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JOURNAL OF
ENVIRONMENTAL
SCIENCES
ISSN 1001-0742
CN 11-2629/X

Journal of Environmental Sciences 2013, 25(Suppl.) S45S49

www.jesc.ac.cn

Simultaneous preconcentration of cadmium and lead in water samples with


silica gel and determination by flame atomic absorption spectrometry
Hongbo Xu , Yun Wu, Jian Wang, Xuewei Shang, Xiaojun Jiang
College of Chemical Engineering, University of Science and Technology Liaoning, Anshan 114051, China

Abstract
A new method that utilizes pretreated silica gel as an adsorbent has been developed for simultaneous preconcentration of trace Cd(II)
and Pb(II) prior to the measurement by flame atomic absorption spectrometry. The eects of pH, the shaking time, the elution condition
and the coexisting ions on the separation/preconcentration conditions of analytes were investigated. Under optimized conditions, the
static adsorption capacity of Cd(II) and Pb(II) were 45.5 and 27.1mg/g, the relative standard deviations were 3.2% and 1.7% (for n =
11), and the limits of detection obtained were 4.25 and 0.60 ng/mL, respectively. The method was validated by analyzing the certified
reference materials GBW 07304a (stream sediment) and successfully applied to the analysis of various treated wastewater samples with
satisfactory results.
Key words: silica gel; lead; cadmium; preconcentration; flame atomic absorption spectrometry (FAAS)

Introduction
Heavy metal pollution is a public health problem. Cadmium is known to be highly toxic for animals, plants and
humans even at low concentrations and can be accumulated in several organs. Experimental and epidemiological
studies has provided substantial evidence that low levels
of long-term exposure to cadmium can attribute to an
increased risk of cancer (Manzoori et al., 2007; Fan et
al., 2012; Shukla et al., 1996). Lead, which produces
several diseases, is one of the most important and widely
distributed pollutants in the environment. Lead is also
one of the most toxic elements and has accumulative
eect (Zodape et al., 2011; Chen et al., 2005). They
are called environmental priority pollutants. Therefore,
the determination of trace amounts of cadmium and lead
in several matrices samples is very important for some
areas, such as environmental chemistry and food control.
Inductively coupled plasma optical emission spectrometry,
inductively coupled plasma mass spectrometry, atomic
absorption spectrometry, UV-Vis spectrometer, etc. have
been used for the determination of the trace metals.
Flame atomic absorption spectrometry (FAAS) is most
commonly used for the determination of the trace metals
(Soylak et al., 2002; Fan et al., 2009). In many cases
the determination of the trace metals in water samples
by FAAS is notably dicult due to the low levels of
these metals in the samples and the high complexity of
* Corresponding author. E-mail: anshanxuhb@163.com

the sample matrices. It is usually necessary to carry out


a separation step prior to the analysis. Some methods
for separation and preconcentration of trace metal ions
have been developed, including ion-exchange (Kim, 2001;
Erdemoglu et al., 2000), liquid liquid extraction (Cristina
et al., 2009; Popova et al., 1991), cloud point extraction
(Durukan et al., 2011; Ulusoy et al., 2011) and solid phase
extraction (SPE) (Parham et al., 2009; Lemos et al., 2007;
Li et al., 2012; Suvardhan et al., 2004). Compared with
conventional solvent extraction method, SPE technique
becomes more popular. The SPE oers several important
advantages: high enrichment factor, high recovery, rapid
phase separation, low cost, low consumption of organic
solvents and the ability of combination with dierent
detection techniques (Pyrzynska, 1999; Ahmed, 2007).
The choice of appropriate sorbent is a critical factor
to obtain full recovery and high enrichment factor in
the SPE procedure. Many sorbents have been used for
preconcentration of metal ions, such as activated carbon
(Ghaedi, 2007), XAD resins (Guo et al., 2004; Tewari
and Singh, 2000), cellulose (De Gustavo et al., 2004),
nanometer titanium dioxide (Liu et al., 2005; Zheng et al.,
2011; Sha et al., 2009), eggshell membrane (Suleiman et
al., 2009) and ion exchange resins (Abollino et al., 2000),
etc.
The molecular formula of silica gel is SiO2 nH2 O, it is
composed of a plurality of polysilicic acid via intermolecular dehydration and formation of a kind of porous material.
It is an amorphous chain and the reticular formation of

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Journal of Environmental Sciences 2013, 25(Suppl.) S45S49 / Hongbo Xu et al.

the silicate polymer particles, and is a hydrophilic polar


adsorbent. Silica gel is by far the most important one in
current use in the environmental pollution control due to
its large surface area, high adsorption capacity, porous
structure and high purity standards (Fritz et al., 1996).
In this work, a sensitive SPE method for the simultaneous preconcentration and determination of cadmium and
lead ions in various real samples using high temperature
treated silica gel as adsorption agent was established. Several experimental variables aecting the method sensitivity
and stability were investigated. Parameters that can aect
the adsorption and elution eciency of the metal ions
were studied. Then, the method was validated by analyzing
the standard reference material (GBW 07304a, stream
sediment) and applied to the analysis of treated wastewater
samples.

Vol. 25

1.4 Adsorption and desorption experiment


A series of standards or sample solutions containing Cd(II)
and Pb(II) were transferred into a 50 mL beaker, and the
pH value was adjusted to the desired value with 0.10 mol/L
HCl and NH3 H2 O. Then the volume was adjusted to 25
mL with double distilled water. A pretreated silica gel of
300 mg was added, and the mixture was shaken vigorously
for 10 min to facilitate adsorption of the metal ions onto
the sorbents. The whole system was stilled for 60 min.
After the solution was centrifuged, the concentrations of
Cd(II) and Pb(II) in the solution were directly determined
by FAAS. The sorbent was then eluted with HNO3 of
optimum concentration and the desorbed metal ions were
measured by FAAS. Then adsorption and desorption rate
were calculated.
1.5 Sample preparation

1 Experimental
1.1 Apparatus
A multifunctional atomic absorption spectrophotometer
(CAAM-2001, Beijing Purkinge Genereal Instrument Co.,
China) was used. All measurements were carried out in
an air-acetylene flame. Cadmium and lead hollow cathode
lamps were used as the radiation source at the wavelengths of 228.8 and 283.3 nm, respectively. The operating
conditions adjusted in the spectrometer were carried out
according to the standard guidelines of the manufacturers.
A pH meter (pHS-25, Shanghai Precision and Scientific
Instrument Corp., China), an centrifuge (80-2, Anke Scientific Instrument Factory, China) and a thermostatic bath
(Guohua Limited Company, China) were used.
1.2 Reagents and solutions
All chemicals used in the experiments were of analytical
grade. All solutions were prepared with doubly distilled
water. Stock standard solutions at a concentration of 1000
g/mL were obtained from the National Institute of Standards (Beijing, China). Working standard solutions were
prepared by appropriate dilution of the stock standard
solutions with doubly distilled water. HCl and NH3 H2 O
solution (obtained from Shanghai Chemical Reagent Company, China) were used for pH adjustment. The pipettes
and vessels used for trace analysis were kept in dilute
nitric acid at least over night and subsequently washed
three times with doubly distilled water. The accuracy of the
method was assessed by analyzing GBW 07304a (stream
sediment).
1.3 Pretreatment of silica gel and surface-area determination
The silica gel was dried in a vacuum oven at 110C for
4 hr and stored for sorption tests. The surface area of the
silica gel was shown by BET analysis to be 400 cm2 /g.

The river water sample was collected from Anshan, Liaoning, China. River water and treated wastewater samples
were filtered through a 0.45 m membrane filter (Tianjin
Jinteng Instrument Factory, China), and acidified to pH 2
with concentrated HCl prior to storage for use. Tap water
samples taken from our research laboratory were analyzed
without pretreatment. The pH value was adjusted to 2 with
concentrated HCl prior to use.

2 Results and discussion


2.1 Eect of pH
pH plays an important role on metal adsorption and
subsequent preconcentration. Proton in acid solution can
protonate binding sites of the chelating molecules, and
hydroxide in basic solution may complex and precipitate
many metals.
The eect of pH (2.08.0) on the adsorption of Cd(II)
and Pb(II) was investigated. Aliquots of 25 mL of the
solutions were tested by equilibrating 300 mg of sorbents.
As can be seen in Fig. 1, the adsorption percentage
increases with the increase of pH and the highest metal
recovery values were found in the pH range 6.08.0.
To avoid hydrolyzing at higher pH and determine these
elements simultaneously, a pH value of 6.0 found to be
the optimum for the quantitative adsorption of Cd(II) and
Pb(II). Therefore, pH 6.0 was selected as the enrichment
acidity for further study.
2.2 Eect of sorbent dosage
The dosage of pretreated silica gel is also an important
factor on the quantitative adsorption of Cd(II) and Pb(II).
The eects of amount of pretreated silica gel on the
sorption of metal ions at optimum pH were examined in
the range of 100400 mg. As can be seen in Fig. 2, the
quantitative recoveries were obtained in range of 300400
mg for Cd(II) and 200400 mg for Pb(II). We select 300

Suppl.

Simultaneous preconcentration of cadmium and lead in water samples with silica gel

Table 2 Eect of concentration and volume of elution solution on the


recovery of Cd(II) and Pb(II) (pH 6.0)

Absorption rate (%)

100
80
60
40
20

Cd(II)
Pb(II)

0
2.0

5.0
6.0
7.0
8.0
pH
Fig. 1 Eect of pH on absorption rate of Cd(II) and Pb(II). Experimental
condition: Cd(II), Pb(II): 1.0 g/mL; sample volume: 25 mL; sorbent
amount: 300 mg; shaking time: 10 min; temperature: 25C.

3.0

4.0

100
Absorption rate (%)

S47

80
60
40
20

Cd(II)
Pb(II)

0
100

150

200
250
300
350
400
Mass of pretreated silica gel (mg)
Fig. 2 Eect of sorbent dosage on absorption rate of Cd(II) and Pb(II).
Experimental condition: Cd(II), Pb(II): 1.0 g/mL; sample volume: 25
mL; shaking time: 10 min; temperature: 25C. pH: 6.0.

HNO3 concentration
(mol/L)

HNO3 volume
(mL)

Pb(II) recovery
(%)

Cd(II) recovery
(%)

0.1
0.1
0.1
0.1
0.5
1.0

5
15
20
25
20
20

86.31
90.72
99.67
101.2
94.8
99.63

49.79
80.21
95.79
97.68
96.75
100.7

time of 20 min. Accordingly, 20.0 mL of 0.10 mol/L HNO3


was used as eluent in the subsequent experiments.
2.5 Adsorption capacities
The adsorption capacity is an important factor because it
determines how much adsorbent is required to quantitatively concentrate the analytes from a given solution. A
300 mg of sorbent was equilibrated with 25 mL of various
concentrations (50500 g/mL) of Cd(II) and Pb(II) for
1 hr at pH 6.0. The separation and preconcentration
procedures (adsorption experiment) described above were
applied. Figure 3 was gained by plotting the concentration
vs. the micrograms of Cd(II) and Pb(II) adsorbed per gram
of pretreated silica gel. From the experiment data, in order
to reach the saturation, the initial metal ions concentrations
were increased till the plateau values (adsorption capacity
values) obtained. The results showed that the maximum
adsorption capacity has been found to be 45.5 mg/g for
Cd(II) and 27.1 mg/g for Pb(II).
2.6 Regeneration performance of silica gel

mg of sorbent for further studies.


2.3 Eect of shaking time
The dierent shaking time (530 min) was studied for the
absorption rate of Cd(II) and Pb(II) by pretreated silica gel.
The results showed that the adsorption of Cd(II) and Pb(II)
was about 95% during the first 5 min, which indicates that
kinetics of equilibrium is very fast (Table 1). We selected
10 min for further studies.

After the adsorption experiment of silica gel, the silica gel


was shaked in HNO3 solution (0.10 mol/L) for 1 hr to
remove the metal ions and ensure complete equilibration.
Then the sorbent was washed with double distilled water
until neutral pH was reached. The operating capacity was
calculated from the loading and elution tests. The results
from three tests yielded < 5% error up to 4 cycles of
repeated experiments. The sorbent showed a better long50

Since the adsorption of cations at pH < 2 is negligible, one


can expect that elution will be favoured in acidic solution.
The elution condition was studied by using various concentrations and volumes HNO3 for the desorption of retained
Cd(II) and Pb(II). The obtained results are shown in Table
2. It was found that 20.0 mL of 0.10 mol/L HNO3 was
sucient for complete elution for both ions with a shaking

Absorption capacity (mg/g)

2.4 Influence of elution condition on recovery

40
30
20
Cd(II)
Pb(II)

10

Table 1 Eect of shaking time on absorption rate

Cd(II)
Pb(II)

5 min

10 min

95.3
94.5

95.1
94.8

Absorption rate (%)


15 min
20 min
95.7
95.2

96.4
95.1

25 min

30 min

97.2
96.3

97.1
96.6

100
200
300
400
Concentration of Cd(II), Pb(II) (g/mL)

500

Fig. 3 Adsorption capacity of pretreated silica gel sorbent for Cd(II) and
Pb(II). Experimental condition: sorbent dosage: 300 mg; sample volume:
25 mL; shaking time: 10 min; temperature: 25C; pH: 6.0.

Journal of Environmental Sciences 2013, 25(Suppl.) S45S49 / Hongbo Xu et al.

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term stability and reusability towards Cd(II) and Pb(II).


2.7 Eects of coexistent ions
The eects of dierent cations and anions on the adsorption of Cd(II) and Pb(II) on pretreated silica gel were
investigated. In these experiments, solutions of 1.0 g/mL
of Cd(II) and Pb(II) containing the added interfering ions
were treated according to the recommended procedure.
The tolerance limit was set as the amount of ions causing
recoveries of the examined elements to be less than 90%.
The results (data not shown) indicated that in excess of
500-fold K(I), Na(I), NO3 , NH+4 , 30-fold Ca(II), Fe(III),
Co(II), Cu(II) and 20-fold Mn(II), Ni(II), Zn(II) ions had
no significant interferences in the preconcentration and
determination of Cd(II) and Pb(II). This is due to the low
adsorbing capacity or rates for interfering ions. It can be
seen that the presence of major potentially interfering ions
has no obvious influences on the determination of Cd(II)
and Pb(II) under the selected conditions.
2.8 Detection limits and precision
Under the optimum conditions, eleven portions of standard
solutions were enriched and analyzed simultaneously following the general procedure. The limit of detection (DL )
can be defined by following equation:
DL = 3

SB
m

(1)

where, SB and m were standard deviation of the blank and


the slope of the calibration graph. DL values were 4.25 and
0.60 ng/mL for Cd(II) and Pb(II), respectively. The relative
standard deviations were 3.2% and 1.7% for Cd(II) and
Pb(II), respectively.
2.9 Accuracy of the method
In order to validate the proposed method, recovery experiments were carried out by certified reference materials
GBW 07304a (stream sediment). Results were the average
Table 3

Analysis of certified reference materials (n = 3)

Vol. 25

of three replicates. As can be seen in Table 3, the analytical


results for the standard material were in good agreement
with the certified values. The recoveries were close to
100% and indicate that the proposed system was helpful
for the determination of Cd(II) and Pb(II) in the real
samples.
2.10 Determination of Cd(II) and Pb(II) in real samples
The proposed method was applied to the determination
of Cd(II) and Pb(II) in tap water, river water, and treated
wastewater samples. These samples were subjected to
preconcentration and metal ions determination using the
proposed procedure. In addition, recovery experiments for
dierent amounts of Cd(II) and Pb(II) were carried out.
The results are given in Table 4. The obtained recoveries
were reasonable for trace Cd(II) and Pb(II) analysis in the
tested water samples, in a range of 95.5%102.0%.

3 Conclusions
The recommended procedure by using the pretreated silica
gel as adsorption agent was successfully employed for
the simultaneous preconcentration and determination of
cadmium and lead in treated wastewater and natural water
samples by FAAS. The method proposed here was simple,
rapid, inexpensive, and had good reproducibility. This
study oered a nonpolluting technique for the preconcentration and determination of trace metals.
Acknowledgments
This work was supported by the National Science Foundation for Young Scientists of China (No. 21107076), the
Scientific Research Foundation of Educational Departmen
of Liaoning Province (No. L2012102), the Administration
Foundation of Science & Technology of Anshan City
(No. 2011MS13). The authors would like to thank Prof.
Xiaojun Jiang for his analytical support and Jian Wang for
his work related to the GBW 07304a (stream sediment)
measurements.

GBW 07304a

Certified
(g/g)

Found
(g/g)

Relative standard
deviation (%)

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Cd(II)
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