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JIEC-2395; No. of Pages 6

Journal of Industrial and Engineering Chemistry xxx (2015) xxxxxx

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Journal of Industrial and Engineering Chemistry

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On-line ame AAS determination of traces Cd(II) and Pb(II) in water

samples using thiol-functionalized SBA-15 as solid phase extractant
S.L. Zhao a,*, F.S. Chen b, J. Zhang a, S.B. Ren a, H.D. Liang a,c,**, S.S. Li a
a
School of Pharmaceutical and Chemical Engineering, Taizhou University, Taizhou 318000, Zhejiang, PR China
b
School of Chemical and Environmental Engineering, Jiujiang University, Jiujiang 332005, Jiangxi, PR China
c
Department of Laboratory & Equipment Management, Taizhou University, Taizhou 318000, Zhejiang, PR China

A R T I C L E I N F O A B S T R A C T

Article history: Mesoporous thiol-functionalized SBA-15 was investigated as a microcolumn packed material for the on-
Received 30 October 2014 line preconcentration of trace amounts of Pb(II) and Cd(II) in water samples before their ame AAS
Received in revised form 26 December 2014 determination. The results indicated that the proposed method was tolerant to the coexistence ions,
Accepted 19 January 2015
offered good linearity and the achievable enhancement factors were 34 for Pb(II) and 41 for Cd(II), and
Available online xxx
the detection limits (3s) of 0.22 mg L 1 and 0.11 mg L 1 and the precision (RSD) for 11 replicate
determination of 30 mg L 1 Pb(II) and 20 mg L 1Cd(II) were 0.4% and 0.3%, respectively.
Keywords:
2015 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights
Lead
reserved.
Cadmium
Determination
Thiol-functionalized SBA-15
Flame AAS

1. Introduction
Lead (II) and cadmium (II) are two of the metal pollutants which
may cause critical environment problems. Accurate determination
of these ions is very important in the context of food, agricultural
chemistry, environmental protection and the monitoring of
environmental pollution [1]. Flame atomic absorption spectrome-
try (AAS) has been widely used to full the determination task.
However, preconcentration and separation procedures such as
liquidliquid microextraction (LME) [2,3], coprecipitation [4],
cloud point extraction (CPE) [5], electro-deposition [6] or solid
phase extraction (SPE) [1,7], etc. are often needed due to the
insufcient detection limits for FAAS and the matrix interferences.
The method of ow inject (FI) on-line preconcentration coupled
with AAS for the ultra-trace level metals sensitive determination
has been generated considerable interest, because it provides
many benets such as reducing solvent use, solvent exposure,
disposal costs and extraction time for sample preparation in
comparison with off-line LME, CPE and SPE [7]. Up to now, various
* Corresponding author. Tel.: +86 576 85137182; fax: +86 576 85137182.
** Corresponding author at: Department of Laboratory & Equipment Management,
Taizhou University, Taizhou 318000, Zhejiang, PR China. Tel.: +86 576 85137182;
fax: +86 576 85137182.
E-mail address: zhscu@163.com (H.D. Liang).
materials such as silica gel and its derivants [810], resins [1115],
fullerene [16], ionic liquid based xerogel [17], biomasses [18],
activated carbon [1922] and multi-walled carbon nanotubes [23
26] have been developed as sorbents for the on-line preconcen-
tration of trace elements before AAS detection.
Ordered mesoporous silica has attracted a great deal of interest,
in recent year, because of its large BET surface areas, high
porosities, controllable and narrowly distributed pore sizes, and
ordered pore arrangements. They are proven to be advantageous or
applicable in adsorption, sensors and catalysis, controlled release,
chromatography and separations [27]. For the adsorption applica-
tions, organic groups (or functional ligands), such as aminopropyl,
ethylenediamine, diethylenetriamine, salicylaldimino and propyl-
thiol etc, are often grafted or incorporated onto mesoporous
materials [27,28], to improve the adsorption capacity and
specicity. Among a wide variety of functional ligands, thiol is
an effective ligand for the complexing of the d-block elements
beneting from their strong electrostatic interaction [29,30]. Pro-
pyl-thiol-functionalized mesostructured silicas, have been devel-
oped and used for the off-line selective sorption of heavy metals,
such as Cu2+, Cd2+, Hg2+, Pt2+ and Pd2+ [2730]. However, the
careful literature survey indicates that a few works have reported
the utilization of this kind of material for the on-line preconcen-
tration in FI Analysis system [31,32]. So, the aim of the present
work is to apply thiol-functionalized SBA-15 (HS-SBA-15) to
FI-AAS detection system for the traces lead and cadmium ions

http://dx.doi.org/10.1016/j.jiec.2015.01.015
1226-086X/ 2015 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights reserved.

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2 S.L. Zhao et al. / Journal of Industrial and Engineering Chemistry xxx (2015) xxxxxx
preconcentration and determination. It is expected that its
properties such as regular morphology and porous structure,
highly specic surface area with abundant functions on the
surface, hydrothermal stability and negligible swelling capacity
will greatly benet the resistances to swelling/shrinking, reducing
the pressure drop under the analytical conditions, and also
providing high reproducible enhancement factors.
2. Materials and methods
2.1. Apparatus
A FIA-3100 ow injection system (Vital Instruments Co. Ltd,
Beijing, China) based on PLD (Programable Logic Device), consists
of an electromagnetic valve (EV), two peristaltic pumps (P1 and
P2), an 8-port injector valve (IV) and a home-made microcolumn (a
PTFE tube with an inner diameter of 0.5 cm and a length of 2.0 cm).
A TAS 990 Flame AAS (Beijing Purkinje General Instrument Co.,
Ltd. Beijing, China), equipped with hollow cathode Cd and Pb lamps
(Beijing Shu-Guang-Ming Electronic Lighting Instrument Co., Ltd.
Beijing, China), was used for the metal elements determination.
The instrument conditions, such as, wavelength (228.8 nm for Cd
and 283.3 nm for Pb, respectively), slit width (0.4 nm for both) and
the ame conditions (2.2 L min 1 acetylene and 9.4 L min 1 air,
respectively) were employed according to the standard recom-
mendations. The peak height (or maximum absorbance) was used
for quantitative analysis [22].
The sample digestion was conducted by using Qwave-2000
microwave digestion system (QMDS, Questron Co., Missisauga
Canada). All instrumental parameters for the sample digestion
were chosen according to the recommendations of the EPA [7,22].
A Delta320 METTLER (METTLER Toledo, USA) pH meter was
used to monitor the pH of the solutions.
The WaterPro water system (Labconco Corporation, Kansas
City, MO, USA) was used to provide the doubly deionized water
(DDW, 18.2 MV cm 1) for the experiments.
2.2. Reagents and chemicals
Tri-block poly (ethylene oxide)-poly (propylene oxide)-poly
(ethylene oxide), (Pluronic P123, PEO20PPO70PEO20), purchased
from Aldrich (Milwaukee, WI, USA), was used as the structure-
directing agent. Tetraethoxysilane (TEOS, from Sinopharm Chemi-
cal Reagent Co., Ltd.) was employed as the silica precursor. (3-
mercaptopropyl) trimethoxysilane (MPTMS, Nengde Chemicals,
Nanjing, China) was selected as the thiol-functionalized reagent.
Hydrochloric acid, sulfuric acid and nitric acid solutions, were
prepared by direct dilution from the concentrated solutions
(Sinopharm Chemical Reagent Co., Ltd.). Diluted hydrochloric acid
and sodium hydroxide were used to adjust the pH value of the
solutions, wherever suitable. Standard solutions of Cd(II) and Pb(II)
were prepared daily by appropriately diluting corresponding stock
solutions (1000 mg L 1, BW 079804 for Cd and BW 079802 for Pb,
respectively, NRCSM, Beijing, China) with DDW. The certied
reference materials (CRM, from NRCSM, Beijing, China) were used
after the following treatment [22,23]: 0.2000 g of rice our (GBW
08511) or tea leaves (GBW 07605)) was mixed with 5 mL of
concentrated HNO3 and 2 mL HClO4 in a sealed Teon cup and
digested with Qwave-2000 microwave digestion system to obtain
a clear solution. Subsequently, the solution was slowly evaporated
until white fumes appeared to discharge volatile compounds, such
as nitrate and chloride ions. After cooling, the digest was adjusted
to the optimal pH range with appropriate buffer solution and
diluted to a nal volume of 50 mL with DDW.
The working solutions were prepared by accurately diluting
aliquots of the standard solutions immediately prior to their use.
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All the other reagents used were of the highest available purity
and at least of analytical grade without further purication.
2.3. Synthesis of HS-SBA-15
Mesostructured silica materials functionalized with propyl-
thiol were prepared by the one-pot solgel incorporation and
hydrothermally synthesis method according to the general
procedure previously reported [30]. In a typical synthesis, 2 g of
Pluronic P123 was dissolved under stirring in 15 g of DDW at room
temperature, and then 60 g of 2 M HCl was added. After heating to
40 8C, TEOS was added to the solution and stirred for 50 min before
adding MPTMS. The molar composition of the mixture was
0.017 P123: 5.88 HCl: 197 H2O: 1 silica (0.8 TEOS + 0.2 MPTMS).
The reactant mixture was stirred for 20 h and nally aged for 24 h
at 100 8C in a polypropylene bottle. The solid products were
recovered by ltration and dried in air. The template was removed
by Soxhlet extraction with ethanol as extractant. After a 24 h
circumuence extraction, the solid was collected and dried at 60 8C
in an electric vacuum drying oven for 24 h. The obtained material
was marked with HS-SBA-15.
The procedure for the SBA-15 preparation was similar to HS-
SBA-15 except for the absence of MPTMS.
(Electronic Supplementary Information (ESI) available contain-
ing the XRD Patterns, N2 adsorption-desorption isotherms, BJH
pore size distribution curves, FTIR spectra, SEM/TEM images,
analysis of surface groups and TGA curves)
2.4. Microcolumn preparation and general procedure
The microcolumn in the FI system was prepared by packing
approximately 60 mg of HS-SBA-15 in the PTFE tube and end-capped
with glass wool. It was connected to the injector valve with PTFE
tubing. Before use, the packed column was repeatedly washed with
DDW, eluent and DDW until no metal signal detected with AAS.
The FI operation sequence for the preconcentration and
separation, as shown in Fig. 1 and Table 1, respectively, was
conducted according to the literatures [8,21]. In the preconcentra-
tion step, P1 delivered the sample solution through the column at a
designed ow rate, thus, the metal ions were retained on the
adsorbent. P2 introduced the eluent to FAAS for baseline,
simultaneously. After nishing the sampling, P1 was stopped,
while P2 started to work and the IV was automatically switched to
the inject position. So the eluent was carried through the column
for eluting the retained analytes and sent into AAS, where the
absorbance signals were monitored. Finally, the IV was automati-
cally switched back to the loading position and EV was also
switched. At the same time, P2 was stopped, P1 started to work and
delivered the buffered solution through the column for the column
recovery.
In order to obtain high sensitivity, accurate and reproducible
results, buffered 30 mg L 1 Pb(II) or 20 mg L 1 Cd(II) solutions were
selected for the optimization of the sampling (sample acidity,
sampling rate and extration time) and elution conditions (eluting
medium, eluent concentration and eluting rate) in the FI
preconcentration system [21]. In all of these processes, 0.6 mol L 1
1 of HCl was used as the eluent. The interferences of coexisting ions
and the reusability of the column were tested under the optimized
conditions.
3. Results and discussion
3.1. Optimization of the sampling and eluting conditions
The adsorption of metal ions on thiol fountionlized silicates is
mainly due to the complex formation within the sorbents and
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Fig. 1. Schematic for the on-line FI-AAS determination Pb and Cd. BS: Buffered
Solution; P1 and P2: peristaltic pumps; W: waste; EV: Electromagnetic Valve. Valve
position: (a) and (c) Loading; (b) Inject.
those ions with a strong local afnity will be preferably adsorbed.
Therefore, an appropriate pH value can not only improve the
adsorption efciency, but also depress interferences from the
matrix, because. [3133] In this work, metal solutions were
adjusted to a pH range of about 310 for the acidity effect
evaluation and the sampling rates were set at 4.5 mL min 1 for the
evaluation of the effect of acidity. As showing in Fig. 2, the signal of
the metals increased rapidly as the solution pH increased from 3 to
5 and then kept constant in the pH range of about 56. This effect
was due largely to the protonation of the sulfur atom of the SH
group at high acidity, which diminishes the ability of the thiol
groups to be involved in chelating the ions from solution [29
31]. The decrease in absorbance at pH above 6 is probably due to
the hydrolysis of metal ions. When pH is higher than 6, heavy
metals in dilute solution existed in the forms of M(OH)+, M(OH)2
(aqueous), M(OH)3 , and some other species, e. g., M2(OH)3+,
M3(OH)42+, M4(OH)44+ etc. [34] The formation of hydroxo-
complexes diminishes the availability of the ions for complexation
with the functional groups on the sorbent. It is perceptible that,
there are modest bounces in the signals of determined ions at the
pH of about 10.7, which may generated by aggregation of the
Table 1
Operational sequence of FI system for the preconcentration and separation of trace Pb and Cd.
Step Function Time (s) Pumped medium
1 (Fig. 1a) Preconcentration 60 Sample
0.6 mol L
2 (Fig. 1b) Elution 20 0.6 mol L
3 (Fig. 1c) Column recovery 20 Buffered solution
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3
Fig. 2. Effect of pH on the preconcentration. All other conditions as in Fig. 1 and
Table 1.
M(OH)2 precipitation onto sorbent at a higher pH value. To achieve
a high retention efciency and good selectivity, a pH value of
5.5 was recommended for the subsequent work.
Sample loading rate and loading time are the important
parameters in the FI-AAS system because they determine the
contact time, the velocity and the volume of the samples on the
sorbent [7], which will affect the sorption equilibration and
retention of the detected ions on the solid phases and also the
sample consumption. As shown in Fig. 3, the signals of the analytes
increased almost linearly as sample loading rate increased up to
7.5 mL min 1. At a sampling rate of 7.5 mL min 1 with 60 s, the
peak heights of Pb(II) and Cd(II) were 0.146 and 0.282, respectively.
Additionally, at this sampling rate, the peak height for Pb(II) or
Cd(II) were linear increased with increasing the loading time up to
at least 100 s (see Fig. 4). The results indicated that the adsorption
equilibrium of the ions on the sorbents is fast and the column has a
relative high adsorption capability for the ions under the analysis
conditions. It is apparent that a high sampling rate or/and a long
sampling time will conduce to a high enhancement factor or save
experiment time, which however will result in large sample
consumption and is also limited by the back-pressure produced by
the column. Furthermore, long sampling time will decrease the
sample throughput. So 4.5 mL min 1 of sampling rate with a 60 s
loading time was chosen for the both ions in the subsequent
experiments, in order to maintain the stability of the preconcen-
tration system with a reasonable degree of sensitivity and
relatively high sampling throughput [22].
The choice of elution conditions is also important for the FI
preconcentration system. In view of the preconcentration/elution
of ions involving the ion-exchange cycles of ions with protons,
stronge acids, such as nitric, hydrochloric and sulphuric acid
solutions were therefore taken into account for the elution of ions.
However, nitric acid is not suitable for this method, imputable to
its oxidizing property, which will oxidize thiol groups on the
1
Flow rate (mL min ) Valve position
Pump1 Pump 2
4.5 Off
1
HCl 4.3 for Pb Loading
5.5 for Cd
1
HCl Off 4.3 for Pb Injection
5.5 for Cd
On Off Loading
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Fig. 3. Effect of sample loading rate on the preconcentration. All other conditions as
in Fig. 1 and Table 1.
Fig. 4. Effect of sample loading time on the preconcentration. All other conditions as
in Fig. 1 and Table 1.
sorbent [35,36] and sulphuric acid is not well suited to FAAS
analysis because of its complex interference effects and the
precipitation formation with ions [37]. So, hydrochloric acid
solutions were selected. The effect of the concentration of
hydrochloric acid on the signals of the two ions is illustrated in
Fig. 5. The results show that signals of the two ions were increasing
gradually with the initial increase in the concentration of the
eluent. The strongest signals were reached at concentrations equal
to 0.6 mol L 1 for Cd(II) and 0.4 mol L 1 for Pb(II), and there were
no notable increases in the analytical signal when a further
concentrated hydrochloric acid was used. The elution of the ions is
a process of ion-exchange, when the lower concentration of
elutions used, the retained ions can not be thoroughly exchange by
the protons, consequently give lower signals. Whereas, with the
concentration of the eluent increasing the signals for the both
retained ions can reach the maximum. Therefore, 0.6 mol L 1
hydrochloric acid was chosen for the elution of both ions.
The effect of eluting rate on the metal signals was studied
ranging from 3.1 to 7.5 mL min 1 with 20 s eluting. The results
indicate (as shown in Fig. 6) that the analytical signals for both
metals exhibited initial increase and then decrease trends. At a
lower eluting rate, the retained ions can also not be thoroughly
desorbed due which deliveres insufcient eluent. However, the
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Fig. 5. Effect of HCl concentration on the elution. All other conditions as in Fig. 1 and
Table 1.
Fig. 6. Effect of HCl ow rate on the elution. All other conditions as in Fig. 1 and
Table 1.
desorbed ions will be diluted by the extra eluent at an excessively
high a eluting rate. The best results were achieved when the
eluting rates were about 5.5 mL min 1 for Cd(II) and 4.3 mL min 1
for Pb(II), respectively.
3.2. Interference studies
The interference of coexisting ions on the detection must been
conducted, because it links directly to the performance of the
proposed method. Representative alkali and alkali earth metal
ions, such as Na(I), K(I), Mg(II), Ca(II), Ba(II), typical transition
metal ions but without afnity to the thiol ligand, such as Cr(III),
Mn(II), Fe(III), some common ions with high afnity to the thiol
group, including Zn(II), Cu(II), Cd(II) (for Pb determination), Pb(II)
(for Cd determination), Hg(II), Ag(I) and some common anions,
such as Cl , NO3 , SO42 , etc. were tested individually. It was
considered interference when species caused variations of the
analyte signal more than 5% [1].
The testing results showed that 1000-fold Na(I), K(I), Cl , NO3 ,
SO24 , 500-fold Mg(II), Ca(II), Ba(II), 200-fold Cr(III), Mn(II), Fe(III),
Zn(II) and 30-fold Cu(II), Cd(II) (for Pb), Pb(II) (for Cd), Hg(II), Ag(I)
did not interfere with the analytes determination. These results
indicate that HS-SBA-15 had a high selectivity for the two ions. The
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thiol group, a soft base, would intensively interact with Cd(II) and
Pb(II), classied as soft acids, may provide the selective environ-
ment against alkali metal, alkali earth metal ions and some of the
transition metal ions. High adsorption capacity for Cd(II) and Pb(II),
to some extent, would also provided the toleration against the
other ions with high afnity to the thiol group.
3.3. Reusability of the packed column
The reusability of the packed column in this proposed method
was studied by measuring the response signals of the metals and
counting the number of runs in a working day. It was found that the
column could be used repeatedly for more than 200 operational
cycles and provide invariable retention efciency, which indicate
that both the material and the packed column are of good stability
under the optimized conditions in the courrent proposed method.
3.4. Performance of the FI-AAS system and application to the sample
analysis
The performances of the presented method were evaluated
under optimal experimental conditions. With a sampling rate of
4.5 mL min 1 for 60 s of preconcentration, the enhancement
factors (EF), obtained by comparing the slopes of the linear
portion of the calibration curves before and after the on-line
extraction [10], were 34 for Pb(II) and 41 for Cd(II), respectively,
with a sample throughput of 45 h 1. The sorbent also provided
good linearity (R-squared for both metals were both above 0.999),
with calibration functions of A1 (absorbance) = 0.00942 C (concen-
tration of Cd(II) in mg L 1) 0.00033 for trace Cd(II) and
A = 0.00351 C (concentration of Pb(II) in mg L 1) 0.0012 for
Pb(II), in the range of 260 mg L 1, and the detection limits (3s)
were 0.22 mg L 1 (Pb) and 0.11 mg L 1 (Cd), respectively. And the
precisions (RSD, n = 11) were 0.4% for the level of 30 mg L 1 of Pb
and 0.3% for the level of 20 mg L 1 Cd, respectively.
Two CRMs, GBW 07605 (tea), GBW 08511 (Rice our) and three
real water samples (water 1, 2 and 3, are a commercial mountain
spring water, a river water and a groundwater, respectively) were
analysed for the evaluation the accuracy and the application
performance of the proposed method. The results were listed in
Table 2. As shown, the determined concentrations of Pb and Cd in
the CRMs by using this method agreed well with the certied
values and the mean recoveries (three duplications) of fortied
samples were in the range of 96104% for both Pb and Cd.
Table 3 compares several sorbents reported in the literatures
with HS-SBA-15 for on-line preconcentration of Pb(II) or/and

Table 2
Analytical results (mean  s, n = 3) for the determination of trace Pb and Cd in the certied reference material and real samples under the optimal conditions.

Sample Concentration of Pb Concentration of Cd

Certied Added Found Recovery/% Certied Added Found Recovery/%

1
GBW 07605 (tea) (mg g ) 4.40  0.30 0 4.32  0.07
5.0 9.27  0.11 99.0
1
GBW 08511 (Rice our) (mg g ) 0.50  0.02 0 0.51  0.01
0.50 1.03 104
1
Water 1 (mg L ) <1000 0 2.27  0.01 - 0 0.93  0.01
2 4.26  0.02 99.5 2 3.01  0.02 104
1
Water 2 (mg L ) 0 4.05  0.02 0 0.9  0.01
5 9.02  0.03 99.4 1 1.91  0.02 101
1
Water 3 (mg L ) 0 5.04  0.03 0 4.03  0.03
5 10.01  0.05 101.2 5 9.01  0.03 99.6

Table 3
*
Comparison of the essential features of methods developed for the determination of Pb and Cd.
1
Sorbent Chelating material Analyte PT (s) EF (min) DL (mg L ) f (/h)

SG (off-line) [9] Gallic acid Cd 100 0.87

Pb 200 0.58
SG [8] PAN Pb 80 101 0.24 45
SH-SG [9] Cd 45 56 0.07 55
RP-C18 [10] 1,10-Ph Cd 30 32
PDI-18 [11] Cd 120 110 0.08
Amberlite XAD-4 [13] ATP Cd 180 99 0.3 18
Amberlite XAD-2 [14] NPTT Pb and Cd 60 0.22 and 0.16
Amberlite XAD-2010 [15] Na-DDTC Pb, Cd 0.080.26
Fullerene [16] APDC, 8-HQ Cd 120 110 0.3
Vermicompost [18] Cd 240 46 0.4
Pb 62 8.8
Humic acid [18] Cd 240 27 0.8
Pb 83 12.1
AC (off-line) [19] MTB Cd - 1000 <1
AC [20] PR Pb - 100 1
MWCNT [23] Cd 60 24 0.3 45
MWCNT [24] Pb 44.2 2.6 14
MWCNT [25] Tartrazine Cd 40 0.8
Pb 40 6.6
Block copolymer [38] Pb 50 1.82
SH-SBA-15 [this work] Pb 60 34 0.22 45
Cd 60 41 0.11
*
The methods are based on the on-line preconcentration coupled with AAS except the rst entry.
PT Preconcentration time, EF Enhancement factor, DL Detection limit, f sampling frequency, SG Silica gel, APDC ammonium pyrrolidinedithiocarbamate, PAN 1-(2-
Pyridylazo)-2-Naphthol, 1,10-Ph 1,10-Phenanthroline, ATP 2-aminothiophenol, NPTT 3-(2-nitrophenyl)-1H-1,2,4-triazole-5(4H)-thione, MTB methyl thymol blue, ATP 2-
aminothiophenol, PR Pyrogallol Red, DDTP O, O-diethyldithiophosphate, PDI-18 poly(octadecyl diitaconate), MWCNT Multi-walled carbon nanotubes, AC Active carbon,
Block copolymer Polyhydroxybutyrate-b-polyethyleneglycol.

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