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Electrochimica Acta xxx (2006) xxx–xxx

Experimental study and mathematical model on remediation


of Cd spiked kaolinite by electrokinetics
Michele Mascia a,∗ , Simonetta Palmas a,1 , Anna Maria Polcaro a,1 ,
Annalisa Vacca a , Aldo Muntoni b
a Dipartimento di Ingegneria Chimica e Materiali, Università Degli Studi di Cagliari, Piazza d’Armi, 09123 Cagliari, Italy
b Dipartimento di Geoingegneria e Tecnologie Ambientali, Università Degli Studi di Cagliari, Piazza d’Armi, 09123 Cagliari, Italy
Received 19 October 2005; received in revised form 28 March 2006; accepted 14 April 2006

Abstract
An experimental study on electrokinetic removal of cadmium from kaolinitic clays is presented in this work, which is aimed to investigate
the effect of surface reactions on the electrokinetic process. Enhanced electrokinetic tests were performed in which the pH of the compartments
was controlled. Cadmium spiked kaolin was adopted in the experimental runs. On the basis of the experimental results, a numerical model was
formulated to simulate the cadmium (Cd) transport under an electric field by combining a one-dimensional diffusion-advection model with a
geochemical model: the combined model describes the contaminant transport driven by chemical and electrical gradients, as well as the effect of
the surface reactions. The geochemical model utilized parameters derived from the literature, and it was validated by experimental data obtained
by sorption and titration experiments. Electrokinetic tests were utilized to validate the results of the proposed model. A good prediction of the
behaviour of the soil/cadmium ions system under electrical field was obtained: the differences between experimental and model predicted profiles
for the species considered were less than 5% in all the examined conditions.
© 2006 Elsevier Ltd. All rights reserved.

Keywords: Electrokinetics; Cadmium transport; Surface reactions; Mathematical model; Geochemical model

1. Introduction the wide variation in the characteristics of soils and pollu-


tants, requires different methods to remediate contaminated
Soil contamination by heavy metals is increasing in various soils.
sites including residential and industrial areas: evidences of soil Among the techniques usually adopted, flushing [3] and phy-
pollution by heavy metal were found in Europe, United States toremediation [4] are highly effective, but their applicability is
and Asia [1]. This pollution may be caused by several hazardous strongly dependent on the hydraulic permeability of the soil, as
materials which were improperly dumped, causing a dispersion well as on the surface metal–soil interactions; thus the in situ
of toxic substances in the environment; moreover, leaching of remediation of clayey soils by means of these techniques may
soils, and solid wastes by rainwater may contaminate surface result too expensive, due to the low values of hydraulic perme-
and ground waters. Waste materials containing heavy metals ability of these soils.
may derive from several industrial processes: cadmium and lead Electroremediation is a potentially important technique for
are contained in the wastes deriving from electrowinning of zinc, fine-grained soils: this technique has been investigated for
as well as in those deriving from dressing of blende [2]. consolidation and stabilisation of clayey materials since the
Remediation of soils polluted by heavy metal ions is late 1930s; more recently the use of electrokinetic remediation
an important issue of the environmental engineering, since techniques was studied for decontamination of clayey soils
polluted by heavy metals, both in situ and ex situ [5–8]. Elec-
troremediation of polluted sites is based on the application of
∗ Corresponding author. Tel.: +39 070 6755059; fax: +39 070 6755067.
a potential difference or a low intensity direct current between
E-mail address: mmascia@dicm.unica.it (M. Mascia). two electrodes inserted in the soil [9]. If the contaminant species
1 ISE member. are charged, they move by ionic migration towards one of the

0013-4686/$ – see front matter © 2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.electacta.2006.04.066

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electrodes, depending on the sign of their electric charge, where Table 1


they can be recovered [10]. Characteristics of the kaolinite utilized in the experimental study
As far as mobilization and removal of heavy metal ions from pH 5.2
clayey soil is considered, the interaction between the pollutants Total carbon 0
and the soil surface mainly depends on the characteristics of Cation exchange capacity,CEC (cmol kg−1 ) 9.9
the active sites at the soil surface. Different active sites lead Major cations (cmol kg−1)
to different retention mechanisms, thus an accurate representa- Na 2.96
Ca 9.8
tion of the soil surface is a relevant issue of the electrokinetic
K 0.96
process. To this aim, a geochemical model, such as those usu- Mg 3.48
ally adopted to describe the thermodynamics of the soil–cations
interactions can be effective. As can be found in the literature,
most of the geochemical models describe the interactions in Erba), were used; the main characteristics are summarized in
terms of equilibrium reactions between the dissolved ions and Table 1.
two different charged sites at the soil surface [11,12]. The ion The experimental apparatus utilized for the electrokinetic
exchange reactions are attribute to fixed charge sites resulting tests consists of four main parts: soil cell, electrode compart-
form isomorphous substitutions on layer lattice, whereas surface ments, electrolyte solution reservoirs, and power supply.
complexation reactions are attribute to oxides (FeOOH, Al2 O3 , The cell (Fig. 1) measures 30 cm length and 6 cm inner
SiO2 , TiO2 ) and other variable charged sites at the edge of par- diameter. The soil in the cell is separated from the electrode
ticles [13]. compartment by two porous stones. The anode is a titanium
During electrokinetics process, the equilibria at the soil sur- sheet covered by RuO2 whereas a carbon plate constituted the
face are modified by the acid front, generated by oxidation of cathode.
water occurring at the anode, which advances towards the cath- The electrode compartments containing 500 cm3 of elec-
ode, as well as by the basic front, due to the reduction of water trolyte solution are equipped with vents for discharging the
at the cathode, which moves towards the anode. oxygen and hydrogen produced by the electrolysis of water
The basic front may cause precipitation of heavy metals as at both electrodes. Two electrolyte reservoirs (500 cm3 ) were
hydroxides, decreasing the effectiveness of the process. More- adopted: the electrolyte solutions were recirculated in both elec-
over, a low electrical conductivity region can be originated where trode compartments by peristaltic pumps.
the migrating hydrogen and hydroxyl ions meet. In order to The polluted soil specimen was prepared by equilibrating
prevent these problems, several enhanced processes have been for 24 h the kaolinite sample with aqueous solutions of cad-
developed, which are based on the control of pH near the cath- mium nitrate (100 mg dm−3 of Cd2+ ) with a mechanic stirrer;
ode by addition of acidic solutions [14,15] or on the use of ion the slurry was then placed in the cell and compacted for 120 h at
exchange membranes to prevent penetration of OH in the soil 2 kg cm−2 before starting with the electrokinetic runs. The tests
[16]. were realized applying a constant voltage equal to 50 V between
Other enhancement techniques were presented [17,18], the electrodes: the cathodic and anodic potential measured dur-
depending on the contaminant and the surface characteristics ing the runs were −1.8 and 1.5 V versus SCE, respectively.
of the soil, and different versions of the process were proposed, The electroosmotic permeability coefficient keo was experi-
such as cation selective membrane, ceramic casting, Lasagna, mentally determined by measuring the flow rate of water through
electrochemical ion exchange, electrokinetic bioremediation, the soil sample under electric field at different values of elec-
electrochemical geooxidation, and electrosorb [19,20]. trolyte pH. Values of keo were calculated by linear regres-
In any case, a mathematical representation of the behaviour sion of experimental data of flow rate versus potential: values
of the soil–cation systems under electrical field is a useful tool of 0.17 × 10−10 (pH 3.5; R2 = 0.99) and 8.8 × 10−10 (pH 7;
to understand the process. In the literature, a great number R2 = 0.98) were obtained, which are in agreement with other
of one-dimensional models have been proposed, in which the values reported in the literature [1,21].
removal of different species was represented [1,5,21]. Math- The tortuosity of the specimen was obtained by break-
ematical modelling of elecrokinetic remediation, through two- through curves of Cl− ions, following the procedure suggested
dimensional approximations, is also the subject of several recent by Alshawabkeh et al. [22]: a value of 0.4 was obtained.
papers [10].
In this work the results of an experimental study on elec-
trokinetic removal cadmium from a sample of kaolinitic clay
are presented; the experimental data were modeled by combin-
ing a one-dimensional electrokinetic transport model with a two
sites geochemical model.

2. Experimental

Electrokinetic experiments at constant potential were carried


out in this work: samples of kaolinite clay (supplied by Carlo Fig. 1. Electrokinetic cell.

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Enhanced electrokinetic tests were performed at constant


potential gradient of 1.5 V cm−1 in which both electrolyte com-
partments initially contained 0.001 M nitric acid. The pH of the
compartments were monitored during the runs, and if neces-
sary, adjusted to value of 3–4 by adding appropriate amounts of
nitric acid or NaOH, in order to avoid precipitation of cadmium
hydroxides near the cathode or dissolution of the clay lattice
near the anode. Samples of catholyte were withdrawn and anal-
ysed for pH and Cd2+ concentration (polarography, Metrohm
instrument).
At the end of each experiment the soil sample was extracted
from the cell and divided into 10 layers. The layers were then
divided in two samples to obtain pH value and metal concentra- Fig. 2. Titration curve of the kaolinitic clay utilized in this work: experimental
(symbols) and model predicted data (curves).
tion in liquid and soil phase. pH and liquid phase concentration of
cadmium were obtained by suspending the samples in deionised interactions between the surface of the examined clay and H+
water (1:10, w/w), and analysing the supernatant after centrifu- ions were experimentally studied through titration experiments.
gation at 5000 rpm for 30 min. The total amount of cadmium was Fig. 2 shows the experimental values (symbols), obtained by
obtained by the same procedure using 1 M nitric acid. The solid titration runs of the soil considered, i.e. the experimental values
phase concentration was obtained by difference (total-liquid). of pH consequent to the addition of acid (positive values) or base
The electrode used as cathode was washed with 0.1 M nitric (negative values).
acid in order to quantify the cadmium, which was deposited for In order to numerically interpret the data in Fig. 2, the equi-
reduction at the electrode. librium reactions between H+ ions and the variable charge sites
All the electroremediation experiments were performed in may be considered, since the fraction of proton adsorbed due to
triplicate: the samples were compacted with the same load at ion exchange become important only at pH below 3 [23]. The
the same times, and connected in parallel to the power sup- protonation/deprotonation reactions of the variable charge sites
ply. A good repeatability of the data was obtained in all the may written as:
experimental conditions investigated, all the values of pH and
concentrations measured differed by less than 5%. SOH + H+ → SOH2 + (2)
Preliminary sorption and titration experiments were per-
SOH → SO− + H+ (3)
formed in order to investigate the interaction between cadmium
ions and soil surface. where SOH represents the generic variable charge site, such as
Titration experiments on the soil samples were carried out by the surface hydroxyl groups deriving from edge sites of layered
suspending 5 g of clay in 50 ml of 0.02 M NaClO4 in a mechanic silicate minerals: according to the literature, they can be silanol
stirrer. Aliquots of HNO3 or NaOH at concentration of 0.1 or groups (SiOH) or aluminol groups (AlOH), but it is likely that
1 M were added to the clay suspensions to give an initial pH the groups involved in adsorption are mostly AlOH [24].
value between 2.7 and 11.7. The clay suspensions were shaken The fraction of CEC due to the fixed charge sites being α, we
in closed polypropylene tubes: pH of the suspension was contin- can write:
uously monitored until change in time of pH was not observed
SOHtot = (1−α)CEC = SOH + SOH2 + + SO− (4)
(typically 24 h).
In the sorption experiments, 5 g of clay were equilibrated where SOH2 + represents the concentration of H+ ions retained
with 50 ml of Cd(NO3 )2 at different initial concentration C0 in a by the soil. By combining Eq. (4), with the equilibrium equations
mechanic stirrer; pH of the slurries was monitored and adjusted related to protonation and deprotonation of the sites (Eqs. (2) and
to pre-fixed values by adding proper amounts of HNO3 or NaOH. (3)), we obtain:
Equilibrium time of 48 h was determined by preliminary kinetic
(1 − α)CECK1HSOH [H+ ]
tests. The samples were then centrifuged at 5000 rpm for 30 min SOH2 + = qH+ = (5)
and decanted to separate liquid and solid phases. The liquid 1 + K2HSOH /[H+ ] + K1HSOH [H+ ]
phase was analysed for the equilibrium ion concentrations Ce . The curve in Fig. 2 was calculated by combining the mole bal-
The solid phase concentrations qi were calculated as: ance in Eq. (1) with Eq. (5), in which the equilibrium constants
were derived from the literature (see Table 2) [23], whereas the
V 0
qi = [C − Cie ]. (1)
m i Table 2
Thermodynamic parameters for the soil–cation interactions
3. Results and discussion log K1HSOH (Eq. (2)) 3.24
log K2HSOH (Eq. (3)) −7.15
In the first phase of this work, the interaction between the sur- log KCdSOH (Eq. (6)) −3.2
log KCd/Ca (Eq. (7)) 1.03
face of the examined clay and the dissolved species were studied
X− /CEC ratio (α) 0.30
by means of titration experiments and adsorption isotherms. The

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parameter α was the only adjustable one. A value of 0.3 allowed reaction of these sites with the heavy metal ion (Eq. (6)):
the best agreement between experimental and calculated data.
KCdSOH
As far as the retention of cadmium ions is considered, Fig. 3 [SOCd+ ] =
shows the sorption isotherms of Cd2+ ions onto kaolinitic clay: 1 + K2HSOH /[H+ ] + K1HSOH [H+ ]
the trend of cadmium concentration in solid phase shows an [SOHtot ]
× [Cd2+ ] (8)
initial linear increase, and it tends to an asymptotic value at [H+ ]
higher values of the Cd2+ concentration in water; moreover, a
strong dependence from the pH of the ions retained by the soil Moreover, since at low Cd2+ concentrations X2 Ca  X2 Cd, we
can be observed. can write:
In order to model the Cd2+ sorption on kaolinite, the addi-
1
tional complexation and exchange equilibria were utilized, with X2 Ca = αCEC (9)
the following assumptions: all the indigenous cations of the 2
kaolinite were considered as equivalent calcium; the complexa- And equilibrium (7) can be adopted to evaluate the amount of
tion reactions of Ca2+ ions were neglected. Cd+2 retained by X− sites:

SOH + Cd2+ → SOCd+ H+ (6) [X2 Cd] = KCd/Ca


[X2 Ca]
[Cd2+ ] (10)
[Ca2+ ]
XCa + Cd2+ → XCd + Ca2+ (7)The total amount of adsorbed cadmium may be expressed as:
 
KCdSOH 1−α 1/2α
qCd2+ = CEC + K [Cd2+ ] (11)
1 + K2HSOH /[H+ ] + K1HSOH [H+ ] [H+ ]
Cd/Ca
[Ca2+ ]

The straight lines depicted in Fig. 3 were calculated by Eq. (11)


The equilibrium relations of reactions (6) and (7) can be
with the parameters reported in Table 2; as can be seen from the
numerically solved along with Eq. (5) and the corresponding
figure, a good agreement with the experimental data is obtained
mole balances (Eq. (1)) to model the sorption isotherms. In
at low cadmium concentration.
this work the model was solved by using the PHREEQC-code,
In the second phase of the work, the transport of cadmium
widely adopted in the literature for geochemical applications
ions under electrical field was experimentally investigated by
[13]. The value of α obtained from titration curves was utilized,
enhanced electrokinetic tests.
whereas the initial values of the equilibrium constants for the
The transport of Cd2+ ions during the electrokinetic experi-
reactions (6) and (7) were adjusted to obtain the best agree-
ments was then modeled by a traditional advection–dispersion
ment between experimental and model predicted data, starting
model. The model takes into account the two transport mecha-
from literature values [13]. Fig. 3 shows the curves calculated,
nisms basically involved in the electrokinetic phenomena, elec-
compared with experimental data, whereas Table 2 reports the
tromigration and electroosmosis; both mechanisms are affected
parameters of the model.
by several parameters such as pH, ionic strength and electric
The geochemical model equations can be simplified at
properties of the soil. Electromigration is the flux of charged
low values of Cd2+ concentration, such as these consid-
species towards the electrodes and it is a function of electrical
ered in the electrokinetic tests of this work: considering that
potential gradient, effective ionic mobility, which can be theo-
SOHtot  SOCd+ , Eq. (4) can be utilized as balance of SOH
retically estimated using the Nernst–Einstein relation.
sites. The solid phase concentration of Cd at the SOH sites may
be derived by combining Eq. (5) and the constant related to the Di∗ zi F
Jiem = u∗i ci ∇(−Φ) = ci ∇(−Φ) (12)
RT
where R and T are the universal gas constant and the absolute
temperature, respectively.
The electroosmotic flow rate depends on the soil surface char-
acteristics, in particular on the concentration of charges, both
fixed and pH-dependent, and it is usually expressed as:
εζn
Jw = −keo ∇Φ = ∇Φ (13)
μ
The electroosmotic permeability coefficient depends on the
zeta potential of the soil, on the viscosity of the fluid as well
as on electrical permittivity and porosity of the soil. The total
Fig. 3. Sorption isotherms of Cd2+ ions at different pH: symbols refer to exper- mass flux can be estimated by considering the mass transport,
imental data, curves refer to model predicted data and straight lines refer to data due to diffusion, electromigration and electroosmotic advection;
calculated by Eq. (11). Empty symbols, pH 4.5; full symbols, pH 6.5. for one-dimensional implementation the mass balance of the i-th

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species can be written as: cathodic compartment as a function of the treatment time. As can
be observed, a good agreement between experimental and calcu-
∂ci ∂ 2 ci ∂ci ∂Φ
= Di∗ 2 + (u∗i + keo ) + Ri (14) lated data is obtained, confirming the validity of the hypotheses.
∂t ∂x ∂x ∂x In particular, the good prediction of the trend of cadmium con-
Under the experimental conditions adopted in this work, the centration can be observed, which presents a maximum deriving
term Ri accounts for the sorption processes; since the sorption from the competition between the flux of pollutant towards the
rate is large, instantaneous equilibrium can be assumed between cathode and its removal by reduction at the cathode surface.
species in liquid phase and sorbed onto the clay surface [22], The model was also utilized to predict the space profiles along
and Ri can be expressed as: the electrokinetic column.
Experimental and model predicted data of H+ and Cd2+
ρk ∂qi ρk ∂ci ∂qi
Ri = − =− (15) concentration profiles are presented in Fig. 5(a and b). Data in
ε ∂t ε ∂t ∂ci Fig. 5(a) were obtained after 240 h of treatment, whereas data
by combining Eqs. (14) and (15) we obtain: in Fig. 5(b) were obtained after 350 h. The advance of acid front
  can be seen from the results: the simple enhancement strategy
∂ci ρk ∂qi ∂ 2 ci ∂ci ∂Φ
1+ = Di∗ 2 + (u∗i + keo ) (16) utilized, control of the cathodic pH, was able to maintain the pH
∂t ε ∂ci ∂x ∂x ∂x values in the range from four to five, along the specimen, avoid-
Eqs. (5), (10) and (11), respectively were utilized to obtain the ing the detrimental effect of the pH jump evidenced by several
term ∂qi /∂ci for H+ , Ca2+ , and Cd2+ ions in Eq. (16), values of authors during unenhanced tests [1]. As far as the cadmium
Di∗ of 20x10−10 [m2 s−1 ] (H+ ), and 7x10−10 [m2 s−1 ] (other concentration is considered, the removal of the pollutant can be
cations) were used. observed: the control of cathodic pH avoided the precipitation
Eq. (16) was integrated with a finite elements software; the
boundary conditions were written considering the mass balances
at the cathodic and anodic compartments: taking into account the
electrolysis of water at the electrodes and the experimentally
observed cathodic reduction of cadmium, assumed under mass
transfer control, the mass balances for Cd2+ , H+ and other cations
are the following.

⎨ ∂cH = I − S (u∗ + k )c
eo H
x=0 ∂t FVa Va H (17a)

ci = 0

⎪ ∂cH S ∗ (1 − η)I

⎪ = (uHi + keo )cH −

⎪ ∂t Vc FVc

⎨ ∂c
i S ∗
x=L = (u + keo )ci (17b)

⎪ ∂t Vc i



⎪ ∂c S ∗
⎩ Cd = (u + keo )cCd − a · Km CCd
∂t Vc Cd
Fig. 4 shows the comparison of experimental and model pre-
dicted data for Cd2+ and other cations (as equivalent Ca2+ ) in the

Fig. 4. Trend in time of Cd2+ ions (full symbols) and other cations as equivalent Fig. 5. Comparison between experimental (symbols) and model predicted
calcium (empty symbols), in the cathodic compartment during electrokinetic test (lines) profiles of pH and Cd2+ ions concentration after 240 h (5a) and 340 h
at ψ = 1.5 V cm−1 : experimental (symbols) and model predicted data (lines). (5b) of electrokinetic treatment at ψ = 1.5 V cm−1 .

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of cadmium hydroxide near the cathodic compartment. As KiSOH equilibrium constant for i-th compound and SOH site
can be seen from the figures, the pH and Cd2+ concentration Km mass transfer coefficient of Cd2+ ions [m s−1 ]
profiles calculated by the model are reasonably agreed with qi concentration of the i-th chemical species in solid phase
those of experiments. The use of a physically based equation to [mol g−1 ]
describe the effect of pH on clay–ion interactions [25] avoided Ri sorption rate term in the transport equation
the discrepancy obtained by other authors, which was attributed [mol s−1 dm−3 ]
to a wrong estimation of the Ri term [1] utilized in its model. SOH pH-dependent sites
u∗ = Di∗ zi F/RT effective ionic mobility of the i-th chemical
4. Conclusions species [m2 V−1 s−1 ]
Va anolyte volume [m3 ]
Experimental study and numerical modeling were utilized to Vc catholyte volume [m3 ]
investigate on the Cd transport in low-permeability kaolinitic X − exchange site
clays under electrical field. zi charge of the i-th chemical species
The results confirm the effectiveness of electrokinetic tech-
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[m2 V−1 s−1 ] 1927.
KCd/Ca Cd/Ca ion exchange equilibrium constant

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