento, G. M., Constantino, V. R. L., Landers, R., &
Temperini, M. L. A. (2004). Aniline polymerization into mont-
morillonite clay: a spectroscopic investigation of the interca-
lated conducting polymer. Macromolecules, 37, 9373–9385.
Forster, C. F. (2003). Wastewater treatment and technology.
London: Thomas Telford.
Garribba, E., Micera, G., Sanna, D., & Chruscinska, E. L.
(2003). Oxovanadium(IV) complexes of quinoline deriva-
tives. Inorganica Chimica Acta, 348, 97–106.
Grossmann, K., & Scheltrup, F. (1998). Studies on the mecha-
nism of selectivity of the auxin herbicide quinmerac. Pesti-
cide Science, 52, 111–118.
Gu, B., Schmitt, J., Chen, Z., Liang, L., & McCarthy, J. F.
(1995). Adsorption and desorption of different organic mat-
ter fractions on iron oxide. Geochimica et Cosmochimica
Acta, 59, 219–229.
Gupta, V. K., Ali, I., & Saini, V. K. (2006). Adsorption of 2,4-D
and carbofuran pesticides using fertilizer and steel industry
wastes. Journal of Colloid and Interface Science, 299, 556–
563.
Hamdaoui, O., & Naffrechoux, E. (2007). Modeling of adsorp-
tion isotherms of phenol and chlorophenols onto granular
activated carbon. Part II. Models with more than two pa-
rameters. Journal of Hazardous Materials, 147, 401–411.
Hermosín, M. C., Celis, R., Facenda, G., Carrizosa, M. J.,
Ortega-Calvo, J. J., & Cornejo, J. (2006). Bioavailability
of the herbicide 2,4-D formulated with organoclays. Soil
Biology and Biochemistry, 38, 2117–2124.
Ho, Y. S., & McKay, G. (1999). Pseudo-second-order model for
sorption processes. Process Biochemistry, 34, 451–465.
Huang, F. C., Lee, F. J., Lee, C. K., & Chao, H. P. (2004). Effects
of cation exchange on the pore and surface structure and
adsorption characteristics of montmorillonite. Colloid Sur-
face A, 239, 41–47.
Jaynes, W. F., & Boyd, S. A. (1991). Clay mineral type and organic
compound sorption by hexadecyltrimethylammonium-
exchanged clays. Soil Science Society of American Journal,
55, 43–48.
Kiss, E., Petrohan, K., Sanna, D., Garribba, E., Micera, G., &
Kiss, T. (2000). Solution speciation and spectral studies on
oxovanadium(IV) complexes of pyridinecarboxylic acids.
Polyhedron, 19, 55–61.
Environ Monit Assess (2013) 185:10365–10375
Klumpp, E., Ortega, C. C., & Klahre, P. (2004). Sorption of 2,4-
dichlorophenol on modified hydrotalcites. Colloids and
Surfaces A: Physicochemical and Engineering Aspects,
230, 111–116.
Kul, A. R., & Koyunchu, H. (2010). Heavy metal removal from
municipal solid waste fly ash by chlorination and thermal
treatment. Journal of Hazardous Materials, 179, 332–339.
Lee, D. K., Char, K., Lee, S. W., & Park, Y. W. (2003). Structural
changes of polyaniline/montmorillonite nanocomposites
and their effects on physical properties. Journal of Mate-
rials Chemistry, 13, 2942–2947.
Lozano, C. D., Suárez, G. F., Cazorla, A. D., & Linares, S. A.
(2009). Porous texture of carbons. In F. Beguin & E.
Frackowiak (Eds.), Carbons for electrochemical energy stor-
age and conversion systems (pp. 115–162). Boca Raton: CRC.
Noyan, H., Onal, M., & Sarikaya, Y. (2007). The effect of
sulphuric acid activation on the crystallinity, surface area,
porosity, surface acidity, and bleaching power of a bentonite.
Food Chemistry, 105, 156–163.
Nzengung, V. A., Voudrias, E. A., Nkedi-Kizza, P., Wampler, J. M.,
& Weaver, C. E. (1996). Organic cosolvent effects on sorption
equilibrium of hydrophobic organic chemicals by organoclays.
Environmental Science and Technology, 30, 89–96.
Oyanedel-Craver, V. A., Fuller, M., & Smith, J. A. (2006).
Simultaneous sorption of benzene and heavy metals onto
two organoclays. Journal of Colloid and Interface Science,
309, 485–492.
Özcan, A., Ömeroglu, C., Erdogan, Y., & Özcan, A. S. (2006).
Modification of bentonite with a cationic surfactant: an
adsorption study of textile dye reactive blue 19. Journal of
Hazardous Materials, 140, 173–179.
Pernyeszi, T., Kasteel, R., Witthuhn, B., Klahre, P., Vereecken,
H., & Klumpp, E. (2006). Organoclays for soil remediation:
adsorption of 2,4-dichlorophenol on organoclay/aquifer
material mixtures studied under static and flow conditions.
Applied Clay Science, 32, 179–189.
Redding, A. Z., Burns, S. E., Upson, R. T., & Anderson, E. F.
(2002). Organoclay sorption of benzene as a function of
total organic carbon content. Journal of Colloid and Inter-
face Science, 250, 261–264.
Richard, W. G., Walter, J., & Weber, J. R. (2001). Evaluation of
shale and organoclays as sorbent additives for low-
permeability soil containment barriers. Environmental Sci-
ence and Technology, 35, 1523–1530.
Salavagione, H. J., Amorós, D. C., Tidjane, S., Belbachir, M.,
Benyoucef, A., & Morallon, E. (2008). Effect of the intercalated
cation on the properties of poly(o-methylaniline)/maghnite clay
nanocomposites. European Polymer Journal, 44, 1275–1284.
Salman, J. M., & Hameed, B. H. (2010). Adsorption of 2,4-
dichlorophenoxyacetic acid and carbofuran pesticides onto
granular activated carbon. Desalination, 256, 129–135.
Seki, Y., & Yurdakoc, K. (2005). Paraquat adsorption onto clays
and organoclays from aqueous solution. Journal of Colloid
and Interface Science, 287, 1–5.
10375
Sing, K., Everet, D., Haul, R., Moscou, L., Pierotty, R.,
Rouquerol, J., et al. (1985). Reporting physisorption data
for gas/solid systems with special reference to the determi-
nation of surface area and porosity. Pure and Applied
Chemistry, 57, 603–619.
Smith, J., Jaffe, P., & Chiou, C. (1990). Effect of ten quaternary
ammonium cations on tetrachloromethane sorption to clay
from water. Environmental Science and Technology, 24,
1167–1172.
Smith, J. A., & Galan, A. (1995). Sorption of nonionic organic
contaminants to single and dual organic cation bentonites
from water. Environmental Science and Technology, 29,
685–692.
Sotelo, J. L., Ovejero, G., Delgado, J. A., & Martínez, I. (2002).
Comparison of adsorption equilibrium and kinetics of four
chlorinated organics from water onto GAC. Water
Research, 36, 599–608.
Sui, H., Li, X. G., Huang, G. Q., Zhang, Y., & Gao, X. F. (2003).
The in-situ remediation technologies for soils contaminated
by organic chemicals. Techniques and Equipment for Envi-
ronmental Pollution Control, 4, 41–45.
Temuulin, J., Jadambaa, T. S., Burmaa, G., Erdenechimeg, S. H.,
Amarsanaa, J., & MacKenzie, K. J. D. (2004). Characteri-
sation of acid activated montmorillonite clay from Tuulant
(Mongolia). Ceramics International, 30, 251–255.
Wang, X. R., Wu, S. N., & Li, W. S. (1997). Contaminated
environment remediation with organoclay minerals. Envi-
ronmental Chemistry, 16, 1–14.
Wiles, M. C., Huebner, H. J., McDonald, T. J., Donnelly, K. C.,
& Phillips, T. D. (2005). Matrix-immobilized organoclay
for the sorption of polycyclic aromatic hydrocarbons and
pentachlorophenol from groundwater. Chemosphere, 59,
1455–1464.
Wu, C. S., Huang, Y. J., Hsieh, T. H., Huang, P. T., Hsieh, B. H.,
Han, Y. K., et al. (2008). Studies on the conducting nano-
composite prepared by in situ polymerization of aniline
monomers in a neat (aqueous) synthetic mica clay. Journal
of Polymer Science Part A: Polymer Chemistry, 46, 1800–
1809.
Yapar, S., Ozbudak, V., Dias, A., & Lopes, A. (2005). Effect of
adsorbent concentration to the adsorption of phenol on
hexadecyltrimethylammonium-bentonite. Journal of Haz-
ardous Materials B, 121, 135–139.
Yasser, Z. N., & Jamal, M. S. (2004). Adsorption of phenanthrene
on organoclays from distilled and saline water. Journal of
Colloid and Interface Science, 269, 265–273.
Zehhaf, A., Benyoucef, A., Berenguer, R., Quijada, C., Taleb, S.,
& Morallon, E. (2012). Lead ion adsorption from aqueous
solutions in modified Algerian montmorillonites. Journal
of Thermal Analysis and Calorimetry, 110, 1069–1077.
Zhou, Q., Frost, R. L., He, H. P., & Xi, Y. F. (2006). Changes in
the surfaces of adsorbed para-nitrophenol on HDTMA
organoclay. The XRD and TG study. Journal of Colloid
and Interface Science, 307, 50–55.