Adnan Menderes University, 4th AACD Congress, 29 Sept-3 Oct.

2004, Kuadas-AYDIN, TURKEY

Proceedings Book 104.DOC

DETERMINATION OF COPPER, CADMIUM AND LEAD IN

SEAWATER AND MINERAL WATER BY FLAME ATOMIC
ABSORPTION SPECTROMETRY AFTER COPRECIPITATION WITH
ALUMINUM HYDROXIDE
Gleren Dner, Asl Ege
Istanbul Technical University, Faculty of Science and Letters, Chemistry Department, Maslak, 34469
Istanbul, TURKEY; E-mail: doner@itu.edu.tr, egea@itu.edu.tr

Abstract
An aluminum hydroxide coprecipitation method for the determination of cadmium,
copper and lead by flame atomic absorption spectrometry in aqueous solutions,
seawater and mineral water samples has been investigated. The coprecipitation
conditions, such as the effect of the pH, the amount of carrier element, the effect of
possible matrix ions and the time were examined in detail for the studied elements. It
was found that cadmium, copper and lead are coprecipitated quantitatively ( 95%) with
aluminum hydroxide at pH 7 with low RSD values of around 2-3 %. Detection limits
(3) were 6 ng ml-1 for Cd, 3 ng ml-1 for Cu and 16 ng ml-1 for Pb. The method
proposed was validated by the analysis of HPS 312205 seawater standard reference
material.
1. Introduction
The direct determination of the trace metals in sea water and mineral waters by
atomic absorption spectrometry (AAS) is very difficult due to the low levels of metal
ions and also interferic influences of main components of the water samples. In many
instances, it has been necessary to use a preconcentration method prior to analysis.
Several preconcentration techniques are used for this purpose including solvent
extraction, ion exchange, chelating resins, solid-phase extraction, adsorption and
coprecipitation. Among these techniques, coprecipitation method is particularly
proposed to preconcentrate trace elements from matrices that adversely influence atomic
absorption spectrometric detection. A number of metal hydroxides such as iron (III),
indium, gallium, aluminum, cerium (IV), lanthanum, magnesium, scandium, zirconium
have been widely used and successfully applied for the preconcentration of trace metal
ions from different media [1-5]. In addition, there is no significant study on the use of
aluminum hydroxide for the preconcentration of trace elements in seawater and mineral
water samples. Flame atomic absorption spectrometry (FAAS) is much more convenient
technique and it has much more advantages comparing the other AAS method, graphite
furnace atomic absorption spectrometry (GFAAS). The matrices are not as effective in
FAAS as in GFAAS and FAAS provides larger working range than GFAAS does.
These are the most important advantages of FAAS.
In this study, taking advantages of FAAS, an aluminum hydroxide
coprecipitation method has been investigated for the separation/preconcentration of
cadmium copper and lead in aqueous solutions, seawater and mineral water samples
prior to their flame atomic absorption spectrometric determination. The influence of the
various analytical parameters on the recovery for the examined elements, such as pH,
amount of carrier element and Na2CO3, matrix ions, the settling time etc. was discussed.
2. Materials and Method
2.1. Apparatus and Reagents
An Analytic Jena Vario 6 atomic absorption spectrometer equipped with an airacetylene burner was used for the determination of copper, cadmium and lead. Copper,

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Adnan Menderes University, 4th AACD Congress, 29 Sept-3 Oct.2004, Kuadas-AYDIN, TURKEY
Proceedings Book 104.DOC

cadmium and lead hollow cathode lamps were used as the spectral radiation sources.
The wavelengths were 324.8 nm for Cu, 228.8 nm for Cd and 217.0 nm for Pb. The pH
adjustment was controlled using WTW pH 340-A/SET 2 pH meter.
All chemicals were of analytical-reagent grade (Merck). Distilled-deionized
water was used throughout. Stock solutions (1000mgl-1) of Cu, Cd and Pb were
prepared from titrisol standards (Merck) and working standard solutions were prepared
fresh daily by appropriately diluting the stock solutions.
Seawater samples were collected from Istanbul Bosphorous and mineral water
samples were purchased from a local market.
2.2. Method Development
The coprecipitation method was optimized with aqueous solutions prior to its
application to the real samples. First, 650 l of 1 M Na2CO3 solution and then 300 l of
1 M Al(NO3)3.9H2O solution (8.1mg Al) were added to 50 ml of a solution containing
5g of Cu and Cd and 10g of Pb in a centrifuge tube. Sodium carbonate amount was
enough to adjust the pH=7. The solution was centrifuged at 3500 rpm for 20minutes.
The supernatant was decantated and the precipitate was dissolved with 500 l of 4M
HNO3. Cu, Cd and Pb were determined in 2,5 ml of the final solutions by FAAS.
3. Results and Discussion
3.1 Study of the optimum conditions for coprecipitation
Firstly, the influence of the pH on the recovery of trace level of Cu, Cd and Pb
were examined. The pH was adjusted to 4-11 by changing the amount of added Na2CO3
solution while the amount of aluminum in solution was constant. As can be seen from
Fig.1, the recovery of all elements increased with an increase in pH and quantitative
results were obtained for all studied elements at pH 7. For further experiments, the pH 7
was chosen as optimum pH.

Recovery %

100
: Cu
: Cd
: Pb

80
60
40
20
0
3

11

pH

Figure 1. Effect of pH on the recovery of Cd, Cu, and Pb coprecipitation with

aluminum hyroxide (amount of analytes: 10 g of Pb, 5g of Cu and Cd, n=3)
Secondly, settling time which is important for the quality of coprecipitation was
optimized working with 5-30 minutes time period of the centrifugation. Consequently,
for the completion of coprecipitation, 20 minutes are necessary. Then, the necessary
amount of aluminum for coprecipitation was selected experimentally. As it can be seen
from Table 1,the recoveries for all studied elements were quantitative after 8.1mg of Al.
In addition, to detect potential interferences on the coprecipitation of studied
elements, various amounts of Cl- and SO4-2 ions which are the major components of
mineral water and seawater were added to the solution containing trace amount of
analytes and the optimized procedure was applied. The results show that large amounts

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Adnan Menderes University, 4th AACD Congress, 29 Sept-3 Oct.2004, Kuadas-AYDIN, TURKEY
Proceedings Book 104.DOC

of chloride (10,000 mgl-1) and sulfate (200 mgl-1) did not interfere to determination
of examined elements.
Table 1: Effect of aluminum amount on coprecipitation (amount of analytes: 10 g of
Pb, 5g of Cu and Cd, n=3)
Amount of Al, mg
Recovery, %
Pb
Cu
Cd
4.0
903
923
872
8.1
992
982
993
16.2
1002
973
1002
3.2. Method validation and analytical performance
The utility of the present method was evaluated by examining the recovery of
studied elements from seawater, mineral water and standard reference seawater (HPS
312205) samples spiked with the studied analytes. The obtained results are given in
Table 2, indicating that the proposed method is applicable to analyze the water samples
containing trace amount of Cu, Cd and Pb after 125 fold preconcentration.
Table 2: Recovery of analyte spikes from seawater and mineral water (n=3) (Sample
volume: 250 ml for sea water, 200 ml for mineral water)
Sample

Seawatera

Mineral
Water

Seawaterb

a
b

Added
(g)
0

Pb
Found
(g)
n.d.

Cu
Found
(g)
n.d.

Recovery,
%

Added
(g)
0

Added
(g)
0

Recovery,
%

6
8

Cd
Found
(g)
n.d.

Recovery,
%

5.60.1

93

1.90.1

95

7.30.1

91

3.70.1

92

1.80.1

90

3.50.1

88

10

9.00.2

90

5.50.1

0
6
8

n.d.
5.60.1
7.50.2

93
94

0
2
4

n.d.
1.80.1
3.60.1

92

5.20.1

87

90
90

0
2
4

n.d.
1.80.1
3.60.1

90
90

10

9.00.3

90

n.d

5.40.2

90

5.30.2

88

2.30.1

92

n.d

4.50.1

90

2.5

4.60.1

92

2.5

2.20.1

88

7.50.2

94

6.10.1

94

3.60.1

90

Seawater of Istanbul Bosphorous, n.d. not detected

Standard Reference Seawater (HPS 312205) (Certified values: 0.004mg/kg Pb, 0.01mg/kg Cu, 0.0001 mg/kg Cd)

4.Conclusion
Coprecipitation with aluminum hydroxide has been successfully applied to Cu,
Cd and in seawater and mineral water samples with acceptable accuracy and precision.
References
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2. Divrikli, U., Elci, L. (2002) : Anal. Chim. Acta 452, 231-235.
3. Nielsen, S., Sloth, J. J., Hansen, E. H. (1996) : Analyst 121, 31-35.
4. Kujirai, O., Yamada, K. (1996) : Fresenius J. Anal. Chem. 354, 428-431.
5. Takeda, K., Akamatsu, C., Ishikawa, Y. (1994) Anal. Chim. Acta 298, 375-379.

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