Colloids and Surfaces A: Physicochem. Eng.

Aspects 446 (2014) 172178

Contents lists available at ScienceDirect

Colloids and Surfaces A: Physicochemical and

Engineering Aspects
journal homepage: www.elsevier.com/locate/colsurfa

Interactions between sulfa drug sulfadiazine and hydrophobic

talc surfaces
Guocheng Lv a , Zhaohui Li a,b,c, , Nicole Hoeppner c , Limei Wu a , Libing Liao a
a
b
c

School of Materials Science and Technology, China University of Geosciences, Beijing 100083, China
Department of Earth Science, National Cheng Kung University, 1 University Road, Tainan 70101, Taiwan
Geosciences Department, University of WisconsinParkside, Kenosha, WI 53141-2000, USA

h i g h l i g h t s

g r a p h i c a l

a b s t r a c t

Adsorption of sulfadiazine (SDZ) on

talc followed a linear type isotherm.

Higher SDZ removal was found at

high and low solution pH.

Simulation showed interactions of

benzene ring and O of SDZ with Mg
of talc.
Hydrogen bonding between N of SDZ
and broken bond of O of talc also
played a role.

a r t i c l e

i n f o

Article history:
Received 26 July 2013
Received in revised form
30 December 2013
Accepted 15 January 2014
Available online 29 January 2014
Keywords:
Adsorption
Hydrogen bonding
Simulation
Sulfadiazine
Talc

a b s t r a c t
Interactions between sulfadiazine (SDZ), a sulfa drug antibiotic, and talc, a low charge 2:1 phyllosilicate,
were investigated under batch experimental conditions. The SDZ adsorption on talc was instantaneous,
with a very large rate constant and a fast rate, although with a low amount. SDZ adsorption followed a
linear sorption isotherm, suggesting that the hydrophobic interact instead of cation exchange was more
like responsible for the uptake of SDZ. Solution pH had a unique inuence on SDZ adsorption. The solute
distribution coefcient was low in pH 37 range and increase at even lower and higher pH conditions.
Molecular simulation suggested that the interactions between the benzene ring as well as the O of SDZ
and the Mg in the octahedral site of talc was partially responsible for SDZ uptake. In addition, the hydrogen
bonding between the N in the amine as well as in the hetero ring and the broken bond of O on the 010
plane of talc also contributed to SDZ uptake by talc.
2014 Elsevier B.V. All rights reserved.

1. Introduction
With the recent advancement in analytical methods and instrumentations, many monitoring studies were conducted to document
the presence and distribution of pharmaceuticals and personal care
products (PPCPs) in the environment. Among the PPCPs, the widely

Corresponding author at: Geosciences Department, University

WisconsinParkside 900 Wood Road, Kenosha, WI 53141-2000, USA.
Tel.: +1 262 595 2487; fax: +1 262 595 2056.
E-mail address: li@uwp.edu (Z. Li).
0927-7757/$ see front matter 2014 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.colsurfa.2014.01.014

of

distribution of antibiotics, such as tetracycline (TC), ciprooxacin

(CIP), and sulfa drugs, even at the efuent after the wastewater
treatment was reported in numerous cases [13]. In surface water,
half of the 139 rivers surveyed in the United States had detection
of antibiotics [4]. Extensive use of antibiotics in animal feeding
operation also resulted in their signicant accumulation in soil.
As soil is a major repository for antibiotics in the environment,
the transport and fate of antibiotics in soil can be strongly inuenced by their adsorption process to soil components [2]. Most
of the studies on interactions between antibiotics and soil components were focused on clay minerals [58], metal oxides or
hydroxides [9], quartz [10], as well as soil organic matters [1113].

G. Lv et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 446 (2014) 172178

Cation exchange interaction was attributed to the most important

mechanism for the uptake of cationic antibiotics onto clay minerals, thus, minerals with high cation exchange capacities (CEC) were
good candidates for the removal of cationic drugs from water [6,7].
In addition to the study of interactions between antibiotics and soil
components, the effect of adsorbed antibiotics on the antimicrobial activities was also conducted. The antibacterial activity of TC
could be maintained even after being adsorbed on montmorillonite
[14]. Thus, the presence of antibiotics in the environment would
also increase bacterial resistances to antibiotics acclaimed to the
persistent low dose conditions [15].
Sulfadiazine (SDZ) or 2-sulfanilamidopyrimidine is an antibiotic
belonging to the group of sulfonamides (SAs), which were widely
used in human therapy and veterinary medicine, especially in poultry, pig, and calf livestock [12,16]. It was the second highest sold
antibiotics in UK with a usage of 14 t in 2000 [15]. Most of the
studies on adsorption and desorption of SDZ were on soils or soilmanure systems [16,17]. Adsorption of SAs to mineral soil colloids
was weaker and resulted in a stronger desorption from clay-size
fractions [17]. Neutral and cationic SA species did not intercalate into swelling clay mineral montmorillonite, but interacted
primarily with external surfaces [18]. Like other SAs, sulfachloropyridazine has a low adsorption potential and was, thus, likely to
be highly mobile [19]. Adsorption of the SA antibiotics sulfanilamide, sulfadimethoxine, and sulfapyridine was also conducted on
model soil organic matters using Fluka humic acid [13]. Adsorption of the amphoteric SAs was nonlinear and pH dependent and
stronger adsorption to humic acid than to the oligomer was related
to the more complex structure and functional group diversity of
humic acid [13]. On a mass basis, organic matter had higher afnity
for neutral SA antimicrobials than do smectite clays [12]. Modeling and molecular mechanics calculations of antibioticsoil organic
matter complexes showed preferred site-specic adsorption via
hydrogen bonds and van der Waals interactions [17]. The presence
of manure increased the adsorption tendency of SDZ signicantly
[16].

173

Talc is a trioctahedral 2:1 phyllosilicate. Due to limited isomorphic substitution, talc surface is hydrophobic with minimal CEC.
Talc was commonly used as additives to many drug tablets, presumably due to its inert surface. However, studies on interactions
between drugs and talc surfaces were limited. Adsorption of CIP on
talc resulted in a capacity of 740 g/g, corresponding to 2.2 mol/g
[20] in comparison to 1.0 mmol/g on a Ca-montmorillonite [6]. The
amount of cimetidine adsorbed on talc was even less, at 290 g/g,
equivalent to only 1.2 mol/g [21]. And the adsorption of chlorpheniramine (CP) on talc resulted in a capacity of 0.06 mmol/g and
was attributed to hydrophobic interaction [22].
This goal of this study was to investigate the interactions
between SDZ and hydrophobic talc, a phyllosilicate with limited
surface charge, in order to better understand the fate and transport of SDZ in the environment on one hand, and to understand the
effect of hydrophobicity and solution chemistry on the removal of
SDZ by low-charge clay minerals on the other hand.
2. Materials and methods
The talc used was purchased from Acros. It has a chemical formula of Mg3 Si4 O10 (OH)2 , a mean particle size less than 200 mesh
(<0.075 m), and an external surface area of 2.3 m2 /g measured
by a multi-point BET method. Due to low isometric substitution in
tetrahedral and octahedral sites, talc had essential no permanent
surface charge [23] and its extremely low CEC was originated from
its pH dependent surface charges.
The sulfadiazine (CAS no.: 68-35-9), also called 2sulfanilamidopyrimidine, was purchased from Alfa Aesar (Ward
Hill, MA, USA). It has a molar mass of 250.28 g/mol and a log KOW
value of 0.09 [17]. It has two dissociation constants: pKa1 at
2.282.71 and refers to the protonation of the NH2 -group and pKa2
at 6.456.52 and refers to the deprotonation of the sulfonamido
group [24,25]. Its speciation under different pH conditions is
illustrated in Fig. 1. The equilibrium constant for the species
distribution between a neutral and zwitterionic (Kt ) form of SDZ

N
NH

NH2
O

N +
NH

pKa1

pKa2
Kt

NH2

N +

N
N

O
N S

NH2
Fig. 1. Speciation of SDZ.

O
N S

NH2

G. Lv et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 446 (2014) 172178

3.1. Kinetics of SDZ adsorption

The kinetic study showed that the adsorption of SDZ on talc was
almost instantaneous (Fig. 2). The data were tted to the pseudorst-order, pseudo-second-order, and Elovich kinetic models. Only
the pseudo-second-order kinetics tted the data well. The integrated rate law of the pseudo-second-order kinetics is:
kq2e t
1 + kqe t

0.26

0.25

0.24

(1)

where k (kg/mmol-h) is the rate constant of adsorption, qe

(mmol/kg) is the amount of solute adsorbed at equilibrium, and
qt (mmol/kg) is the amount of solute adsorbed on the surface of

100

y = 3.82x + 0.07
r2=1.000

80
60
40
20
0
0

10

15

20

25

Time (h)
0.23

10

15

20

25

Time (h)
Fig. 2. Kinetic study of SDZ adsorption on talc. The line is the pseudo-second-order
t to the observed data and the inset is the plot of Eq. (2).

the adsorbent at any time, t. Eq. (1) can be re-arranged into a linear
form
1
1
t
=
+
t
qt
qe
kq2e

(2)

where kqe 2 is the initial rate (mmol/kg-h). Fitting the experimental

data to the pseudo-second order kinetic model resulted in a coefcient of determination r2 of 0.9999, an initial rate of 14 mmol/kg-h,
a rate constant of 205 kg/mmol-h, and a qe of 0.26 mmol/kg.
The initial rate and qe are much smaller than the initial rate of
700 mmol/kg-h and the qe of 50 mmol/kg for CP adsorption on talc
[22]. But the rate constant of 205 kg/mmol-h for SDZ adsorption on
talc is much larger than the rate constant of 0.23 kg/mmol-h for CP
adsorption on the same talc [22]. The large rate constant conrmed
instantaneous SDZ adsorption on talc. The initial rate was slightly
less than 53 mmol/kg-h for TC adsorption on kaolinite [29].
3.2. SDZ adsorption isotherm
The Langmuir, Fruendlich, and linear isotherms were used to
characterize SDZ adsorption on talc. The linear form of the Freundlich model is expressed as:
log CS = log Kf +

1
CL
n

(3)

where CS and CL are the solute concentrations on solid (mmol/kg)

and in solution (mmol/L), Kf is the Freundlich constant (mmol/kg), a
measure of the adsorption capacity of the adsorbent, and 1/n is the
heterogeneity factor, a constant relating to adsorption intensity or
surface heterogeneity. The linear adsorption isotherm is expressed
as:
CS = Kd CL

3. Results and discussion

qt =

0.27

t/qt (h-kg/mmol)

is 102.17 [24], suggesting a dominant species of SDZ0 instead of

SDZ , when solution pH was between 2.7 and 6.4 (Fig. 1). Its
reported water solubility varied from 265 mg/L at pH 5.5 and 25 C
to 5690 mg/L at pH 8 and 37 C [25]. A solubility as low as 77 mg/L
was also reported [17].
The initial SDZ concentration varied from 0.01 to 0.08 mmol/L
for the adsorption isotherm study and was xed at 0.08 mmol/L
for kinetic, pH dependent, and temperature studies. To each 50mL centrifuge tube, 10 mL of SDZ solution and 1.0 g of talc were
combined and shaken at 150 rpm for 24 h at which equilibrium
could be reached based on the kinetic study. For the kinetic study
the equilibration time varied from 0.25 to 24 h, and for the temperature study, the equilibrium temperature was set at 296, 306,
316, and 326 K. After the mixtures were centrifuged at 3800 rpm
for 10 min, the supernatants were ltered through 0.45 m syringe
lters before being analyzed for equilibrium SDZ concentrations.
The SDZ concentration was measured using a UV-Vis spectrophotometer at the wavelength of 275 nm. Calibrations were
made using standards of 0.002, 0.01, 0.02, 0.05, and 0.08 mmol/L
with regression coefcients all greater than 0.998. The amount
of SDZ adsorbed was calculated from the difference between the
initial and equilibrium concentrations.
The point of zero charge (pzc) was determined using a potentiometric titration method. The pzc is the pH at which the net
adsorption of potential-determining ions, H+ and OH , on variablecharged surfaces is independent of electrolyte concentration [26].
To each 50 mL beaker, one gram of talc and 20 mL of NaCl solution
at concentrations of 0.01, 0.1, and 1.0 M were mixed and the pH stabilized. Aliquots of 0.2 mL of 0.01 M NaOH or HCl were added to the
mixture and the pH recorded. The pH at the intercept of titration
curves under different ionic strengths indicates the pzc [27].
The FTIR spectra were acquired on a Jasco FT/IR-4100 Spectrometer equipped with a ZnSe attenuated total reection accessory. The
spectra were obtained from 650 to 4000 cm1 by accumulating 256
scans at a resolution 4 cm1 .
Molecular simulation was performed under the module Forcite
of Materials Studio 5.0 software to investigate the interactions
between SDZ and talc in aqueous solution. The talc model was
constructed and the atomic coordinates were derived from the
b = 9.12 A,
c = 18.85 A,
=  = 90 ,
space group of C2/c with a = 5.27 A,
= 100.016 [28]. The supercell of the model was made of 12 talc
unit cells at 3a 2b 2c. On the surface of XOZ, the area was

15.81 A 37.70 A.
The established model was optimized geometrically. The temperature was set at 298 K and time was 1 ns with a time step of 1 fs.
Universal force eld was used during simulation. The Ewald summation method was used to calculate the electrostatic interaction.
After the system reached equilibrium, the NVT kinetic simulation
was performed under the same time constant and temperature conditions. The data were collected on the last 500 ps for later analyses.

Amount SDZ adsorbed (mmol/kg)

174

(4)

where Kd is the solute distribution coefcient between the solid

and the solution.
Freundlich model was used to t the adsorption of sulfachloropyridazine on a clay loam and a sandy loam with the 1/n
close to unity, suggesting that a linear isotherm might be an alternative model for its adsorption [19]. In this study, the adsorption of
SDZ followed a similar trend. The Langmuir t resulted in an r2 of
0.68 and a negative sorption maximum. The Langmuir model was
based on charge-limited or surface-limited monolayer adsorption.
The low r2 value suggested that neither surface charge nor surface area should be the limiting factor for SDZ adsorption on talc.
The Freundlich t ended with an r2 of 0.98, but the best t to the
observed data was the linear sorption isotherm with an r2 of 0.99
and a Kd value of 5.6 L/kg (Fig. 3), in comparison to a Kd values of

G. Lv et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 446 (2014) 172178

175

Amount SDZ adsorbed (mmol/kg)

0.3

0.2

y = 5.62x - 0.04
r2=0.99
0.1

0.0
0.00

0.01

0.02

0.03

0.04

0.05

0.06

Equilibrium SDZ concentration (mmol/L)

Fig. 3. Adsorption of SDZ on talc. The solid and dashed lines are the linear and
Freundlich ts to the observed data.

1.4 to 2.8 L/kg for SDZ adsorption on soil [17], 1.8 and 0.9 L/kg for
sulfachloropyridazine adsorption on a clay loam and sandy loam
soil, respectively [19], and to 0.07 to 0.91 L/kg for sulfadimethoxine
and sulfamethoxazole adsorption on soils [5]. The larger Kd value in
this study suggested that the hydrophobic surface of talc resulted
a higher SDZ uptake, an indication of hydrophobic interaction in
effect.
The adsorption of other ionizable antibiotics such as TC and CIP
onto swelling clay minerals such as montmorillonite and rectorite
was tted well to the Langmuir isotherm, suggesting a surfacelimited or charge-limited adsorption [6,7]. Similarly, the adsorption
of CP on montmorillonite and talc also tted to the Langmuir sorption isotherm well [22]. Fitting to the linear sorption isotherm
rather than the Langmuir isotherm suggested a different sorption
mechanism for SDZ adsorption on talc. At the equilibrium solution concentration of 0.055 mmol/L, the amount of SDZ adsorbed
was 0.25 mmol/kg (Fig. 3) in comparison to the CEC of talc at about
10 mmol/kg [30], again suggesting that cation exchange may not
contribute to SDZ adsorption on talc.
3.3. Effect of solution pH on SDZ adsorption
Solution pH had a drastic effect on SDZ adsorption on talc. Using
the pKa1 and pKa2 values of 2.7 and 6.4 for SDZ [24], the dominant
species of SDZ was in a cationic form when solution pH was <2.7,
a neutral molecular form between pH 2.7 and 6.4, and an anionic
form when pH > 6.4. When solution pH increased from 2 to 4, the
amount of SDZ adsorbed decreased from 0.4 to 0.2 mmol/kg (Fig. 4).
On the other hand, as the solution pH increased from 5 to 10, the SDZ
adsorption increased back from 0.2 to 0.4 mmol/kg (Fig. 4). The Kd
values followed a similar trend, varying from 3 to 9 L/kg, suggesting that the minimal SDZ adsorption occurred when neutral SDZ
molecules were present in solution (Figs. 14). In comparison, the
Kd of sulfamethazine on ve soils decreased monotonically as solution pH increased from 5.5 to 9.0 [31]. Literature data of Kd for SDZ
were scarce and were restricted to a narrow pH range (6.97.5) [32],
resulting in a small variation of the observed Kd of 1.4 to 2.8 L/kg
[17]. In general, the amphoteric SAs behave as weak acids and form
salts in strongly acidic or basic solutions [2]. This salt-forming tendency might also be responsible for the higher Kd values at low and
high solution pH conditions.
Contributions of different species to the overall Kd can be related
to the mass fraction () and the Kd of each species by:
Kd = KdSDZ+ + + KdSDZ0 0 + KdSDZ

(5)

where the superscripts SDZ+ , SDZ0 , and SDZ refer to cationic, zwitterionic or molecular, and anionic forms of SDZ, respectively. The

Fig. 4. SDZ adsorption on talc as affected by equilibrium solution pH ( with left

y-axis) and Kd as affected by solution pH ( right y-axis). The solid line is the tted
Kd as a function of pH and the vertical dashed lines are the pKa values of SDZ; (b)
speciation of SDZ under different pHs.

values are a function of solution pH and pKa values of the solute.

A multi-variable regression was performed using + , 0 , and
against Kd under different pH conditions with the intercept forced
to zero. The tted results are 8.7, 1.9, and 8.6 L/kg for Kd SDZ+ , Kd SDZ0 ,
and Kd SDZ , respectively, with an r2 of 0.98 (Fig. 4). The calculated
Kd SDZ0 is only 1/4 of that of Kd SDZ+ or Kd SDZ , conrming that neutral
species of SDZ had less afnity to talc surfaces.
3.4. Effect of temperature on SDZ adsorption
The adsorption of SDZ on talc decreased as the equilibrium
temperature increased at initial SDZ concentrations of 0.04 and
0.08 mmol/L (Fig. 5), suggesting an exothermic reaction. The
relationship between Kd and the thermodynamic parameters of
adsorption is expressed as
ln Kd =

H
S
+
RT
R

(6)

where H is the change in enthalpy, S is the change in entropy, R

is the gas constant, and T is the reaction temperature in K. The free
energy (G) of adsorption can be determined by
G = H TS

(7)

The calculated thermodynamic parameters are listed in Table 1.

The negative G values indicated attractive interactions between
SDZ and talc, thus a spontaneous adsorption of SDZ on talc. However, the G values were less negative compared to 8 kJ/mol
for TC adsorption on silica [10], and to 8 kJ/mol for promethazine hydrochloride adsorption on iron rich smectite [33]. Also,
the small negative G values suggested that the adsorption of SDZ
on talc was relatively weak, owing to physical adsorption such as

176

G. Lv et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 446 (2014) 172178

Table 1
Thermodynamic values of SDZ adsorption on talc at different temperatures and initial concentrations.
Cini (mM)

Ln(Kd ) (L/kg)

0.04
0.08

G (kJ/mol)

296 K

306 K

316 K

326 K

296 K

306 K

316 K

326 K

1.43
1.67

1.22
1.48

1.18
1.44

1.02
1.34

3.7
4.1

3.2
3.8

3.1
3.7

2.7
3.5

1.6

S (kJ/mol-K)

10.1
5.7

0.02
0.01

(a)
y = 688x - 0.8
r2=0.95

1.4

120

Transmittance (%)

Initial conc. = 0.08 mmol/L

Ln (Kd)

H (kJ/mol)

1.2

y = 1210x - 2.7
r2=0.83

1.0

Initial conc. = 0.04 mmol/L

0.8
0.0030

SDZ

110
100

328 K
318 K

90

308 K

80

Raw talc
0.0031

0.0032

0.0033

70
3700

0.0034

1/T

(b)

Fig. 5. SDZ adsorption on talc as affected by equilibrium temperature. The solid lines
are the t to Eq. (6).

hydrophobic or electrostatic interaction. The small negative change

in S indicated that spontaneous adsorption due to entropy was
not favored. While, the negative H value suggested that SDZ
adsorption on talc was an exothermic process, agreeing well with
the G value (Table 1). Therefore, a decrease in temperature should
facilitate the adsorption of SDZ onto talc.

Transmittance (%)

120
100

3500

3300

3100

2900

2700

900

700

SDZ
328 K
318 K
308 K
Raw talc

80
60

3.5. FTIR analyses

40

The FTIR spectra of raw talc and SDZ-adsorbed talc from an initial concentration of 0.08 mmol/L at different temperatures were
more or less identical. Only minute peaks at 1093 and 2978 cm1
appeared after SDZ adsorption on talc (Fig. 6), due to the lower
amount of SDZ uptake.
The NH2 vibration absorption peaks are at 3424 and 3354 cm1
with NH stretching of sulfonamide at 3269 cm1 and its corresponding bending band at 1652 cm1 [34]. The stretching
frequency of the sulfonamide NH was reported at 3379 cm1
for its acidic character of the molecules and the calculated and
experimental in-plane NH mode was at 1499 and 1454 cm1 ,
respectively [35]. The absence of 3424 and 3354 cm1 for SDZ
monomer indicated that the NH2 was not existent [36]. On
the contrary, the broadening and shifted stretching NH peak at
3345 cm1 was a strong evidence of the presence of NH3 + [34].
However, in this study, the broader peak was located at 3390 cm1
(Fig. 6a). For raw talc, this peak is at 3440 cm1 . Thus, this broader
peak may be attributed to the interaction of NH3 + with talc surfaces.
In a study of interactions between SDZ and poly dendrimer a
new band at 1633 cm1 appeared and was probably due to the
bending mode of SDZNH2 group [34]. In this study, a weak band
remained at 1652 cm1 , which could be resulted from the NH3 +
bending of sulfonamide rather than the bending mode of SDZNH2
group.
The vibrations at 1324 and 1150 cm1 were attributed to symmetric and asymmetric vibration absorption peaks of SO2 [36].
They were absent after adsorbed on talc. The bands at 1150 and
1092 cm1 were assigned to symmetric SO2 N and substituted benzene ring [37]. After SDZ adsorption on talc, two smaller peaks at

20
1700

1500

1300

Wavenumber

1100

(cm1)

Fig. 6. FTIR spectra of raw talc, solid SDZ and SDZ-adsorbed talc under different equilibrium solution temperature. The vertical lines are new peaks after SDZ adsorption
on talc.

1093 and 1053 cm1 appeared (Fig. 6b). These two bands may be
originated from the bands at 1150 and 1092 cm1 . If this assumption was valid, the adsorption of SDZ on talc may involve in the
interactions between the N of the sulfonamide and the substituted
benzene ring with the surface of talc. Similarly, the interaction
between SDZ and high silica zeolite Y was found involving in multiple weak H-bond and van der Waals type interactions between
the amine protons of SDZ and lattice oxygen atoms and hydrophobic interactions between the aromatic rings and zeolite cage walls
[35].
3.6. Discussion on SDZ adsorption sites and mechanism
The pzc determined in this study is about 7.7 (Fig. 7), agreeing well with the 7.7 0.45 [38]. The surface charge of talc was
determined to be 3 meq/kg [39], about the same magnitude of
5.3 mmol/kg as determined by benzyltrimethylammonium adsorption [40]. The surface potential of talc basal plane was found to
be largely independent of solution pH, while the surface potential of the edge surfaces reversed from positive to negative at pH
around 8 [41]. Still, signicant amount of SDZ adsorption was found
even when solution pH was much higher than 7.7 (Fig. 4). Thus,

G. Lv et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 446 (2014) 172178

-200
-150

mmolc/kg

-100
-50
0
50
100
150
200

10

pH
Fig. 7. Titration curves for determination of pzc of talc at NaCl concentrations of
0.01 M (), 0.1 M (), and 1.0 M ().

177

hydrogen bonding between N on the N-substituted benzene ring as

well as the N of the sulfonamide and the OH of the broken bond on
the 010 surface could be responsible partly for the SDZ adsorption
(Fig. 8). Moreover, the interactions between the benzene ring as
well as the partially negatively charged O of SDZ and the Mg in
the octahedral sites of talc may also contribute to SDZ adsorption
(Fig. 8). Under alkaline conditions, polysaccharide could directly
interact with the hydroxiated talc surface by hydrogen bonding;
thus, it was not the hydrophobicity of the surface of talc, but the
metallic sites of talc that contributed to enhanced adsorption [46].
Sorption of SAs by humic substances was mainly driven by the
aromatic amino group which also formed covalent bonds with phenolic humic substances [11]. The lack of humic substances for the
pure phase talc resulted in a much lower SDZ adsorption.

4. Conclusions
the surface charge cannot be accounted for SDZ adsorption on talc,
further conrming that hydrophobic interaction, rather than electrostatic interaction, was more responsible for the uptake of SDZ
on talc.
The external surface area of talc was 2.3 m2 /g. At SDZ adsorption of 0.25 mmol/kg, the calculated SDZ adsorption density would
be about 1500 A 2 per SDZ molecule on a monolayer coverage. In
addition, the amount of SDZ adsorbed at 0.25 mmol/kg was much
lower than the CEC of talc at about 10 mmol/kg [30]. Thus, neither
the surface area nor the CEC of talc was the limiting factor for SDZ
adsorption.
In comparison to other phyllosilicates, talc is quite hydrophobic.
The hydrophilic part of the surface area estimated by benzyltrimethylammonium adsorption was 2 m2 /g, accounting for 20%
of the total surface area of talc [40]. Adsorption of naphthalene on
talc in aqueous solution was strongly dominated by the hydrophobic surface of the talc and the major mechanism was due to van
der Waals force [42]. Hydrophobic interaction was attributed to
the adsorption of guar, a natural nonionic polysaccharide, onto the
hydrophobic sites of talc [43]. Thus, the hydrophobic interaction
may play an important role in SDZ adsorption. Similarly, for painkiller drug acetaminophen, it adsorption on activated carbon was
greatly reduced as the surface became more hydrophilic [44].
Hydrogen bonding rather than electrostatic or hydrophobic
force was proposed as one of the main driving forces for guar
adsorption on talc [45]. Due to the presence of N in SDZ, hydrogen bonding between N of the molecule and OH on the talc surface
may be attributed more to adsorption of SDZ on talc. Simulation of
interactions between SDZ and talc in aqueous solution showed that

Fig. 8. Molecular dynamic simulation showing attractive interactions between SDZ

and talc (0 1 0) surface. The N is indicated by blue, O by red, C by gray, H by white, and
S by yellow dots. The N on the benzene ring and N of the sulfonamide of the top SDZ
molecule interacted with OH on talc (0 1 0) via hydrogen bonding. The bottom SDZ
molecule showed the interactions between octahedral Mg of talc and NH2 and O
of SDZ. (For interpretation of the references to color in this gure legend, the reader
is referred to the web version of this article.)

The adsorption of SDZ on talc was almost instantaneous and

followed a linear adsorption isotherm with a Kd values between 3
and 9 L/kg under neutral and high or low pH conditions. Although
talc has small cation exchange capacity and specic surface area,
the amount of SDZ adsorbed was not limited by these factors. Due
to the fact that higher Kd values were found at higher and lower
pH conditions, it was anticipated that hydrogen bonding played a
major role on SDZ adsorption on talc. The interactions between the
benzene ring as well as O of SDZ and the Mg in the octahedral sites
of talc were also speculated to account for SDZ adsorption on talc.
Hydrophobic interaction may also contribute to SDZ adsorption on
talc, but to a lesser degree.

Acknowledgments
The research was support by a grant from Wisconsin Groundwater Research Council. Sam Leick helped with the experiments.

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