Applied Clay Science 87 (2014) 254–259

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Applied Clay Science

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

Research paper

Copper, lead and cadmium removal by Ca Al layered double hydroxides

Ricardo Rojas ⁎
INFIQC-CONICET, Departamento de Fisicoquímica, Facultad de Ciencias Químicas, Universidad Nacional de Córdoba, Argentina

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

Article history: Layered double hydroxides are increasingly studied as heavy metal scavengers due to their acid/base buffering
Received 1 July 2013 capacity that leads to hydroxide precipitation. Their intercalation with ligands such as edta also provides active
Received in revised form 26 October 2013 sites for heavy metal chelation to these solids. In this work, both mechanisms are studied in Ca–Al layered double
Accepted 4 November 2013
hydroxides (LDHs) with a Friedel's salt layered structure and intercalated with either nitrate (Ca–Al–NO3) or
Available online 2 December 2013
[Ca(edta)]2− (Ca–Al–[Ca(edta)]). With this aim, the acid–base buffering capacity of these solids was determined
Keywords:
and their removal behavior studied as a function of equilibrium concentration and pH. The solids presented high
Friedel's salts instability, Ca2+ ions being selectively leached at pH values as high as 8. As a consequence, high affinity and large
Heavy metal removal removal capacity of Cu2+, Cd2+ and Pb2+ were obtained for Ca–Al–NO3 by a hydroxide precipitation mechanism.
Acid–base buffering The removal capacity of Ca–Al–[Ca(edta)] was quite similar, however, a portion of heavy metal ions was solubi-
Precipitation lized due to [Ca(edta)]2− release. The heavy metal hydroxides obtained by the Ca–Al LDH removal action pro-
Chelation duced immobilization at pH values lower than those produced by simple alkalinization.
© 2013 Elsevier B.V. All rights reserved.

1. Introduction
Heavy metals are important pollutants produced by both natural
processes and human activities; they are strictly regulated due to their
persistence, mobility in aqueous environments and toxicity for living
beings. A wide variety of techniques (such as chemical precipitation,
ion-exchange, adsorption and electrochemical methods) are used for
heavy metal remediation in wastewater, groundwater and sediments
(Fu and Wang, 2011; Hashim et al., 2011; Peng et al., 2009). One of
the most extended methods includes chemical precipitation as hydrox-
ide: pH values higher than 8 greatly reduce the solubility of different
heavy metal hydroxides, afterwards removed from wastewaters by
filtration or flocculation. Nevertheless, this process generates large
volumes of low density, highly hydrated sludge, posing disposal and
dewatering problems. The media pH must also be strictly controlled to
avoid dissolution of amphoteric metal ions. A further important tech-
nique for heavy metal removal is the use of ion exchangers (natural in-
organic solids such as zeolites or synthetic resins) and sorbents (mainly
activated carbon, in addition to clays, bioadsorbents or industrial by-
products) (Hashim et al., 2011). These solids present sites at their
surface or bulk that bind heavy metal ions either by electrostatic inter-
actions (such as in clay minerals) and/or coordinate bonding (ion
exchange resins) (F. Liu et al., 2011).
Layered double hydroxides (LDHs) are intercalation compounds with
a brucite (Mg(OH)2)-like layer structure. In the case of hydrotalcite-like
compounds, the isomorphic substitution of divalent by trivalent ions
(Evans and Slade, 2006; Wypych and Satyanarayana, 2004) produces a
⁎ Tel.: +54 3514334169; fax: +54 3514334188.
E-mail address: rrojas@fcq.unc.edu.ar.
positive charge excess and intercalation of anions that share the interlayer
domain with solvent molecules (usually water). The Friedel's salt struc-
ture is slightly different from that of hydrotalcite as the divalent ion is
sevenfold-coordinated, the seventh position being occupied by a water
molecule (Qian et al., 2012). LDHs are studied as scavengers of pollutants
as varied as oxoanions, heavy metals, phenols or pesticides (Rojas, 2012)
due to their anion exchange, acid base and adsorption reactions.
LDHs remove heavy metal ions by two mechanisms: chemical pre-
cipitation and chelation (Liang et al., 2013). In the first case, LDH
weathering reactions lead to pH increase and precipitation of metal hy-
droxides. These weathering reactions are partial in mildly acidic media,
divalent ions being selectively dissolved (Jobbágy and Regazzoni, 2011).
Heavy metal hydroxide precipitation is produced either as part of LDH
structure or in a separate phase. Thus, Cu2+, Ni2+, Co2+ and Zn2+ remov-
al by Mg–Al LDHs was produced by substitution of the M2+ ions of the
layers (Komarneni et al., 1998) and Zn2+ ions were also removed from
aqueous solutions by Ca–Al LDHs, leading to formation of a Zn–Al LDH
(Q. Liu et al., 2011). Contrarily, Pb2+ removal by a Mg–Al–CO3 LDH led
to the precipitation of Pb2+ salts such as lead carbonate chloride (PbCO3-
PbCl2) and lead hydroxide chloride (Pb(OH)Cl) (Park et al., 2007). On the
other hand, LDHs have been intercalated with ligands such as citrate,
malate and tartrate, edta, diethylenetriaminepentaacetate, meso-(2,3)-
dimercaptosuccinate, among others (Kameda et al., 2008, 2010, 2011;
Pavlovic et al., 2009; Pérez et al., 2006). The solids obtained showed re-
moval capacity for heavy metal ions such as Ni2+, Cu2+, Cd2+, Pb2+,
Sc3+ or La3+ due to a interlayer chelation mechanism, the heavy metal af-
finity being determined by the formation constant of the corresponding
complex (Kameda et al., 2008).
In a previous work (Rojas et al., 2009), the incorporation of edtaH2−2
to the interlayer of Zn–Al LDHs was explored. The sorbent was obtained

0169-1317/$ – see front matter © 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.clay.2013.11.015
 R. Rojas / Applied Clay Science 87 (2014) 254–259
by anion exchange between a nitrate intercalated Zn–Al–LDH and
edtaH2−2 anions, which produced partial erosion of the layers and inter-
calation of [Zn(edta)]2− chelates instead of the ligand. Although both
removal capacity and LDH affinity for heavy metal ions were high,
Cu2+ removal leaded to release of Zn2+ ions, an environmental pollut-
ant (Toxicological Review of Zinc and Compounds, 2005).
The substitution of Zn2+ by Ca2+ in the hydroxylated layers and the
intercalation of [Ca(edta)]2− anions instead of edtaH2−2 are expected to
prevent layer dissolution by the interlayer anion and to minimize the
toxicity of the sorbent. They are also intended to maximize its removal
capacity and affinity for heavy metal ions, due to the high solubility of
calcium hydroxide and the low formation constant of [Ca(edta)]2−
complex. The use of Ca–Al LDHs is also convenient as they can be obtain-
ed from waste produced by the bauxite refinery industry (red mud)
(Palmer et al., 2009) and can be immobilized as a component of Portland
cement (Navarro-Blasco et al., 2013).
The aim of this work is to study the structural aspects, reactivity and
heavy metal removal capabilities of Ca–Al LDHs intercalated either with
nitrate or [Ca(edta)]2−. The structure of the solids was studied by chem-
ical analysis, powder X-ray diffraction (PXRD) and infrared spectrosco-
py, while their reactivity was determined by acid–base potentiometric
titrations. Their heavy metal removal capacity was studied as a function
of heavy metal concentration and pH, whereas solid residues were char-
acterized by PXRD.
2. Materials and methods
2.1. Synthesis and characterization
Reagent-grade chemicals (Baker, Anedra) and high-purity water
(18 MΩ MilliQ, Millipore System) were used unless otherwise stated.
Syntheses were performed in N2 atmosphere to prevent, or at least min-
imize, carbonate incorporation by the samples.
A nitrate-intercalated sample was first prepared by the
coprecipitation method at constant pH (He et al., 2006). 100 mL of a so-
lution containing 0.3 mol Ca(NO3)2·4H2O and 0.1 mol Al(NO3)3·9H2O
was added dropwise to a flask containing 100 mL of a 0.1 mol L−1
KNO3 solution under vigorous stirring, while pH was set constant at
11 by controlled addition of 2 mol L−1 NaOH. Once the addition of reac-
tants was finished the mixture was aged for 24 h, separated by centrifu-
gation and washed three times with water. Half of the resulting slurry
was dried at 50 °C (Ca–Al–NO3 sample) and the remaining slurry was
used to prepare the [Ca(edta)]2− intercalated solid (Ca–Al–[Ca(edta)])
by ion exchange. A 200 mL solution of this anion was prepared with
0.25 mol Ca(NO3)2·4H2O and 0.25 mol Na2H2edta and its pH was set
at 9 by addition of a 2 mol L−1 NaOH solution. The slurry was dispersed
in this solution and the mixture was heated in an autoclave at 90 °C for
24 h. Finally, the solid obtained was separated, washed and dried as
previously described.
Ca and Al content of the samples was determined by atomic absorp-
tion spectrometry (AAS) in a Varian AA240 apparatus. The solid was dis-
solved in HNO3 and diluted to meet the calibration range. Powder X-ray
diffraction (PXRD) patterns were recorded in a Phillips X'pert Pro in-
strument using a CuKα lamp (λ = 1.5408 Å) at 40 kV and 40 mA be-
tween 3° and 70° (2θ) in step mode (0.05°, 1.2 s) and FT-IR spectra
were obtained from KBr pellets (1:100 sample/KBr ratio) in a FT-IR
Bruker IFS28 instrument.
To determine the acid–base reactivity of the solids, proton uptake
(ΓH) vs. pH curves were registered using acid–base potentiometric titra-
tions, following procedures similar to those described in previous works
(Rojas and Giacomelli, 2013). The curves were registered using a
Titrando 905 automatic titrator (Metrohm) controlled by Tiamo soft-
ware and coupled to a Metrohm 9.0262.100 combined pH electrode
and a Dosino 800 dosing unit. ΓH (mol mol− 1) was calculated as
ΓH = nH / M, where nH (mol/g) is the amount of H+ consumed and
M is the formula weight of the corresponding Ca–Al LDH.
255
The apparent hydrodynamic diameter (d) and zeta potential (ζ) were
determined by dynamic light scattering (DLS) and electrophoretic light
scattering (ELS), respectively, in a Delsa Nano C instrument (Beckman
Coulter). The measurements were performed in 0.1 g L−1, 0.05 mol L−1
KNO3 dispersions of the corresponding samples, ultrasonically dispersed
for 30 min. d values were obtained from the autocorrelation function
(g(2)) using the cumulants method while electrophoretic mobilities were
converted to ζ using the Smoluchowski equation.
2.2. Heavy metal removal capacity
Cu2+, Pb2+ and Cd2+ ion removal by LDHs was studied as a function
of the metal ion concentration and pH. The experiments were per-
formed with 1 g L−1, 0.05 mol L−1 KNO3 dispersions with increasing
initial concentration (Ci) of the corresponding heavy metal ion up to
0.35 mmol L−1. These dispersions were allowed to equilibrate for 3 h
under gentle up and down shaking and subsequently centrifuged. The
equilibrium concentration (Ceq) was determined by AAS at the
corresponding wavelength (Cu, λ = 324.8 nm; Cd, λ = 326.1 nm;
Pb, λ = 383.3 nm). The residues of the experiment performed in
Ci = 0.20 mmol L−1 were characterized by PXRD.
Finally, the removal pH dependence was assessed in 1 g L−1 disper-
sions of Ca–Al–NO3 or Ca–Al–[Ca(edta)] in 0.20 mmol L−1 solutions of
the corresponding heavy metal nitrate ([KNO3] = 0.05 mol L−1). Por-
tions were taken at different pH values, adjusted by addition of HNO3
or NaOH 0.1 mol L−1. After centrifugation, heavy metal concentration
was determined in the supernatants. To allow comparison, the data
were expressed as % removal, obtained as (Ci − Ceq) · 100 / Ci. As a
reference, the same experiment was performed in the absence of the
samples to obtain the dissolution profile of the heavy metal hydroxides,
in this case produced by addition of NaOH as removal agent/precipitant.
3. Results and discussion
3.1. Characterization of the samples
The PXRD pattern of Ca–Al–NO3 sample (Fig. 1A) showed peaks
of calcium aluminum nitrate hydroxide hydrate (PDF reference code
50-0652), a solid with a Friedel's salt structure and cell parameters
a = 5.74 Å, c = 17.2 Å. Nevertheless, although all the pattern peaks
can be indexed in a single phase, the presence of amorphous Ca(OH)2
cannot be disregarded. [Ca(edta)]2− anion intercalation (Ca–Al–[Ca(edta]
sample, Fig. 1B) increased the c parameter (=24 Å), as corresponding to
the larger size of this anion; the a parameter remained unaffected. The
interlayer distance (12 Å) was lower than that in previous works with
[Zn(edta)]2− intercalated Zn–Al–LDHs (Zn–Al–[Zn(edta)]) (Rojas et al.,
2009). The gallery height (7.2 Å), obtained by subtraction of the layer
width (4.8 nm) (Park et al., 2007) was also lower than the average
anion size (9–10 Å, as determined by single crystal XRD experiments of
complex salts) (Li et al., 2004). [M(edta)]2− anion disposition was then
different in the interlayers of Ca–Al–[Ca(edta)] and Zn–Al–[Zn(edta)]
(Rojas et al., 2009). In the former, the metal ion faced the layers and the
size of the chelate in this direction was small. In the latter, the metal ion
pointed a parallel direction, the larger dimension of the chelate being per-
pendicular to the layer (Supplementary material, Fig. S1). These different
dispositions were related to the lower charge density of Ca–Al–[Ca(edta)]
with respect to Zn–Al–[Zn(edta)], as a decreased Zn/Al atomic ratio was
produced in the latter due to selective Zn(OH)2 dissolution.
The FT-IR spectra of both samples (Supplementary material, Fig. S2)
showed lattice vibrations of the Ca–Al–LDH layers at 420–422 cm−1
(Ca–O) and 518–530 cm−1 (Al–O), similar to those previously obtained
for OH− intercalated Ca–Al LDHs (Plank et al., 2006). Bands correspond-
ing to vibration modes of the interlayer anion are also registered. Ca–Al–
NO3 exhibited bands at 1385 cm−1, characteristic of nitrate anions; Ca–
Al–[Ca(edta)] showed strong bands at 1597 and 1411 cm−1, assigned
to symmetric and antisymmetric vibration modes of \COO− groups.
256 R. Rojas / Applied Clay Science 87 (2014) 254–259

Fig. 2. Proton uptake (ΓH) vs. pH curves of Ca–Al–NO3 and Ca–Al–[Ca(edta)].

As a result, ΓH reached a plateau around 5 mol mol−1 at pH = 8.

On the other hand, Ca–Al–[Ca(edta)] sample displayed more differ-
entiated ΓH gaps, Ca–Al LDH layer dissolution (Eq. (2)) being displaced
to lower pH values, due to the higher affinity of the [Ca(edta)]2− anions
and the consequent solid stabilization.
To complete the description of the solids, their hydrodynamic diam-
eter and zeta potential vs. pH profiles were determined (Supplementary
Fig. 1. PXRD patterns of Ca–Al–NO3 (A) and Ca–Al–[Ca(edta)] (B) samples as well as of the
material, Fig. S3). Both samples showed d values of a few micrometers at
residues obtained after removal of Cu2+, Cd2+ and Pb2. The interplanar distance of the pH = 11. An increase in particle size was observed as pH decreased due
main (00l) peaks are included in the case of LDH phases. to dissolution of the samples and Al(OH)3 formation. On the other hand,
ζ vs. pH curves showed oppositely charged particles at pH = 11, positive
for Ca–Al–NO3, negative for Ca–Al–[Ca(edta)], which confirmed that
Similar bands have been reported for metal–edta complexes either [Ca(edta)]2− affinity for Ca–Al LDHs was higher than that of NO− 3 . The
as salts or intercalated (Rojas et al., 2008). No significant NO− 3 curves converged as the pH decreased, in agreement with the presence
anion or edtaH− 2 bands were recorded for this sample, indicating of Al(OH)3 particles in both cases.
that [Ca(edta)]2 − was the main interlayer anion.
Based on the PXRD patterns and FT-IR spectra, the chemical compo- 3.2. Heavy metal removal
sition of the samples (Table 1) was proposed considering that a single
Ca–Al–LDH phase, completely intercalated with NO− 3 or [Ca(edta)]
2−
, In order to study heavy metal removal by Ca–Al LDHs, dependence
was obtained. The experimental weight/weight percentage composi- on Ce (Fig. 3) and pH (Fig. 4) was determined. The phases formed during
tion was quite in agreement with those calculated with the proposed the scavenging process were also characterized by PXRD (Fig. 1).
formula (between parentheses). As expected, the exchange with the In all cases, a steep ΓM increase in Ce values near 0 was registered for
chelate instead of the ligand prevented the layer dissolution observed Ca–Al–NO3 (Fig. 3A). Thus, heavy metal concentrations lower than
in previous works (Pérez et al., 2006; Rojas et al., 2009). 0.2 ppm were achieved for dispersions with Ci values as high as
The acid base reactivity of the solids (Fig. 2) was essential to its be- 11 ppm (Cu2 +), 9 ppm (Cd2 +) and 17 ppm (Pb2 +). The affinity for
havior as heavy metal precipitant. ΓH increased with decreasing pH at heavy metals was then quite higher than that obtained for Mg–Al
values as high as 10–11 for both samples. Ca2+ ion were selectively dis- or Zn–Al LDHs (Liang et al., 2010, 2013), which need to be functional-
solved in two steps as pH decreased: first ΓH increased at a steady rate ized with ligands to improve this aspect. With the increase in Ce values,
up to 2 mol mol−1, ascribed to a Ca/Al decrease maintaining the LDH the curves reached a plateau, the maximum ΓM values being around 6.0,
structure. This reaction can be described as: 3.2 and 4.7 mmol g−1 for Cu2+, Cd2+ and Pb2+ respectively. These
þ
values are higher than that obtained for NO− 3 intercalated Zn–Al and
Ca3:0 AlðOHÞ8:0 NO3 ·3 H2 O þ 2H →Ca2:0 AlðOHÞ6 NO3 ·3 H2 O Mg–Al LDHs, and also higher than that found for the removal of Pb2+
2þ
þ Ca þ 2 H2 O ð1Þ by a Ca–Al,Fe LDH (Liang et al., 2013). Only in the case of Cd2+ removal
by a chloride intercalated Ca–Al LDH, a similar capacity was reported
although some amorphous Ca(OH)2 dissolution cannot be discarded. In (Liang et al., 2013). Although the wide range of experimental conditions
a second step a sharp ΓH increase was produced indicating that Ca–Al– makes it difficult to compare the performance of Ca–Al–NO3 sample
LDH layers were dissolved according to the following equation: with that of previously reported LDHs, the optimized performance of
these solids seems to be evident, even when compared to LDHs interca-
þ 2þ −
Ca2:0 AlðOHÞ6:0 NO3 ·3 H2 O þ 3 H →2:0 Ca þ NO3 þ 6 H2 O lated with ligands. The precipitation mechanism, leading to the forma-
þ AlðOHÞ3 : ð2Þ tion of the corresponding heavy metal hydroxides, determined the
removal behavior. Consequently, the remarkable heavy metal removal
by Ca–Al–NO3 was ascribed to its large buffering capacity, while the
low heavy metal concentrations obtained were attributed to the higher
Table 1 solubility of the Ca(OH)2 hydroxide compared to that of Mg(OH)2 or
Chemical analysis and chemical formulae of the synthesized samples. Zn(OH)2 (Table 2). The buffering capacity of Ca–Al–NO3 also prevented
the pH media from reaching values higher than 10 (Fig. 3C), even in a
Sample %Ca %Al %H2O Ca/Al Proposed formula
large excess of the precipitant (points at low Ce values). pH control is
Ca–Al–NO3 30.9 6.8 11.5 3.0 Ca3.0Al(OH)8.0NO3·3H2O important in order to prevent dissolution of amphoteric heavy metals
Ca–Al–[Ca(edta)] 27.5 5.7 9.5 3.4 Ca2.9Al(OH)7.8[Ca(edta)]0.5·3H2O
at high pH values, which is one of the main drawbacks of precipitants
 R. Rojas / Applied Clay Science 87 (2014) 254–259
Fig. 3. Heavy metal removal (ΓM) and pH vs. concentration at equilibrium (Ceq) curves of Ca–Al–NO3 (A and C) and Ca–Al[Ca(edta)] (B and D).
such as lime (Fu and Wang, 2011). As Ce increased and the buffering ca-
pacity was exhausted, pH decreased to meet the corresponding heavy
metal hydroxide equilibrium.
The main difference between the removal mechanisms for Cu2+,
Pb2+ and Cd2+ involved the solids obtained as residues, as shown by
the PXRD patterns in Fig. 1A. Copper removal was produced by substitu-
tion of all Ca2+ ions in the LDH layers, which changed from a Friedel's
salt to a hydrotalcite-like structure. Thus, the PXRD pattern of the resi-
dues after Cu2+ removal showed, exclusively, peaks of Cu–Al–LDH
with rhombohedral symmetry and cell parameters c = 25.8 Å and
a = 3.12 Å. The removal reaction can then be written as follows:
2þ
Ca3 AlðOHÞ8 NO3 ·3 H2 O þ 3Cu →Cu3 AlðOHÞ8 NO3 · n H2 O
2þ
þ 3 Ca :
−1
Thus, ΓM at the plateau (6.0 mmol g ) was quite similar to the
Ca2+ content of Ca–Al–NO3 (6.3 mmol g−1). Its high removal capacity
and efficiency were explained by the higher stability of Cu–Al–LDHs
257
compared to that of Ca–Al–LDHs, due to the lower solubility of copper
hydroxide compared to that of calcium hydroxide (Table 2).
The removal mechanism of Cd2+ was similar to that of Cu2+, since it
precipitated as a LDH phase; yet, in this case, the layer structure remained
unchanged. Only peaks of a cadmium aluminum hydroxide nitrate
(Cd4Al2(OH)12(NO3)2·3H2O, PDF reference code 43-0478) with
Friedel's salt structure and cell parameters a = 5.69 and Å c = 16.5 Å
was registered in the PXRD pattern of the residue (Fig. 1A, Ca–Al–
NO3 + Cd2+). ΓCd was quite lower, increasing almost vertically up to
3.2 mmol g−1, which was attributed to the formation of a solid with a
M/Al atomic ratio lower than that in the initial Ca–Al–LDH or Cu–Al–
LDH and consequently limited byAl3+ availability. Thus, the removal re-
action can be written as
ð3Þ 2þ
Ca3 AlðOHÞ8 NO3 ·3 H2 O þ 2 Cd →Cd2 AlðOHÞ6 NO3 ·nH2 O
2þ −
þ 3 Ca þ 2 OH : ð4Þ
Finally, in the case of Pb2+, the maximum ΓM registered was interme-
diate between that of Cd2+ and Cu2+. In this case, hydroxide precipitation
258 R. Rojas / Applied Clay Science 87 (2014) 254–259

Fig. 4. % removal vs. pH curves of Cu2+ (A), Cd2+ (B) and Pb2+ (C) in the presence of Ca–
Al–NO3 and Ca–Al–[Ca(edta)]. As a reference, % uptake vs. pH curves in the absence of the
samples (precipitation by NaOH addition) is also provided (solid lines).
was not produced as a LDH phase as evident by the PXRD pattern (Fig. 1A,
Ca–Al–NO3 + Pb2+), which exclusively showed peaks of a lead hydrox-
ide nitrate (Pb3(OH)5NO3, PDF reference code 22-0659). The removal re-
action can be described with the following equation:
inhibition, [Ca(edta)]2− anion release was around 0.9 mmol g−1, near
the edta anion content of the solid (1.0 mmol g−1). Nevertheless,
anion release was at least partially reverted with increasing Ceq in the
case of Cu2+ and Cd2+, as demonstrated by the PXRD patterns of the
residues after heavy metal removal (Fig. 1B). Thus, the residue after
Cu2+ removal (Fig. 1B, Ca–Al–[Ca(edta)] + Cu2+) showed peaks corre-
sponding to a [Cu(edta)]2− intercalated sample, with cell parameters
c = 37.8 Å and a = 3.06 Å, while no peak of the nitrate intercalated
phase was obtained. A [Cd(edta)]2 − intercalated phase was also reg-
istered for Cd2+ removal residue (Fig. 1B, Ca–Al–[Ca(edta)] + Cd2+),
the cell parameters being c = 24.0 Å and a = 5.66 Å. However, peaks
corresponding to the nitrate-intercalated solid were also found in this
case. Finally, no LDH phase was obtained due to Pb2+ sorption, the
only crystalline phase being the same as that for Ca–Al–NO3.
The removal dependence on pH, closely related to the stability of the
residues produced, was also studied (Fig. 4). As a reference, the uptake
profile in the absence of the samples, by the addition of NaOH as precip-
itant, was also provided (solid line). A 100% removal was produced at
pH = 10 for all heavy metal ions in the case of Ca–Al–NO3; it only
reached 80% for Ca–Al–[Ca(edta)]. This decrease was consistent with
the heavy metal ion solubilization by edta chelates previously described.
As pH decreased the heavy metal hydroxides formed in the presence of
Ca–Al LDHs were selectively dissolved at a pH similar to that in their ab-
sence. Nevertheless, some differences were found between the % re-
moval vs. pH profiles in the presence and absence of the samples.
Thus, Cu2+ % removal decrease displaced towards lower pH values for
Ca–Al–[Ca(edta)], while it was only produced for Ca–Al–NO3 in the
case of Cd2+ and for both samples in the case of Pb2+. These results in-
dicated that the solids formed during the removal process were, in some
cases, more stable than the hydroxides formed by simple NaOH addi-
tion. The aluminum hydroxide formed after the LDH layer weathering
also partially displaced the removal decrease due to adsorption reac-
tions (Potter and Yong, 1999; Sprycha, 1989). As a consequence, the
complete inhibition of the removal capacity of the samples was pro-
duced at pH values lower than those for the hydroxides produced by
simple NaOH addition, which meant an important advantage of Ca–
Al–LDHs.

2þ 2þ
Ca3 AlðOHÞ8 ðNO3 Þ·3 H2 O þ 3 Pb →Pb3 ðOHÞ5 NO3 þ 3 Ca 4. Conclusions
þ AlðOHÞ3 þ 3 H2 O ð5Þ
Nitrate and [Ca(edta)]2− intercalated Ca–Al–LDHs were obtained by
where Al(OH)3 precipitated as an amorphous phase that produced no dif- coprecipitation at constant pH and anion exchange, respectively. These
fraction peaks in the PXRD patterns. solids showed high instability with pH, calcium hydroxide being se-
In the case of Ca–Al–[Ca(edta)], similar ΓM (Fig. 3B) and pH (Fig. 3D) lectively and completely dissolved at pH values as high as 8. As a con-
values to those of Ca–Al–NO3 were obtained at high Ceq, indicating that sequence, Ca–Al–NO3 achieved equilibrium concentrations lower
precipitation of the metal hydroxides was also the main removal mech- than 0.2 ppm for dispersions with initial concentrations higher
anism for this sample. On the other hand, no removal was produced and than 10 ppm and a removal capacity up to 6 mmol g− 1. These hy-
pH suspension remained almost constant until Ceq = 0.04 mmol L−1 droxides precipitated as LDH phases in the case of Cu2 + and Cd2 +,
for Cu2 +, Pb2 + or Cd2 +. These ions were stabilized in solution by while for Pb2 + a hydroxide nitrate was formed. The solids exhibited
[Ca(edta)]2 − anions released from the sample by ion exchange or removal capacity at pHs lower than those found by simple alkalinization
weathering (Rojas et al., 2009). According to the Ceq range of removal due to a higher stability of the residues obtained and to the adsorption
processes at the surface of the Al(OH)3 particles produced during LDH
layer weathering. In view of these results, Ca–Al–NO3 was considered
a suitable candidate to produce heavy metal scavenging in wastewaters
Table 2 with high pollutant concentrations. The [Ca(edta)]2 intercalation did
Formation constants of edta chelates (K[M(edta)]) and solubility products of
the hydroxides (pKSP) of the metal ions involved in this study.
not improve Ca–Al LDH performance, as the chelates were partially re-
leased either by anion exchange or weathering, leading to heavy metal
Ion log (K[M(edta)])a pKSPb solubilization. Nevertheless, Ca–Al–[Ca(edta)]-type solids are an inter-
Ca 2+
10.7 5.3 esting tool for the synthesis of LDH M–Al–[M(edta)] solids with M
Al3+ 16.1 32.3 being metals such as Cu, Cd, etc. or their mixture.
Cu2+ 18.8 19.7
Cd2+ 16.5 13.6
Pb2+ 18.0 4.9 Acknowledgments
Mg2+ 8.7 11.3
Zn2+ 16.5 16.5 The financial support of CONICET, SeCyT-UNC and FONCyT (Project
a
Baes and Mesmer (1976). 2010–2116) is gratefully acknowledged. This work forms part of the ac-
b
Skoog et al. (1988). tivities of RIARTAS network of CYTED. Thanks to Mara L. Parello for her
 R. Rojas / Applied Clay Science 87 (2014) 254–259
collaboration during the experiments, to Dr. Carla E. Giacomelli for her
continuous support and to Carolina Mosconi for English proofreading.
Appendix A. Supplementary data
Schematization of [M(edta)]2− disposition in Ca–Al and Zn–Al LDHs.
FT-IR spectra, hydrodynamic diameter vs. pH and zeta potential vs. pH
curves of the samples. Supplementary data associated with this article
can be found, in the online version, at http://dx.doi.org/10.1016/j.clay.
2013.11.015.
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