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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
School of Pharmaceutical and Chemical Engineering, Taizhou University, Taizhou 318000, Zhejiang, PR China
School of Chemical and Environmental Engineering, Jiujiang University, Jiujiang 332005, Jiangxi, PR China
Department of Laboratory & Equipment Management, Taizhou University, Taizhou 318000, Zhejiang, PR China


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.
2015 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights
Thiol-functionalized SBA-15
Flame AAS

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

1226-086X/ 2015 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights reserved.

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preconcentration and determination. It is expected that its All the other reagents used were of the highest available purity
properties such as regular morphology and porous structure, and at least of analytical grade without further purication.
highly specic surface area with abundant functions on the
surface, hydrothermal stability and negligible swelling capacity 2.3. Synthesis of HS-SBA-15
will greatly benet the resistances to swelling/shrinking, reducing
the pressure drop under the analytical conditions, and also Mesostructured silica materials functionalized with propyl-
providing high reproducible enhancement factors. thiol were prepared by the one-pot solgel incorporation and
hydrothermally synthesis method according to the general
2. Materials and methods procedure previously reported [30]. In a typical synthesis, 2 g of
Pluronic P123 was dissolved under stirring in 15 g of DDW at room
2.1. Apparatus 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
A FIA-3100 ow injection system (Vital Instruments Co. Ltd, adding MPTMS. The molar composition of the mixture was
Beijing, China) based on PLD (Programable Logic Device), consists 0.017 P123: 5.88 HCl: 197 H2O: 1 silica (0.8 TEOS + 0.2 MPTMS).
of an electromagnetic valve (EV), two peristaltic pumps (P1 and The reactant mixture was stirred for 20 h and nally aged for 24 h
P2), an 8-port injector valve (IV) and a home-made microcolumn (a at 100 8C in a polypropylene bottle. The solid products were
PTFE tube with an inner diameter of 0.5 cm and a length of 2.0 cm). recovered by ltration and dried in air. The template was removed
A TAS 990 Flame AAS (Beijing Purkinje General Instrument Co., by Soxhlet extraction with ethanol as extractant. After a 24 h
Ltd. Beijing, China), equipped with hollow cathode Cd and Pb lamps circumuence extraction, the solid was collected and dried at 60 8C
(Beijing Shu-Guang-Ming Electronic Lighting Instrument Co., Ltd. in an electric vacuum drying oven for 24 h. The obtained material
Beijing, China), was used for the metal elements determination. was marked with HS-SBA-15.
The instrument conditions, such as, wavelength (228.8 nm for Cd The procedure for the SBA-15 preparation was similar to HS-
and 283.3 nm for Pb, respectively), slit width (0.4 nm for both) and SBA-15 except for the absence of MPTMS.
the ame conditions (2.2 L min 1 acetylene and 9.4 L min 1 air, (Electronic Supplementary Information (ESI) available contain-
respectively) were employed according to the standard recom- ing the XRD Patterns, N2 adsorption-desorption isotherms, BJH
mendations. The peak height (or maximum absorbance) was used pore size distribution curves, FTIR spectra, SEM/TEM images,
for quantitative analysis [22]. analysis of surface groups and TGA curves)
The sample digestion was conducted by using Qwave-2000
microwave digestion system (QMDS, Questron Co., Missisauga 2.4. Microcolumn preparation and general procedure
Canada). All instrumental parameters for the sample digestion
were chosen according to the recommendations of the EPA [7,22]. The microcolumn in the FI system was prepared by packing
A Delta320 METTLER (METTLER Toledo, USA) pH meter was approximately 60 mg of HS-SBA-15 in the PTFE tube and end-capped
used to monitor the pH of the solutions. with glass wool. It was connected to the injector valve with PTFE
The WaterPro water system (Labconco Corporation, Kansas tubing. Before use, the packed column was repeatedly washed with
City, MO, USA) was used to provide the doubly deionized water DDW, eluent and DDW until no metal signal detected with AAS.
(DDW, 18.2 MV cm 1) for the experiments. The FI operation sequence for the preconcentration and
separation, as shown in Fig. 1 and Table 1, respectively, was
2.2. Reagents and chemicals conducted according to the literatures [8,21]. In the preconcentra-
tion step, P1 delivered the sample solution through the column at a
Tri-block poly (ethylene oxide)-poly (propylene oxide)-poly designed ow rate, thus, the metal ions were retained on the
(ethylene oxide), (Pluronic P123, PEO20PPO70PEO20), purchased adsorbent. P2 introduced the eluent to FAAS for baseline,
from Aldrich (Milwaukee, WI, USA), was used as the structure- simultaneously. After nishing the sampling, P1 was stopped,
directing agent. Tetraethoxysilane (TEOS, from Sinopharm Chemi- while P2 started to work and the IV was automatically switched to
cal Reagent Co., Ltd.) was employed as the silica precursor. (3- the inject position. So the eluent was carried through the column
mercaptopropyl) trimethoxysilane (MPTMS, Nengde Chemicals, for eluting the retained analytes and sent into AAS, where the
Nanjing, China) was selected as the thiol-functionalized reagent. absorbance signals were monitored. Finally, the IV was automati-
Hydrochloric acid, sulfuric acid and nitric acid solutions, were cally switched back to the loading position and EV was also
prepared by direct dilution from the concentrated solutions switched. At the same time, P2 was stopped, P1 started to work and
(Sinopharm Chemical Reagent Co., Ltd.). Diluted hydrochloric acid delivered the buffered solution through the column for the column
and sodium hydroxide were used to adjust the pH value of the recovery.
solutions, wherever suitable. Standard solutions of Cd(II) and Pb(II) In order to obtain high sensitivity, accurate and reproducible
were prepared daily by appropriately diluting corresponding stock results, buffered 30 mg L 1 Pb(II) or 20 mg L 1 Cd(II) solutions were
solutions (1000 mg L 1, BW 079804 for Cd and BW 079802 for Pb, selected for the optimization of the sampling (sample acidity,
respectively, NRCSM, Beijing, China) with DDW. The certied sampling rate and extration time) and elution conditions (eluting
reference materials (CRM, from NRCSM, Beijing, China) were used medium, eluent concentration and eluting rate) in the FI
after the following treatment [22,23]: 0.2000 g of rice our (GBW preconcentration system [21]. In all of these processes, 0.6 mol L 1
08511) or tea leaves (GBW 07605)) was mixed with 5 mL of 1 of HCl was used as the eluent. The interferences of coexisting ions
concentrated HNO3 and 2 mL HClO4 in a sealed Teon cup and and the reusability of the column were tested under the optimized
digested with Qwave-2000 microwave digestion system to obtain conditions.
a clear solution. Subsequently, the solution was slowly evaporated
until white fumes appeared to discharge volatile compounds, such 3. Results and discussion
as nitrate and chloride ions. After cooling, the digest was adjusted
to the optimal pH range with appropriate buffer solution and 3.1. Optimization of the sampling and eluting conditions
diluted to a nal volume of 50 mL with DDW.
The working solutions were prepared by accurately diluting The adsorption of metal ions on thiol fountionlized silicates is
aliquots of the standard solutions immediately prior to their use. mainly due to the complex formation within the sorbents and

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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
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 increased almost linearly as sample loading rate increased up to
position: (a) and (c) Loading; (b) Inject. 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
those ions with a strong local afnity will be preferably adsorbed. Cd(II) were linear increased with increasing the loading time up to
Therefore, an appropriate pH value can not only improve the at least 100 s (see Fig. 4). The results indicated that the adsorption
adsorption efciency, but also depress interferences from the equilibrium of the ions on the sorbents is fast and the column has a
matrix, because. [3133] In this work, metal solutions were relative high adsorption capability for the ions under the analysis
adjusted to a pH range of about 310 for the acidity effect conditions. It is apparent that a high sampling rate or/and a long
evaluation and the sampling rates were set at 4.5 mL min 1 for the sampling time will conduce to a high enhancement factor or save
evaluation of the effect of acidity. As showing in Fig. 2, the signal of experiment time, which however will result in large sample
the metals increased rapidly as the solution pH increased from 3 to consumption and is also limited by the back-pressure produced by
5 and then kept constant in the pH range of about 56. This effect the column. Furthermore, long sampling time will decrease the
was due largely to the protonation of the sulfur atom of the SH sample throughput. So 4.5 mL min 1 of sampling rate with a 60 s
group at high acidity, which diminishes the ability of the thiol loading time was chosen for the both ions in the subsequent
groups to be involved in chelating the ions from solution [29 experiments, in order to maintain the stability of the preconcen-
31]. The decrease in absorbance at pH above 6 is probably due to tration system with a reasonable degree of sensitivity and
the hydrolysis of metal ions. When pH is higher than 6, heavy relatively high sampling throughput [22].
metals in dilute solution existed in the forms of M(OH)+, M(OH)2 The choice of elution conditions is also important for the FI
(aqueous), M(OH)3 , and some other species, e. g., M2(OH)3+, preconcentration system. In view of the preconcentration/elution
M3(OH)42+, M4(OH)44+ etc. [34] The formation of hydroxo- of ions involving the ion-exchange cycles of ions with protons,
complexes diminishes the availability of the ions for complexation stronge acids, such as nitric, hydrochloric and sulphuric acid
with the functional groups on the sorbent. It is perceptible that, solutions were therefore taken into account for the elution of ions.
there are modest bounces in the signals of determined ions at the However, nitric acid is not suitable for this method, imputable to
pH of about 10.7, which may generated by aggregation of the its oxidizing property, which will oxidize thiol groups on the

Table 1
Operational sequence of FI system for the preconcentration and separation of trace Pb and Cd.
Step Function Time (s) Pumped medium Flow rate (mL min ) Valve position

Pump1 Pump 2

1 (Fig. 1a) Preconcentration 60 Sample 4.5 Off

0.6 mol L HCl 4.3 for Pb Loading
5.5 for Cd
2 (Fig. 1b) Elution 20 0.6 mol L HCl Off 4.3 for Pb Injection
5.5 for Cd
3 (Fig. 1c) Column recovery 20 Buffered solution On Off Loading

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Fig. 3. Effect of sample loading rate on the preconcentration. All other conditions as Fig. 5. Effect of HCl concentration on the elution. All other conditions as in Fig. 1 and
in Fig. 1 and Table 1. Table 1.

Fig. 4. Effect of sample loading time on the preconcentration. 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.

sorbent [35,36] and sulphuric acid is not well suited to FAAS desorbed ions will be diluted by the extra eluent at an excessively
analysis because of its complex interference effects and the high a eluting rate. The best results were achieved when the
precipitation formation with ions [37]. So, hydrochloric acid eluting rates were about 5.5 mL min 1 for Cd(II) and 4.3 mL min 1
solutions were selected. The effect of the concentration of for Pb(II), respectively.
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 3.2. Interference studies
gradually with the initial increase in the concentration of the
eluent. The strongest signals were reached at concentrations equal The interference of coexisting ions on the detection must been
to 0.6 mol L 1 for Cd(II) and 0.4 mol L 1 for Pb(II), and there were conducted, because it links directly to the performance of the
no notable increases in the analytical signal when a further proposed method. Representative alkali and alkali earth metal
concentrated hydrochloric acid was used. The elution of the ions is ions, such as Na(I), K(I), Mg(II), Ca(II), Ba(II), typical transition
a process of ion-exchange, when the lower concentration of metal ions but without afnity to the thiol ligand, such as Cr(III),
elutions used, the retained ions can not be thoroughly exchange by Mn(II), Fe(III), some common ions with high afnity to the thiol
the protons, consequently give lower signals. Whereas, with the group, including Zn(II), Cu(II), Cd(II) (for Pb determination), Pb(II)
concentration of the eluent increasing the signals for the both (for Cd determination), Hg(II), Ag(I) and some common anions,
retained ions can reach the maximum. Therefore, 0.6 mol L 1 such as Cl , NO3 , SO42 , etc. were tested individually. It was
hydrochloric acid was chosen for the elution of both ions. considered interference when species caused variations of the
The effect of eluting rate on the metal signals was studied analyte signal more than 5% [1].
ranging from 3.1 to 7.5 mL min 1 with 20 s eluting. The results The testing results showed that 1000-fold Na(I), K(I), Cl , NO3 ,
indicate (as shown in Fig. 6) that the analytical signals for both SO24 , 500-fold Mg(II), Ca(II), Ba(II), 200-fold Cr(III), Mn(II), Fe(III),
metals exhibited initial increase and then decrease trends. At a Zn(II) and 30-fold Cu(II), Cd(II) (for Pb), Pb(II) (for Cd), Hg(II), Ag(I)
lower eluting rate, the retained ions can also not be thoroughly did not interfere with the analytes determination. These results
desorbed due which deliveres insufcient eluent. However, the 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 factors (EF), obtained by comparing the slopes of the linear
Pb(II), classied as soft acids, may provide the selective environ- portion of the calibration curves before and after the on-line
ment against alkali metal, alkali earth metal ions and some of the extraction [10], were 34 for Pb(II) and 41 for Cd(II), respectively,
transition metal ions. High adsorption capacity for Cd(II) and Pb(II), with a sample throughput of 45 h 1. The sorbent also provided
to some extent, would also provided the toleration against the good linearity (R-squared for both metals were both above 0.999),
other ions with high afnity to the thiol group. 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
3.3. Reusability of the packed column 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)
The reusability of the packed column in this proposed method were 0.22 mg L 1 (Pb) and 0.11 mg L 1 (Cd), respectively. And the
was studied by measuring the response signals of the metals and precisions (RSD, n = 11) were 0.4% for the level of 30 mg L 1 of Pb
counting the number of runs in a working day. It was found that the and 0.3% for the level of 20 mg L 1 Cd, respectively.
column could be used repeatedly for more than 200 operational Two CRMs, GBW 07605 (tea), GBW 08511 (Rice our) and three
cycles and provide invariable retention efciency, which indicate real water samples (water 1, 2 and 3, are a commercial mountain
that both the material and the packed column are of good stability spring water, a river water and a groundwater, respectively) were
under the optimized conditions in the courrent proposed method. analysed for the evaluation the accuracy and the application
performance of the proposed method. The results were listed in
3.4. Performance of the FI-AAS system and application to the sample Table 2. As shown, the determined concentrations of Pb and Cd in
analysis the CRMs by using this method agreed well with the certied
values and the mean recoveries (three duplications) of fortied
The performances of the presented method were evaluated samples were in the range of 96104% for both Pb and Cd.
under optimal experimental conditions. With a sampling rate of Table 3 compares several sorbents reported in the literatures
4.5 mL min 1 for 60 s of preconcentration, the enhancement 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/%

GBW 07605 (tea) (mg g ) 4.40  0.30 0 4.32  0.07
5.0 9.27  0.11 99.0
GBW 08511 (Rice our) (mg g ) 0.50  0.02 0 0.51  0.01
0.50 1.03 104
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
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
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.
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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