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Adsorption of cadmium on different granulometric soil fractions: Inuence of organic

matter and temperature


Estelle Roth
a,
, Valrie Mancier
b
, Bernard Fabre
c
a
Laboratoire Groupe de Spectromtrie Molculaire Atmosphrique, UMR 6089, Universit de Reims Champagne Ardenne, Moulin de la Housse, case 16-17, BP 1039,
F-51687 Reims Cedex 2, France
b
LACM-DTI, LRC-CEA 0534/EA 4302, UFR Sciences Exactes et Naturelles, BP 1039, F-51687 Reims Cedex 2, France
c
Laboratoire Gestion des Risques et Environnement, EA 2334, 3 bis rue Alfred Werner, F-68093 MULHOUSE Cedex, France
a b s t r a c t a r t i c l e i n f o
Article history:
Received 7 July 2011
Received in revised form 13 March 2012
Accepted 22 April 2012
Available online 30 July 2012
Keywords:
Cadmium
Sorption isotherms
Sorption kinetics
Soil organic matter
Soil coarse fraction
Kinetic and thermodynamic studies are carried out at low initial cadmium concentration on a soil sample
extracted from Aspach le Bas in Eastern France. It can be concluded from kinetic experiments that the implied
process is of pseudosecond order. Rate constants, relaxation times and activation energy are calculated. The
energy value determined in this study (40 kJ mol
1
) shows that the process implies both physisorption and
chemisorption.
The inuence of soil particle size (i.e. of the initial soil and its different fractions: sand, coarse silt, ne silt and
clay), organic matter and temperature on the cadmium sorption capacity is also investigated. The Langmuir
and the DubininRadushkevich models are chosen to analyze these thermodynamic experiments. The
isotherms have revealed that the Cd
2+
sorption is enhanced by increasing temperature and organic matter
for all the fraction but the sand (in this last case, no temperature or organic matter have changed Cd
2+
sorption). Thermodynamics parameters (G, H and S) are determined from experimental isotherms
tting following three methods used in the literature. It can be deduced from the different results that
adsorption (exo or endothermic according to the fraction). Finally, a mean free energy of adsorption is
obtained via DubininRadushkevich model and conrms that the two types of sorption (physical and
chemical) act in the whole process.
2012 Elsevier B.V. All rights reserved.
1. Introduction
Industrial activities and agricultural soils are an important source of
heavy metal pollution due to fertilisers, sewage sludge, pesticides,
herbicides and fungicides (Bourrelier and Berthelin, 1995; Juste,
1990). These metals can be either accumulated in plants (Hooda and
Alloway, 1995; Sauerbeck and Styperek, 1988) or leached in the
groundwater. They induce therefore a risk of food chain contamination
(Declotre, 1998; Lacatusu et al., 1996). Studies on metal sorption by
soils are considered of great importance to explain the mechanism of
soil pollution and to estimate the extent of retention by soils.
Among the heavy metals, cadmium, whose concentration in
fertilizers ranges from 0.2 to 186.0 g g
1
(Grant et al., 2002), is
potentially very toxic to mammals, aquatic lives and aerial plant
growth (Johri et al., 2010).
First studies on cadmium toxicity were published in the 70s (John
et al., 1972). Since, the inuence of organic matter content, pH (these
two parameters having moreover a synergy effect), temperature,
initial contaminant concentration and ionic strength on the sorption
characteristics have been widely investigated (Aguilar-Carrillo et al.,
2006; El-Kamash et al., 2005; Huang et al., 2007). Several studies
focus on cadmium adsorption on an isolated soil component like
clay with or without the presence of humic acid (Hizal and Apak,
2006; Lai et al., 2002) or kaolinite (Angove et al., 1997, 1998). In
such cases, when a single soil component is isolated, a surface
complexation sorption model is usually derived. Overall soils are
tested too and the adsorption capacity is discussed regarding soil
properties (Adhikari and Singh, 2003; Appel and Ma, 2002;
Hosseinpur and Dandanmozd, 2010; Kim and Fergusson, 1992;
Wang et al., 2009). However, the inuence of the soil particle size is
rarely studied in detail (John et al., 1972; Kim and Fergusson, 1992).
In the present work, sorption experiments at 10, 20 and 30C are
conducted on different granulometric soil fractions at very low initial
cadmium concentration (0.5 to 10 mg L
1
). This choice allows for the
simulation of diffuse trace element contamination. First, kinetic
experiments are performed on the whole soil to assess conditions
for isotherm studies and adsorption kinetics is discussed. Afterwards,
sorption experiments are done on four soil fractions obtained after
sieving (the initial soil, sand, coarse silt, ne silt and clay) in the
presence of organic matter or after its removal. Isotherms are then
Geoderma 189190 (2012) 133143
Corresponding author. Tel.: +33 326 91 32 31; fax: +33 326 91 31 47.
E-mail address: estelle.roth@univ-reims.fr (E. Roth).
0016-7061/$ see front matter 2012 Elsevier B.V. All rights reserved.
doi:10.1016/j.geoderma.2012.04.010
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j our nal homepage: www. el sevi er . com/ l ocat e/ geoder ma
analyzed by the Langmuir and the DubininRadushkevich models.
These models give information about the soil retention capacity and
the strength by which the contaminant is held to the soil. The
inuence of temperature, organic matter and granulometric size on
the Cd sorption has also been researched.
Thermodynamic parameters issued fromisothermanalysis give an
insight on the sorption mechanism from an initial non-equilibrium
state. In the literature, several methods have been used to get the
adsorption equilibrium constant used for the determination of free
energy. A critical discussion about this equilibrium is thus presented.
At least, three methods are used to determine sorption constant and
derive thermochemical data (G, H and S).
2. Theoretical aspects
2.1. Concerning the kinetic approach
Kinetic studies regarding the determination of activation energy
constitute a simple way to assess to the mechanisms that control
the adsorption process.
The two most widely used kinetic models have been used in this
study to investigate the sorption mechanism. In the pseudo-rst-
order model, based on Lagergren equation, the rate is function of
the concentration of non occupied sites (Ho and McKay, 1999b):
dq
t
dt
k
1
: q
e
q
t
1
where q
t
(mg g
1
) is the amount of sorbed cadmium at t time, q
e
(mg g
1
) is the amount of sorbed cadmium at equilibrium i.e. at
innite time and k
1
is the pseudo-rst-order rate constant.
The integrated form is the following:
log q
e
q
t
log q
e

k
1
2:303
t 2
A plot of log(q
e
q
t
)=f(t) allows for the determination of q
e
via the
intercept of the plot with the Y-axis and k
1
via the slope value.
The pseudo-second-order model is based on the bulk concentration
and is also independent of the sorbed solute concentration (Ho and
McKay, 1999b):
dq
t
dt
k
2
: q
e
q
t

2
_
3
the integrated equation is:
t
q
t

1
k
2
: q
e

2

t
q
e
4
where k
2
is the pseudo-second order rate constant. k
2
and q
e
are
obtained from the slope and the intercept of the plot of
t
q
t
versus t
with Y-axis.
2.2. Concerning the thermodynamic approach
2.2.1. Presentation of tting models
The partitioning coefcient K
d
of a metal toward a soil is an
important parameter for examining of contaminant migration
through the subsurface natural soil to groundwater. If K
d
is low, the
soil has little or no ability to slow the contaminant movement. For a
K
d
value of 0 it will travel at the rate of inltration of water. In
contrast, high K
d
values signify the substrate does not leach and on
site remediation may be possible. Considering the importance of
this parameter in risk assessment and remediation management,
the United States Environmental Protection Agency dedicated a
complete study and discussion about the partitioning coefcient
meaning and its determination (USEPA, 1999).
The K
d
values are usually obtained from laboratory experiments at
constant temperature. Three methods to measure K
d
can be found:
the in-situ batch method (that is used in this work), the laboratory
ow-through (or column) method and the eld modelling method.
In batch experiments K
d
is determined as:
K
d

q
e
C
e
5
where q
e
is the substrate concentration in the soil at equilibrium
(g g
1
) and C
e
the remaining substrate concentration in the solution
at equilibrium (mg L
1
). K
d
is given in mL g
1
by Eq. (5) or L mol
1
by the following Eq. (6):
K
d

q
e
C
e
: M
Cd2
6
where M
Cd2+
is molecular the molecular weight of cadmium (i.e.
112.4 g mol
1
).
Dening the partitioning coefcient as above implies that the
adsorption of the contaminant is a linear isotherm adsorption model.
But this is an approximation at low initial contaminant concentration
and often contaminant adsorption on soils deviates from linearity.
Isotherm models such as Langmuir and DubininRadushkevich
models were developed and are largely used in the literature to t
adsorption. The rst model (Langmuir) was originally proposed to
describe adsorption of gas molecules onto homogeneous solid surfaces
(crystalline materials) that exhibit one type of adsorption site
(Langmuir, 1918). It has been extended to describe the adsorption of
solutes onto solid adsorbents including heterogeneous solids such as
soils.
The Langmuir model for adsorption isotherm is dened by:
q
e

q
max
K
L
C
e
1 K
L
C
e

7
where q
max
is the maximum adsorption capacity (mg g
1
or
mol g
1
) and K
L
is the Langmuir constant related to the energy of
adsorption (L mg
1
or L mol
1
), q
e
being always the substrate
concentration in the soil at equilibrium (same unit as q
max
).
The theory of the Langmuir model implies that adsorption is
monolayer and is based on the fact that the bonding energy of all the
sites is uniform. But it is often not realistic in complex systems like soils.
The second adsorption model is the DubininRadushkevich
isotherm (Dubinin, 1975) which does not require homogeneous
adsorption sites. It is then well adapted for the adsorption of trace
constituents. The equation used here is the following:
q
e
q
max
exp K
DR

2
_ _
8
with
RT ln 1
1
C
e
_ _
9
where q
max
is the maximum solute adsorption capacity (mg g
1
) and
K
DR
the DubininRadushkevich constant (mol J

). These two
parameters are deduced from the intercept and the slope of the plot
of ln(q
e
) versus
2
.
Fitting experiments with the DubininRadushkevich model
provides a value of an absolute mean free energy of adsorption |E|
in J mol
1
:
E j j
1

2K
DR
_ 10
134 E. Roth et al. / Geoderma 189190 (2012) 133143
Energies between 1 and 8 kJ mol
1
signify physical adsorption
phenomenon (Van der Walls interactions) and energies between 9
and 16 kJ mol
1
are characteristic of chemical sorption or ion
exchange (ionic or covalent bounding) (Donat et al., 2005). Between
8 and 9 kJ mol
1
, it can be supposed that the both adsorption types
are implied in the whole process.
The Langmuir model is based on physicochemical processes for
which the bonding energy of all the adsorbing sites is the same
(Petruzzelli et al., 1985) with a single sorption layer. This model ts
well the sorption at low cadmium concentrations where the rst
sorption layer is still not completed. For high initial cadmium concen-
tration, the Langmuir model is not adapted since it underestimates
the adsorbed cadmium, especially for the samples without organic
matter. Organic matter provides indeed supplementary sites (for
adsorption or ion exchange) and when removed, the rst layer of
cadmium is completed with a lower initial Cd concentration. The
point is particularly clear for the nest granulometric fractions that
often provide more sorption sites. The DubininRadushkevich model
is suitable at low concentration for trace contaminants and is more
general than the Langmuir model as not requiring homogeneous
adsorption sites and constant adsorption potential (USEPA, 1999).
In this study, the initial concentrations of cadmium[Cd
2+
]
0
are weak
(b10 mg L
1
): the Langmuir and the DubininRadushkevich models are
thensuitable. They provide important data suchas maximumadsorption
capacities and adsorption afnities by interpreting K
L
and |E| values.
2.2.2. Adsorption thermodynamic aspects
A great number of papers use isotherms to calculate thermo-
dynamics parameters for adsorption using fundamental thermody-
namic relations:
G RT lnK 11
where G is the Gibb's free energy and K is the sorption constant at
equilibrium:
Cd
2
in solution
k
ads
k
des
Cd
2
adsorbed on soil fraction
R is the ideal gas constant (8.31 J K
1
mol
1
), T is the tempera-
ture (K), k
ads
is the adsorption rate constant and k
des
is the desorption
rate constant.
The enthalpy H and the entropy S are then calculated using:
G HTS 12
The principal difculty lies in calculating the real thermodynamic
adsorption constant K
0
which should be rigorously unitless as a rate
of activities (Biggar and Cheung, 1973):
K K
adim real

a
Cd
2
soil fraction
a
Cd
2
solution


S
C
S

e
C
e

k
ads
k
des
13
where a
i
is the activity of Cd
2+
in phase i, C
S
(mol L
1
) and C
e
(mol L
1
) are respectively the amount at equilibrium of solute
adsorbed on the soil and of solute per volume of solvent in the
solution, and
S
and
e
are the activity coefcients of the adsorbed
solute and of the solute in the solution at equilibrium.
To calculate K experimental values of C
e
and C
s
are necessary and
if C
e
is directly obtained by experiments, C
s
has to be calculated by
Eq. (14):
C
S
1:091:
qe
s
N
M
i
_ _
1=3
14
where (g.cm
3
) is the solvent volumetric mass, M
i
(g mol
1
) the
solvent molecular weight, s (cm
2
g
1
) the surface area of the
adsorbent i.e. specic surface and N (mol
1
) Avogadro's number.
q
e
, dened before, is expressed here in g g
1
.
This equation, derived fromthe work of Biggar and Cheung (1973)
works that dene C
S
as:
C
S

=M
i
A
s
Nq
e
15
where A (cm
2
), the cross sectional area of the solvent, is obtained via
Eq. (16):
A 1:091 10
16
M
i
10
24
N
_ _
2=3
16
the expression of C
s
becomes Eq. (14) if Eqs. (15) and (16) are combined.
C
s
and C
e
being known, K is obtained by plotting ln(C
S
/C
e
) versus
C
S
and extrapolating C
S
to zero.
Papers referring to Biggar and Cheung (1973) usually make the
following assumption (Adhikari and Singh, 2003; Mohapatra and
Anand, 2007):
C
S

m
soil
q
e
V
17
where m
soil
is the mass of soil (g) and V the volume of solution (L).
Thus the adsorption constant becomes the ratio between the mass
of metal adsorbed per liter solution in contact with the adsorbent
surface, C
s
, and the concentration of remaining metal in the solution
at equilibrium C
e
and Eq. (13) becomes:
K K
adim

m
soil
q
e
VC
e
18
the activity coefcient being equal to about 1 since the studied
solutions are very dilute in cadmium. In this form K
adim
is unitless.
Some other authors consider K
0
is equal to K
d
(Eq. (5)) and perform
thermodynamic calculations with this value (Aguilar-Carrillo et al.,
2006). In these approach, since K
d
(if not in a linear adsorption case)
is concentrationdependant for the reasons previously detailed, thermo-
dynamic calculations are performed either for each initial contaminant
concentration for each temperature or obtained by plotting ln K
d
versus
C
e
and extrapolating to zero. K
d
(L mol
1
) is determined using Eq. (6)
and then used for the calculation of Gibb's free energy G according
to Eq. (11). The plot Gversus temperature is then drawn to determine
the enthalpy H(equal to ordinate origin) and the entropy S (equal to
plot slope).
According to a third approach, thermodynamic calculations are
performed using coefcients identied in adsorption models namely
K=K
L
(L mg
1
) derived from Langmuir model (Angove et al., 1997;
Gupta and Rastogi, 2008; Huang et al., 2007).
As a matter of fact the thermochemical adsorption constant is
difcult to be properly established and the Gibb s free energy will
be highly dependent on the magnitude of K. As an example K
d
expressed in L mol
1
(Eq. (6)) and K
adim
as dened in Eq. (18) are
linked by the equation:
K
d
K
adim

V
m
soil
M
Cd2
19
For example, at 20 C in the present study (m
soil
=5 g, V=0.1 L),
the Gibb's free energy calculated with either K
d
or K
adim
is
1974 J mol
1
since:
RT lnK
d
RT lnK
adim
RT ln
V
m
soil
M
Cd2
_ _
RT lnK
adim
1974 20
135 E. Roth et al. / Geoderma 189190 (2012) 133143
These different approaches (K calculated as () the partition
coefcient K
d
in L mol
1
(Eq. (6)), () the dimensionless constant
K
adim
(Eq. (18)), () the Langmuir constant K
L
in L mol
1
) have
been employed to estimate the thermodynamic adsorption constant.
Thermodynamic results derived from these three ways are discussed.
3. Experimental
3.1. Soil and granulometric fractions
The soil was sampled in Eastern France at Aspach le Bas (Alsace
Haut Rhin). Its properties are listed in Table 1 and indicate that it
has very high silt content and low organic matter content. The soil
sampling was realised from the surface horizon (030 cm). Soil
samples were stored at ambient temperature, air dried and rst
sieved at 250 m. By further sieving three soil fractions are obtained:
>50 m: SanD (SD)
between 20 and 50 m: Coarse Silt (CS)
b20 m: Fine Silt and Clay (FSC)
The organic matter (OM) was removed by H
2
O
2
treatment at
70 C, according to the French standard procedure AFNOR NFX 31
107 (AFNOR, 1983). The removal of organic matter is controlled by
the organic carbon level in soils according to the AFNOR French
standard procedure NFX 31-109 (AFNOR, 1993).
The different fractions obtained are named: Soil+OM (S+OM) for
the initial soil without any treatment and SoilOM (SOM) for the
initial soil after the organic matter removal. The Sand+OM fraction
(SD+OM), the Coarse Silt+OM fraction (CS+OM) and the Fine Silt
and Clay+OM fraction (FSC+OM) are obtained by successive sieving
of the whole soil (Soil+OM). The Sand-OM fraction (SD-OM), the
Coarse Silt-OM fraction (CS-OM) and the Fine Silt and Clay-OM
fraction (FSC-OM) are isolated from the Soil-OM according to the
same sieving procedure.
3.2. Tools
3.2.1. Analytical tools
The Cd
2+
concentration in solutions was determined using ame
atomic absorptionspectroscopy VARIANAA20. The amount of cadmium
adsorbed was obtained by calculating the difference between the initial
and the residual cadmium concentration in the solution.
3.2.2. Data processing
To t the experimental data, the software Kaleidagraph (version
3.09) was employed.
3.3. Kinetic experiments
Batch kinetic studies were done to determine the rate of cadmium
adsorption. The experiments were performed in a High Density
PolyEthylene (HDPE) ask to avoid absorption of Cd
2+
on the vessel
wall. Before beginning kinetic experiments, these 125 mL receptacles
were lled with 5 g of whole soil without any treatment and 100 mL
of Ca(NO
3
)
2
10
2
mol L
1
to adjust the ionic strength. This Ca(NO
3
)
2
concentration has been chosen in accordance with Petruzzelli works
(Petruzzelli et al., 1985). Indeed, at high ionic strength the soil
metal sorption capacity decreases: Ca
2+
ions enter in competition
with Cd
2+
ions. The ionic strength chosen for our experiment was
low enough to avoid competition. The pH was adjusted to 6.0 to
keep the natural soil pH. The asks were shaken in a thermostated
bath for 2 h at the studied temperature+/1 C to reach thermal
equilibrium. Shaking period nished, the soil was then exposed to
metal solutions for about 6 h and samples were collected at different
times. The sorbent was removed by ltration and the ltrate Cd
2+
concentration C
e
was determined.
3.4. Batch sorption experiments
They were performed in the same conditions as before on soil or
its granulometric fractions in the presence or absence of OM. The Cd
introduction was performed via injection of some micro-litres of a
1 g L
1
Cd solution in order to obtain initial cadmium concentrations
between 0.5 and 10 mg L
1
. These small volumes of Cd additions did
not change the nal volume of the solution. After 2h, residual
cadmiumconcentration in solution at equilibriumC
e
was determined.
4. Results and discussion
4.1. Kinetic experiments
Fig. 1 shows the kinetic experimental results obtained at 20 C and
30 C on the initial soil without removing organic matter.
It can be seen that the sorbed amount of cadmium q
t
is enhanced
when temperature increases. The same tendency has already been
observed for lead ions by Ho and Ofomaja (2005). This phenomenon
can be explained by an endothermic adsorption reaction and will be
veried in Sections 4.2 and 4.3.
The experimental value of q
e
is obtained when t tends to innity
in accordance with equilibrium (Table 2).
The curves are treated either by pseudo-rst-order or pseudo-
second-order kinetics. The corresponding plots log (q
e
q
t
)=f(t)
and
t
q
t
f t are shown in Fig. 2a and b. The obtained parameters
are summarized on Table 2. The best t (higher r) is clearly found
for the pseudo-second-order model and the corresponding values of
q
e
derived from the pseudo-second order are closer to the
experimental determination of q
e
on kinetic curves (Table 2).
Pseudo-second-order kinetics often better t the kinetic of sorption
than the Lagergren equation especially at high times. In fact, the latter is
not applicable on the whole range of time but only at short time, at the
beginning of the adsorption process (Ho and McKay, 1999a, 1999b).
Moreover, pseudo-second order process can easily be explained by
the retention of metals through several steps: rst the metal is fast
sorbed by the external soil surface and then enters slowly in the soil
pores maybe by diffusion (Brummer et al., 1988; Selim et al., 1992).
Table 1
Soil characteristic: soil fraction in mass percentage, CEC and pH.
Sand
(SD)
Coarse silt
(CS)
Fine silt and clay
(FSC)
Organic matter
(OM)
CEC
meq/kg
pH
16.3% 34.4% 47.3% 2.0% 96 5.9
0.00
0.01
0.02
0.03
0.04
0.05
0.06
0.07
0.08
0.09
0 100 200 300 400
q
t

a
b
s

(
m
g
/
g
)
t (min)
20C
30C
Fig. 1. Sorption of cadmium by initial soil without any treatment at different
temperatures. Points are experimental data, lines are ts with the pseudo-second-
order model.
136 E. Roth et al. / Geoderma 189190 (2012) 133143
El-Kamash et al. (2005), Wang et al. (2009) and Saha and Sanyal (2010)
have shown the same kinetic tendency for cadmium on synthetic
zeolite, loess soil and clayey soil respectively.
It can also be seen in Table 2 that cadmium ions are more quickly
adsorbed on soil when temperature increases since the rate constant
increases by 25% between 20C and 30C.
The relaxation time t
r
is determined according to Roels (1983)
denition. It corresponds to the time of which half of maximum
amount of adsorbate has been adsorbed on the sorbent. Liu (2008)
recalls that if the adsorption process is related to a second-order
kinetic process, it is dependent on the "availability of adsorption
sites on the surface of adsorbent rather than adsorbate concentration
in bulk solution". k
2
implied in Eq. (4) is related to the true rate
constant k
2
true
by Eq. (21):
k
true
2
k
2
:q
e
21
This equation shows that k
2
and q
e
are interrelated and not
independent constants as they are determined from the plot of
t
q
t
f t . It comes:
t
r

1
k
true
2

1
k
2
:q
e
22
The t
r
values obtained from theory (Eq. (22)) and from
experimental data are reported in Table 3.
Calculated and experimental t
r
are close and, as expected from
previous results, theoretical and experimental relaxation times
decrease when temperature increases. Moreover 95% of the
maximum sorption capacity is attained in about 50 min conrming
that the procedure employed for batch experiments is consistent
with a C
e
determination done after 2 h (Section 3.4).
Finally, the rise in temperature leads at the same time to an
increase in the reaction rate and the sorbed amount of cadmium on
sorbent. To qualify the mechanism implied in the sorption (physical
or chemical), the activation energy is calculated using Eq. (23):
E
a
R:
T
a
:T
b
T
a
T
b
: ln
k
true
2;a
k
true
2;b
_ _
23
Inthepresent work(T
a
=20 C=293 K; T
b
=30 C=303 K; k
2, a
true
=
0.226 g mg
1
min
1
; k
2,b
true
=0.364 g mg
1
min
1
), E
a
is equal to
35.1 kJ mol
1
. This value of E
a
, near to 40 kJ mol
1
, is an intermediate
value representing both physisorption and chemisorption (Ho and
Ofomaja, 2005; Nollet et al., 2003).
4.2. Isotherms
4.2.1. Isotherm shape
The experimental adsorption isotherms are presented in Figs. 3, 4
and 5. Before modelling the isotherms, special attention is given to
their shape. Indeed, for Giles and Smith (1974), the curve shape is
largely dependent on the mechanism implied in the adsorption
process and is a tool to dene it. It can be rst noticed that the
isotherms do not exhibit any asymptotic values. This point can easily
be explained by the fact that the studied cadmium concentrations are
low and therefore, saturation of the soil is never reached. In the
present work and according to the terms employed by Giles (Giles
and Smith, 1974), the shape of most of the experimental curves is
the typical L-curves one, corresponding to a classical Langmuir
Table 2
Pseudo-rst order and pseudo-second order kinetic parameters obtained using the linear method.
Experimental Calculated
Pseudo-rst order Pseudo-second order
T
(C)
q
e
(mg g
1
)
q
e
(mg g
1
)
k
1
(min
1
)
r
2
q
e
(mg g
1
)
k
2
(g mg
1
min
1
)
r
2
20 0.058 0.00860 0.0163 0.710 0.060 3.73 0.9997
30 0.078 0.00967 0.0156 0.835 0.078 4.68 0.9999
-6
-5
-4
-3
-2
-1
0
0 50 100 150 200 250 300 350 400
a
20C
30C
l
o
g

(
q
e
-
q
t
)
t (min)
0
1000
2000
3000
4000
5000
6000
7000
0 50 100 150 200 250 300 350 400
b
20C
30C

t
/
q
t

(
m
i
n
/
m
g
/
g
)
t (min)
Fig. 2. Pseudo-rst-order (a) and pseudo-second order (b) plot of Cd(II) ions sorption
on initial soil at different temperatures. Points are experimental data, lines are linear
regressions.
Table 3
Theoretical and experimental relaxation time t
r
.
Temperature
(C)
Theoretical
a
t
r
(min)
Experimental
b
t
r
(min)
20 4.4 2.7
30 2.8 2.2
a
t
r
is calculated with the Eq. (22).
b
t
r
is directly obtained on graphics for q
t

q
e
2
.
137 E. Roth et al. / Geoderma 189190 (2012) 133143
curve. The L shape is observed for soil fractions whatever the
temperature except for soil in the presence of organic matter (S+OM).
For L-curves the loading of the contaminant on the solid decreases as
sites become occupied by solute and leads to the typical curve shape.
Giles and Smith (1974) consider that the activation energy for the
adsorption/desorption of the studied ion independent on the other
components (solvent or other molecules likely to be adsorbed). Thus in
each studied soil fraction adsorption site energies are of quite the same
range order.
In the case of (S+OM) fraction, the curve shape is S-curve (Giles
and Smith, 1974). This type of shape is typical of interactions of
solutesolid interactions whose strength increases as the concen-
tration of solute decreases. In this particular case, many different
adsorption sites exist resulting in non-unique adsorption energies
and/or competition between the studied ion and complexed ligands
(Sposito, 1984).
Knowing the Langmuir t for each soil fraction (sand (SD), coarse
silt (CS) and ne silt and clay (FSC)), we attempted to sum the curves
0.00
0.02
0.04
0.06
0.08
0.10
0.12
0.14
0 2 4 6
q
e

(
m
g
/
g
)
Ce (mg/L)
b) S-MO
10C
20C
30C
0.00
0.02
0.04
0.06
0.08
0.10
0.12
0.14
0 2 4 6
q
e

(
m
g
/
g
)
Ce (mg/L)
c) SD+OM
10C
20C
30C
0.00
0.02
0.04
0.06
0.08
0.10
0.12
0.14
0 2 4 6
q
e

(
m
g
/
g
)
Ce (mg/L)
d) SD-OM
10C
20C
30C
0.00
0.02
0.04
0.06
0.08
0.10
0.12
0.14
0 2 4 6
q
e

(
m
g
/
g
)
Ce (mg/L)
e) CS+OM
10C
20C
30C
0.00
0.02
0.04
0.06
0.08
0.10
0.12
0.14
0 2 4 6
q
e

(
m
g
/
g
)
Ce (mg/L)
f) CS-OM
10C
20C
30C
0.00
0.02
0.04
0.06
0.08
0.10
0.12
0.14
0 2 4 6
q
e

(
m
g
/
g
)
Ce (mg/L)
g) FSC+OM
10C
20C
30C
0.00
0.02
0.04
0.06
0.08
0.10
0.12
0.14
0 2 4 6
q
e

(
m
g
/
g
)
Ce (mg/L)
h) FSC-OM
10C
20C
30C
0.00
0.02
0.04
0.06
0.08
0.10
0.12
0.14
0 2 4 6
q
e

(
m
g
/
g
)
Ce (mg/L)
a) S+OM
10C
20C
30C
Fig. 3. First type of representation for the isotherms of Cd sorption on the soil (S) and its different fractions (SD, CS and FSC) before removal (+OM) and after removal (OM) of
organic matter at different temperatures. Points are experimental data ( 10 C, 20 C, 30 C), lines are ts with Langmuir model.
138 E. Roth et al. / Geoderma 189190 (2012) 133143
representative of a granulometric fraction weighted by their
respective mass percent in the whole soil. The obtained curve is a
theoretical isotherm that models the whole soil and can be compared
to the Langmuir t of the experimental soil isotherm to evaluate the
inuence of sieving. The theoretical curves of soil with and without
OM are given in Fig. 4 (S+OM theo and SOM theo in thick black
and gray lines respectively). The theoretical soil isotherms reveal
that the soil cannot be considered as a simple weighted addition of
its different granulometric fractions (SD+CS+FSC) (Fig. 4).
Competition for cadmium sorption on sites from the different
granulometric fractions and/or interaction between the soil fractions
due to their structure might occur inside the whole soil and would
explain its singular behaviour from this point of view. Noteworthy
is the fact that the sand can t correctly the theoretical behaviour of
the soil in the most cases, even if this fraction is not the major one.
4.2.2. Langmuir model parameters
Although the Langmuir model is not suitable for the whole soil
with organic matter fraction (S+OM) due to its particular shape as
discussed previously, all experimental curves have been tted using
the Langmuir Eq. (7) and these ts are represented on the curves
(Figs. 3, 4 and 5) by the lines (dotted or not). Table 4 reports
parameters obtained and the correlation coefcient r
2
. The Langmuir
model gives rather satisfactory results, except for soil+OM fraction
(Fig. 3a) for the reasons mentioned before.
Except for the whole soil, for which the Langmuir model is not
adapted as mentioned before, the values of K
L
reported in Table 4
are more or less constant for each fraction at a given temperature,
with or without removal of organic matter. They range between
0.042 and 0.185 L mg
1
(Table 4). These K
L
values are of the same
order as those provided by Taqvi et al. (2007) for Cd adsorption on
beach sand (0.17 L mg
1
at 293 K). Some authors report for various
soils values between 0.058 and 0.122 L mg
1
(Adhikari and Singh,
2003) or between 0.04 10
3
and 0.045 L mg
1
(Usman, 2008). A
value of 0.087 L mg
1
was found for clay at 298 K (Baker, 2009). On
the contrary, studying adsorption of cadmium on a loess soil, Wang
et al. (2009) found ten times stronger K
L
values.
The K
L
parameter gives the strength of adsorption. When compared
to other metal, Cd generally has lower K
L
, implying a lower adsorption
strength and adsorption capacities (Baker, 2009; Usman, 2008).
q
max
values range between 0.19 and 0.50 mg g
1
(Table 4). These
values are low compared to other studies (Baker, 2009; Wang et al.
0.00
0.02
0.04
0.06
0.08
0.10
0.12
0.14
0 2 4 6
q
e

(
m
g
/
g
)
Ce (mg/L)
0.00
0.02
0.04
0.06
0.08
0.10
0.12
0.14
0 2 4 6
q
e

(
m
g
/
g
)
Ce (mg/L)
0.00
0.02
0.04
0.06
0.08
0.10
0.12
0.14
0 2 4 6
q
e

(
m
g
/
g
)
Ce (mg/L)
0.00
0.02
0.04
0.06
0.08
0.10
0.12
0 2 4 6
q
e

(
m
g
/
L
)
Ce (mg/L)
0.00
0.02
0.04
0.06
0.08
0.10
0.12
0.14
0 2 4 6
q
e

(
m
g
/
g
)
Ce (mg/L)
0.00
0.02
0.04
0.06
0.08
0.10
0.12
0.14
0.14
0 2 4 6
q
e

(
m
g
/
L
)
Ce (mg/L)
a) 10C
c) 20C
e) 30C
b) 10C
d) 20C
f) 30C
Fig. 4. Second type of representation for the isotherms of Cd sorption before removal (+OM) and after removal (-OM) of organic matter on the soil ( S+OM, SOM) and its
different fractions ( SD+OM, SDOM, CS+OM, CSOM, FSC+OM, FSCOM) at different temperatures. Points are experimental data, line are t curves with
Langmuir model. Thick lines represent theoretical curves of soil fraction containing organic matter ( S+OM theo) or not ( SOM theo) following the mass composition
of soil.
139 E. Roth et al. / Geoderma 189190 (2012) 133143
0.00
0.02
0.04
0.06
0.08
0.10
0.12
0.14
q
e

(
m
g
/
g
)
d) 10C
SD+OM
SD-OM
0.00
0.02
0.04
0.06
0.08
0.10
0.12
0.14
q
e

(
m
g
/
g
)
0.00
0.02
0.04
0.06
0.08
0.10
0.12
0.14
0 2 4 6
q
e

(
m
g
/
g
)
Ce (mg/L)
0.00
0.02
0.04
0.06
0.08
0.10
0.12
0.14
q
e

(
m
g
/
g
)
g) 10C
CS+OM
CS-OM
0.00
0.02
0.04
0.06
0.08
0.10
0.12
0.14
q
e

(
m
g
/
g
)
h) 20C
0.00
0.02
0.04
0.06
0.08
0.10
0.12
0.14
0 2 4 6
q
e

(
m
g
/
g
)
Ce (mg/L)
i) 30C
0.00
0.02
0.04
0.06
0.08
0.10
0.12
0.14
q
e

(
m
g
/
g
)
FSC+OM
FSC-OM
0.00
0.02
0.04
0.06
0.08
0.10
0.12
0.14
q
e

(
m
g
/
g
)
0.00
0.02
0.04
0.06
0.08
0.10
0.12
0.14
0 2 4 6
q
e

(
m
g
/
g
)
Ce (mg/L)
0.00
0.02
0.04
0.06
0.08
0.10
0.12
0.14
q
e

(
m
g
/
g
)
a) 10C
Soil+OM
Soil-OM
0.00
0.02
0.04
0.06
0.08
0.10
0.12
0.14
q
e

(
m
g
/
g
)
b) 20C
0.00
0.02
0.04
0.06
0.08
0.10
0.12
0.14
0 2 4 6
q
e

(
m
g
/
g
)
Ce (mg/L)
c) 30C
e) 20C
f) 30C
j) 10C
k) 20C
l) 30C
Fig. 5. Third type of representation for the isotherms of Cd sorption before removal (+OM) and after removal (OM) of organic matter on the soil ( S+OM, SOM) and its
different fractions ( SD+OM, SDOM, CS+OM, CSOM, FSC+OM, FSCOM) at different temperatures. Points are experimental data, line are t curves with
Langmuir model.
140 E. Roth et al. / Geoderma 189190 (2012) 133143
2009) including that of Taqvi et al. (2007) who report a value of
0.84 mg g
1
for beach sand. Thus, we can conclude that the
adsorption capacity of our soil is quite low.
Fig. 4 and Table 4 show that FSC adsorb the most followed by sand.
Spark (Spark and Swift, 1994; Spark et al., 1995) and Zachara and
Smith (1994) reported that the adsorption capacity is linked to the
surface site density and that the presence of clay minerals enhances
the adsorption capacity. A general tendency of adsorption capacities
can be drawn out. Adsorption capacities decrease as follow: SFC+
OM>CS+OM~SD+OM>soil+OM. The work of Kim and Fergusson
(1992) concerning Cd adsorption capacities of different granulometric
fraction of a New Zealand soil is in agreement with these results.
Nevertheless, these maximum adsorption capacities have to be
considered carefully: in the experimental curves q
e
only reaches about
25% to 50% of the maximum adsorption capacities. Fittings are thus
done only on the beginning of the isotherm. This could explain the
discrepancies with some authors (Baker, 2009; Wang et al. 2009).
4.2.3. Organic matter effect
Organic matter widely inuences the isotherms excepted for sand
(Fig. 5). The concentration of cadmium in soil at equilibrium q
e
is
higher when OM remains (Table 4). For coarse silt samples (Fig. 5g,
h, i) and ne silt and clay (Fig. 5j, k, l), this observation is accorded
with the fact that these materials have numerous adsorption sites
due to the high specic area. On the opposite side, organic matter
has relatively little inuence on the sand fraction (Fig. 5d, e, f) due
to the fact that this material is naturally poor in OM. These points
are conrmed in Table 4: except for the SD fraction (for which q
max
value is independent of OM). q
max
is higher when OM remains in
the sample for a specic fraction at a given temperature. Choi
(2006) have already shown that cadmium adsorption decreases
with organic matter removal. OM favors indeed adsorption and
many works are in accordance with this conclusion. So, for Masset
et al. (2000), humic substances enhance the sorption of positive
ions by making the surface more negative.
4.2.4. Temperature effect
Temperature inuences the role of organic matter or the type of
adsorption sites occupied by OM on the material (except for sand)
(Fig. 5). Indeed, for the soil (Fig. 5a, b, c) and the FSC (Fig. 5j, k, l)
fractions, the gap between the isotherms obtained with and without
OM decreases with temperature. For the CS fraction (Fig. 5g, h, i),
the inverse phenomenon is observed. The implied mechanisms have
then opposite signs froma thermodynamic point of view (exothermic
in the rst case, endothermic in the second). This point is in
accordance with Tables 5, 6 and 7 (Section 4.3).
Moreover Fig. 3 allows to study the temperature effect on
isotherms, which varies according to the nature of the sorbent, the
metal and the solution physical conditions (pH, ionic strength). In
our case, generally a temperature increase improves adsorption
(only not for CSMO where a 10 C isotherm curve is higher than
the two others). This observation implies that the sorption process
is endothermic and this point will be conrmed by enthalpy
calculations (the values must be then positive) in thermodynamics
Section 4.3. (Tables 5, 6 and 7).
The temperature aids the sorption process through activating the
sorption sites (Lee et al., 1998; Raji and Anirhudan, 1977). The FSC
fraction is generally the granulometric part of the soil that has the better
adsorption, with or without organic matter (Fig. 4). The evolution of
q
max
with temperature in Table 4 conrms this phenomenon.
4.3. Thermodynamics studies
The Gibb's free energies G were obtained from Eq. (11) using
three methods to determine K. K is derived either from the Langmuir
constant K
L
(in L mol
1
) (Table 5), from K
d
(Table 6) or from the
dimensionless constant K
adim
as dened by Eq. (18) (Table 7).
Although the two latter free energies are linked by Eq. (20) their
values are given in Tables 6 and 7 because signs can switch from
negative to positive between the two calculations.
Free energies derived from the Langmuir constant (Table 5) and
partitioning coefcients (Table 6) are all negative indicating a
spontaneous sorption process whereas free energies derived from
K
adim
(Table 7) exhibit positive values for the soil at 10 C with or
without organic matter and for the soil without organic matter at
20 C. However, it has been already noticed that the soil fraction is
not tted well by Langmuir model.
G values calculated from Langmuir are one order of magnitude
greater (as they reach around 20 kJ mol
1
(Table 5)) than the values
determined by the two other methods (around 1 kJ mol
1
) (Tables 6
and 7). Nevertheless, all values reveal physical adsorption process in
accordance with the kinetic results.
The enthalpies and entropies obtained from Eq. (12) have the same
sign and are in the same range order whatever the model of K. The
entropies are exactly the same when determined from K
d
(Table 6) or
K
adim
(Table 7). The relation between these two calculations (Eq. (20))
Table 4
Langmuir parameters obtained from isotherm of Cd sorption at 10 C, 20 C and 30 C.
S+MO SMO SD+MO SDMO CS+MO CSMO FSC+MO FSCMO
10 C q
max
(mg g
1
) 0.43 0.29 0.34 0.36 0.38 0.26 0.31 0.24
K
L
(L mg
1
) 0.055 0.042 0.083 0.087 0.059 0.091 0.152 0.105
r 0.97 0.99 0.98 0.99 0.98 0.99 0.99 0.99
20 C q
max
(mg g
1
) 0.19 0.25 0.34 0.33 0.32 0.20 0.44 0.24
K
L
(L mg
1
) 0.185 0.072 0.093 0.126 0.091 0.088 0.100 0.167
r 0.99 0.98 0.99 0.98 0.99 0.99 0.99 0.99
30 C q
max
(mg g
1
) 0.26 0.23 0.32 0.23 0.40 0.21 0.50 0.34
K
L
(L mg
1
) 0.112 0.115 0.132 0.155 0.085 0.088 0.095 0.115
r 0.99 0.99 0.99 0.99 0.99 0.99 0.99 0.98
Table 5
Thermodynamic calculations using Eq. (11) with K
0
=K
L
(L mol
1
).
S+MO SMO SD+MO SDMO CS+MO CSMO FSC FSCMO
10 C G (kJ mol
1
) 20.5 19.9 21.5 21.6 20.7 21.7 22.9 22.0
20 C G (kJ mol
1
) 24.2 21.9 22.5 23.3 22.5 22.4 22.7 23.9
30 C G (kJ mol
1
) 23.8 23.8 24.2 24.6 23.1 23.2 23.3 23.8
H (kJ mol
1
) 24.7 35.9 16.6 20.5 12.7 1.3 16.6 2.9
S (J mol
1
K
1
) 162 197 134 149 119 73 22 89
141 E. Roth et al. / Geoderma 189190 (2012) 133143
nally concerns only enthalpy values. The positive values of the
enthalpies indicate the sorption is endothermic: cadmium ions had
probably to displace more than one water molecule so as to can adsorb
on soil. Endothermic process is also explained by the need for solvated
ions to lose part of their hydration sheath before sorption (Donat et al.,
2005). This process is then enhanced with temperature in main cases.
Two fractions, namely CSMOandFSC+MO, have anopposite behaviour
where the adsorption is not favored with temperature. Entropies are
positive (just not for CSMO) indicating the adsorption is irreversible.
Enthalpies and entropies for the whole soil are of the same order range
as those determined on a loess soil by Wang et al. (2009).
Sorption energies calculated with the DubininRadushkevich model
(Eq. (10)) range between 8.2 and 9.9 kJ mol
1
(cf Table 8). This order
range is between physical and chemical indicating a mix of phenomena
and a probable specic adsorption process where surface complexation
might occur. This conclusion conrms the interpretation of activation
energy value determined by means of the kinetic experiments. For a
single soil fraction, generally sorption energies increase slightly with
temperature and the highest values (about 10 kJ mol
1
) are found at
30 C for S+OM, SD with or without OM and FSC+OM indicating a
stronger adsorption with temperature. The sorption energy values are
roughly constant at a given temperature for all the fractions, maybe
because the DubininRadushkevichmodel is independent of adsorption
site homogeneity and consequently the sites type in the different
fractions.
5. Conclusion
The kinetic adsorption of cadmium on the studied soil sample
(extracted in Eastern France at Aspach le Bas) is a pseudosecond
order process and the concerned sorption is both chemical and physical
under our experiments conditions. Thermodynamic parameters of the
adsoprtion process (G, Hand S) are determined fromexperimental
isothermtting using three methods employed in literature. It turn out
that the Cd adsorption is endothermic and irreversible for most of the
soil fractions. Temperature generally favors the sorption process.
Adsorption isotherm for the soil show an S-like curve proving
adsorption results from complex phenomena including interaction
and competition and this, only when OM remains. When sieved, the
different fraction isotherms exhibit typical Langmuir curves. OM when
present even at a low mass percent (2%) improves the adsorption
capacity.
Generally speaking it comes that the adsorption capacities decrease
as follow: SFC+OM>SC+OM~SD+OM>soil+OM. Cd sorption is
moreover generally enhanced by temperature. (dj exprim dans la
phrase prcdente: Temperature generally favors the sorptionprocess.,
non ? A mon avis, on peut supprimer une des deux phrases du coup).
Experiments reveal that the cadmiumsorptioncapacity is low(less to
0.5 mg g
1
) at low initial concentrations (10 mg L
1
maximum). As a
conclusion, this soil provides low retention strength and low adsorption
capacity for Cd as indicated by the Langmuir model. Leaching can be
expected when diffuse Cd contamination occurs in this soil.
Appendix. Nomenclature
A cross sectional area of the solvent (cm
2
)
a
i
activity of Cd
2+
in phase i
C
e
amount at equilibrium of solute per volume of solvent in
the solution (mg L
1
or mol L
1
)
C
S
amount at equilibrium of solute adsorbed on the soil per
volume of solvent in solution (mg L
1
or mol L
1
)
[Cd
2+
]
0
introduced initial cadmium concentration (mol L
1
)
E free energy of adsorption (J mol
1
)
E
a
activation energy (J mol
1
)
G Gibb's free energy (kJ mol
1
)
H enthalpy (kJ mol
1
)
k
1
pseudo-rst-order rate constant of sorption (min
1
)
k
2
pseudo-second-order rate constant of sorption (g mg
1
min
1
)
k
2
true
true pseudo-second order rate constant (g mg
1
min
1
)
Table 6
Thermodynamic calculations using Eq. (11) with K=K
d
. (K
d
is taken in L mol
1
) and is calculated with Eq. (6) i.e. K
d

q
e
Ce
:M
Cd2
).
S+MO SMO SD+MO SDMO CS+MO CSMO FSC+MO FSCMO
10 C G (kJ mol
1
) 0.7 0.9 2.7 2.9 2.3 7.9 3.8 2.4
20 C G (kJ mol
1
) 3.4 1.7 3.3 3.2 2.9 2.3 4.0 3.9
30 C G (kJ mol
1
) 4.2 2.9 3.6 3.5 3.3 2.0 4.1 3.4
H (kJ mol
1
) 47.6 26.7 10.8 5.4 10.4 9.6 2.8 11.3
S (J mol
1
K
1
) 171 97 47 29 45 25 4 50
Table 7
Thermodynamic calculations using Eq. (11) with K K
a dim

msoil q
e
VCe
(Eq. (18)).
S+MO SDMO SD+MO SDMO CS+MO CSMO FSC+MO FSCMO
10 C G (kJ mol
1
) 1.2 1.0 0.8 1.0 0.4 6.1 1.9 0.5
20 C G (kJ mol
1
) 1.5 0.2 1.3 1.3 1.0 0.3 2.0 1.9
30 C G (kJ mol
1
) 2.1 0.8 1.6 1.5 1.3 0.07 2.1 1.4
H (kJ mol
1
) 49.6 28.7 12.7 7.3 12.4 7.6 0.9 13.3
S (J mol
1
K
1
) 171 97 47 29 45 25 4 50
Table 8
Sorption energy E in kJ mol
1
calculated with Dubinin Radushkevich isotherm.
S+MO SMO SD+MO SDMO CS+MO CSMO FSC+MO FSCMO
10 C 7.5 8.8 8.3 8.7 8.3 8.6 8.7 8.8
20 C 9.4 8.7 9.2 8.2 8.9 9.3 9.2 9.2
30 C 9.8 8.6 9.6 9.5 9.3 8.7 9.9 9.0
142 E. Roth et al. / Geoderma 189190 (2012) 133143
k
ads
adsorption rate constant
k
des
desorption rate constant
K sorption constant (varied unity dened in main text) for
the equilibrium
Cd
2
in solution
k
ads
k
des
Cd
2
adsorbed on soil fraction
K
d
partitioning coefcient (mL g
1
or L mol
1
)
K
DR
DubininRadushkevich constant (mol J

).
K
L
Langmuir constant related to the energy of adsorption
(L mg
1
or L mol
1
)
M
i
molecular weight of an element or molecule i (g mol
1
)
m
soil
mass of soil (g)
N Avogadro's number (mol
1
).
q
t
amount of solute sorbed at time t (mg g
1
)
q
e
amount of solute sorbed at innite time i.e. at equilibrium
(generally in mg g
1
, sometimes in g g
1
as claried in
main text)
q
max
maximum adsorption capacity (mg g
1
or mol g
1
)
R ideal gas constant (i.e. 8.31 J K
1
mol
1
)
r
2
correlation coefcient
s the surface area of the adsorbent i.e. specic surface (cm
2
g
1
)
S entropy (J mol
1
K
1
)
T temperature (C or K).
t
r
relaxation time (min)
V volume of solution (L)

S
activity coefcient of the adsorbed solute at equilibrium

e
activity coefcient of the solute in the solution at equilibrium
solvent volumetric mass (g cm
3
)
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