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JOURNAL OF
ENVIRONMENTAL
SCIENCES
ISSN 1001-0742
CN 11-2629/X
www.jesc.ac.cn
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
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Vol. 25
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.
Suppl.
Simultaneous preconcentration of cadmium and lead in water samples with silica gel
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 (%)
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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
40
30
20
Cd(II)
Pb(II)
10
Cd(II)
Pb(II)
5 min
10 min
95.3
94.5
95.1
94.8
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.
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m
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Vol. 25
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 (%)
References
Cd(II)
Pb(II)
0.90 0.05
68 3
0.94 0.04
65 5
1.3
1.6
Abollino O, Aceto M, Sarzanini C, Mentasti E, 2000. The retention of metal species by dierent solid sorbents mechanisms
Table 4
Cd(II)
Pb(II)
Added
(g/L)
Found
(g/L)
Recovery
(%)
Found
(g/L)
River water
Recovery
(%)
Treated wastewater
Found
Recovery
(g/L)
(%)
0
10
20
0
10
20
BDL
9.8 0.2
19.4 0.2
1.8 0.5
11.5 0.2
20.9 0.2
98.0
97.0
97.0
95.5
BDL
9.9 0.2
19.5 0.2
4.2 0.3
13.9 0.2
23.5 0.2
99.0
97.5
97.0
96.5
BDL
9.8 0.2
19.4 0.3
2.4 0.2
12.1 0.2
22.8 0.1
BDL: below detection limit; : not detected. Data are expressed as mean S.D. (n = 3)
98.0
97.0
97.0
102.0
Suppl.
Simultaneous preconcentration of cadmium and lead in water samples with silica gel
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