Escolar Documentos
Profissional Documentos
Cultura Documentos
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
0013-4686/$ – see front matter © 2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.electacta.2006.04.066
Please cite this article in press as: M. Mascia et al., Electrochim. Acta (2006), doi:10.1016/j.electacta.2006.04.066
+Model
EA-12008; No. of Pages 6 ARTICLE IN PRESS
2 M. Mascia et al. / Electrochimica Acta xxx (2006) xxx–xxx
2. Experimental
Please cite this article in press as: M. Mascia et al., Electrochim. Acta (2006), doi:10.1016/j.electacta.2006.04.066
+Model
EA-12008; No. of Pages 6 ARTICLE IN PRESS
M. Mascia et al. / Electrochimica Acta xxx (2006) xxx–xxx 3
Please cite this article in press as: M. Mascia et al., Electrochim. Acta (2006), doi:10.1016/j.electacta.2006.04.066
+Model
EA-12008; No. of Pages 6 ARTICLE IN PRESS
4 M. Mascia et al. / Electrochimica Acta xxx (2006) xxx–xxx
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:
Please cite this article in press as: M. Mascia et al., Electrochim. Acta (2006), doi:10.1016/j.electacta.2006.04.066
+Model
EA-12008; No. of Pages 6 ARTICLE IN PRESS
M. Mascia et al. / Electrochimica Acta xxx (2006) xxx–xxx 5
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 .
Please cite this article in press as: M. Mascia et al., Electrochim. Acta (2006), doi:10.1016/j.electacta.2006.04.066
+Model
EA-12008; No. of Pages 6 ARTICLE IN PRESS
6 M. Mascia et al. / Electrochimica Acta xxx (2006) xxx–xxx
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-
niques to remove Cd2+ ions from kaolinitic clayey soils: in References
particular, the simple enhancement adopted, acidic conditioning
of catholyte, allowed to avoid the major defects of the conven- [1] S.O. Kim, J.J. Kim, S.T. Yun, K.W. Kim, Water Air Soil Pollut. 150 (2003)
tional electrokinetic processes highlighted by several authors, 135.
[2] A.M. Polcaro, M. Mascia, S. Palmas, A. Vacca, G. Tola, Environ. Eng. Sci.
such as a sharp pH jump and possible precipitation of Cd hydrox- 20 (6) (2003) 607.
ides in the region near the cathode, as a result of migration of [3] J. Virkutyte, M. Sillanpaa, P. Latostenmaa, Sci. Total Environ. 289 (1–3)
hydroxyl ions generated by electrolysis of water at the cathode (2002) 97.
[22,25]. [4] B. Kos, H. Grcman, D. Lestan, Plant Soil Environ. 49 (12) (2003) 548.
The utilization of a geochemical model to describe the inter- [5] Y.B. Acar, A.N. Alshawabkeh, Environ. Sci. Technol. 27 (1993) 2638.
[6] S. Pamukcu, J.K. Wittle, Environ. Prog. 11 (3) (1992) 241.
action between soil surface and dissolved ions allowed to model [7] G.R. Eykholt, D.E. Daniel, J. Geotech. Eng. 8 (1994) 431.
the process starting from a low number of experimental data, [8] R.E. Hicks, S. Tondorf, Environ. Sci. Technol. 28 (12) (1994) 2203.
which can be easily obtained by sorption experiments, and a [9] K.R. Reddy, S. Chinthamreddy, Waste Manag. 19 (4) (1999) 269.
low number of adjustable parameters. [10] C. Vereda-Alonso, J.M. Rodriguez-Maroto, R.A. Garcia-Delgado, U.
Gomez-Lahoz, F. Garcia-Herruzo, Chemosphere 54 (7) (2004) 895.
[11] B. Baeyens, M.H. Bradbury, J. Contam. Hydrol. 27 (3–4) (1997) 199.
Acknowledgement [12] M.H. Bradbury, B. Baeyens, J. Contam. Hydrol. 27 (3–4) (1997) 223.
[13] D.A. Dzombak, F.M.M. Morel, Surface Complexation
This research was supported by the Italian Ministry of Uni- Modelling—Hydrous Ferric Oxide, John Wiley, New York, 1990.
versity and Research, through the project PON Siti, in the frame- [14] S.K. Puppala, A.N. Alshawabkeh, Y.B. Acar, R.J. Gale, M. Bricka, J. Haz-
work of the program PON 2000–2006. ard. Mater. 55 (1–3) (1997) 203.
[15] D.M. Zhou, C.F. Deng, L. Cang, Chemosphere 56 (3) (2004) 265.
[16] H.K. Hansen, L.M. Ottosen, S. Laursen, A. Villumsen, Sep. Sci. Technol.
Appendix A. Nomenclature 32 (15) (1997) 2425.
[17] K.R. Reddy, S. Chinthamreddy, Adv. Environ. Res. 7 (2) (2003) 353.
[18] D.M. Zhou, R. Zorn, C. Kurt, J. Environ. Sci. 15 (3) (2003) 396.
ci [19] M.A. Oyanader, P.E. Arce, A. Dzurik, I. E. C. Res. 44 (16) (2005) 6200.
concentration of the i-th chemical species in aqueous
[20] S.V. Ho, C. Athmer, P.W. Sheridan, B.M. Hughes, R. Orth, D. McKenzie,
phase [mol dm−3 ] P.H. Brodsky, A. Shapiro, R. Thornton, J. Salvo, D. Schultz, R. Landis, R.
CEC cation exchange capacity [mol kg−1 ] Griffith, S. Shoemaker, Environ. Sci. Technol. 33 (1999) 1086.
Di ∗ effective diffusion coefficient of the i-th chemical [21] D.S. Schultz, J. Hazard. Mater. 55 (1997) 81.
species [m2 s−1 ] [22] A.N. Alshawabkeh, Y.B. Acar, J. Geotech. Eng. 122 (3) (1996) 186.
F faraday constant 96,500 [C eq−1 ] [23] F.J. Huertas, L. Chou, R. Wollast, Geochimi. Cosmochimi. Acta 62 (3)
(1998) 417.
Jiem electromigrative flux [mol m−2 s−1 ] [24] M.J. Angove, B.B. Johnson, J.D. Wells, J. Colloid Interface Sci. 204 (1998)
Jw electroosmotic flux [m s−1 ] 93.
keo = εζξ/μ Electroosmotic permeability coefficient [25] S.O. Kim, J.J. Kim, K.W. Kim, S.T. Yun, Sep. Sci. Technol. 39 (8) (2004)
[m2 V−1 s−1 ] 1927.
KCd/Ca Cd/Ca ion exchange equilibrium constant
Please cite this article in press as: M. Mascia et al., Electrochim. Acta (2006), doi:10.1016/j.electacta.2006.04.066