Journal of Colloid and Interface Science 274 (2004) 613–624

www.elsevier.com/locate/jcis

Dodecyl sulfate–hydrotalcite nanocomposites for trapping chlorinated

organic pollutants in water
Hongting Zhao ∗ and Kathryn L. Nagy 1
Department of Geological Sciences, University of Colorado, Boulder, CO 80309, USA
Received 28 August 2003; accepted 15 March 2004
Available online 24 April 2004

Abstract
A series of hybrid organic–inorganic nanocomposite materials was synthesized by three different procedures using sodium dodecyl sulfate
(DDS) and magnesium–aluminum layered double hydroxide (Mg/Al LDH with a Mg/Al molar ratio of 2 to 5). Both the pH of the exchange
medium (6.5 to 10) and the Mg/Al molar ratio of the LDH affected the basal spacing, the content of DDS retained and the orientation of the
DDS chains within the interlamellar space. For LDH with higher charge density (Mg/Al = 2 and 3), DDS molecules likely formed a perpen-
dicular monolayer within the LDH interlayer and the solution pH had little effect on the basal spacing, with a mean and standard deviation
of 25.5 ± 0.4 Å. However, for LDH with lower charge density (Mg/Al = 4 and 5), DDS molecules more likely formed an interpenetrating
bilayer, and the basal spacing significantly increased with increasing pH, with a mean and standard deviation of 32.7 ± 5.2 Å. Sorption of
trichloroethylene and tetrachloroethylene by DDS-LDH varied with synthesis conditions, LDH type and DDS configuration in the interlayer.
DDS-Mg3 Al-LDH had the highest affinity for both trichloroethylene and tetrachloroethylene in water, either comparable to or as much as
four times higher than other clay-derived sorbents, followed by DDS-Mg4 Al-LDH and DDS-Mg5 Al-LDH. DDS-Mg2 Al-LDH had the lowest
sorption affinity although the highest amount of DDS. The pH of the exchange solution also affected the amount of DDS retained by the LDH
as well as the sorption efficiency. Mg3 Al-LDH has a charge equivalent area of 32.2 Å2 /charge, which allows the formation of optimal DDS
configuration within its interlayer, thus resulting in the highest affinity for the chlorinated compounds. The DDS-Mg/Al-LDHs can be easily
synthesized either ex situ or in situ at low temperature, indicating the feasibility of practical applications. The results obtained by controlling
the synthesis procedure suggest that different arrangements of DDS molecules in the LDH interlayers can be obtained and optimized for the
sorption of specific sorbates.
 2004 Elsevier Inc. All rights reserved.

Keywords: Layered double hydroxide; Hydrotalcite; Dodecyl sulfate; Anionic surfactant; Sorption; Organic pollutants; Trichloroethylene;
Tetrachloroethylene; Intercalation; Organoclay

1. Introduction exchanged 2:1 clay minerals (organoclays) have been stud-

Organic contamination of soil and water is a worldwide
issue [1]. Removal of organic pollutants from the environ-
ment or immobilization in situ are major goals of wastewater
treatment and cleanup efforts. In the past decade, great effort
has been devoted to developing new sorbents and stabilizers
for hydrophobic organic compounds (HOCs) by the pillar-
ing of inorganic layered compounds with polynuclear com-
plex ions or bulky organic molecules [2,3]. Organic cation-
* Corresponding author. Present address: Sandia National Laboratories,
MS 0779, Albuquerque, NM 87111, USA. Fax: +1-505-844-2348.
E-mail address: hzhao@sandia.gov (H. Zhao).
1 Present address: Department of Earth and Environmental Sciences,
University of Illinois at Chicago (MC-186), Chicago, IL 60607, USA.
0021-9797/$ – see front matter  2004 Elsevier Inc. All rights reserved.
doi:10.1016/j.jcis.2004.03.055
ied extensively for this purpose [4–8].
Layered double hydroxides (LDHs), or hydrotalcite-like
compounds, have been investigated mainly because of their
potential industrial uses such as catalysts, ion-exchangers,
optical hosts, ceramic precursors, and antacids [9,10]. LDHs
with various intercalated anions are used for catalysts and
separation supports [11–13]. LDHs are antitypes of 2:1
clay minerals with positively charged metal oxide/hydroxide
sheets compensated by anions in the interlayers. LDHs can
be readily synthesized under laboratory conditions, with eas-
ily controllable chemical composition of the layer and inter-
layer domains [14,15]. The general formula of an LDH [9]
is given as

ξ + n−
M1−x MIII
x (OH)2 Aξ/n ·zH2 O,
614 H. Zhao, K.L. Nagy / Journal of Colloid and Interface Science 274 (2004) 613–624
where M is Li+ or a divalent cation such as Ca2+ , Mg2+ ,
Ni2+ , Co2+ , Zn2+ , Mn2+ or Cu2+ , MIII is a trivalent cation
such as Al3+ , Cr3+ , Co3+ , Ni3+ , Mn3+ , Fe3+ , V3+ or
Ga3+ , and A is an interlayer anion such as Cl− , NO− 3,
ClO− 4 , CO 2−
3 , or SO 2−
4 . The M 2+ /M3+ ratio generally ranges
from 1 to 5 [9].
Positively charged LDH structures can sorb contaminants
such as phenols [16], radioactive 131 I [17], chromate [18],
and selenate/selenite [19]. However, inorganic parent LDH
crystallites have low sorption affinity for nonionic HOCs in
water, because LDHs are hydrophilic [20–23]. Intercalation
of organic anions, such as surfactants, into the interlayer can
alter LDH surface properties from hydrophilic to hydropho-
bic and result in enhanced sorption capacity for nonionic
organic pollutants [24]. Recently, a few reports [20,21,24–
30] have been published on the use of organic-modified LDH
for removing organic pollutants from water and results in-
dicate the further potential of these materials for that pur-
pose. For example, previous study [25] found that sorption
of large guest molecules, e.g., pyrene, by an organic acid-
exchanged Li/Al-LDH could be regulated by varying the
chain length of the carboxylic acids or type of anion with
LDH. This sieving effect has been demonstrated in its appli-
cation as a stationary phase in gas chromatography [29,30].
The selectivity of a hydrophobic LDH toward organic liquid
mixtures has also been reported [24], and this material was
suggested for use as a stationary phase in gas chromatog-
raphy or as self-assembled films [29,30] in membrane and
separation design. Organohydrotalcites have been studied as
pesticide sorbents [27,28] for use in decontamination or as
slow-release sources. You et al. [23] recently investigated
dodecylbenzenesulfonate-exchanged LDH as a sorbent for
trichloroethylene and tetrachloroethylene; however, no sig-
nificant difference in sorption capacity was found among
the products derived from Mg/Al LDH with different charge
density.
Despite numerous investigations of the intercalation re-
actions of organic anionic species in LDHs [11,29–38], de-
tailed understanding of the resulting sorptive properties for
HOCs is still lacking. Also, the ease of synthesis and struc-
tural controllability would make such LDH-based materials
advantageous for practical applications, including in situ for-
mation.
Therefore, to optimize the use of LDH-based materials as
sorbents for HOCs in water, it is necessary to understand the
factors and synthetic conditions that determine their efficacy.
We have investigated the pillaring reactions of Mg/Al-LDH
of varying layer charge with DDS, a commonly studied sur-
factant, and the use of these phases for sorption of HOCs.
Trichloroethylene and trichloroethylene were chosen as rep-
resentative HOCs due to their common occurrence in aque-
ous solutions [1]. Layer charge density, synthesis conditions,
and interlamellar structure are shown to affect sorbent effi-
ciency.
2. Materials and methods
2.1. Synthesis of Mg/Al LDH
A series of Mg/Al LDH solids was prepared by simul-
taneously adding dropwise an aqueous solution of sodium
hydroxide (2.0 M) and a mixed aqueous solution of magne-
sium chloride and aluminum chloride (total metal concen-
tration of 1 M with a Mg2+ /Al3+ molar ratio of 2.0, 3.0,
4.0, or 5.0) into a large plastic beaker containing 100 mL
deionized water which had been boiled and stored under
nitrogen before use. Nitrogen was bubbled throughout the
titration process to minimize dissolved carbonate. Previous
studies showed that carbonate anions are often difficult to ex-
change in Mg/Al, Ca/Al, and Ni/Al hydroxides [9]. During
the titration, the temperature and pH of the reaction mixture
were maintained at 23 ± 1 ◦ C and 10 ± 0.2, respectively. The
suspension was stirred for three hours, transferred to plastic
bottles, and placed in an oven at 65 ◦ C for 4 days. After cool-
ing to room temperature, the suspension was centrifuged and
the precipitate washed extensively using deionized water un-
til free of chloride (AgNO3 test). The products were dried at
65 ◦ C, ground, and stored in polyethylene bottles before use.
2.2. DDS-LDH preparation
Sodium dodecyl sulfate (DDS) (>98% CH3 (CH2 )11 O
SO3 Na, Aldrich) was incorporated into LDH interlayers via
three different procedures, each conducted under bubbling
nitrogen to minimize dissolved carbonate. In the first, the
ex situ exchange route, a known mass of LDH was placed
into a plastic beaker and allowed to react with DDS (40–
50 mL 0.1 M DDS solution per 1 g LDH) for 2 days at
65 ◦ C. The supernatant was decanted, and the solids were
reacted again with a fresh solution for 2 days at 65 ◦ C. The
suspensions were shaken occasionally during the reaction
periods. The organic derivatives were washed 6 times with
deionized water (∼200 mL) and one time with a 1:1 wa-
ter/ethanol mixture, dried at 65 ◦ C, ground, and stored in
polyethylene bottles before use. Ex situ products were de-
noted as DDS-Mgx Al-LDH(ex). The second procedure was
similar to the first except that DDS was introduced into the
LDH interlayer at different pH values (6.5, 8.5, and 10.0)
at a DDS:LDH ratio of 12 mmol/g. The mixture of LDH
and water (∼1 g/20 mL) was homogenized by stirring be-
fore adding the DDS solution. The pH was maintained at
6.5 ± 0.2, 8.5 ± 0.2, or 10 ± 0.2 by addition of either 0.1 N
NaOH or 0.1 N HCl. After stirring at room temperature for
3 days, the products were centrifuged and treated as de-
scribed in the first method. These products are denoted as
DDS-Mgx Al-LDH(pH). The third method was an in situ
synthesis: separate solutions of dissolved metals (total con-
centration of 1 M with a molar Mg2+ /Al3+ value of 2, 3,
4, and 5) and 2 M NaOH were added dropwise into 60–
130 mL of 0.1 M DDS solution to give a DDS:LDH ratio of
12 mmol/g at room temperature. Preliminary investigation
 H. Zhao, K.L. Nagy / Journal of Colloid and Interface Science 274 (2004) 613–624 615

indicated that when the molar ratio of DDS:LDH was <1,

some LDH coexisted with the DDS-LDH complex, as re-
vealed by XRD. Therefore, the DDS:LDH molar ratio used
was >1.5. The pH was maintained at 10 ± 0.2. After stirring
for one day at room temperature, the mixture was transferred
to an oven at 65 ◦ C for 3 days, and then subjected to the same
procedures as above. These products were denoted as DDS-
Mgx Al-LDH(in).

2.3. Instrumental

Organic carbon analysis was performed on the synthe-

sized products with a high temperature combustion/alkalin-
ity titration method using elemental analyzer (Model 1106)
(Carlo Erba Strumentazione, Milan, Italy). X-ray diffrac-
tion (XRD) analyses were carried out using a Scintag XDS
2000 diffractometer with Cu Kα radiation. Electrophoretic
mobilities were measured using a Malvern Zetasizer 3000
(Malvern, England) with solid concentrations of 0.005%
(w/w) and 0.01 M NaCl. pH was adjusted using NaOH
and HCl to values ranging from 4 to 12 and solutions
were equilibrated for 24 h before measurement. Composi-
tional analyses were conducted by dissolving approximately
40 mg of calcined (600 ◦ C for 5 h) sample in 100 mL 20%
(v/v) HNO3 and assaying by ICP atomic emission spec-
troscopy. Samples were imaged using TappingMode atomic
force microscopy (AFM) with a Digital Instruments Mul-
timode Nanoscope IIIa, silicon (TESP) tips, and a 15 µm
range scanner. Scanning electron microscope (SEM) pho-
tomicrographs were obtained using an ISI scanning electron
microscope.
2.4. Sorption isotherms for trichloroethylene and
tetrachloroethylene
Sorption isotherms were determined using batch equili-
bration at 25 ± 1 ◦ C [39]. Investigation of the sorption ki-
netics over 48 h showed that equilibrium was reached within
16 h. Trichloroethylene and tetrachloroethylene (HOC) con-
centrations were quantified to within ±3% using a Hewlett
Packard 5980 Series II gas chromatograph equipped with an
electron capture detector and an HP-5 capillary column with
He carrier gas. Controls without solids were run in paral-
lel for each concentration of organic investigated. The HOC
recovery was on average ∼93%, indicating a small loss to
vessel walls and/or volatilization. The data were not cor-
rected for this loss.
3. Results
3.1. Parent LDH solid characterization
Representative XRD patterns (Fig. 1) of the parent LDH
materials are similar to published patterns [10]. The molar
Mg/Al ratios of the final products are fairly close to those
Fig. 1. Representative X-ray diffraction patterns of parent Mg3 Al-LDH and
ex situ synthesized DDS-Mg3 Al-LDH.
of the reactants (Table 1). Inorganic carbon contents of the
prepared products were measured to be less than 0.2%, in-
dicating slight carbonate contamination during the synthesis
procedure. With decreasing Al substitution, the basal spac-
ing gradually increased from 7.74 up to 8.22 Å as a result of
weaker coulombic attraction between the positively charged
layers and the negatively charged interlayer anion Cl− [40].
Conversely, increasing the proportion of Al in the layers
increased unit layer charge, charge density, and estimated
anion exchange capacity (AEC) [41]. LDH was reported to
have high anion exchange capacity generally ranging from
200 to 500 meq/100 g [42].
3.2. DDS-LDH solids characterization
3.2.1. DDS content
The organic carbon contents (O.C. (%, w/w)) in the pre-
pared products (Table 2) are relatively consistent with the
decrease in Mg/Al ratio and the corresponding increase in
AEC. All of the DDS-LDH products prepared in situ show
similar elemental Mg and Al composition to those prepared
ex situ. However, their DDS contents and basal spacing are
slightly different from those prepared in situ (Table 2). For
example, for LDH with higher charge density (Mg/Al = 2
and 3), products prepared in situ have higher DDS contents
than those prepared ex situ. In contrast, for LDH with lower
charge density (Mg/Al = 4 and 5), the opposite tendency is
observed.
616 H. Zhao, K.L. Nagy / Journal of Colloid and Interface Science 274 (2004) 613–624

Table 1
Properties of the synthesized Mg1−x Alx -LDH
Properties Mg2 Al-LDH Mg3 Al-LDH Mg4 Al-LDH Mg5 Al-LDH
Al3+ substitution,a x 0.333 (0.301)e 0.250 (0.254) 0.198 (0.205) 0.171 (0.176)
Basal spacing (d003 ), Å 7.74 8.01 8.14 8.22
Unit cell a,b Å 3.052 3.068 3.076 3.083
Layer unit area,c Å2 8.067 8.152 8.194 8.232
Layer charge density, e+ /Å2 0.041 0.031 0.024 0.021
Equivalent area, Å2 /charge 24.4 32.3 41.7 47.6
AECd (meq/100 g) 402 325 273 241
a Calculated based upon chemical analysis.
b a = 2d
100 . √ 2
1−x Alx (OH)2 octahedral unit = 3(a /2).
c Area of a Mg
d Anion exchange capacity (AEC) was estimated assuming 2H O per unit cell [41].
2
e Numbers in parentheses are data for in situ synthesized DDS-Mg/Al LDH products. The products were calcined at 600 ◦ C for 6 h before undergoing
elemental analysis.

Table 2
Total organic carbon content (O.C., %) and basal spacings (d003 , Å) of DDS-Mg/Al-LDH products synthesized via different methods
Ex situ In situ pH 6.5 pH 8.5 pH 10.0
O.C. d003 O.C. d003 O.C. d003 O.C. d003 O.C. d003
(%) (Å) (%) (Å) (%) (Å) (%) (Å) (%) (Å)
DDS-Mg2 Al-LDH 29.5 (54.3/98.0)a 25.8 31.7 (58.3/106) 26.4 27.5 (50.6/91.3) 25.8 27.1 (49.9/90.1) 25.8 25.8 (47.5/85.7) 26.0
DDS-Mg3 Al-LDH 26.7 (49.1/99.6) 24.3 27.3 (50.2/102) 25.1 21.8 (40.1/81.3) 25.2 21.0 (38.6/78.3) 25.0 24.5 (45.1/91.5) 25.4
DDS-Mg4 Al-LDH 24.8 (45.6/102) 27.8 22.3 (41.0/92.0) 28.6 19.2 (35.3/79.1) 27.2 17.9 (32.9/73.8) 30.7 19.4 (35.7/80.0) 36.6
DDS-Mg5 Al-LDH 25.8 (47.5/116) 29.2 21.8 (40.1/97.6) 31.2 20.6 (37.9/92.2) 27.4 16.1 (29.6/72.0) 33.8 16.0 (29.4/71.5) 40.3
a Numbers in parentheses are data for the calculated DDS weight percentage (%) in the products and the corresponding estimated exchange percentage (%)
based upon AEC.

Based upon estimated AEC, the maximum possible DDS
content is 55.4, 49.3, 44.6, and 41.1% for Mg2 Al-LDH,
Mg3 Al-LDH, Mg4 Al-LDH, and Mg5 Al-LDH, respectively.
Thus, exchange of interlayer chloride by dodecyl sulfate
proceeds to ∼100% of theoretically estimated AEC values
for the ex situ DDS-LDHs, with the exception of Mg5 Al-
LDH(ex) which proceeds up to ∼116%.
Overall, both ex situ and in situ products have relatively
high DDS saturation (∼100%), close to that required for
electroneutrality. Samples that contained DDS in excess of
that needed to satisfy the layer charge likely had neutral
Na–DDS on internal and external surfaces via hydrophobic
attraction [11].
Because previous studies have shown that OH− has high
affinity for LDH [43,44], we investigated DDS intercalation
reactions at pH 6.5, 8.5, and 10 and assessed the material
sorptivity for HOCs. Low pH values were not investigated
because the LDH lattice can withstand only short exposure
to mildly acidic solutions (pH ∼4.5) [45] or else dissolves
rapidly (pH < 4) [46].
All samples synthesized as a function of pH for a nar-
row range of the ratio DDS:LDH have lower DDS contents
than those exchanged ex situ and in situ (Table 2). Only 72
to 92% of the estimated AEC was compensated, presumably
due to competition with OH− , the starting molar DDS:LDH
ratio, and shorter reaction time. In fact, the content of DDS
retained by Mg2 Al-LDH and Mg5 Al-LDH generally de-
creased with increasing pH. However, for Mg3 Al-LDH and
Mg4 Al-LDH, the content of DDS first decreased and then
increased to values at pH 10.0 that were higher than the
concentrations in the other LDH samples. For comparison,
Pavan et al. [36] also reported that an increase in pH (from 7
to 9) resulted in a decrease in the amount of adsorbed DDS
by Mg2 Al-CO3 LDH.
3.2.2. Basal spacing
Intercalation of DDS into the LDH interlayer resulted
in increased basal spacing, similar to those reported pre-
viously [9,11,33,35]. Representative XRD patterns (Fig. 1)
of the DDS-LDH materials are similar to published pat-
terns [10]. The basal spacing (Table 2) generally increased
with increase in Mg/Al ratio and decrease in charge den-
sity. However, DDS-Mg2Al LDH had a slightly higher basal
spacing (25.9 ± 0.3 Å) than DDS-Mg3 Al LDH (25.0 ±
0.4 Å). Also, all products prepared in situ have greater basal
spacing (ranging from 24.3 to 29.2 Å) than those prepared
ex situ (ranging from 25.1 to 31.2 Å), suggesting a control
by the synthesis conditions.
The pH values of the exchange medium had only slight
effects on the basal spacings of Mg2 Al-LDH and Mg3 Al-
LDH (25.5 ± 0.4 Å), but significant effects on those of
Mg4 Al-LDH and Mg5 Al-LDH, ranging from 27 up to 40 Å
(32.7 ± 5.2 Å) (Table 2). Clearfield et al. [11] reported that
DDS intercalation in synthetic Ni4 Al-LDH was significantly
affected by pH. They found that varying pH from 5 to 10
caused the basal spacing of the DDS-Ni4 Al-LDH to range
 H. Zhao, K.L. Nagy / Journal of Colloid and Interface Science 274 (2004) 613–624 617

Fig. 2. AFM image of parent Mg3 Al-LDH.

(a) (b)

Fig. 3. SEM images of (a) parent Mg3 Al-LDH and (b) DDS-Mg3 Al-LDH(ex) (short bar = 100 nm).

from 25.9 to 42 Å, respectively, and the amount of retained
DDS to decrease. They reported a basal spacing as high as
47.6 Å for Ni4 Al-LDH when pH was higher than 10.
3.2.3. Morphology
AFM analysis (Fig. 2) indicated that untreated LDH con-
sisted of thin, hexagonal, plate-like crystals 0.2–0.5 µm in
size. In contrast, DDS-LDH particles agglomerated via hy-
drophobic interactions and were not easily imageable (data
not shown). The SEM images (Fig. 3) indicated that DDS re-
tention dramatically changed the LDH particle morphology.
The DDS-Mg3Al-LDH particles are agglomerated and the
surfaces are more diffuse and not as sharp as that of Mg3 Al-
LDH, suggesting that there might be excess DDS draped
over the particles on outer surfaces, as observed previously
by others [34–36].
This was further confirmed by electrophoretic mobility
(EM) measurements (data not shown) on these two sam-
ples. Within the pH range of 5–11, all the synthesized LDHs
had positive EM while DDS-Mg/Al-LDHs(ex) had nega-
tive EM. (The isoelectric point of LDHs was reported to
be >11.0 [47,48].) For example, Mg2 Al-LDH had an EM
in 0.01 M NaCl of +3.5 µm s−1 /V cm−1 in (at pH ∼5.02),
while DDS-Mg2 Al-LDH(ex) had an EM of approximately
−1.7 µm s−1 /V cm−1 (at pH ∼5.57). This indicates that the
interaction of DDS with LDH caused the charge reversal and
may be a result of sorption onto the external surfaces of the
LDH, in agreement with previous results [36,38].
618 H. Zhao, K.L. Nagy / Journal of Colloid and Interface Science 274 (2004) 613–624
Fig. 4. Sorption isotherms for trichloroethylene and tetrachloroethylene at
25 ± 1 ◦ C by DDS-LDH materials synthesized ex situ.
3.3. HOC sorption by DDS-LDH products
Despite some data sets that visually show slight curva-
ture, all sorption isotherms can be fit with straight lines,
with correlation coefficients typically in the range of 0.96
to 0.99 (Figs. 4–6). Linear isotherms suggest that a parti-
tioning process controlled the sorption [49]. As expected,
untreated LDH has low affinity for both trichloroethylene
and tetrachloroethylene, due to the hydrophilicity of the
LDH surfaces. Linear sorption of HOCs commonly has been
observed on surfactant-modified clays and soil organic mat-
ter [50–53]. This linear sorption behavior can be described
simply by
Qs = Kd Ce ,
where Qs is the amount of solute sorbed (mg/kg), Ce is the
equilibrium aqueous solute concentration (mg/L), and Kd
Fig. 5. Sorption isotherms for trichloroethylene and tetrachloroethylene at
25 ± 1 ◦ C by DDS-LDH materials synthesized in situ.
is the sorption coefficient, which corresponds to the ratio
of the amount (mg/kg) of the sorbed chemical to its equi-
librium aqueous concentration (mg/L). Higher Kd values
correspond to a greater degree of sorption. For direct com-
parison and reflecting the dominant influence of the solid-
phase organic carbon on the sorption of organic solutes, the
sorption coefficient often is normalized on an organic-matter
basis [5],
Kom = Kd /foc ,
where Kom is the organic matter-normalized partition coef-
ficient and foc is the fractional organic carbon content of the
sorbent (Tables 3 and 4).
By using relative sorptivity (Kom /Kow ) [6], the sorptive
efficiency of the organic matter in DDS-LDH materials as a
partitioning medium can be compared with that of octanol.
The relative sorptivity for various DDS-LDH products was
plotted in Fig. 7. Only the Kom /Kow values for some DDS-
Mg3 Al-LDH products were greater than unity, suggesting
that, in these products, DDS-derived organic matter formed
 H. Zhao, K.L. Nagy / Journal of Colloid and Interface Science 274 (2004) 613–624 619

Fig. 6. Sorption isotherms for tetrachloroethylene at 25 ± 1 ◦ C by DDS-LDH materials synthesized as a function of solution pH. (The data were grouped and
labeled for clarity.)

Table 3
Selected parameters for the sorption of trichloroethylene and tetrachloroethylene by DDS-Mg/Al-LDH
Trichloroethylene Tetrachloroethylene
(log Kow a = 2.61; solubilityb = 1155 mg/L) (log Kow = 3.40; solubility = 150 mg/L)
Kd c log Kom d Kd log Kom
DDS-Mg2 Al-LDH(ex) 46 1.92 176 2.51
DDS-Mg3 Al-LDH(ex) 252 2.71 1030 3.32
DDS-Mg4 Al-LDH(ex) 142 2.49 535 3.07
DDS-Mg5 Al-LDH(ex) 131 2.44 504 3.03
DDS-Mg2 Al-LDH(in) 71 2.09 294 2.71
DDS-Mg3 Al-LDH(in) 202 2.60 855 3.23
DDS-Mg4 Al-LDH(in) 159 2.58 678 3.21
DDS-Mg5 Al-LDH(in) 147 2.56 630 3.20
ow = the log of partition coefficient value between octanol and water [21].
a log K
b Aqueous solubility data were from Zhao and Vance [21] and references therein.
c K = sorption coefficient between the DDS-Mg/Al-LDH and water. For direct comparison, all isotherm data were evaluated by linear regression equation
d
(R > 0.96).
om = the log value of organic-matter-normalized sorption coefficient. Kom = Kd [100/(%O.C. × foc )], where foc equals to the molecular weight
d log K
of the DDS divided by the weight of C in the DDS (≈1.84).

a much better partitioning medium than octanol. Octanol is
considered to be relatively hydrophilic as compared with the
C12 alkyl groups of DDS [6].
Results shown in Tables 3 and 4 and Fig. 7 clearly
indicate that the sorption efficiency varies with synthesis
method and product composition. The DDS-Mg3 Al-LDH
sample prepared at pH 10 has much higher sorptivity for
trichloroethylene than the other DDS-Mg3 Al-LDH samples,
all of which sorb both HOCs to a greater extent than the
other materials. DDS-Mg2 Al-LDH always shows the low-
est sorption affinity for both trichloroethylene and tetra-
chloroethylene within each synthesis series, as much as 5–9
times lower than the DDS-Mg3 Al-LDH.
Sorption of trichloroethylene and tetrachloroethylene by
DDS-LDH does not follow a trend with increasing or-
ganic content, but rather varies with the DDS configura-
620 H. Zhao, K.L. Nagy / Journal of Colloid and Interface Science 274 (2004) 613–624

Table 4 DDS-Mg/Al(pH) products have relatively higher sorptive ef-

Sorption coefficients (Kd ) and corresponding log Kom values for the sorp- ficiency than those prepared ex situ.
tion of tetrachloroethylene by DDS-Mg/Al-LDH synthesized at various pH The synthetic medium pH affected not only the basal
values
spacing of both DDS-Mg4Al-LDH and DDS-Mg5 Al-LDH,
pH value of exchange medium but also the DDS-loading as compared to that from the ex
pH 6.5 pH 8.5 pH 10.0 situ/in situ syntheses. Values of log Kom decreased slightly
DDS-Mg2 Al-LDH 151 (2.47)a 154 (2.50) 132 (2.44) with increasing pH of the exchange medium with a mean
DDS-Mg3 Al-LDH 1090 (3.43) 1090 (3.45) 1160 (3.41)b and standard deviation of 3.16 ± 0.04. The increase of pH
DDS-Mg4 Al-LDH 514 (3.19) 507 (3.17) 476 (3.11)
generally resulted in less DDS retained and a larger inter-
DDS-Mg5 Al-LDH 587 (3.19) 443 (3.17) 380 (3.11)
a Numbers in parentheses are log K
layer thickness, which may have caused the lower uptake of
om values. HOCs.
b DDS-Mg Al-LDH(pH 10) had a K value of 280 and log K
3 d om of 2.79
for trichloroethylene. Overall, sorption of trichloroethylene and tetrachloro-
ethylene by DDS-LDHs is equal to or greater than sorp-
tion by organoclays, surfactant-templated materials, and
other clay-derived materials. Previous studies showed that
HDTMA-exchanged Wyoming smectite has a log Kom value
of 2.30 for trichloroethylene [52], and HDTMA-modified
zeolite has a log Kom value of 2.82 for tetrachloroethyl-
ene [53]. As-synthesized surfactant-templated mesoporous
materials (MCM-41) have a log Kom value of 2.40 for tri-
chloroethylene and 2.99 for tetrachloroethylene [36], while
β-cyclodextrin intercalated Mg/Al LDH has a log Kom value
of 2.65 for trichloroethylene and 2.89 for tetrachloroethyl-
ene [20,21]. However, dodecylbenzenesulfonate-exchanged
LDHs were reported to have high log Kom value for trichlo-
roethylene (2.68 ± 0.04) and tetrachloroethylene (3.28 ±
0.05) [23].

4. Discussion

The results show that reaction between DDS and Mg/Al-

Fig. 7. Relative sorptivity (Kom /Kow ) of various DDS-LDH products.
tion, synthesis conditions and LDH composition. For exam-
ples, DDS-Mg4-Al-LDH and DDS-Mg5 Al-LDH have sim-
ilar intermediate sorption affinities. DDS-Mg2Al-LDH and
DDS-Mg3 Al-LDH have similar surfactant loadings and d-
spacings (e.g., for those synthesized at pH 10), but quite
different affinities for HOCs.
With the exception of DDS-Mg3 Al-LDH, the in situ
synthesized DDS-LDHs sorbed trichloroethylene and tetra-
chloroethylene more strongly than those of corresponding
products synthesized ex situ. DDS-Mg3 Al-LDH synthesized
ex situ, but exchanged as a function of pH, shows the most
sorption for both trichloroethylene and tetrachloroethylene,
suggesting that the synthetic conditions must affect the
molecular configuration of DDS within the LDH interlayer
and thereby the resulting sorption properties. For tetra-
chloroethylene, with the exception of DDS-Mg2 Al-LDH, all
LDHs yields products with varying DDS contents, basal
spacing and different sorption capacities for trichloroethyl-
ene and tetrachloroethylene. The differences in HOC sorp-
tion must arise from the DDS configuration within Mg/Al
LDH interlayer and be related to charge density. To better
elucidate the possible reasons, specific parameters need to
be considered.
We first considered the LDH layer thickness of 4.78 Å
[54] and the van der Waals end-to-end length of dodecyl
sulfate, estimated from the chemical structure, of 20.8 Å
[55]. Based on products with a basal spacing (d003 ) in the
neighborhood of 26 Å, such as DDS-Mg2 Al-LDH and DDS-
Mg3 Al-LDH, we deduce that DDS molecules likely form a
perpendicular monolayer. For the perpendicular monolayer
structures, the DDS chains should stand upright with all
chains in an all-trans conformation [56], considering that
half of the positive charges are neutralized from each side
of the layer.
For products with a basal spacing >26 Å, such as DDS-
Mg4 Al-LDH and DDS-Mg5 Al-LDH, a perpendicular bi-
layer arrangement is probable in which the DDS molecules
overlap to some degree (Fig. 2) [9,11]. However, the DDS
chains could be either partially overlapped as illustrated
in Fig. 8 or they could be tilted with only partial or no
 H. Zhao, K.L. Nagy / Journal of Colloid and Interface Science 274 (2004) 613–624
(a)
Fig. 8. Schematic arrangement of DDS molecules within the LDH interlayer (a) perpendicular monolayer (∼26 Å); (b) and (c) interpenetrating bilayer (>26 Å)
(not to scale).
overlap [11], resulting in open spaces between neighbor-
ing chains. Using chemical graphics modeling, Clearfield
et al. [11] calculated that for products with a basal spacing
of 36.4 Å, the DDS chains might form a bilayer arrange-
ment with a tilt angle of 49.4◦ in which there is no DDS
overlap. Therefore, the range of observed basal spacing for
DDS-Mg4 Al-LDH and DDS-Mg5 Al-LDH could result from
different angles of tilt or overlap (Fig. 2).
To evaluate the role of charge density on DDS configu-
ration and thereby on HOC sorption, it is necessary to con-
sider other parameters. The cross-sectional area of dodecyl
sulfate is estimated to be ∼28 Å2 [35] and the estimated
cross-sectional areas for long-chain alcohols and carboxylic
acids are approximately 23 Å2 [57]. The sulfate headgroup
enlarges the cross-sectional area of DDS. Based upon the
properties of the synthesized LDHs, the charge equivalent
area (Å2 /charge), or available area per monovalent anion
was calculated to be 24.4, 32.3, 41.7, and 47.6 Å2 for LDH
with Mg:Al ratios of 2:1, 3:1, 4:1, and 5:1, respectively (Ta-
ble 1). On the other hand, the molecular diffusion volume
of trichloroethylene and tetrachloroethylene was estimated
to be 155 and 184 A3 , respectively, and both have an esti-
mated critical molecular dimension of 6.7 Å (length) × 6.5 Å
(width) × 3.7 Å (thickness) [21]. It is reasonable to con-
clude that for Mg2 Al-LDH, the DDS molecule narrowly fits
into the equivalent area, leaving insufficient space to accom-
modate trichloroethylene and tetrachloroethylene molecules.
Thus, sorption of HOCs by DDS-Mg2 Al-LDH likely arises
from DDS sorbed on external surfaces of the LDH.
Crepaldi et al. [37] reported a basal spacing as high as
47 Å for a DDS-Zn2Cr-LDH. Zn2 Cr-LDH has a slightly
smaller charge equivalent area (22.7 Å2 ) compared to that
of Mg2 Al-LDH (24.4 Å2 ). Apparently DDS just fits into the
charge equivalent area, thus forcing it to form a perpendicu-
lar bilayer with minimum overlap and a high basal spacing.
The difference in charge equivalent area between Mg2 Al-
LDH and Mg3 Al-LDH might also contribute to the observed
higher basal spacing of the former over that of the latter.
Compared to Mg2 Al-LDH, Mg3 Al-LDH has an available
area per monovalent anion larger than the cross-sectional
621
(b) (c)
area of the DDS molecule, thus leaving more free space
for accommodating HOCs. Assuming DDS molecules are
closely packed, the intermolecular free distance is estimated
to be ∼1.8 Å, suggesting that both trichloroethylene and
tetrachloroethylene could not readily penetrate into the in-
termolecular space. However, uptake of HOCs may occur if
the DDS molecules are flexible and can move within the in-
terlayer.
For Mg4 Al-LDH and Mg5 Al-LDH, the available area per
monovalent anion is much larger than required to accommo-
date DDS. Also, the DDS molecules may not be perpendic-
ular to the layer as in Mg2 Al-LDH and Mg3 Al-LDH. This
would result in higher basal spacing, more loosely packed
DDS, and more free intermolecular space—as much as 2 to
10 times as that in Mg2 Al-LDH and Mg3 Al-LDH. Though
more free space would presumably enhance the uptake of
HOCs, the sorption results indicate that this configuration is
not as effective as the hypothesized more structured config-
uration in the Mg3 Al-LDH interlayer.
A schematic representation of charge distribution and
resulting DDS configuration within LDH interlayers can
be constructed assuming that Mg2+ and Al3+ cations are
regularly distributed in the LDH layer and the unit cell
(a) parameter represents the distance between two adjacent
cations [37] (Fig. 9). The diagram shows that DDS mole-
cules within the LDH interlayers with lower charge den-
sity (Mg/Al = 4 and 5) likely form a much loosely packed
arrangement than that in LDH interlayers with high charge
density (Mg/Al = 2 and 3).
A decrease in DDS loading supposedly would increase
the interlayer free space, as in Mg2 Al-LDH and Mg3 Al-
LDH, and thus enhance HOC sorption. However, this was
not observed for Mg2 Al-LDH. For example, DDS-Mg2 Al-
LDH(pH 10) has similar tetrachloroethylene sorption to that
of DDS-Mg2 Al-LDH(ex), while the former has much higher
DDS loading (54.3%) than the latter (47.5%). This phenom-
enon is explained as follows.
Due to hydrophobic attraction among DDS molecules as
well the relatively high charge density of LDH, DDS more
likely may be aggregated in bundles rather than be evenly
622 H. Zhao, K.L. Nagy / Journal of Colloid and Interface Science 274 (2004) 613–624
Fig. 9. Schematic representation of DDS arrangement as related to Mg/Al-LDH charge density [37] (not to scale).
Fig. 10. Relative sorptivity (Kom /Kow ) of DDS-Mgx Al-LDH products as
a function of estimated DDS exchange percentage (%) (tetrachloroethy-
lene—solid line; trichloroethylene—broken line).
distributed within the interlayers [24]. Therefore, although
different synthesis methods may decrease the DDS content,
as for Mg2 Al-LDH, they might not affect the localized DDS
configuration. For DDS-Mg2Al-LDH, if sorption of HOCs
occurs largely in the portion of DDS sorbed to the exter-
nal LDH surface, this would explain the slight increase in
uptake of HOCs by DDS-Mg2 Al-LDH(in), which has the
highest DDS loading, sorbs more HOC than other Mg2 Al-
LDH-derived products (Fig. 10).
An interesting opposite phenomenon is observed for
DDS-Mg3Al-LDH; a reduction in DDS loading enhances
the sorptive efficiency (Fig. 10). Unlike Mg2 Al-LDH,
Mg3 Al-LDH has a lower charge density and a probable reg-
ular distribution of DDS in the interlayers. Reduced DDS
loading, to some degree, could increase the intermolecular
space and better accommodate HOCs. Fig. 10 indicates that
it is possible to choose an optimal DDS loading in Mg3 Al-
LDH to achieve the highest sorptive efficiency and thus
produce a material that is more cost-effective. This may
explain why DDS-Mg2Al-LDH(pH 10) and DDS-Mg3 Al-
LDH(pH 10), though having similar surfactant loadings and
d-spacings, have quite different sorption affinity for HOCs.
Unlike DDS-Mg2 Al-LDH and DDS-Mg3 Al-LDH prod-
ucts, which have relatively constant basal spacing regard-
less of the DDS content and synthetic condition, the basal
spacing for DDS-Mg4 Al-LDH and DDS-Mg5 Al-LDH prod-
ucts vary significantly. As a result, DDS content, basal
spacing and the DDS configuration would cooperatively af-
fect the sorption behavior for HOCs and make the sorption
behavior more complicated (Fig. 10). For example, DDS-
Mg4 Al-LDH(pH 6.5) and DDS-Mg4 Al-LDH(pH 10) have
quite similar DDS loadings (35.3 and 35.7%, respectively),
but quite different basal spacings (27.2 and 36.6 Å, re-
spectively), and the former has higher sorptivity for tetra-
chloroethylene than the latter (Fig. 7). This suggests that the
increase in the basal spacing leads to a reduction in sorp-
tion, due to the greater intermolecular distance and the less
effectiveness as a partition medium. This is also the case for
DDS-Mg5Al-LDH(pH 8.5) and DDS-Mg5 Al-LDH(pH 10).
 H. Zhao, K.L. Nagy / Journal of Colloid and Interface Science 274 (2004) 613–624
On the other hand, for DDS-Mg4Al-LDH(ex) and DDS-
Mg4 Al-LDH(pH 6.5), which have similar basal spacing
(27.2 and 27.8 Å, respectively) and different DDS loading
(45.6 and 35.3%, respectively), the latter has higher sorption
efficiency for tetrachloroethylene than the former. This sug-
gests that, when basal spacing is relatively constant, a slight
reduction in DDS loading can enhance the HOC uptake.
We expect that an optimal DDS loading is required for
high sorptive efficiency. Further decrease in DDS loading
would not necessarily result in higher sorption for DDS-
Mg3,4,5Al-LDH products. A decrease in DDS content would
result in a decrease in layer charge compensation neces-
sitating an increase in the content of the charge-balancing
Cl− anion. The presence of Cl− should increase the overall
hydrophilicity within the LDH interlayer. Therefore, a com-
bination of optimal DDS loading, basal spacing and DDS
configuration is required to achieve maximum sorptive effi-
ciency. The LDH with Mg/Al molar ratio of 3:1 accommo-
dates the optimal amount of DDS and forms the most effec-
tive partition medium in its interlamellar domain. The effect
of substrate charge density on sorption of HOCs by DDS-
LDHs is evident from this study. Similar mineral-charge
effects on HOC sorption have also been observed with
organic-cation-exchanged cationic clays (organoclays) [4–
6].
The DDS-Mg/Al-LDH materials investigated here may
exhibit totally different sorption behaviors for other or-
ganic compounds of different sizes and/or shapes. Although
DDS-Mg4 Al-LDH and DDS-Mg5 Al-LDH have lower sorp-
tion affinity for trichloroethylene and tetrachloroethylene
as compared to DDS-Mg3 Al-LDH, their greater interlayer
spacing may make them more effective in accommodat-
ing larger guest molecules than trichloroethylene and tetra-
chloroethylene, such as polynuclear aromatic compounds.
Similarly, DDS-Mg2 Al-LDH may be effective for smaller
guest molecules. Regulation of the charge density or Mg/Al
molar ratio thus would lead to products with unique proper-
ties for various guest organic compounds.
5. Conclusions
A series of organic–inorganic nanocomposite materials
were synthesized using sodium dodecyl sulfate (DDS) and
magnesium–aluminum layered double hydroxide (Mg/Al
LDH with a Mg/Al molar ratio of 2 to 5. Layer spac-
ing is sufficient for DDS molecules to orient in a proba-
ble monolayer or interpenetrating bilayer-type arrangement
within the LDH interlayers depending on synthesis con-
ditions. Both the pH value of the exchange medium and
the Mg/Al molar ratio of the LDH affect the basal spac-
ing and the arrangement of DDS within the LDH inter-
layer. Sorption of trichloroethylene and tetrachloroethylene
by DDS-LDH does not follow a simple trend with increas-
ing organic content, but rather varies with probable DDS
configuration, synthesis conditions and LDH composition.
623
Generally, the sorption affinity is in the order DDS-Mg3 Al-
LDH > DDS-Mg4 Al-LDH ∼ = DDS-Mg5Al-LDH > DDS-
Mg2 Al-LDH. DDS-Mg3Al-LDH had the highest affinity for
both HOCs in water, either comparable to or as much as four
times higher than other clay-derived sorbents; DDS-Mg2 Al-
LDH had the lowest sorption affinity though it contains the
highest amount of DDS and the sorption is believed to occur
on edge/external surface area. Mg3 Al-LDH has the optimal
charge density for forming an effective partition medium
with LDH interlayer.
Acknowledgments
The authors acknowledge research support from the U.S.
Department of Defense through the Strategic Environmen-
tal Research and Development Program (SERDP) and in
part a student research grant from the Clay Minerals Soci-
ety to H.T. Zhao. We also thank G.F. Vance, University of
Wyoming, for kindly allowing use of his gas chromatograph,
J.B. Harsh, Washington State University, for the use of the
Zetasizer, and Dr. R.P. Bontchev, Sandia National Labora-
tories, for helping with the drawing of schematic structural
models. We also would like to thank two reviewers whose
comments helped to improve the manuscript.
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