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JOURNAL OF
ENVIRONMENTAL
SCIENCES
ISSN 1001-0742
CN 11-2629/X
Journal of Environmental Sciences 2013, 25(Suppl.) S45–S49 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 effects 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 the sample matrices. It is usually necessary to carry out


a separation step prior to the analysis. Some methods
Heavy metal pollution is a public health problem. Cadmi- for separation and preconcentration of trace metal ions
um is known to be highly toxic for animals, plants and have been developed, including ion-exchange (Kim, 2001;
humans even at low concentrations and can be accumu- Erdemoglu et al., 2000), liquid liquid extraction (Cristina
lated in several organs. Experimental and epidemiological et al., 2009; Popova et al., 1991), cloud point extraction
studies has provided substantial evidence that low levels (Durukan et al., 2011; Ulusoy et al., 2011) and solid phase
of long-term exposure to cadmium can attribute to an extraction (SPE) (Parham et al., 2009; Lemos et al., 2007;
increased risk of cancer (Manzoori et al., 2007; Fan et Li et al., 2012; Suvardhan et al., 2004). Compared with
al., 2012; Shukla et al., 1996). Lead, which produces conventional solvent extraction method, SPE technique
several diseases, is one of the most important and widely becomes more popular. The SPE offers several important
distributed pollutants in the environment. Lead is also advantages: high enrichment factor, high recovery, rapid
one of the most toxic elements and has accumulative phase separation, low cost, low consumption of organic
effect (Zodape et al., 2011; Chen et al., 2005). They solvents and the ability of combination with different
are called environmental priority pollutants. Therefore, detection techniques (Pyrzynska, 1999; Ahmed, 2007).
the determination of trace amounts of cadmium and lead The choice of appropriate sorbent is a critical factor
in several matrices samples is very important for some to obtain full recovery and high enrichment factor in
areas, such as environmental chemistry and food control. the SPE procedure. Many sorbents have been used for
Inductively coupled plasma optical emission spectrometry, preconcentration of metal ions, such as activated carbon
inductively coupled plasma mass spectrometry, atomic (Ghaedi, 2007), XAD resins (Guo et al., 2004; Tewari
absorption spectrometry, UV-Vis spectrometer, etc. have and Singh, 2000), cellulose (De Gustavo et al., 2004),
been used for the determination of the trace metals. nanometer titanium dioxide (Liu et al., 2005; Zheng et al.,
Flame atomic absorption spectrometry (FAAS) is most 2011; Sha et al., 2009), eggshell membrane (Suleiman et
commonly used for the determination of the trace metals al., 2009) and ion exchange resins (Abollino et al., 2000),
(Soylak et al., 2002; Fan et al., 2009). In many cases etc.
the determination of the trace metals in water samples The molecular formula of silica gel is SiO2 ·nH2 O, it is
by FAAS is notably difficult due to the low levels of composed of a plurality of polysilicic acid via intermolecu-
these metals in the samples and the high complexity of lar dehydration and formation of a kind of porous material.
It is an amorphous chain and the reticular formation of
* Corresponding author. E-mail: anshanxuhb@163.com
S46 Journal of Environmental Sciences 2013, 25(Suppl.) S45–S49 / Hongbo Xu et al. Vol. 25

the silicate polymer particles, and is a hydrophilic polar 1.4 Adsorption and desorption experiment
adsorbent. Silica gel is by far the most important one in
A series of standards or sample solutions containing Cd(II)
current use in the environmental pollution control due to
and Pb(II) were transferred into a 50 mL beaker, and the
its large surface area, high adsorption capacity, porous
pH value was adjusted to the desired value with 0.10 mol/L
structure and high purity standards (Fritz et al., 1996).
HCl and NH3 ·H2 O. Then the volume was adjusted to 25
In this work, a sensitive SPE method for the simultane-
mL with double distilled water. A pretreated silica gel of
ous preconcentration and determination of cadmium and
300 mg was added, and the mixture was shaken vigorously
lead ions in various real samples using high temperature
for 10 min to facilitate adsorption of the metal ions onto
treated silica gel as adsorption agent was established. Sev-
the sorbents. The whole system was stilled for 60 min.
eral experimental variables affecting the method sensitivity
After the solution was centrifuged, the concentrations of
and stability were investigated. Parameters that can affect
Cd(II) and Pb(II) in the solution were directly determined
the adsorption and elution efficiency of the metal ions
by FAAS. The sorbent was then eluted with HNO3 of
were studied. Then, the method was validated by analyzing
optimum concentration and the desorbed metal ions were
the standard reference material (GBW 07304a, stream
measured by FAAS. Then adsorption and desorption rate
sediment) and applied to the analysis of treated wastewater
were calculated.
samples.
1.5 Sample preparation
1 Experimental The river water sample was collected from Anshan, Liaon-
ing, China. River water and treated wastewater samples
1.1 Apparatus were filtered through a 0.45 µm membrane filter (Tianjin
A multifunctional atomic absorption spectrophotometer Jinteng Instrument Factory, China), and acidified to pH 2
(CAAM-2001, Beijing Purkinge Genereal Instrument Co., with concentrated HCl prior to storage for use. Tap water
China) was used. All measurements were carried out in samples taken from our research laboratory were analyzed
an air-acetylene flame. Cadmium and lead hollow cathode without pretreatment. The pH value was adjusted to 2 with
lamps were used as the radiation source at the wave- concentrated HCl prior to use.
lengths of 228.8 and 283.3 nm, respectively. The operating
conditions adjusted in the spectrometer were carried out 2 Results and discussion
according to the standard guidelines of the manufacturers.
A pH meter (pHS-25, Shanghai Precision and Scientific 2.1 Effect of pH
Instrument Corp., China), an centrifuge (80-2, Anke Sci-
pH plays an important role on metal adsorption and
entific Instrument Factory, China) and a thermostatic bath
subsequent preconcentration. Proton in acid solution can
(Guohua Limited Company, China) were used.
protonate binding sites of the chelating molecules, and
1.2 Reagents and solutions hydroxide in basic solution may complex and precipitate
many metals.
All chemicals used in the experiments were of analytical
The effect of pH (2.0–8.0) on the adsorption of Cd(II)
grade. All solutions were prepared with doubly distilled
and Pb(II) was investigated. Aliquots of 25 mL of the
water. Stock standard solutions at a concentration of 1000
solutions were tested by equilibrating 300 mg of sorbents.
µg/mL were obtained from the National Institute of Stan-
As can be seen in Fig. 1, the adsorption percentage
dards (Beijing, China). Working standard solutions were
increases with the increase of pH and the highest metal
prepared by appropriate dilution of the stock standard
recovery values were found in the pH range 6.0–8.0.
solutions with doubly distilled water. HCl and NH3 ·H2 O
To avoid hydrolyzing at higher pH and determine these
solution (obtained from Shanghai Chemical Reagent Com-
elements simultaneously, a pH value of 6.0 found to be
pany, China) were used for pH adjustment. The pipettes
the optimum for the quantitative adsorption of Cd(II) and
and vessels used for trace analysis were kept in dilute
Pb(II). Therefore, pH 6.0 was selected as the enrichment
nitric acid at least over night and subsequently washed
acidity for further study.
three times with doubly distilled water. The accuracy of the
method was assessed by analyzing GBW 07304a (stream 2.2 Effect of sorbent dosage
sediment).
The dosage of pretreated silica gel is also an important
1.3 Pretreatment of silica gel and surface-area determi- factor on the quantitative adsorption of Cd(II) and Pb(II).
nation The effects of amount of pretreated silica gel on the
sorption of metal ions at optimum pH were examined in
The silica gel was dried in a vacuum oven at 110°C for
the range of 100–400 mg. As can be seen in Fig. 2, the
4 hr and stored for sorption tests. The surface area of the
quantitative recoveries were obtained in range of 300–400
silica gel was shown by BET analysis to be 400 cm2 /g.
mg for Cd(II) and 200–400 mg for Pb(II). We select 300
Suppl. Simultaneous preconcentration of cadmium and lead in water samples with silica gel······ S47

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


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

80 HNO3 concentration HNO3 volume Pb(II) recovery Cd(II) recovery


Absorption rate (%)

(mol/L) (mL) (%) (%)


60
0.1 5 86.31 49.79
0.1 15 90.72 80.21
40 0.1 20 99.67 95.79
0.1 25 101.2 97.68
20 Cd(II) 0.5 20 94.8 96.75
Pb(II) 1.0 20 99.63 100.7
0
2.0 3.0
5.0 4.0
6.0 7.0 8.0 time of 20 min. Accordingly, 20.0 mL of 0.10 mol/L HNO3
pH
was used as eluent in the subsequent experiments.
Fig. 1 Effect of pH on absorption rate of Cd(II) and Pb(II). Experimental
condition: Cd(II), Pb(II): 1.0 µg/mL; sample volume: 25 mL; sorbent 2.5 Adsorption capacities
amount: 300 mg; shaking time: 10 min; temperature: 25°C.
The adsorption capacity is an important factor because it
100 determines how much adsorbent is required to quantita-
tively concentrate the analytes from a given solution. A
80 300 mg of sorbent was equilibrated with 25 mL of various
Absorption rate (%)

concentrations (50–500 µg/mL) of Cd(II) and Pb(II) for


60 1 hr at pH 6.0. The separation and preconcentration
40
procedures (adsorption experiment) described above were
applied. Figure 3 was gained by plotting the concentration
20 Cd(II) vs. the micrograms of Cd(II) and Pb(II) adsorbed per gram
Pb(II) of pretreated silica gel. From the experiment data, in order
0 to reach the saturation, the initial metal ions concentrations
100
200 150
250 300 350 400 were increased till the plateau values (adsorption capacity
Mass of pretreated silica gel (mg) values) obtained. The results showed that the maximum
Fig. 2 Effect of sorbent dosage on absorption rate of Cd(II) and Pb(II). adsorption capacity has been found to be 45.5 mg/g for
Experimental condition: Cd(II), Pb(II): 1.0 µg/mL; sample volume: 25 Cd(II) and 27.1 mg/g for Pb(II).
mL; shaking time: 10 min; temperature: 25°C. pH: 6.0.
2.6 Regeneration performance of silica gel
mg of sorbent for further studies.
After the adsorption experiment of silica gel, the silica gel
2.3 Effect of shaking time was shaked in HNO3 solution (0.10 mol/L) for 1 hr to
remove the metal ions and ensure complete equilibration.
The different shaking time (5–30 min) was studied for the
Then the sorbent was washed with double distilled water
absorption rate of Cd(II) and Pb(II) by pretreated silica gel.
until neutral pH was reached. The operating capacity was
The results showed that the adsorption of Cd(II) and Pb(II)
calculated from the loading and elution tests. The results
was about 95% during the first 5 min, which indicates that
from three tests yielded < 5% error up to 4 cycles of
kinetics of equilibrium is very fast (Table 1). We selected
repeated experiments. The sorbent showed a better long-
10 min for further studies.
2.4 Influence of elution condition on recovery 50
Absorption capacity (mg/g)

Since the adsorption of cations at pH < 2 is negligible, one 40


can expect that elution will be favoured in acidic solution.
The elution condition was studied by using various concen- 30
trations and volumes HNO3 for the desorption of retained
Cd(II) and Pb(II). The obtained results are shown in Table 20
2. It was found that 20.0 mL of 0.10 mol/L HNO3 was
sufficient for complete elution for both ions with a shaking 10 Cd(II)
Pb(II)
Table 1 Effect of shaking time on absorption rate
0 100 200 300 400 500
Absorption rate (%) Concentration of Cd(II), Pb(II) (μg/mL)
5 min 10 min 15 min 20 min 25 min 30 min
Fig. 3 Adsorption capacity of pretreated silica gel sorbent for Cd(II) and
Cd(II) 95.3 95.1 95.7 96.4 97.2 97.1 Pb(II). Experimental condition: sorbent dosage: 300 mg; sample volume:
Pb(II) 94.5 94.8 95.2 95.1 96.3 96.6 25 mL; shaking time: 10 min; temperature: 25°C; pH: 6.0.
S48 Journal of Environmental Sciences 2013, 25(Suppl.) S45–S49 / Hongbo Xu et al. Vol. 25

term stability and reusability towards Cd(II) and Pb(II). of three replicates. As can be seen in Table 3, the analytical
results for the standard material were in good agreement
2.7 Effects of coexistent ions
with the certified values. The recoveries were close to
The effects of different cations and anions on the adsorp- 100% and indicate that the proposed system was helpful
tion of Cd(II) and Pb(II) on pretreated silica gel were for the determination of Cd(II) and Pb(II) in the real
investigated. In these experiments, solutions of 1.0 µg/mL samples.
of Cd(II) and Pb(II) containing the added interfering ions
2.10 Determination of Cd(II) and Pb(II) in real samples
were treated according to the recommended procedure.
The tolerance limit was set as the amount of ions causing The proposed method was applied to the determination
recoveries of the examined elements to be less than 90%. of Cd(II) and Pb(II) in tap water, river water, and treated
The results (data not shown) indicated that in excess of wastewater samples. These samples were subjected to
500-fold K(I), Na(I), NO−3 , NH+4 , 30-fold Ca(II), Fe(III), preconcentration and metal ions determination using the
Co(II), Cu(II) and 20-fold Mn(II), Ni(II), Zn(II) ions had proposed procedure. In addition, recovery experiments for
no significant interferences in the preconcentration and different amounts of Cd(II) and Pb(II) were carried out.
determination of Cd(II) and Pb(II). This is due to the low The results are given in Table 4. The obtained recoveries
adsorbing capacity or rates for interfering ions. It can be were reasonable for trace Cd(II) and Pb(II) analysis in the
seen that the presence of major potentially interfering ions tested water samples, in a range of 95.5%–102.0%.
has no obvious influences on the determination of Cd(II)
and Pb(II) under the selected conditions. 3 Conclusions
2.8 Detection limits and precision
The recommended procedure by using the pretreated silica
Under the optimum conditions, eleven portions of standard gel as adsorption agent was successfully employed for
solutions were enriched and analyzed simultaneously fol- the simultaneous preconcentration and determination of
lowing the general procedure. The limit of detection (DL ) cadmium and lead in treated wastewater and natural water
can be defined by following equation: samples by FAAS. The method proposed here was simple,
SB rapid, inexpensive, and had good reproducibility. This
DL = 3 (1) study offered a nonpolluting technique for the preconcen-
m
tration and determination of trace metals.
where, SB and m were standard deviation of the blank and
the slope of the calibration graph. DL values were 4.25 and Acknowledgments
0.60 ng/mL for Cd(II) and Pb(II), respectively. The relative This work was supported by the National Science Foun-
standard deviations were 3.2% and 1.7% for Cd(II) and dation for Young Scientists of China (No. 21107076), the
Pb(II), respectively. Scientific Research Foundation of Educational Departmen
2.9 Accuracy of the method of Liaoning Province (No. L2012102), the Administration
Foundation of Science & Technology of Anshan City
In order to validate the proposed method, recovery exper- (No. 2011MS13). The authors would like to thank Prof.
iments were carried out by certified reference materials Xiaojun Jiang for his analytical support and Jian Wang for
GBW 07304a (stream sediment). Results were the average his work related to the GBW 07304a (stream sediment)
Table 3 Analysis of certified reference materials (n = 3)
measurements.

GBW 07304a Certified Found Relative standard References


(µg/g) (µg/g) deviation (%)

Cd(II) 0.90 ± 0.05 0.94 ± 0.04 1.3 Abollino O, Aceto M, Sarzanini C, Mentasti E, 2000. The reten-
Pb(II) 68 ± 3 65 ± 5 1.6 tion of metal species by different solid sorbents mechanisms

Table 4 Determination of analyte ions in water samples using proposed methodology.

Tap water River water Treated wastewater


Added Found Recovery Found Recovery Found Recovery
(µg/L) (µg/L) (%) (µg/L) (%) (µg/L) (%)

Cd(II) 0 BDL – BDL – BDL –


10 9.8 ± 0.2 98.0 9.9 ± 0.2 99.0 9.8 ± 0.2 98.0
20 19.4 ± 0.2 97.0 19.5 ± 0.2 97.5 19.4 ± 0.3 97.0
Pb(II) 0 1.8 ± 0.5 – 4.2 ± 0.3 – 2.4 ± 0.2 –
10 11.5 ± 0.2 97.0 13.9 ± 0.2 97.0 12.1 ± 0.2 97.0
20 20.9 ± 0.2 95.5 23.5 ± 0.2 96.5 22.8 ± 0.1 102.0
BDL: below detection limit; –: not detected. Data are expressed as mean ± S.D. (n = 3)
Suppl. Simultaneous preconcentration of cadmium and lead in water samples with silica gel······ S49

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