Chemical Engineering Journal 171 (2011) 1276–1286

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Chemical Engineering Journal

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Adsorption of heavy metals in acid to alkaline environments by montmorillonite

and Ca-montmorillonite
Liberto de Pablo a,∗ , M. Lourdes Chávez b , Mohamed Abatal a
a
Instituto de Geología, Universidad Nacional Autónoma de México, 04510 México, DF, Mexico
b
Facultad de Química, Universidad Nacional Autónoma de México, 04510 México, DF, Mexico

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

Article history: Adsorption of Hg2+ , Cr3+ , Pb2+ , Cu2+ , Zn2+ , Ba2+ , Ni2+ , Mn2+ , Cd2+ , Ba2+ and Ag+ by Ca-montmorillonite
Received 10 March 2011 from monocationic solutions followed second-order kinetics, attaining removals qe of Pb2+ 6.187 × 102 ,
Received in revised form 11 May 2011 Hg2+ 4.369 × 102 , Cu2+ 2.045 × 102 , Zn2+ 1.576 × 102 , Ag+ 1.375 × 102 , Cr3+ 7.917 × 101 , Ni2+ 7.300 × 101 ,
Accepted 12 May 2011
Ba2+ 6.815 × 101 , Cd2+ 2.003 × 101 and Mn2+ 1.632 × 101 mg g−1 , greater than those by montmorillonite.
Equilibrium adsorption by montmorillonite from bimodal metal + Ca2+ solutions followed the Langmuir
Keywords:
model with adsorptions of Zn2+ 3.477 × 101 , Ba2+ 6.984, Hg2+ 3.681 × 101 , Ni2+ 4.849, Mn2+ 3.820 and Cd2+
Heavy metals adsorption
6.978 mg g−1 , and by Ca-montmorillonite of Zn2+ 3.523 × 101 , Ba2+ 1.073 × 101 and Ni2+ 5.969 mg g−1 .
Montmorillonite adsorption
Ca-montmorillonite adsorption
Within the pH range established by acid cationic solutions and near neutral montmorillonite and Ca-
montmorillonite, at pHs below 5 precipitate oxides and hydroxides of Cr3+ , Pb2+ and Cu2+ while at higher
pHs Hg2 2+ , Zn2+ , Ba2+ , Cd2+ , Ni2+ , Mn2+ and Ag+ remain in solution and are adsorbed as simple and hydroxyl
cations by the clay, keeping the selectivity sequence Hg2 2+ > Zn2+ > Ba2+ > Cd2+ > Ni2+ > Mn2+ .
© 2011 Elsevier B.V. All rights reserved.

1. Introduction
Clay minerals have well-recognized adsorption capabilities
that have extensive industrial, technological, agricultural, and
environmental applications. The smectite minerals, namely mont-
morillonite, have been broadly investigated as adsorbents of heavy
metals from acidic solutions. The adsorption of these metals from
weak acid to alkaline calcic solutions is not as well documented.
Therefore, the present study examines adsorption by montmoril-
lonite and Ca-montmorillonite of Pb2+ , Cu2+ , Cr3+ , Zn2+ , Ba2+ , Hg2+ ,
Ni2+ , Mn2+ , Cd2+ and Ag+ from weak acid to alkaline solutions.
Heavy metals, whether they are simple ions normal in acidic
environments or hydroxyl ions common in weakly acidic to alkaline
media, are a serious environmental problem because of their toxi-
city and abundance. Excessive accumulation of metal ions in living
organisms, including the human body, and ecological systems can
cause decreased stabilization and vegetation of soils, health disor-
ders, and physical, chemical, and biological damage. Heavy metals
are non-biodegradable, making them accumulate to toxic levels in
∗ Corresponding author at: Instituto de Geología, Universidad Nacional Autónoma
de México, Ciudad Universitaria, México, 04510 DF, Mexico. Tel.: +52 555 6224284;
fax: +52 555 6224317.
E-mail address: liberto@servidor.unam.mx (L. de Pablo).
soil available for plant and animal uptake when they are released
into water and soil fluids. This process allows metals to enter the
food chain, which ends with human consumption [1–3].
The adsorption of metals from aqueous acidic solutions
by clay minerals has been extensively investigated [4–14].
Generally, clay minerals adsorb metals from aqueous solu-
tions through cation replacement or by forming surface func-
tional groups that normally observe the selectivity rule of
Ca > Hg > Pb > Cu > Mg > Zn > Co > Ni > Cd. Unlike with acidic solu-
tions, the adsorption of heavy metals from alkaline solutions has
not been investigated intensely. Studies have shown that addi-
tion of Ca2+ promotes alkalinity and retention of Cu2+ and Cd2+
[15]. The technique also improves adsorption by calcareous soil
of Ni2+ , Co2+ and Cu2+ from metal-Ca binary solutions, maintain-
ing the affinity series Pb > Cu > Ni > Cd > Zn [16]. Bhattacharyya and
Gupta [17] described the removal and immobilization of Cd2+ , Pb2+
and Cu2+ by montmorillonite in acid to slightly alkaline media and
that of Cd2+ , Co2+ , Cu2+ , Pb2+ and Ni2+ by acid-activated montmo-
rillonite. Anomalous adsorption of metal, which occurs in excess
of the cation exchange capacity (CEC) of clay, has been investi-
gated for some metals, e.g., Cu2+ and Zn2+ by H-montmorillonite
[18] and Cu2+ by Na- and Ca-montmorillonite [19] and by Cheto
clay [20]. Adsorption by montmorillonite was associated with
swelling [2,21,22]. Adsorption under acidic conditions with tran-
sition from mono- to di-hydrated stages [23] has been shown to

1385-8947/$ – see front matter © 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.cej.2011.05.055
 L. de Pablo et al. / Chemical Engineering Journal 171 (2011) 1276–1286 1277

Table 1 mixture sat for 24 h and was decanted three times in succession.
Composition of montmorillonite from Cuencamé, Durango, Mexico.a
Finally, the solution was washed with deionized water until all Cl−
Chemical composition was removed, which was detected using AgNO3 . Montmorillonite
SiO2 60.96 and Ca-montmorillonite were stored at 60 ◦ C for 3 days before they
Al2 O3 14.49
were lightly crushed and sifted through a 1-mm screen and retained
Fe2 O3 1.49
CaO 0.74
on a 0.075-mm screen.
MgO 5.28 The kinetics of adsorption of heavy metals by montmorillonite
Na2 O 1.62 and Ca-montmorillonite was evaluated by separately adding 1 g of
K2 O 0.55 each adsorbent to 100 ml of 0.1 N solutions of each adsorbate, react-
TiO2 0.15
ing for 16 h, taking aliquots after 1, 2, 3, 4, 5, 10, 12, 14, and 16 h of
H2 O− 8.77
H2 O+ 5.87 contact. Each aliquot was analyzed for Ca2+ and the corresponding
metal cation. The aliquots required centrifugation to separate any
Cation exchange capacity 64
Ca2+ 32
suspended material.
Mg2+ 24 The adsorption isotherms were determined by mixing 0.2 g of
Na+ 7 each adsorbent with 10 ml of metal ion + Ca2+ solutions at con-
K+ 1 centrations of 0.1, 0.05, 0.025, 0.020, 0.015, 0.01, and 0.005 N, the
Mineralogy ratios metal ion/Ca2+ at unity, and the reaction time lasting over
Montmorillonite 85 2 days. After the reaction, the centrifuged liquids were analyzed
Plagioclase 5 for Ca2+ and the corresponding metal by atomic absorption spec-
K-feldspar 3
Opal 5
trometry. Dual metal ion + Ca2+ solutions were used to evaluate
Quartz, glass 2 adsorption of metal ions from Ca-rich liquids and the effect of any
a
mutual interference on adsorption. The speciation of metal ions in
Composition in wt%, cation exchange capacity CEC in meq/100 g.
aqueous solutions were estimated from the MINTEQ program and
represented graphically for a type concentration of 50 ␮M [31,32].
involve exchange of Ca2+ for protons at low pH levels, with the
likely mutual exclusion of both from the smectite interlayer and
the exchange of Ca2+ for H3 O+ [24]; at high pH levels, the X-ray 2.3. Theoretical background
diffraction profile modeling and near-infrared diffuse reflectance
spectroscopy failed to indicate formation of CaOH+ on the smectite The kinetics of adsorption was calculated as a second-order
interlayer [25,26]. The few hydration studies of bi-ionic smectites reaction [33] (Eq. (1)):
[27,28], including those of (Na, Ca)-smectite and (K, Ca)-smectite
[29], have shown that interlayer cations tend to distribute into dqt
= Kv (qe − qt )2 , (1)
distinct interlayers, leading to “demixed” states. dt
The present work describes the kinetics of adsorption by mont-
morillonite and Ca-exchanged montmorillonite of heavy metals where Kv (g mg−1 h−1 ) is the second-order rate constant of adsorp-
from single cation solutions and their equilibrium adsorption tion, qe (mg g−1 ) is the amount of adsorbate (Pb2+ , Cu2+ , Cr3+ , Zn2+ ,
from bimodal cation + Ca2+ solutions. This study contributes to our Ba2+ , Hg2+ , Ni2+ , Mn2+ , Cd2+ and Ag+ ) adsorbed at equilibrium, and
understanding of the adsorption properties of montmorillonite, the qt (mg g−1 ) is the adsorbate contacting the adsorbent at any time
reactions at the clay mineral–adsorbate interface, and the influ- t. At boundary conditions, t varies between 0 and t and qt between
ence of calcium on them. It assists on the prediction of mobility 0 and qt , hence the integrated equation takes the form of Eq. (2)
and behavior of heavy metals in smectite systems and the use of where Kv q2e is the initial adsorption rate:
smectites as geochemical barriers for hazardous materials. It has
t 1
1
the advantage of mimicking the high calcium environment that
= + t, (2)
prevails in calcareous soils, including clays of the Ca-smectite type qt Kv q2e qe
and in Mollisols, Inceptisols, and Vertisols that may consist of more
than 32% calcium carbonate. This study provides insights into the The linear variation of t/qt vs. t allows calculation of qe and
control and remediation of metal pollutants in soils. Kv . The validity of the assumed order of reaction and calculated
equation was tested by comparison between calculated and exper-
2. Materials and methods imental qe [14]. The Freundlich isotherm was also tested to estimate
the kinetics of adsorption at low concentrations or at the beginning
2.1. Materials of the adsorption process but the results did not show improvement
over those determined from Eq. (2).
The adsorption studies were performed on bentonite from The amount of metal adsorbate adsorbed by the mineral was
Cuencamé, in the state of Durango, Mexico. This bentonite con- calculated from mass-balance Eq. (3):
tains 85 wt% montmorillonite, which is associated with minor
K-feldspar, plagioclase, quartz, and opal, is dioctahedral and has Qe M = V (C0 − Ce ), (3)
a cations exchange capacity (CEC) of 0.64 meq g−1 [30] (Table 1).
Because of its high montmorillonite content, the bentonite is where Qe (mg g−1 ) is the final concentration of adsorbate in the
referred to as montmorillonite in this study. adsorbent, C0 is the initial concentration of adsorbate (mg L−1 ),
Ce (mg L−1 ) is the final concentration of adsorbate in solution, M
2.2. Methods (g) is the adsorbent mass, and V (L) is the volume of liquid. The
adsorption equilibrium is described by the isotherm equation with
Reagent exchange solutions were prepared from analytical- parameters corresponding to the surface properties and the affinity
grade reactants dissolved in deionized water. Ca-exchanged of the adsorbent. The Langmuir isotherm assumes that the cation
montmorillonite was prepared by grinding montmorillonite to a uptake on the homogeneous surface of the adsorbent is by adsorp-
particle size of 0.075 mm and added to 1 N CaCl2 solution. The tion of monolayers without interaction between the adsorbate and
1278 L. de Pablo et al. / Chemical Engineering Journal 171 (2011) 1276–1286

Table 2
Kinetics of adsorption of Pb2+ , Cu2+ , Zn2+ , Cr3+ , Ba2+ , Hg2+ , Ni2+ , Mn2+ , Cd2+ and Ag+ by montmorillonite and Ca-montmorillonite.a

Sorbent Cation qe Kv Kv q2e pH

−4
Montmorillonite Pb 2+
1.703 × 10 2
7.632 × 10 170.270 4.8
Ca-montmorillonite 6.187 × 102 6.059 × 10−4 231.910 4.8
Montmorillonite Cu2+ 2.423 × 102 5.406 × 10−4 31.746 4.8
Ca-montmorillonite 2.045 × 102 1.210 × 10−3 50.633 4.8
Montmorillonite Zn2+ 1.546 × 102 4.922 × 10−3 117.688 4.8
Ca-montmorillonite 1.576 × 102 4.820 × 10−3 119.789 4.8
Montmorillonite Cr3+ 7.201 × 101 1.208 × 10−1 626.566 4.8
Ca-montmorillonite 7.917 × 101 3.453 × 10−2 216.450 4.8
Montmorillonite Ba2+ 6.620 × 101 6.481 × 10−3 28.401 4.0
Ca-montmorillonite 6.815 × 101 6.402 × 10−2 29.726 4.0
Montmorillonite Hg2+ 3.855 × 102 1.064 × 10−2 1581.027 4.0
Ca-montmorillonite 4.369 × 102 3.148 × 10−3 600.600 4.0
Montmorillonite Ni2+ 9.534 × 101 1.429 × 10−3 12.994 4.0
Ca-montmorillonite 7.300 × 101 3.337 × 10−3 17.781 4.0
Montmorillonite Mn2+ 1.620 × 101 5.341 × 10−2 14.013 4.0
Ca-montmorillonite 1.632 × 101 8.821 × 10−2 23.491 4.0
Montmorillonite Cd2+ 2.076 × 101 5.427 × 10−2 23.491 4.0
Ca-montmorillonite 2.003 × 101 5.745 × 10−2 23.052 4.0
Montmorillonite Ag+ 7.842 × 101 2.354 × 10−2 144.802 4.0
Ca-montmorillonite 1.375 × 102 9.572 × 10−3 180.864 4.0
a
Intercept and slope defined by Eq. (2), maximum adsorption qe in mg g−1 , rate constant Kv in g mg−1 h−1 , time in h, initial adsorption rate Kv q2e in mg g−1 h−1 .

adsorbent on uniformly distributed adsorption sites. The linear the Langmuir model; the calculated isotherms (R2 0.999–1.0) have
form of the Langmuir isotherm is represented by Eq. (4): the adsorption constant K and maximum adsorption b as indicated
1 1 1 in Table 3.
= + Ce , (4)
Qe b bK
4. Discussion
where Qe (mg g−1 ) is the adsorbate uptake at equilibrium, Ce
(mg L−1 ) is the equilibrium concentration of adsorbate, K (L mg−1 )
4.1. Adsorption kinetics
and b (mg g−1 ) are the Langmuir constants associated with adsorp-
tion energy and maximum adsorption capacity. The slope and
The kinetics of adsorption of heavy metals from monocationic
intercept at the origin of the 1/Qe vs. 1/Ce curve represent the Lang-
solutions was second order, conforming to Eq. (2) (R2 0.998–1.0)
muir parameters [34].
(Table 2, Fig. 1). The initial rate of adsorption, Kv q2e , and the
amount of metal adsorbed at equilibrium, qe , by montmoril-
3. Results
lonite and by Ca-montmorillonite decreased by the progression
Hg2+ > Cu2+ > Pb2+ > Zn2+ > Cr3+ > Ni2+ > Ag+ > Ba2+ > Cd2+ > Mn2+ .
3.1. Adsorption kinetics
The adsorptions of Hg2+ , Cu2+ , Pb2+ and Zn2+ were greater than
those of Ni2+ , Ag+ , Ba2+ , Cd2+ and Mn2+ that were significantly
Kinetics of adsorptions by montmorillonite and Ca-
lower (Table 2). The initial rates of adsorption and the amounts
montmorillonite of Pb2+ , Cu2+ , Cr3+ , Zn2+ , Ba2+ , Hg2+ , Ni2+ ,
of cations adsorbed were larger by Ca-montmorillonite than by
Mn2+ , Cd2+ and Ag+ from monocationic solutions were com-
montmorillonite. The equilibrium solutions in contact showed
pleted and equilibrated after 10 h of contact (Table 2, Fig. 1).
increased contents of Ca2+ that could raise the alkalinity and
The adsorption of Pb2+ , Cu2+ , Cr3+ , Zn2+ and Hg2+ surpassed the
contribute to further precipitation, sustaining earlier studies on
CEC of montmorillonite of 0.64 meq g−1 within the first hour
of contact, whereas the adsorption of Ni2+ and Ba2+ required 2
and 5 h; interestingly, Cd2+ and Mn2+ did not saturate the clay. Table 3
Adsorption was associated with increasing contents of Ca2+ in the Equilibrium adsorption of Pb2+ , Cu2+ , Cr3+ , Zn2+ , Ba2+ , Hg2+ , Ni2+ , Mn2+ and Cd2+ by
equilibrium solution, which were 6–8 times the CEC of the clay for montmorillonite and Ca-montmorillonite.a

Cr3+ , Pb2+ , Cu2+ , Zn2+ and Hg2+ , twice for Ni2+ and Ag+ , and an 8th Sorbent Cation b K
of the CEC for the remaining metal cations. Experimental data fit Montmorillonite Pb 2+
−2.851 × 10 1
−1.300 × 100
to second order kinetics (R2 0.998–1.0) as defined by Eq. (2); the Ca-montmorillonite −2.596 × 101 −1.237 × 100
calculated equilibrium adsorption qe , rate constant Kv , initial rate Montmorillonite Cu2+ −4.399 × 100 −3.385 × 100
of adsorption Kv q2e and equilibrium pH are indicated in Table 2. Ca-montmorillonite −4.337 × 100 −3.673 × 100
Montmorillonite Cr3+ −8.650 × 10−1 −8.903 × 100
Ca-montmorillonite −2.159 × 100 −2.591 × 101
3.2. Adsorption equilibrium Montmorillonite Zn2+ 3.477 × 101 4.780 × 101
Ca-montmorillonite 3.523 × 101 4.615 × 101
Equilibrium adsorptions by montmorillonite and Ca- Montmorillonite Ba2+ 6.984 × 100 1.302 × 100
montmorillonite of metal ions from binary metal cation + Ca2+ Ca-montmorillonite 1.073 × 101 1.551 × 10−1
Montmorillonite Hg2+ 3.681 × 101 1.999 × 10−2
solutions are shown in Table 3 and Fig. 2. The y-intercepts of the
Montmorillonite Ni2+ 4.849 × 100 1.547 × 100
isotherms for Pb2+ , Cu2+ and Cr3+ were negative, with nearly all Ca-montmorillonite 5.969 × 100 1.271 × 100
Cr3+ , Pb2+ , Cu2+ , Zn2+ and Hg2+ removed from their respective Montmorillonite Mn2+ 3.820 × 100 1.229 × 10−1
equilibrium solutions. The remaining cations had positive inter- Montmorillonite Cd2+ 6.978 × 100 8.002 × 10−2
cepts and were only partially depleted from solutions that were a
Intercept and slope defined by Eq. (4), maximum adsorption b in mg g−1 , con-
enriched by corresponding amounts of Ca2+ . Experimental data fit stant K in L mg−1 .
 L. de Pablo et al. / Chemical Engineering Journal 171 (2011) 1276–1286 1279

the fixation of Pb2+ and Zn2+ by Ca-montmorillonite in amounts
equal to the amount of Ca2+ released from the clay when adsorp-
tion was by metal cation/Ca2+ exchange [23,35]. At high pH
levels precipitation occurs and separation becomes 100% effective
[9,36].
4.2. Adsorption equilibrium
Equilibrium adsorption from metal + Ca2+ solutions of greater
ionic strength than the monocationic solutions conformed to
the Langmuir model (Table 3, Fig. 2). At low concentrations the

600 0.03
Ca-mnt mnt

t/qt (h g mg-1)
400 0.02 Ca-mnt
qt (mg g-1)

mnt

200 0.01

Pb Pb
0 0.00
0 4 8 12 0 4 8 12

Time (h) Time (h)

500 0.03
Ca-mnt
mnt
400
Ca-mnt
mnt t/qt (h g mg-1) 0.02
qt (mg g-1)

300

200
0.01
100
Hg Hg
0 0
0 4 8 12 0 4 8 12

Time (h) Time (h)

0.12
160
Ca-mnt mnt
mnt
t/qt (h g mg-1)

120 0.08
qt (mg g-1)

80 Ca-mnt
0.04
40
Cu Cu
0 0.00

0 4 8 12 16 0 4 8 12 16

Time (h) Time (h)

160 0.12

mnt mnt
120 Ca-mnt
t/qt (h g mg-1)

0.08
qt (mg g-1)

Ca-mnt
80

0.04
40

Zn Zn
0 0.00
0 4 8 12 16 0 4 8 12 16

Time (h) Time (h)

Fig. 1. Kinetics of adsorption of Pb2+ , Hg2+ , Cu2+ , Zn2+ , Cr3+ , Ba2+ , Ni2+ , Mn2+ , Cd2+ and Ag+ from monocationic solutions by montmorillonite and Ca-montmorillonite.
1280 L. de Pablo et al. / Chemical Engineering Journal 171 (2011) 1276–1286

100 0.3
Ca-mnt
80
mnt

t/qt (h g mg-1)
0.2

qt (mg g-1)
60 mnt
Ca-mnt

40
0.1
20
Cr Cr
0 0.0
0 4 8 12 16 0 4 8 12 16 20

Time (h) Time (h)

80 0.3

Ca-mnt
Ca-mnt
60

t/qt (h g mg-1)
0.2 mnt
qt (mg g-1)

mnt
40
0.1
20

Ba Ba
0 0.0
0 4 8 12 16 0 4 8 12 16
Time (h) Time (h)

80 0.3

Ca-mnt
Ca-mnt
60 mnt
t/qt (h g mg-1)

0.2
mnt
qt (mg g-1)

40
0.1
20

Ni Ni
0 0.0
0 4 8 12 16 0 4 8 12 16
Time (h) Time (h)

16 1.2
Ca-mnt
mnt
12 mnt
0.8
t/qt (h g mg-1)
qt (mg g-1)

8
Ca-mnt
0.4
4

Mn Mn
0 0.0
0 4 8 12 16 0 4 8 12 16
Time (h) Time (h)

Fig. 1. (Continued )
 L. de Pablo et al. / Chemical Engineering Journal 171 (2011) 1276–1286
24
mnt
20
16
qt (mg g-1)
12 Ca-mnt
8
4 0.2
Cd
0 0.0
0 4 8 12 16
Time (h)
160
120
Ca-mnt
qt (mg g-1)
80
mnt
40
Ag
0 0.00
0 2 4 6 8 10 12 14
Time (h)
Fig. 1. (Continued )
Freundlich adsorption model was applied but calculated correla-
tions failed to show improvements over the Langmuir model. The
amounts of Cr3+ , Pb2+ and Cu2+ adsorbed by the clay were nega-
tive from equilibrated solutions that were nearly totally depleted
of metal. For these cations, Cr3+ , Pb2+ and Cu2+ , precipitation was
the dominant process, not adsorption; the maximum adsorption,
b, was negative signaling lack of adsorption but metal precipita-
tion. A contrasting behavior was shown by the adsorption of Hg2+ ,
Zn2+ , Cd2+ , Ba2+ , Ni2+ and Mn2+ through processes not dominated
by precipitation.
Cation speciation in aqueous solutions [31,32] (Table 4, Fig. 3)
show that Cr3+ at pH 4.2 forms Cr2 O3 and minor Cr(OH)3 , Pb2+
goes into Pb(OH)2 at pH 4.8, Hg2+ at pH >3.2 precipitates Hg(OH)2
but Hg2 2+ forms Hg2 (OH)2 at pH 5.2 and Zn2+ changes to ZnO and
Zn(OH)2 at pH 6.2. These pHs to precipitation vary with concentra-
tion, being higher for dilute than for concentrated solutions. The
low levels of alkalinity of 4.2–4.8 required for precipitation of Cr3+
and Pb2+ can be attained when cationic acidic solutions are placed
in contact with adsorbents like montmorillonite that normally has
a near neutral pH of ∼6.5. Precipitation is slightly more abundant
when Ca-montmorillonite is the adsorbent and Ca2+ moves into
solution (Table 2) or when the adsorbate is in bimodal cation + Ca2+
solutions where additional Ca2+ and greater ionic strength further
support precipitation. Other cations, specifically Hg2 2+ that pre-
cipitates Hg2 (OH)2 at pH 5.2, Zn2+ that forms ZnO and Zn(OH)2
at pH 6.3, Ni2+ that precipitates Ni(OH)2 at pH 7.6, Mn2+ that at
pH 9 forms Mn(OH)2 and Cd2+ that at pH 9.1 turns into Cd(OH)2
precipitate outside the pH range attainable by simple addition of
monocationic acid solutions or bimodal cation + Ca2+ solutions to
montmorillonite or Ca-montmorillonite and are adsorbed by the
clay, through processes free of precipitation. Cations Ag+ , Ba2+ and
Ca2+ remain as simple cations through the acid to alkaline range.
1281
1.0
0.8
Ca-mnt mnt
t/qt (h g mg-1)
0.6
0.4
Cd
20 0 4 8 12 16 20
Time (h)
0.16
mnt
0.12
t/qt (h g mg-1)
0.08
Ca-mnt
0.04
Ag
0 2 4 6 8 10 12 14
Time (h)
Experimental data did not indicate any significant influence of the
ionic radii on adsorption and precipitation; cations of large radius
and low charge density, e.g., Pb2+ and Ba2+ , were precipitated or
adsorbed indistinctly of cations of smaller radii and higher charge
density, e.g., Cr3+ or Mn2+ [36].
The results indicate a divide around a pH of 5 that separates
metal cations that precipitate stable hydroxides and oxides at lower
pH values (e.g., Cr3+ and Pb2+ ) from metal cations that form hydrox-
ides or oxides at greater alkalinities (e.g., Hg2 2+ , Zn2+ , Ni2+ , Ag+ ,
Cd2+ , Mn2+ and Ba2+ ). The divide is not greater than the pH of 5.2
required to precipitate Hg2 (OH)2 ; Zn2+ that at a pH of 6.2 changes
into ZnO and Zn(OH)2 did not precipitate and other cations (e.g.,
Ni2+ , Ag+ , Cd2+ , Mn2+ and Ba2+ ) that require higher pHs for precipi-
tation were directly adsorbed by the clay, through processes free of
precipitation. Cations forming oxides or hydroxides at pH <5 may
achieve total precipitation from concentrated solutions but might
not precipitate from dilute solutions due to the effect of dilution
on raising the pH. Cations that form stable solids at pHs above the
divide are adsorbed normally either as simple cations or as tran-
sient hydroxyl cations. Reeder et al. [37] previously mentioned an
“adsorption edge” or narrow pH range where adsorption efficiency
changes, occurring at pH levels that vary depending on the metal.
In a system like ours defined by acid monocationic solutions
and montmorillonite and Ca-montmorillonite of near neutral pH
or of bimodal cation + Ca2+ solutions and the same sorbents, the pH
varies from acid to slighly alkaline. Within this narrow range of pH
cations are in their simplest form essentially below their pH to pre-
cipitation or they are as more complex hydroxyl cations that attain
their maximum abundance when precipitation starts and decline
it at greater pH levels (Table 4, Fig. 3). As the alkalinity increases,
adsorption sites on the clay surface and on the amphoteric crys-
tal edges are deprotonated and readied to adsorb metal cations;
1282 L. de Pablo et al. / Chemical Engineering Journal 171 (2011) 1276–1286

hydroxyl metal cations attach as inner sphere complexes to the remain in the equilibrating solution suggest that aside from adsorp-
external silanol and aluminol amphoteric positions where the influ- tion by Ca2+ exchange – with formation of outer-sphere complexes
ence of pH is more relevant [36]. The relatively low adsorption of in the interlayer – there is adsorption on the external crystal posi-
Ni2+ , Ag+ , Cd2+ , Mn2+ and Ba2+ plus the low amounts of Ca2+ that tions [38,39]. Adsorption may conform to Eq. (5) or Eq. (6) when

0.10 0.10

0.08 Ca-mnt 0.08 mnt

mnt

1/Qe (g mg-1)
1/Qe (g mg-1)

0.06 0.06

0.04 0.04

0.02 0.02

Pb Hg
0.00 0.00
0 1 2 3 4 5 0.00 0.02 0.04 0.06

1/Ce (L mg-1) 1/Ce (L mg-1)

0.3 0.3

mnt Ca-mnt

Ca-mnt
1/Qe (g mg-1)

0.2 1/Qe(g mg-1) 0.2

mnt

0.1 0.1

Cu Zn
0.0 0.0
0 2 4 6 8 10 0 100 200 300 400

1/Ce (L mg-1) 1/Ce (L mg-1)

0 .5 0.16

Ca-mnt
0.4 Ca-mnt
0.12
mnt
1/Qe (g mg-1)

1/Qe (g mg-1)

mnt
0.3
0.08
0.2

0.04
0.1
Cr Ba
0.0 0.00
0 4 8 12 16 20 0.00 0.02 0.04 0.06 0.08

1/Ce (L mg-1) 1/Ce (L mg-1)

0.4 0.5

0.4
0.3 mnt Ca-mnt
mnt
1/Qe (g mg-1)

1/Qe (g mg-1)

0.3
0.2
0.2

0.1
0.1

Ni Mn
0.0 0.0
0.0 0.2 0.4 0.6 0.8 1.0 0.00 0.02 0.04 0.06 0.08

1/Ce (L mg-1) 1/qe (L mg-1)

Fig. 2. Equilibrium isotherms of the adsorption of Pb2+ , Cu2+ , Cr3+ , Zn2+ , Ba2+ , Hg2+ , Ni2+ , Mn2+ and Cd2+ from bimodal cation + Ca2+ solutions by montmorillonite and
Ca-montmorillonite.
 L. de Pablo et al. / Chemical Engineering Journal 171 (2011) 1276–1286 1283

0.25

0.20 Ca-mnt

1/Qe (g mg-1)
0.15

0.10

0.05

Cd
0.00
0.00 0.01 0.02 0.03

1/qe (L mg-1)

Fig. 2. (Continued ).

there is adsorption plus precipitation. Both reactions generate pro-
tons that would reverse the pH towards the acid side.
S–OH + M2+ + H2 O = S–O–MOH2+ + 2H+
S–O–MOH2+ + M2+ + 2H2 O = S–O–MOH2+ + M (OH)2 (s) + 2H+
Our data complement earlier studies [18,19] that attributed the
adsorption of Cu2+ and Zn2+ in excess of the montmorillonite CEC
to the precipitation of cation hydroxides, differentiating between
adsorption by simple cation exchange at pH 4–7, formation of
hydroxyl cations when the CEC of the clay was exceeded at pHs of 4
and greater, and precipitation of cation hydrates from more alkaline
environments. Adsorption of Cu2+ by Cheto clay in alkaline condi-
tions resulted in agglomeration of copper oxide and replacement of
hydroxyl Ca2+ ions by Cu2+ likely occurring on the edges of the clay
(5) layers [20]. Jung et al. [40] showed that the adsorption of Cu2+ was
through inner-sphere surface complexes at pH 5.90 and by precip-
itation at pH 7.88. The adsorption of Pb2+ and Zn2+ was ascribed to
low ionic strength pH-independent mechanisms consistent with
outer-sphere complexation and high ionic strength pH-dependent
(6)
mechanisms consequent to inner-sphere complexes where Pb2+
would form covalent bonds; precipitation of lead particles on the
clay surface was prone to occur under alkaline conditions [1,23,41].
Polcaro et al. [42] showed that heavy metals were adsorbed at low
pH levels; at pH 6.5 fractions of Pb2+ , Zn2+ and Cd2+ were sorbed
by ion exchange while the remainder was assumed to be sorbed
through surface precipitation. The adsorption of Zn2+ by soils was

Table 4
Cation speciation of Cr3+ , Pb2+ , Cu2+ , Hg2+ , Hg2 2+ , Ni2+ , Zn2+ , Mn2+ , Ag+ , Cd2+ , Ba2+ and Ca2+ in 50.00 ␮M aqueous solutions at pH 1–12.

Cation Conca pH Cations Conca pH Precipitate

Cr 3+
−4.2 1.0–5.4 Cr 3+
−4.2 4.2–12.0 Cr2 O3
−4.2 1.0–8.8 Cr(OH)2+ −8.5 4.2–12.0 Cr(OH)3
−6.8 3.0–6.8 Cr2 (OH)2 4+ , Cr(OH)2 + , Cr3 (OH)4 5+
−8.5 10.0–12.0 Cr(OH)4 −
Pb2+ −1.2 1.0–8.5 Pb2+ −1.2 4.8–12.0 Pb(OH)2
−4.2 1.0–9.3 Pb4(OH)4 4+ , PbOH+ , Pb2 OH3+
−8.0 11.0–12.0 Pb(OH)3 − , Pb(OH)4 2−
Cu2+ −4.2 1–6 Cu2+ −4.2 6.0–12.0 CuO
−6.2 3.2–8.6 CuOH+ , Cu2 (OH)2 2+ −8.5 6.0–12.0 Cu(OH)2
−7.0 10.0–12.0 Cu(OH)4 2− , Cu(OH)3 −
Hg2+ −4.2 1.0–5.2 Hg2+ −4.2 3.0–12.0 Hg(OH)2
−3.2 1.0–7.2 HgOH+
Hg2 2+ −4.2 1.0–5.2 Hg2 2+ −4.2 5.2–12.0 Hg2 (OH)2
−5.2 1.0–5.2 Hg2 (OH)+
−7.0 10.3–12.0 Hg(OH)3 −
Ni2+ −4.2 1.0–7.5 Ni2+ −4.2 7.5–12.0 Ni(OH)2
−6.5 1.0–10.0 NiOH+
−7.0 >10.2 Ni(OH)3 −
Zn2+ −1.1 1.0–6.2 Zn2+ −1.2 6.2–12.0 ZnO
−2.8 1.0–12.0 Zn4 (OH)4 4+ , Zn2 OH3+ , ZnOH+ −5.0 6.2–12.0 Zn(OH)2
−5.0 10.5–12.0 Zn2 (OH)2 2+ , Zn(OH)4 2− , Zn(OH)3 −
Mn2+ −4.2 1.0–12.0 Mn2+ −4.2 7.0–12.0 Mn(OH)2
−6.0 5.0–12.0 MnOH+ , Mn2 (OH)3 3+
−7.0 11.0–12.0 Mn(OH)3 −
Ag+ −4.2 1.0–10.7 Ag+ −4.2 10.6–12.0 Ag2 O
−5.5 7.4–12.0 Ag(OH)2 − −5.6 10.6–12.0 AgOH
Cd2+ −4.3 1.0–9.0 Cd2+ −4.3 9.0–12.0 Cd(OH)2
−5.5 5.5–12.0 Cd(OH)+ −6.5 8.0–12.0 Cd(OH)2
−7.0 10.8–12.0 Cd(OH)3 −
Ba2+ −4.2 1.0–12.0 Ba2+
−9.0 9.0–12.0 BaOH+
Ca2+ −1.0 1.0–12.0 Ca2+
−1.0 5.0–12.0 CaOH+
a
Conc represents the log (ion conc). Data from MINTEQ [32].
1284 L. de Pablo et al. / Chemical Engineering Journal 171 (2011) 1276–1286

Fig. 3. Speciation of Cr3+ , Pb2+ , Cu2+ , Hg2+ , Hg2 2+ , Zn2+ , Ni2+ , Mn2+ , Ag+ , Cd2+ , Ba2+ and Ca2+ in 50 ␮M aqueous solutions in the pH range 1–12 [31,32].
 L. de Pablo et al. / Chemical Engineering Journal 171 (2011) 1276–1286
improved by addition of calcite, by precipitation when metal con-
centration was high and via cation exchange when it was low [43];
the uptake of Zn2+ by montmorillonite occurred rapidly at pH 7.3
on pH-dependent edge sites [44]. The adsorption of Ni2+ and NiOH+
by montmorillonite was shown to increase with pH up to pH 8 after
which precipitation was the dominant process [45]. The adsorption
of Ni2+ and Zn2+ was attributed to pH-independent cation exchange
with formation of outer-sphere complexes on permanent exchange
sites and to pH-dependent surface complexation on amphoteric
surface hydroxyl groups [46]. At pH levels below 5 Ni2+ is elec-
trostatically held, at higher values is adsorbed at the edge sites of
montmorillonite, and at pHs greater than 6 and high Ni2+ concen-
tration precipitation occurs [47–50]. Adsorption of Cu2+ , Ni2+ and
Co2+ by K-montmorillonite was found to increase as the ionic radii
decreased [9].
Results indicate that heavy metals may precipitate or remain
in solution depending on the metal. Within the pH range of our
studies it was established that below pH 6 adsorption from con-
centrated solutions was dominated by precipitation while above
pH 6 adsorption was the principal process. The precise conditions
required for precipitation or adsorption vary within a range estab-
lished by the concentration of solutions, the degree of reaction and
liberation of protons.
5. Conclusions
Adsorption of heavy metals from acid monocationic solutions
by montmorillonite and Ca-montmorillonite of near neutral pH
occurs by precipitation and by adsorption. Precipitation from con-
centrated solutions is common to cations that form oxides and
hydroxides at pH levels below 5 while adsorption predominates
among cations that precipitate at greater pHs or in dilute solutions.
To the former group belong Cr3+ , Pb2+ and Cu2+ and to the latter
belong Hg2+ , Zn2+ Ba2+ , Ni2+ , Mn2+ , Cd2+ and Ag+ . Adsorption is by
Ca2+ exchange and fixation as outer-sphere cations on the clay sur-
face and by fixation of hydroxyl cations as inner sphere complexes
on external amphoteric silanol and aluminol sites. Conditions of
pH to precipitate stable oxides and hydroxides show some varia-
tion due to solution concentration, degree of reaction and liberation
of protons. The stability of precipitated oxides and hydroxides can
be sustained at high pHs in dry systems.
Acknowledgements
The present work was financed through Project P47075000 of
the Consejo Nacional de Ciencia y Tecnologia – CONACYT. The
authors are indebted to K. Shimada for her collaboration and con-
tribution with the analytical work.
References
[1] N.M. Nagy, J. Kónya, M. Beszeda, I. Beszeda, E. Kálmán, Z. Keresztes, K. Papp,
I. Cserny, Physical and chemical formations of lead contaminants in clay and
sediment, J. Colloid Interface Sci. 263 (2003) 13–22.
[2] E. Ferrage, C. Tournassat, E. Rinnert, B. Lanson, Influence of pH on the interlayer
cationic composition and hydration state of Ca-montmorillonite: analytical
chemistry, chemical modeling and XRD profile modelling study, Geochim. Cos-
mochim. Acta 69 (2005) 2797–2812.
[3] R.K. Sharma, M. Agrawal, F. Marshall, Heavy metal contamination of soil and
vegetables in suburban areas of Varanasi, India, Ecotoxicol. Environ. Saf. 66
(2007) 258–266.
[4] A. Mellah, S. Chegrouche, The removal of zinc from aqueous solutions by natural
bentonites, Water Res. 31 (1997) 621–629.
[5] M.J. Angove, B.B. Johnson, J.D. Wells, The influence of temperature on the
adsorption of cadmium(II) and cobalt(II) on kaolinite, J. Colloid Interface Sci.
204 (1998) 93–103.
[6] C.A. Coles, R.N. Yong, Aspects of kaolinite characterization and retention of Pb
and Cd, Appl. Clay Sci. 22 (2002) 39–45.
[7] J.C. Echeverria, E. Churio, J. Garrido, Retention mechanisms of Cd on illite, Clays
Clay Miner. 50 (2002) 614–623.
1285
[8] S.H. Lin, R.S. Juang, Heavy metal removal from water by sorption using stron-
tium on bentonite, J. Hazard. Mater. B 92 (2002) 315–326.
[9] O. Abolino, M. Aceto, M. Malandrinoa, C. Sarzanin, E. Mentasti, Adsorption of
heavy metals on Na-montmorillonite. Effect of pH and organic substances,
Water Res. 37 (2003) 1619–1627.
[10] E. Alvarez-Ayuso, A. Garcia-Sanchez, Removal of heavy metals from wastew-
aters by natural and Na-exchanged bentonites, Clays Clay Miner. 51 (2003)
475–480.
[11] O. Yavuz, Y. Altunkaynak, F. Guzel, Removal of copper, cobalt and manganese
from aqueous solution by kaolinite, Water Res. 37 (2003) 948–952.
[12] F.A. Vega, E.F. Covelo, M.L. Andrade, P. Marcet, Relationships between heavy
metals content and soil properties in soils, Anal. Chim. Acta 524 (2004)
141–150.
[13] E. Tertre, G. Berger, S. Castet, M. Loubet, E. Giffaut, Experimental sorption of
Ni2+ , Cs+ and Ln3+ onto a montmorillonite up to 150 ◦ C, Geochim. Cosmochim.
Acta 69 (2005) 4937–4948.
[14] S.S. Gupta, K.G. Bhattacharyya, Immobilization of Pb(II) Cd(II) and Ni(II) ions
on kaolinite and montmorillonite surfaces from aqueous medium, J. Environ.
Manage. 87 (2008) 46–58.
[15] G. Petruzzelli, G. Guidi, L. Lubrano, Ionic strength effect on heavy metal adsorp-
tion by soil, Commun. Soil Sci. Plant Anal. 16 (1985) 971–986.
[16] R.D. Harter, Competitive sorption of cobalt, copper, and nickel ions by a calcium
saturated soil, Soil Sci. Soc. Am. J. 56 (1992) 444–449.
[17] K.G. Bhattacharyya, S.S. Gupta, Adsorptive accumulation of Cd(II), Co(II), Cu(II),
Pb(II) and Ni(II) from water on montmorillonite: influence of acid activation, J.
Colloid Interface Sci. 310 (2007) 411–424.
[18] F.T. Bingham, A.L. Page, J.R. Sims, Retention of Cu and Zn by H-mnotmorillonite,
Soil Sci. Soc. Am. Proc. 28 (1964) 351–354.
[19] Y. Takahashi, H. Imai, Adsorption of heavy metal cations in montmorillonite,
Soil Sci. Plant Nutr. 29 (1983) 111–122.
[20] J.D. Morton, J.D. Semrau, K.F. Hayes, Geochim. Cosmochim. Acta 65 (2001) 2709.
[21] W.F. Bradley, R.E. Grim, G.F. Clark, A study of the behavior of montmorillonite
on wetting, Zeits. fur Kristall. 97 (1937) 260–270.
[22] D.A. Laird, Layer charge influences on the hydration of expanding 2:1 phyllosil-
icates, Clays Clay Miner. 47 (1999) 630–636.
[23] M. Auboiroux, P. Baillif, J.C. Touraya, F. Bergayab, Apport d’analyses XPS pour
mode et force ionique constante des changes Ca–Cd et Ca–Pb sur une mont-
morillonite calcique, Earth Planetary Sci. 327 (1998) 727–730.
[24] G. Nagelschmidt, C. Tournassat, E. Rinnert, B. Lanson, Influence of pH on the
interlayer cationic composition and hydration state of Ca-montmorillonite:
analytical chemistry, chemical modeling and XRD profile modelling study,
Geochim. Cosmochim. Acta 69 (2005) 2797–2812.
[25] C. Tournassat, J.M. Greneche, D. Tisserand, L. Charlet, The titration of clay
minerals. Part I. Discontinuous back titration technique combined to CEC mea-
surements, J. Colloid Interface Sci. 273 (2004) 224–233.
[26] C. Tournassat, E. Ferrage, C. Poinsignon, L. Charlet, The titration of clay minerals.
Part II. Structural-based model and implications for clay reactivity, J. Colloid
Interface Sci. 273 (2004) 234–246.
[27] T. Iwasaki, T. Watanabe, Distribution of Ca and Na ions in dioctahedral smectites
and interstratified dioctahedral mica/smectites, Clays Clay Miner. 36 (1988)
73–82.
[28] G. Sposito, K.M. Holtzclaw, C. Jouany, L. Charlet, Cation selectivity in
sodium–calcium, sodium–magnesium and calcium–magnesium exchange on
Wyoming bentonite at 298 K, Soil Sci. Soc. Am. J. 47 (1983) 917–921.
[29] J. Mamy, J.P. Gaultier, Etude comparée de l’évolution des montmorillonites
biioniques K–Ca de Camp-Berteaux et du Wyoming sous l’effet des cycles
d’humectation et de dessication, Clay Miner. 14 (1979) 181–192.
[30] L. de Pablo, Diagenesis of oligocene–miocene vitric tuffs to montmorillonite and
K-feldspar deposits, Durango, Mexico, Clays Clay Miner. 38 (1990) 426–436.
[31] I. Puigdomenech, Windows software for the graphical presentation of chemical
speciation, in: 219th ACS National Meeting, Abstracts of Papers, Abstract I&EC-
248, vol. 1, American Chemical Society, San Francisco, CA, March 26–30, 2000.
[32] Environmental Protection Agency, MINTEQ Metal Speciation Equilibrium
Model for Surface and Ground Water, version 4.03, US Environmental Protec-
tion Agency, 960 College Station Road, Athens, GA, USA, 2006.
[33] Y. Ho, G. McKay, Application of kinetic models to the sorption of copper(II) on
to peat, Adsorpt. Sci. Technol. 20 (2002) 797–815.
[34] R.T. Pabalan, F.P. Bertetti, Cation exchange properties of natural zeolites, in:
D. Bish, D. Ming (Eds.), Natural Zeolites: Occurrence, Properties, Applications,
Reviews in Mineralogy and Geochemistry, vol. 45, Mineralogical Society of
America, Washington, 2001, pp. 453–464.
[35] M. Auboiroux, P. Baillif, J.C. Touray, F. Bergaya, Fixation of Zn and Pb by
Ca-montmorillonite in brines and dilute solutions, Appl. Clay Sci. 11 (1996)
117–136.
[36] O. Abolino, A. Giacomino, M. Malandrino, E. Mentasti, Interaction of metal ions
with montmorillonite and vermiculite, Appl. Clay Sci. 38 (2008) 227–236.
[37] R.J. Reeder, M.A. Schoonen, A. Lanzirotti, Metal speciation and its role in bioac-
cessibility and bioavailability, Reviews in Mineralogy and Geochemistry, vol.
64, Mineralogical Society of America, Washington, 2006, 59–113.
[38] M.H. Bradbury, B. Baeyens, Modeling the sorption of Mn(II), Co(II), Ni(II), Zn(II),
Cd(II), Eu(III), Am(III), Sn(IV), Th(IV), Np(V) and U(VI) on montmorillonite:
linear free energy relationships and estimates of surface binding constants
for some selected heavy metals and actinides, Geochim. Cosmochim. Acta 69
(2005) 875–892.
[39] E. Assaad, A. Azzoux, D. Nistor, A.V. Ursu, T. Sajin, D.N. Miron, F. Monette, P.
Niquette, R. Hausler, Metal removal through synergic coagulation-flocculation
1286 L. de Pablo et al. / Chemical Engineering Journal 171 (2011) 1276–1286
using optimized chitosan–montmorillonite system, Appl. Clay Sci. 37 (2007)
258–274.
[40] J. Jung, J. Kim, J. Won Suh, J. Lee, S. Ryu, Microscopic and macroscopic approaches
of Cu(II) removal by FSM-16, Water Res. 35 (2001) 937–942.
[41] M.F. Brigatti, F. Corradini, G.C. Franchini, S. Mazzoni, L. Medici, L. Poppi, Inter-
action between montmorillonite and pollutants from industrial waste-waters:
exchange of Zn2+ and Pb2+ from aqueous solutions, Appl. Clay Sci. 9 (1995)
383–395.
[42] A.M. Polcaro, M. Mascia, S. Palmas, A. Vacca, G. Tola, Competitive sorption of
heavy metal ions by soils, Environ. Eng. Sci. 20 (2003) 607–616.
[43] Y.S. Al-Degs, M.I. El-Barghouth, A.A. Issa, M.A. Khraisheh, G.M. Walker, Sorp-
tion od Zn(II), Pb(II) and Co(II) using natural sorbents: equilibrium and kinetic
studies, Water Res. 40 (2006) 2645–2658.
[44] M.L. Schlegel, A. Manceau, Evidence for the nucleation and epitaxial growth
of Zn phyllosilicate on montmorillonite, Geochim. Cosmochim. Acta 70 (2006)
901–917.
[45] K.G. Bhattacharyya, S.S. Gupta, Kaolinite and montmorillonite as adsorbents for
Fe(III), Co(II) and Ni(II) in aqueous medium, Appl. Clay Sci. 41 (2008) 1–9.
[46] B. Baeyens, M.H. Bradbury, A mechanistic description of Ni and Zn sorption on
Na-montmorillonite. Part I: titration and sorption measurements, J. Contam.
Hydrol. 27 (1997) 199–222.
[47] R. Dahn, A.E.M. Scheidegger, A. Manceau, M.L. Schlegel, B. Baeyens, M.H.
Bradbury, D. Chateigner, Structural evidence for the sorption of Ni(II)
atoms on the edges of montmorillonite clay minerals: a polarized X-
ray absorption fine structure study, Geochim. Cosmochim. Acta 67 (2003)
1–15.
[48] B. Baeyens, M.H. Bradbury, D. Chateigner, Structural evidence for the sorption
of Ni(II) atoms on the edges of montmorillonite clay minerals: a polarized X-
ray absorption fine structure study, Geochim. Cosmochim. Acta 67 (2003) 1–
15.
[49] D. Xu, X. Zhou, X. Wang, Adsorption and desorption of Ni2+ on Na-
montmorillonite: effect of pH, ionic strength, fulvic acid, humic acid and
addition sequences, Appl. Clay Sci. 39 (2008) 133–141.
[50] N. Maarten, A.M. Scheidegger, R. Dahn, D. Chateigner, G. Furrere, Immobi-
lization of Ni by Al-modified montmorillonite: a novel uptake mechanism,
Geochim. Cosmochim. Acta 69 (2005) 4211–4225.