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Chemical Engineering Journal 225 (2013) 535–546

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Chemical Engineering Journal


journal homepage: www.elsevier.com/locate/cej

Binary adsorption of heavy metals from aqueous solution onto natural


clays
E. Padilla-Ortega, R. Leyva-Ramos ⇑, J.V. Flores-Cano
Centro de Investigacion y Estudios de Posgrado, Facultad de Ciencias Quimicas, UASLP, Av. Dr. Manuel Nava No. 6, San Luis Potosi SLP 78210, Mexico

h i g h l i g h t s g r a p h i c a l a b s t r a c t

 Binary adsorption of metals on clays


was interpreted by multicomponent
isotherms.
 Bentonite capacity for adsorbing
Cd(II) was similar to that for
adsorbing Ni(II).
 Zn(II) presented strong antagonism to
the adsorption of Cd(II) on sepiolite.
 Adsorption of Zn(II) on sepiolite was
slightly affected by presence of Cd(II).
 Vermiculite adsorption capacity
toward Pb(II) was higher than that
toward Cu(II).

a r t i c l e i n f o a b s t r a c t

Article history: The binary adsorption of Cd(II)–Ni(II) on bentonite, Zn(II)–Cd(II) on sepiolite and Pb(II)–Cu(II) on vermic-
Received 2 February 2013 ulite was investigated in this work. The experimental binary adsorption data were interpreted using the
Received in revised form 2 April 2013 following multicomponent adsorption isotherms: non-modified, extended and modified Langmuir; non-
Accepted 3 April 2013
modified and modified Redlich–Peterson; extended Freundlich; and Sheindorf–Rebuhn–Sheintuch. The
Available online 11 April 2013
modified Redlich–Peterson multicomponent isotherm best fitted the adsorption data of Cd(II)–Ni(II) on
bentonite and Pb(II)–Cu(II) on vermiculite, while the modified Langmuir multicomponent isotherm best
Keywords:
fitted the data of Zn(II)–Cd(II) on sepiolite. The competitive adsorption of Cd(II)–Ni(II) on bentonite
Adsorption
Binary
revealed that both metals presented very similar antagonism toward the adsorption of the other metal.
Clays The single metal adsorption on sepiolite showed that the Cd(II) adsorption capacity of sepiolite was 1.3
Competitive times greater than that of Zn(II); however, in the binary adsorption, the Zn(II) presented a strong antag-
Heavy metal onism to the adsorption of Cd(II), but Cd(II) did not affected the adsorption of Zn(II). The single adsorption
Multicomponent isotherms isotherms of Cu(II) and Pb(II) on vermiculite revealed that the affinity of the vermiculite towards Pb(II)
was slightly higher than that of the Cu(II). However, in the competitive adsorption, the affinity of Pb(II)
towards the vermiculite was much higher than that of the Cu(II).
Ó 2013 Elsevier B.V. All rights reserved.

1. Introduction teries. Wastewater from these industries normally contains Pb(II),


Cu(II), Cd(II), Ni(II) and Zn(II), and the presence of these metals in
The heavy metals have very diverse applications and are com- wastewater is of great concern because some of these metals are
monly found in wastewater from the mining and metal finishing very toxic to the human health and the environment [1].
industry, refining and smelting of metals, and manufacture of bat- The adsorption is a separation process widely used for the re-
moval of heavy metals from wastewater due to its versatility and
easy operation. Among the most commonly used adsorbents are
⇑ Corresponding author. Tel.: +52 444 826 2440; fax: +52 444 826 2372. activated carbon, biosorbents, natural zeolites, and natural clays.
E-mail address: rlr@uaslp.mx (R. Leyva-Ramos). The individual adsorption of heavy metals from water solution

1385-8947/$ - see front matter Ó 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.cej.2013.04.011
536 E. Padilla-Ortega et al. / Chemical Engineering Journal 225 (2013) 535–546

Nomenclature

ai Redlich–Peterson isotherm constant for metal i, L/g Nm number of experiment data.


aij competition coefficient of component i by component j ni Freundlich isotherm constant for metal i.
bi Redlich–Peterson isotherm constant for metal i, (L/ qi uptake of metal i adsorbed per mass of clay, meq/g.
meq)bi qi,F1 uptake of metal i adsorbed per mass of clay at first equi-
Ci concentration of metal i in aqueous solution at equilib- librium in the displacement experiment, meq/g.
rium, meq/L qi,F2 uptake of metal i adsorbed per mass of clay at second
Ci,exp experimental concentration of metal i, meq/L equilibrium in the displacement experiment, meq/g.
Ci,F final concentration of metal i in aqueous solution at qi,j,cal uptake of metal of i corresponding to data number j cal-
equilibrium, meq/L culated with the multicomponent adsorption isotherm,
Ci,F1 final concentration of metal i at the first equilibrium of meq/g
the displacement experiments, meq/L qi,j,exp experimental uptake of metal i corresponding to data
Ci,F2 final concentration of metal i at the second equilibrium number j, meq/g
of the displacement experiments, meq/L qm,i Langmuir isotherm constant for metal i, meq/g
Ci,0 initial concentration of metal i in aqueous solution, qmax constant of extended Langmuir multicomponent iso-
meq/L therm, meq/g.
%D average percentage deviation. V0 initial volume of solution, L
Ki Langmuir isotherm constant of metal i, L/meq xi, yi, zi extended Freundlich multicomponent isotherm con-
KE,i extended Langmuir multicomponent isotherm constant stants for component i.
for component i, L/meq
ki Freundlich isotherm constant for metal i, meq(11/n) Greek letters
L(1/n)/g. bi Redlich–Peterson isotherm constant for metal i.
m mass of clay, g gi Interaction factor for metal i.
N number of metals in solution.

on these adsorbents has been extensively studied; however, indus- happened in the other way around. The single and multicompo-
trial wastewater normally contains two or more metals. The pres- nent adsorption of Cd(II), Cu(II), Pb(II), and Zn(II) from aqueous
ence of another metal in solution affects the adsorption capacity of solution onto kaolinite was analyzed by Srivastava et al. [24] and
the single metal. Therefore, it is very important to study the mul- their results showed that the adsorption capacity increased in
ticomponent adsorption of heavy metals and to find out about the following orders: Cu(II) < Zn(II) < Pb(II) < Cd(II) in the single
the selectivity or affinity of each metal for a given adsorbent and metal systems, and Pb(II) < Cu(II) < Zn(II) < Cd(II) in the multicom-
to know if there is competition between the metal cations for the ponent system. Srivastava et al. [24] did not interpret the adsorp-
same adsorption sites. tion equilibrium data with the typical multicomponent adsorption
In the last 10 years, the multicomponent or competitive adsorp- isotherm models.
tion of metals from water solution has been investigated on vari- In general, the experimental binary adsorption equilibrium data
ous adsorbents. The following competitive adsorption systems of metals on natural clays has been obtained for few metals and
have been studied: Pb(II)–Zn(II) on sulfured orange peel [2]; clays systems, but no work has been reported regarding the mod-
Pb(II)–Cu(II) on Sphaerotilus natans [3], on cow bone char [4], on eling of the adsorption equilibrium data using the multicomponent
granular activated carbon [5] and on Rhizopus arrhizus [6]; Pb(II)– adsorption isotherms.
Cd(II) on clinoptilolite [7], on green macroalga Caulerpa lentillifera The main objectives of this work were to study the binary
[8] and on calcium alginate [9]; and Pb(II)–Cd(II)–Zn(II) on Eichhor- adsorption of Cd(II)–Ni(II) on bentonite, Zn(II)–Cd(II) on sepiolite
nia crassipes [10]. In these works, it was shown that the Pb(II) pre- and Pb(II)–Cu(II) on vermiculite, and to model the adsorption equi-
sented higher affinity towards these adsorbents than the other librium data with the binary adsorption isotherms. Furthermore, it
metals since the presence of Cu(II), Cd(II) or Zn(II) in water solution was investigated the effect of the presence of Cd(II) on the adsorp-
affected very slightly the mass of Pb(II) adsorbed on these tion of Ni(II) on bentonite, Zn(II) on the adsorption of Cd(II) on
adsorbents. sepiolite, and Pb(II) on the adsorption of Cu(II) on vermiculite
The single adsorption of heavy metals on natural clays has been and vice versa.
extensively investigated since natural clays have a high cation ex-
change capacity, mechanical and chemical stability and low-cost, 2. Single and multicomponent adsorption equilibrium
and are very abundant [11–19]. The main disadvantages are that isotherms
the natural clays have very low or no capacity for adsorbing anio-
nic species [20], and the removal efficiency of clays for heavy met- The adsorption equilibrium data for a single component can be
als is normally less than that of natural zeolites. The adsorption normally interpreted by the Langmuir, Freundlich and Redlich–
mechanisms of metal cations on natural clays have been argued Peterson isotherms, which are represented mathematically as
and reviewed in various works [21]. follows:
The binary adsorption of metals on bentonite [22], beidellite 1=ni
qi ¼ ki C i ð1Þ
[23], kaolinite [24], montmorillonite [25] and smectite [26] have
been examined very superficially in recent works, but the binary
qm;i K i C i
adsorption of metals on sepiolite and vermiculite has not been qi ¼ ð2Þ
1 þ K iCi
investigated. Zhi-rong and Shao-qi [22] evaluated the adsorption
of Cu(II)–Ni(II) on a bentonite from Gaomiaozi (Mongolia, China)
ai C i
and found that the capacity of the bentonite for adsorbing Cu(II) qi ¼ b
ð3Þ
decreased slightly by the presence of the Ni(II) and the same trend 1 þ bi C i i
E. Padilla-Ortega et al. / Chemical Engineering Journal 225 (2013) 535–546 537

Table 1 ðn1 Þþx1 ðn1 Þþx2


Chemical composition of bentonite (B), sepiolite (S) and vermiculite (V). k1 C 1 1 k2 C 2 2
q1 ¼ q2 ¼ ð9Þ
C x11 þ y1 C z21 C x22 þ y2 C z12
Clay Weight percentage (%)
SiO2 Al2O3 Na2O CaO K2O MgO Fe2O3 (g) Sheindorf–Rebuhn–Sheintuch isotherm (SRSI) [31]:
 
B 59.4 15.7 0.84 3.04 2.70 3.52 4.48 ! n1 1
S 53.3 6.92 5.55 3.99 1.72 17.3 2.09
X
N i

V 36.5 9.9 0.16 1.53 4.28 23.0 13.5


qi ¼ ki C i aij C j ð10Þ
j¼1

where aii = ajj = 1.


Table 2 The competition and interaction factors of the multicomponent
Cation exchange capacity (CEC) and textural properties of bentonite (B), sepiolite (S)
isotherms were estimated using the Micromath Scientist software,
and vermiculite (V).
which is based upon the optimization algorithm of Levenberg–
Clay CEC Surface area Pore volume Average pore Marquardt. The minimizing function was the following:
(meq/g) (m2/g) (cm3/g) diameter (nm)
B 1.06 41.7 0.063 5.9 X
2 X
Nm

S 0.44 194 0.30 6.2 Least squares ¼ ðqi;j;exp  ¼ qi;j;cal Þ2 ð11Þ


V 0.42 15.2 0.049 13.0 i¼1 j¼1

The average percentage deviation was estimated with the fol-


lowing equation:
The multicomponent adsorption isotherms are normally ob- "  #
Nm  
tained by extending the above single component adsorption iso- 1Xi¼2
1 X qi;j;exp  qi;j;cal 
%D ¼    100% ð12Þ
therms and can be classified accordingly to the single adsorption 2 i¼1 N m j¼1  qi;j;exp 
isotherm that originated the multicomponent isotherm. The fol-
lowing multicomponent adsorption isotherms were used in this
work:
3. Materials and experimental methods

(a) Non-modified Langmuir multicomponent isotherm (NLMI)


3.1. Natural clays
[9]:
The calcium bentonite employed in this work was obtained
qm;i K i C i from a location in Guadalcazar, San Luis Potosi, Mexico. The sepio-
qi ¼ P ð4Þ
1 þ Nj¼1 K j C j lite sample was supplied by the company SEPIOLSA, and it was col-
lected from a location near Madrid, Spain. The vermiculite sample
(b) Extended Langmuir multicomponent isotherm (ELMI) [27]: was provided by the company Virginia Vermiculite, situated in Vir-
qmax K E;i C i ginia, USA. The particle average diameter of the three clays was
qi ¼ P ð5Þ
1 þ Nj¼1 K E;j C j 0.375 mm.

(c) Modified Langmuir multicomponent isotherm (MLMI) with


3.2. Characterization of clays
an interaction factor gi [28–30]:
qm;i K i ðC i =gi Þ The chemical composition of the clays was determined follow-
qi ¼ PN ð6Þ
1þ j¼1 K j ðC j =gj Þ ing the method proposed by Rettig et al. [32] and using an atomic
absorption spectrometer, PerkinElmer, model AAnalyst. The cation
(d) Non-modified Redlich–Peterson multicomponent isotherm exchange capacity (CEC) was quantified with the method proposed
(NRPMI) [29,30]: by Ming and Dixon [33]. The chemical composition and CEC of the
ai C i clays are shown in Tables 1 and 2, respectively. The textural prop-
qi ¼ PN bj
ð7Þ
1þ erties (surface area, mean pore and pore volume) of the clays were
j¼1 bj C j
determined using the N2-BET method. The analysis was performed
(e) Modified Redlich–Peterson multicomponent isotherm in a surface area and porosimetry analyzer, Micromeritics, model
(MRPMI) with an interaction factor gi [29]: ASAP 2010, and the results are given in Table 2.
ai ðC i =gi Þ The crystalline species present in the natural clays were identi-
qi ¼ PN bj
ð8Þ fied by X-ray diffraction (XRD) analysis, and the XRD patterns were
1þ j¼1 bj ðC j =gj Þ
obtained with a diffractometer, Rigaku, DMAX 2000. The examina-
(f) Extended Freundlich multicomponent isotherm (EFMI) tion of the XRD patterns showed that the main crystalline species
[9,29]: present in the clay samples were Montmorillonite (main compo-

Table 3
Parameter values of the Langmuir, Freundlich and Redlich–Peterson isotherms for the single metal adsorption on bentonite (B), sepiolite (S) and vermiculite (V) at T = 25 °C.

Clay Metal pH Langmuir Freundlich Redlich–Peterson


qm (meq/g) K (L/meq) %D k (meq11/n L1/n/g) n %D a (L/meq) b (L/g)b b %D
B Ni 7 0.581 0.875 5.47 0.246 2.49 5.45 0.753 1.84 0.829 2.88
Cd 0.692 2.41 7.31 0.413 3.15 10.1 1.81 3.05 0.906 6.45
S Cd 7 0.403 5.71 12.3 0.279 3.44 18.6 4.86 14.8 0.836 5.00
Zn 0.265 6.65 2.21 0.247 3.11 1.44 570 2308 0.680 1.55
V Pb 4 0.579 0.984 11.2 0.255 3.18 7.71 1.52 4.48 0.797 7.84
Cu 0.513 0.686 6.32 0.205 2.45 3.05 0.768 2.66 0.737 2.99
538 E. Padilla-Ortega et al. / Chemical Engineering Journal 225 (2013) 535–546

nent of bentonite), sepiolite and vermiculite. Besides, the sepiolite 0.7


contained dolomite as an impurity.

Metal uptake on bentonite, meq/g


0.6
3.3. Determination of heavy metals in aqueous solutions
0.5

The concentrations of Cd(II), Cu(II), Ni(II), Pb(II) and Zn(II) in 0.4


water solutions were quantified by atomic absorption spectros-
copy. The absorbance of a sample was measured using a double- 0.3
beam atomic absorption spectrophotometer, Varian, model Spec-
trAA-20, and the concentration of a metal was calculated from a 0.2
calibration curve prepared with standard solutions of the heavy Cd(II)
0.1 Ni(II)
metal. All the heavy metal solutions were prepared from Cd(NO3)2
4H2O, Cu(NO3)22.5H2O, Ni(NO3)22.6H2O, Pb(NO3)2 and Zn(NO3)2 0.0
0 1 2 3 4 5 6
6H2O, respectively, and the solution pH was adjusted by mixing
proper volumes of 0.01 M HNO3 and NaOH solutions. Concentration of the metal at equilibrium, meq/L
(a)
3.4. Method for obtaining the adsorption equilibrium data
0.4
The experimental adsorption equilibrium data for the single and

Metal uptake on sepiolite, meq/g


binary metal systems were obtained in a batch adsorption mode.
The batch adsorber was a 50 mL conical vial. A volume of 40 mL 0.3
of a single or binary metal solution and 0.2 g of clay were poured
into the adsorber. The metal solution had a predetermined initial
concentration of one metal or two metals, and the solution was pre- 0.2
pared at a predetermined pH by mixing proper volumes of 0.01 M
HNO3 and NaOH solutions. The adsorber was placed in a thermo-
static bath, and the metal solution and clay were left in contact until 0.1
equilibrium was attained. The solution pH was measured frequently
Cd(II)
with a potentiometer, Termo Electron Corporation, model Orion 420
Zn(II)
A+, and was adjusted periodically by adding few drops of 0.01 M 0.0
HNO3 and NaOH solutions. The total volume of 0.01 M NaOH and 0.0 0.2 0.4 0.6 0.8 1.0
HNO3 solutions added to the adsorber was less than 0.3 mL. Conse- Concentration of the metal at equilibrium, meq/L
quently, the initial volume of the solution was assumed to remain (b)
constant during the adsorption. Preliminary runs showed that
7 days was enough to reach equilibrium. After 7 days a sample of 0.6
the solution was taken out, and the final concentration of each metal
Metal uptake on vermiculite, meq/g

was determined by the method previously described. The mass of 0.5


each metal adsorbed was estimated by performing a mass balance
of metal i that can be mathematically expressed as: 0.4

V 0 ðC i;0  C i;F Þ
qi ¼ ð13Þ 0.3
m

0.2
3.5. Procedure for performing the displacement experiments
0.1
The displacement experiment consisted of two stages. First, an Pb(II)
adsorption equilibrium experiment of metal i was carried out as Cu(II)
0.0
described above and the amount of metal i adsorbed was calcu- 0 2 4 6 8 10
lated using the Eq. (13). This stage was called as the first equilib- Concentration of the metal at equilibrium, meq/L
rium and the equilibrium conditions of metal i were denoted as (c)
qi,F1 and Ci,F1.
The procedure for the second stage was as follows. After Fig. 1. Single adsorption isotherms of (a) Cd(II) and Ni(II) on bentonite at pH = 7, (b)
approaching the first equilibrium, a sample of the adsorber solu- Cd(II) and Zn(II) on sepiolite at pH = 7 and (c) Cu(II) and Pb(II) on vermiculite at
pH = 4. The lines represent the Redlich–Peterson isotherm. T = 25 °C.
tion was taken out and an aliquot of a standard solution with a
known concentration of the metal j and the same pH as the adsor-
ber solution was poured into the adsorber solution. The volume of using Eq. (13) and the amount of metal i that was not displaced
the sample (1 mL) was the same as that of the aliquot to keep the or remained adsorbed was estimated by performing a mass bal-
volume of the adsorber solution constant (V = 40 mL). The initial ance of metal i:
concentration of the metal j in the adsorber solution was calculated
from the initial concentration of the standard solution of metal 2
V
and the dilution factor (1/40). The pH of the adsorber solution qi;F2 ¼ qi;F1 þ ðC i;F1  C i;F2 Þ ð14Þ
was kept constant as described earlier. The clay and binary metal m
solution were allowed to reach equilibrium, which was called sec- The first term in the right side of Eq. (14) represents the amount
ond equilibrium. Afterwards, the solution was sampled and the of metal i adsorbed in the first equilibrium, and the second term
concentrations of both metals at equilibrium were quantified as corresponds to the amount of metal i displaced or desorbed in
described before. The amount of metal j adsorbed was calculated the second equilibrium.
E. Padilla-Ortega et al. / Chemical Engineering Journal 225 (2013) 535–546 539

Table 4
Metal selectivity and physicochemical property sequences.

Property Metal sequence


Bentonite Cd(II) > Ni(II) Sepiolite Cd(II) > Zn(II) Vermiculite Pb(II) > Cu(II)
Electronegativitya Ni(1.91) > Cd(1.69) Cd(1.69) > Zn(1.65) Pb(2.33) > Cu(1.9)
Ionic radius, Å Cd(0.97) > Ni(0.69) Cd(0.97) > Zn(0.74) Pb(1.19) > Cu(0.73)
Softnessb Cd(3.04) > Ni(2.82) Cd(3.04) > Zn(2.34) Pb(3.58) > Cu(2.89)
Hydrolysis constantc Ni(9.9) > Cd(10.1) Zn(9.0) > Cd(10.1) Pb(7.6)  Cu(7.5)
Ionization potential Cd(8.99) > Ni(7.64) Zn(9.39) > Cd(8.99) Cu(7.73) > Pb(7.42)
a
Pauling electronegativity.
b
Softness values from Misono et al. [39].
c
Hydrolysis constant, pK, is for the reaction: Me2+ + H2O = Me(OH)+ + H+.

Table 5
Parameters of the multicomponent isotherm models for the binary adsorption of Cd(II) and Ni(II) on bentonite, Cd(II) and Zn(II) on sepiolite, and Pb(II) and Cu(II) on vermiculite.

Model Single isotherm parameters Interaction factors Bentonite Sepiolite Vermiculite


Parameters %D Parameters %D Parameters %D
NLMI 4 0 49 87 20
MLMI 4 2 gCd = 1.85 11 gCd = 1.24 22 gPb = 1.05 10
gNi = 0.569 gZn = 0.088 gCu = 1.48
ELMI 0 3 qmax = 0.575 11 qmax = 0.274 24 qmax = 0.545 9
KE,Ni = 1.86 KE,Zn = 107 KE,Pb = 1.06
KE,Cd = 1.95 KE,Cd = 10.7 KE,Cu = 0.442
NRPMI 6 0 33 43 11
MRPMI 6 2 gCd = 1.42 10 gCd = 0.739 42 gPb = 0.828 8
gNi = 0.614 gZn = 0.584 gCu = 1.01
EFMI 4 6 xNi = 0.390 12 xZn = 0.105 24 xPb = 0.644 8
yNi = 0.152 yZn = 0.105 yPb = 0.137
zNi = 1.29 zZn = 1.13 zPb = 1.10
xCd = 0.546 xCd = 0.847 xCu = 0.462
yCd = 1.17 yCd = 5.02 yCu = 1.32
zCd = 0.672 zCd = 0.806 zCu = 0.621
SRSI 4 4 aCd,Cd = 1 15 aCd,Cd = 1 26 aPb,Pb = 1 12
aCd,Ni = 2.41 aCd,Zn = 12.8 aPb,Cu = 0.39
aNi,Ni = 1 aZn,Zn = 1 aCu,Cu = 1
aNi.Cd = 0.58 aZn,Cd = 0.026 aCu,Pb = 5.59

4. Results and discussion isotherm whereas the Freundlich and Langmuir models are two-
parameter isotherms.
4.1. Single metal adsorption isotherms on natural clays The single metal adsorption equilibrium data and the Redlich–
Peterson isotherms of Cd(II) and Ni(II) on bentonite, Cd(II) and
The single metal and clay systems investigated in this work Zn(II) on sepiolite, and Cu(II) and Pb(II) on vermiculite, are graphed
were Cd(II) and Ni(II) on bentonite at pH = 7, Cd(II) and Zn(II) on in Figs. 1a–c, correspondingly. As seen in Fig. 1a, the capacity of
sepiolite at pH = 7, and Cu(II) and Pb(II) on vermiculite at pH = 4. bentonite for adsorbing Cd(II) is higher than that of Ni(II). For
The solution pH was chosen as the pH where the clay presented example, the amount of Ni(II) and Cd(II) adsorbed on bentonite
a reasonable adsorption capacity towards both metals, and no me- was 0.44 and 0.64 meq/g, respectively, when the concentration of
tal precipitation occurred in the solution. In all the systems, the the metal at equilibrium was 5 meq/L. The selectivity ratio, S(Cd/
temperature of the solution was 25 °C. Ni), can be calculated from the following equation:
The Langmuir, Freundlich and Redlich–Peterson isotherms were
fitted to the experimental adsorption equilibrium data for a single qCdðIIÞ 0:64
metal. The parameters or constants of these isotherms as well as SðCd=NiÞ ¼ ¼ ¼ 1:45 ð15Þ
qNiðIIÞ 0:44
the average percentage deviations are shown in Table 3. The %D
ranged from 2.21% to 12.3%, 1.44% to 18.6% and 1.55% to 7.84% Thus, the bentonite capacity towards Cd(II) was 1.45 times
for the Langmuir, Freundlich and Redlich–Peterson isotherms, greater than that towards Ni(II). The maximum capacity of an Ira-
respectively. It was assumed that the isotherm model that best nian bentonite for adsorbing Cd(II) was found to be 0.762 meq/g
fitted the adsorption equilibrium data was the model, which (0.381 mmol/g) at pH = 6 [34], this capacity is higher than that re-
presented the lowest %D. Accordingly to this criterion, the ported in this work. The differences in the adsorption capacities
Redlich–Peterson isotherm best fitted 4 out of the 6 single metal can be attributed to the sources of the bentonite.
clay systems shown in Table 3. Furthermore, the Freundlich model For a metal concentration at equilibrium of 0.8 meq/L, the
provided slightly better interpretation of 2 of the 6 single metal capacity of the sepiolite for adsorbing Cd(II) and Zn(II) was 0.33
systems than the Redlich–Peterson Isotherm. Thus, it was consid- and 0.22 meq/g, correspondingly, and the S(Cd/Zn) was approxi-
ered that the Redlich–Peterson isotherm best fitted the single mately 1.5. This means that the Cd(II) capacity of the sepiolite
adsorption equilibrium data. This result can be attributed to was 1.5 times greater than that of Zn(II). Alvarez-Ayuso and
the fact that the Redlich–Peterson model is a three-parameter García-Sánchez [35] found similar adsorption capacities for a
540 E. Padilla-Ortega et al. / Chemical Engineering Journal 225 (2013) 535–546

sepiolite from Zaragoza, Spain. In the case of the vermiculite, the The interpretation of the multicomponent experimental data
uptake of Pb(II) and Cd(II) was 0.50 and 0.46 meq/g, respectively, was also performed with the following Freundlich-type isotherm
when the metal concentration at equilibrium was 8 meq/L. There- models: the extended Freundlich multicomponent isotherm (EFMI)
fore, the affinity of vermiculite towards Pb(II) was slightly higher and Sheindorf–Rebuhn–Sheintuch isotherm (SRSI). Both isotherm
than that of Cu(II) and the S(Pb/Cu) was close to 1.1. However, a models used the single component Freundlich isotherm parame-
vermiculite from Brazil presented the metal affinity order of ters and various interaction and competition factors. Based upon
Cu(II) > Pb(II) [36]. Again, this discrepancy in the metal affinity the values of %D, the EFMI fitted the experimental data slightly bet-
order may be due to the different origins of the vermiculite. ter than the SRSI because the %D of EFMI was lower than that of the
The metal affinity sequence of clays is normally associated with SRSI for the three binary metal-clay systems. As an example, for the
the metal physicochemical properties. The hydrated ionic radii of Pb(II)–Cu(II)/vermiculite system, the %D of EFMI was 8%, whereas
the metals increased in the following order: Pb (4.01 Å) > Ni
(4.04 Å) > Cu (4.19 Å) > Cd (4.26 Å) > Zn (4.30 Å) [37]. The discrep-
ancies in the adsorption capacities of the clays towards the metals
0.7
cannot be ascribed to accessibility of the metal cations to the clays qpred = 1.1 q exp
pores because the average pore diameter of the bentonite, sepiolite

Metal uptake predicted, meq/g


0.6
and vermiculite (see Table 2) was at least 14, 15 and 31 times
greater than the hydrated ionic radii of the metals. 0.5
Auboiroux et al. [38] used the Hard Soft Acid–Base (HSAB) the-
0.4 qpred = q exp
ory to explain the metal affinity sequence in a Ca-Montmorillonite,
and argued that the metal affinity sequence was due to differences 0.3
on electronegativity and softness of metal cations. The metal affin- qpred = 0.9 q exp
ity and the physicochemical property sequences for each clay are 0.2
shown in Table 4, and the properties were reported by Kinraide
MRPMI
and Yermiyahu [37]. Examination of the sequences in Table 4 re- 0.1
Ni(II)
veals that the affinity of the metals on the clays is dependent upon Cd(II)
0.0
the softness and ionic radius of the metal cations, but no upon 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7
Pauling electronegativity, hydrolysis constant and ionization po- Experimental metal uptake, meq/g
tential. No further examination of the affinity sequences was con-
ducted since the metal affinity order for each clay was only
(a)
obtained for two metals. 0.5
qpred = 1.1 q exp
4.2. Multicomponent adsorption isotherms
Metal uptake predicted, meq/g

0.4
qpred = q exp
The values of the multicomponent adsorption isotherm con-
stants and the average percentage deviation are shown in Table 5. 0.3
The multicomponent adsorption equilibrium data were interpreted
with the three multicomponent adsorption models based on the
0.2 qpred = 0.9 q exp
Langmuir isotherm. The values of the % D shown in Table 5 indi-
cated that the non-modified Langmuir multicomponent isotherm
(NLMI) cannot fit the experimental data since the average percent- 0.1
MLMI
age deviation ranged from 20% to 87%. This result can be explained Zn(II)
recalling that this isotherm does not incorporate any parameter Cd(II)
0.0
accounting for the interactions between metal ions of different 0.0 0.1 0.2 0.3 0.4 0.5
species and competition among metal cations. On the other hand, Experimental metal uptake, meq/g
the modified Langmuir multicomponent isotherm (MLMI) and ex-
(b)
tended Langmuir multicomponent isotherm (ELMI) adjusted rea-
sonably well the experimental data since both isotherms
0.7
provided very similar %D, ranging from 9% to 24%. However, the
qpred = q exp
MLMI was considered as the best option of these Langmuir-type
Metal uptake predicted, meq/g

0.6
models because the MLMI uses the single metal Langmuir isotherm
parameters. All the parameters of the ELMI have to be estimated by 0.5
fitting the multicomponent adsorption equilibrium data, and no qpred = 1.1 q exp
0.4
information of the single metal Langmuir isotherm is required.
The non-modified (NRPMI) and modified Redlich–Peterson 0.3
multicomponent isotherms (MRPMI) were fitted to the experimen- qpred = 0.9 q exp
tal adsorption equilibrium data, and the %D of the MRPMI was al- 0.2
ways lower than that of the NRPMI (see Table 5). For example, the MRPMI
MRPMI presented a %D of 10% for the Cd(II)–Ni(II)/bentonite sys- 0.1
Cu(II)
tem, whereas the %D of NRPMI was 33%. This result was attributed Pb(II)
0.0
to the fact that the NRPMI comprised 6 parameters from the single 0.0 0.1 0.2 0.3 0.4 0.5 0.6
component R–P isotherms; meanwhile, the MRPM included 6 Experimental metal uptake, meq/g
parameters from the single component R–P isotherm plus 2 inter-
action factors related to the multicomponent interactions. In other
(c)
words, the MRPMI better fitted the data because the multicompo- Fig. 2. Comparison between the metal uptake predicted with the best model and
nent interactions were incorporated into this model. This is why the experimental metal uptake. (a) Cd(II)–Ni(II) on bentonite, (b) Cd(II)–Zn(II) on
the MRPMI model was chosen over the NRPMI model. sepiolite and (c) Cu(II)–Pb(II) on vermiculite.
E. Padilla-Ortega et al. / Chemical Engineering Journal 225 (2013) 535–546 541

that of SRSI was 12%. For a binary system, 6 and 4 additional fitting best models predicted reasonably well the experimental data.
parameters related to multicomponent interactions are required The MRPMI model overpredicted the uptake of Cd(II) on bentonite,
by the EFMI and SRSI models. In the case of SRSI, the number of but underpredicted the uptake of Ni(II) on bentonite. The uptake of
additional parameters is only 2 instead of 4, since the parameters Zn(II) on sepiolite was overpredicted by MLMI model whereas the
a11 and a22 are equal to 1. Thus, the SRSI was considered to better Cd(II) uptake on sepiolite was underpredicted.
adjust the experimental data than the EFMI.
Based upon the lowest value of %D, the best models were
MRPMI, MLMI and MRPMI for the binary adsorption of Cd(II)–Ni(II) 4.3. Binary adsorption of Cd(II) and Ni(II) on bentonite
on bentonite, Zn(II)–Cd(II) on sepiolite and Pb(II)–Cu(II) on vermic-
ulite, respectively. The values of %D for the above models were 10%, The binary adsorption equilibrium data of Cd(II)–Ni(II) on ben-
22% and 8%, respectively. tonite and the prediction of MPRMI model are plotted in Fig. 3a and
The interpretation of the binary adsorption data was also ana- b. The effect of the presence of Ni(II) on the uptake of Cd(II) can be
lyzed by comparing the amount of metal adsorbed predicted with seen in Fig. 3a, and in the concentration of Ni(II) ranging from 0 to
the best model, qpred, vs. the experimental amount of metal ad- 2 meq/L, the uptake of Cd(II) diminished drastically while increas-
sorbed, qexp. The plots qpred vs. qexp for the three binary-metal sys- ing the concentration of Ni(II) at equilibrium. Then, the uptake of
tems are shown in Fig. 2a–c. To help analyze the fitting results, the Cd(II) diminished slightly for concentrations of Ni(II) greater than
straight lines qpred = qexp, qpred = 1.1 qexp and qpred = 0.9 qexp were 2 meq/L. For example, at a concentration of Cd(II) at equilibrium
also graphed in these Figures. These lines represent exact predic- of 5 meq/L, the uptake of Cd(II) adsorbed was 0.60, 0.41, 0.33 and
tion, overpredicted by 10% deviation and underpredicted by 10% 0.30 meq/g, when the concentration of Ni(II) at equilibrium was
deviation. The results plotted in Fig. 2a–c clearly showed that the of 0, 2, 4 and 5 meq/L, respectively. The capacity of the bentonite
for adsorbing Cd(II) decreased 32%, 20% and 9% when the concen-
0.7
Uptake of Cd(II) adsorbed, meq/g

Uptake of Zn(II) adsorbed, meq/g


0.05 0.10 0.15 0.20 0.25 0.30
0.6
0.5
0.4
0.3
0.2
0.1

1.
Co n 0 0 . 8
0

5 .6
7 4 c en .5 0
Conc
6 5 4 3 q/ L t ra t 0 . 6 0 0 .4 0 q/L
entrat 3 2 , me io n 0 .3 , me
ion of 1 0 1
2
f C d(II) .
of C 4 0 . 2 0 .2 Z n(II)
Ni(II) o d (I I . 1 no f
, meq 0 tion ), m 0 0
0
ratio
/L oncentra eq/L Concent
C
(a) (a)
0.7

0.20 0.25 0.30


Uptake of Ni(II) adsorbed, meq/g

Uptake of Cd(II) adsorbed, meq/g


0.6
0.5
0.4

0.0 0.05 0.10 0.15


0.3
0.2
0.1
0

5 10 0. 8 1 .0
8 0 .8
4
3 6 eq/L Conc 0.6 0 .6 eq/L
Conc
entrat 4 II) , m entrat 0 .4 0 .4 Cd(I
I), m
f Ni (
2
ion of 1 2 o io n of Z 0.2 0 .2 o f
Cd(II 0 0 tion n(II), 0 0
ratio
n
), meq/L c entra meq/L cent
Con Con
(b) (b)
Fig. 3. Binary adsorption isotherms of Cd(II)–Ni(II) on bentonite. The surfaces are Fig. 4. Binary adsorption isotherms of Cd(II)–Zn(II) on sepiolite. The surfaces are
predicted with the MRPMI model. (a) Cd(II) uptake and (b) Ni(II) uptake at pH = 7 predicted with the MLMI model. (a) Zn(II) uptake and (b) Cd(II) uptake. pH = 7 and
and T = 25 °C. T = 25 °C.
542 E. Padilla-Ortega et al. / Chemical Engineering Journal 225 (2013) 535–546

0.30
CEC = 0.436 meq/g
Uptake of Zn(II) adsorbed, meq/g

0.25

0.5
Total uptake of metals, qT, meq/g
0.20

0.4
0.15

0.3
0.10
Concentration of Cd(II) on equilibrium, meq/L

0.2
0.05 0 0.2 0.4
0.6 0.8 1
0.00

0.1
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9
Concentration of Zn(II) at equilibrium, meq/L

0
(a) 1.0
Con 0.8
cen 0.6 0.6
0.4 trat 0.4 eq/L
ion 0.4 I), m
Concentration of Zn(II) at equilibrium, meq/L of C 0.2 0.2 f Zn(I
io n o
Uptake of Cd(II) adsorbed, meq/g

d(II
0 0.2 0.4 0.6 1 ), m 0 0
n centrat
eq/ L Co
0.3

Fig. 6. Total uptake of metals adsorbed on sepiolite at pH = 7 and T = 25 °C. The


surface is predicted by the MLMI model.
0.2

of Zn(II) on sepiolite at pH = 7 and T = 25 °C, respectively. Also, the


0.1
adsorption isotherm surfaces of Cd(II) and Zn(II) adsorbed on sepi-
olite were drawn with the MLMI model. This model was used suc-
cessfully by Ho and McKay [40] and Leyva-Ramos et al. [41] to
0.0
0.0 0.2 0.4 0.6 0.8 1.0 represent the binary adsorption isotherms of Co(II) and Ni(II) on
Concentration of Cd(II) at equilibrium, meq/L peat, and Cd(II) and Zn(II) on activated carbon, respectively.
The adsorption isotherm surface of Zn(II) (Fig. 4a) shows that
(b) the uptake of Zn(II) does not change by varying the concentration
Fig. 5. (a) Adsorption isotherms of Zn(II) at various isoconcentrations of Cd(II) and
of Cd(II) at equilibrium. For example, at a concentration of Zn(II) at
(b) Cd(II) at various isoconcentrations of Zn(II) on sepiolite at pH = 7 and T = 25 °C. equilibrium of 0.8 meq/L, the uptake of Zn(II) adsorbed was
The lines represent the MLMI model. smoothly reduced from 0.26 to 0.24 meq/g when the concentration
of Cd(II) was raised from 0 to 0.8 meq/L.
tration of Ni(II) at equilibrium was varied from 0 to 2, 2 to 4 and 4 As seen in Fig. 4b, the adsorption isotherm surface of Cd(II)
to 5 meq/L, correspondingly. exhibits a very different behavior. The uptake of Cd(II) adsorbed
The adsorption isotherm surface of Ni(II) on bentonite is shown was substantially decreased by increasing the concentration of
in Fig. 3b and the dependence of the uptake of Ni(II) on the concen- Zn(II). For example, at an equilibrium concentration of Cd(II) of
tration of Cd(II) at equilibrium is depicted in this figure. The uptake 0.8 meq/L, the amount of Cd(II) adsorbed was 0.32, 0.075, 0.042,
of Ni(II) diminished slightly due to the competition of the Cd(II), 0.03 and 0.02 meq/g for a concentration of Zn(II) of 0, 0.2, 0.4, 0.8
and the reduction of the Ni(II) uptake was almost proportional to and 1 meq/L, respectively. This means that the Cd(II) adsorption
the enhancement of the Cd(II) concentration. At a Ni(II) concentra- capacity of sepiolite was reduced near 77% when the concentration
tion at equilibrium of 5 meq/L, the uptake of Ni(II) adsorbed was of at equilibrium of Zn(II) was slightly changed from 0 to 0.2 meq/L.
0.53, 0.39, 0.32 and 0.29 meq/g for a concentration of Cd(II) at The adsorption isotherms of Zn(II) at various isoconcentrations
equilibrium of 0, 2, 4 and 5 meq/L, respectively. The capacity of of Cd(II), and the adsorption isotherms of Cd(II) at various isocon-
the bentonite for adsorbing Ni(II) was diminished 26%, 18% and centrations of Zn(II) are shown in Fig. 5a and b, respectively. The
9% by raising the concentration of Cd(II) at equilibrium from 0 to isotherms of Zn(II) or Cd(II) were predicted with the MLMI model
2, 2 to 4 and 4 to 5 meq/L, correspondingly. by keeping constant the concentration of the other metal. These
The single adsorption isotherms of Cd(II) and Ni(II) on bentonite at graphs are very useful for observing the decrease in the uptake
pH = 7 (Fig. 1a) indicated that the S(Cd/Ni) of the bentonite was 1.45 of a metal by the presence of the other metal. Fig. 5a shows that
at concentration of metal at equilibrium of 5 meq/g. However, the the Zn(II) adsorption capacity of the sepiolite was slightly affected
competitive adsorption data revealed that the S(Cd/Ni) was 1.03 by the presence of Cd(II); however, in the Fig. 5b, it can be clearly
when the concentrations of both metals at equilibrium were observed that at a concentration of Cd(II) at equilibrium of
5 meq/L. In the competitive adsorption, the uptake of Cd(II) decreased 0.8 meq/L, the uptake of Cd(II) adsorbed diminished from 0.33 to
to a greater extent than that of Ni(II). Therefore, the Ni(II) exhibited 0.02 meq/g, increasing the concentration of Zn(II) from 0 to
greater antagonism to Cd(II) during the competitive adsorption. 0.8 meq/L. This means that the capacity of the sepiolite for adsorb-
ing Cd(II) was decreased 16.5 times due to the competition of
Zn(II).
4.4. Binary adsorption of Cd(II) and Zn(II) on sepiolite At the concentrations at equilibrium of 0.8 meq/L, the S(Cd/Zn)
was 1.5 for the single adsorption isotherms of Cd(II) and Zn(II),
Fig. 4a and b show the competitive adsorption equilibrium data whereas the S(Cd/Zn) was 0.08 for the competitive adsorption.
of Zn(II) in the presence of Cd(II) and that of Cd(II) in the presence Hence, the Zn(II) exhibited strong antagonism in the competitive
E. Padilla-Ortega et al. / Chemical Engineering Journal 225 (2013) 535–546 543

0.7
Second Equilibrium of Pb(II) for [Cu(II)] 0 (meq/L):

Uptake of Pb(II) adsorbed, meq/g


0.6 1.3 3.2 6.3 12.5
0.6

Single Adsorption
0.5 Isotherm of Pb(II)
Uptake of Cu(II) adsorbed, meq/g
0.5

0.4
0.4

0.3

0.2
0.3

0.1
0.2

First equilibrium of Pb(II)


0.0
0 1 2 3 4 5 6 7
0.1

Concentration of Pb(II) at equilibrium, meq/L


(a)
0

12
10 12
Co n 10
cen 8 6 8 0.7
trat 6 eq/L
ion
of P 4 2 II), m Second Equilibrium of Cu(II) for [Pb(II)]0 (meq/L):

Uptake of Cu(II) adsorbed, meq/g


4 C u (
b(II 2 n of 0.6 1.3 3.2 6.3 12.5
), m 0 0 ratio
eq/L o n cent
C 0.5
Single Adsorption
Isotherm of Cu(II)

(a) 0.4

0.3

0.2
0.6

0.1
Uptake of Pb(II) adsorbed, meq/g
0.5

0.0
0 2 4 6 8 10 12
Concentration of Cu(II) at equilibrium, meq/L
0.4

(b)
0.3

Fig. 8. Displacement of Pb(II) adsorbed on vermiculite by adsorption of Cu(II) at


pH = 4 and T = 25 °C. (a) Uptake of Pb(II) and (b) uptake of Cd(II).
0.2

4.5. Binary adsorption of Cu(II) and Pb(II) on vermiculite


0.1

At pH = 4 and T = 25 °C, the experimental competitive adsorp-


0

12
10 12 tion data of Cu(II) and Pb(II) on vermiculite as well as the adsorp-
Con 10
cen 8 8 tion surface predicted with the MRPMI model are illustrated in
trat /L
ion 6 6 meq Fig. 7a and b.
of C 4 2 4 Pb (II),
u(II 2 n of The effect of the presence of Pb(II) on the capacity of the ver-
), m 0 0 ratio
eq/L on cent miculite for adsorbing Cu(II) is graphed in Fig. 7a. The competitive
C
adsorption surface of Cu(II) shows that the presence of Pb(II) re-
(b) duced drastically the uptake of Cu(II) adsorbed on the vermiculite.
A very large reduction of the uptake of Cu(II) adsorbed can be
Fig. 7. Binary adsorption isotherms of Cu(II)–Pb(II) on vermiculite. The surfaces are
noted when the concentration of Pb(II) at equilibrium was varied
predicted with the MRPMI model. (a) Cu(II) uptake and (b) Pb(II) uptake. pH = 4 and
T = 25 °C. in the range from 0 to 3 meq/L. The decrease of the uptake of Cu(II)
was less pronounced for a Pb(II) concentration above 3 meq/L. For
example, at a concentration of Cu(II) at equilibrium of 8 meq/L, the
adsorption of Cd(II), whereas the Cd(II) did not affect the compet- uptake of Cu(II) was 0.46, 0.23, 0.17 and 0.15 meq/g when the con-
itive adsorption of Zn(II) or did not present antagonism. centration of Pb(II) at equilibrium was 0, 3, 6 and 8 meq/L. These
The total metal uptake on the sepiolite is calculated by adding results reveal that the vermiculite capacity for adsorbing Cu(II) de-
the amount of Cd(II) adsorbed and the amount of Zn(II) adsorbed creased 50% and 12% by raising the concentration of Pb(II) from 0
on sepiolite. The total metal uptake is represented as qT = qCd(II) + to 3 meq/L and from 6 to 8 meq/L, correspondingly.
qZn(II). The adsorption surface of qT is shown in Fig. 6, and this The binary adsorption surface of Pb(II) in the presence of Cu(II)
adsorption surface was graphed using the MLMI models of Cd(II) is depicted in Fig. 7b and the uptake of Pb(II) adsorbed on vermic-
and Zn(II). It can be observed that the adsorption surface levels ulite was very slightly affected by the competition of Cu(II). At a
off at qT = 0.27 meq/g. Hence, both metals are competing for the concentration of Pb(II) of 8 meq/L, the amount of Pb(II) adsorbed
same cationic sites of the sepiolite. Besides, qT = 0.27 meq/g is was 0.52, 0.43, 0.38 and 0.37 meq/g while the concentration of
shorter than the CEC capacity of the sepiolite (CEC = 0.44 meq/g). Cu(II) was 0, 3, 6 and 8 meq/L, respectively. These results revealed
This result can be attributed to the fact that some cationic sites that the capacity of vermiculite for adsorbing Pb(II) was reduced
of the clays are not available or accessible to both Cd2+ and Zn2+ 17% and 3% by varying the concentration of Cu(II) from 0 to 3,
ions. and 6 to 8 meq/L, respectively.
544 E. Padilla-Ortega et al. / Chemical Engineering Journal 225 (2013) 535–546

0.7 0.7
Second Equilibrium of Cu(II) with [Pb(II)] 0 (meq/L): Cu(II)

Metal uptake predicted with MRPMI, meq/g


qpred = 1.1 qexp
Uptake of Cu(II) adsorbed, meq/g

1.3 3.2 6.3 12.5 Pb(II)


0.6
0.6
First Equilibrium of Cu(II)
0.5 qpred = qexp
Single Adsorption 0.5
Isotherm of Cu(II)
0.4
0.4
0.3
qpred = 0.9 qexp
0.3
0.2

0.1 0.2

0.0 0.1
0 2 4 6 8 10 12
Concentration of Cu(II) at equilibrium, meq/L
0.0
(a) 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7
Experimental metal uptake, meq/g
0.7
Second Equilibrium of Pb(II) with [Cu(II)]0 (meq/L):
(a)
Uptake of Pb(II) adsorbed, meq/g

0.6 1.3 3.2 6.3 12.5


0.6

Metal uptake predicted with MRPMI, meq/g


0.5 qpred = 1.1 qexp
0.5
0.4

0.3 0.4 qpred = qexp

0.2
0.3
0.1

0.0 0.2 qpred = 0.9 qexp


0 2 4 6 8 10 12
Concentration of Pb(II) at equilibrium, meq/L
0.1
(b) Cu(II)
Pb(II)
Fig. 9. Displacement of Cu(II) adsorbed on vermiculite by adsorption of Pb(II) at 0.0
0.0 0.1 0.2 0.3 0.4 0.5 0.6
pH = 4 and T = 25 °C. (a) Uptake of Cu(II) and (b) uptake of Pb(II).
Experimental metal uptake, meq/g
The results of the competitive adsorption of Pb(II)–Cu(II) onto (b)
vermiculite have demonstrated that the Pb(II) ions presented a
higher affinity for the cationic sites of the vermiculite than the Fig. 10. Comparison between the metal uptake predicted with the MRPMI model
Cu(II) ions. For metal concentrations at equilibrium of 8 meq/L, and the experimental metal uptake. (a) Displacement of Pb(II) adsorbed on
vermiculite by Cu(II), and (b) displacement of Cd(II) adsorbed on vermiculite by
the single adsorption isotherms indicated that the S(Pb/Cu) of ver-
Pb(II).
miculite was 1.1 (see Fig. 1c); however, the S(Pb/Cu) was approxi-
mately 2.5 for the binary adsorption. In other words, the
vermiculite was much more selective towards Pb(II) than to Cu(II)
in the competitive adsorption. The Pb(II) ions presented strong
ment experiments only Pb(II) was present in the solution. The
antagonism against the adsorption of Cu(II), whereas the Cu(II)
competitive adsorption occurred when Cu(II) was added to the
ions exhibited light antagonism against the adsorption of Pb(II).
solution of Pb(II) at equilibrium. The Pb(II) adsorbed on the vermic-
This behavior cannot be predicted from the single metal adsorption
ulite was displaced from the adsorption sites so that Cu(II) can be
isotherms.
adsorbed on the cationic sites. The experimental displacement
adsorption data is denoted as the second equilibrium and the up-
4.6. Displacement of Cu(II) and Pb(II) adsorbed on the vermiculite take of Pb(II) at the second equilibrium was diminished by the
competition of the Cu(II). As shown in Fig. 8a, the amount of Pb(II)
The displacement of a metal adsorbed on vermiculite was per- adsorbed at the second equilibrium was dependent on the initial
formed by adsorbing a single metal on vermiculite, and attaining concentration of Cu(II) because greater competition of Cu(II) oc-
adsorption equilibrium. Subsequently, the metal adsorbed on the curred by increasing the initial concentration of Cu(II) in the solu-
vermiculite was displaced from the adsorption sites by adding an- tion. At an initial concentration of Cu(II) of 1.3 meq/L, the uptake of
other metal into the adsorber solution. The displacement or Pb(II) at the second equilibrium was very similar to that at the first
desorption of the metal adsorbed was attributed to the competi- equilibrium. Hence, the Pb(II) adsorbed on the vermiculite was not
tion by the other metal for the adsorption sites. displaced by Cu(II) for an initial concentration of Cu(II) below
1.3 meq/L of Cu(II). However, the uptake of Pb(II) was reduced con-
4.6.1. Displacement of the Pb(II) adsorbed on the vermiculite siderably when the initial concentration of Cu(II) was 12.5 meq/L.
The single adsorption equilibrium data and isotherm of Pb(II) For example, at a concentration of Pb(II) at equilibrium of 2 meq/
on vermiculite is plotted in Fig. 8a. The data and isotherm are de- L, the uptake of Pb(II) was almost halved when the initial concen-
noted as the first equilibrium since in the first stage of the displace- tration of Cu(II) was 12.5 meq/L.
E. Padilla-Ortega et al. / Chemical Engineering Journal 225 (2013) 535–546 545

On the other hand, the adsorption equilibrium data of Cu(II) at sepiolite presented a very different behavior. In the binary adsorp-
the second equilibrium is graphed in Fig. 8b. No data was reported tion, it was noted that Zn(II) presented a strong antagonism against
at the first equilibrium since no Cu(II) was present in the first stage the adsorption of Cd(II); however, Cd(II) did not affected the
of the displacement experiments. As a reference, the single adsorp- adsorption of Zn(II). The uptake of Cd(II) in the presence of Zn(II)
tion isotherm of Cu(II) on vermiculite is also shown in Fig. 8b. The was reduced up to 16.5 times due to the competition of the Zn(II)
uptake of Cu(II) at the second equilibrium was always below the for the same cationic sites of the sepiolite.
single adsorption isotherm and as expected, the uptake of Cu(II) The single component adsorption isotherms of Cu(II) and Pb(II)
was diminished by raising the initial concentration of Pb(II) in on vermiculite revealed that the selectivity of the vermiculite to-
the first equilibrium. wards Pb(II) was slightly higher than that of the Cu(II). However,
in the competitive adsorption, the affinity of Pb(II) for the vermic-
4.6.2. Displacement of the Cu(II) adsorbed on the vermiculite ulite was much higher than that of the Cu(II). The Pb(II) presented
In Fig. 9a are plotted the experimental single adsorption equi- stronger antagonism against the simultaneous adsorption of Cd(II),
librium data of Cu(II) as well as the single adsorption isotherm of but not in the other way around.
Cu(II). This information is from the first stage or first adsorption The displacement experiments of Cu(II) and Pb(II) adsorbed on
equilibrium of Cu(II) on the vermiculite. In the second stage, the vermiculite by the other metal showed that both metals can be
uptake of Cu(II) adsorbed was decreased because the Cu(II) was desorbed by the presence of the other metal. Furthermore, the
displaced by the Pb(II) added to the solution. The uptake of Cu(II) amount of Cu(II) displaced by the adsorption of Pb(II) is greater
at the second equilibrium was dependent on the initial concentra- than the amount of Pb(II) displaced by the adsorption of Cu(II).
tion of Pb(II), and was always shorter than the uptake of single The amount of Cu(II) and Pb(II) displaced was up to 88% and 58%,
Cu(II). A comparison between Figs. 8a and 9a shows that a larger respectively.
amount of Cu(II) adsorbed is displaced by the Pb(II) than the other
way around. Moreover, the amount of Pb(II) adsorbed on vermicu- References
lite at the second equilibrium is exhibited in Fig. 9b and the uptake
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sorbed on the vermiculite at low and high initial concentrations of sulfured orange peel, Desalination 275 (2011) 212–216.
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