Talanta 52 (2000) 637 643

www.elsevier.com/locate/talanta

Solid phase extraction and determination of lead in soil and

water samples using octadecyl silica membrane disks
modified by
bis[1-hydroxy-9,10-anthraquinone-2-methyl]sulfide and flame
atomic absorption spectrometry
Mojtaba Shamsipur a,*, Farhad Raoufi b, Hashem Sharghi c
a

Department of Chemistry, Razi Uni6ersity, Kermanshah, Iran

Department of Chemistry, Tehran Uni6ersity, Tehran, Iran
c
Department of Chemistry, Shiraz Uni6ersity, Shiraz, Iran

Received 6 November 1999; received in revised form 28 February 2000; accepted 20 March 2000

Abstract
A simple, reliable and relatively fast method has been developed to selectively separate and concentrate trace
amounts of lead from aqueous samples for the measurement by flame atomic absorption spectrometry. By the passage
of aqueous samples through an octadecyl-bonded silica membrane disk modified by a recently synthesized bis(anthraquinone)sulfide, Pb2 + ions adsorb quantitatively and almost all matrix elements will pass through the disk to
drain. The retained lead ions are then stripped from the disk by minimal amount of acetic acid as eluent. The
proposed method permitted large enrichment factors of about 300 and higher. The limit of detection of the proposed
method is 50 ng Pb2 + per 1000 ml. The effects of various cationic interferences on the recovery of lead in binary
mixtures were studied. The method was successfully applied to the determination of lead in soil and water samples.
2000 Elsevier Science B.V. All rights reserved.
Keywords: Lead(II); SPE; Octadecyl silica disks; Bis(anthraquinone)sulfide; Flame atomic absorption spectrometry

1. Introduction
The selective concentration, separation and determination of lead at trace levels is of special
importance. This metal is among those heavy
* Corresponding author. Tel.: +98-831-723307; fax: + 98831-831618.

elements that are of major interest in environmental protection due to its cumulative toxicity and
well known health risk to animals and human
[1,2]. Because of its widespread application as fuel
additive, lead is emitted into the biosphere in
considerable amounts [3]. The spectrophotometric
methods [4] and atomic absorption spectrometry
[5] are among the most common methods employed for the determination of lead in solutions.

0039-9140/00/$ - see front matter 2000 Elsevier Science B.V. All rights reserved.
PII: S 0 0 3 9 - 9 1 4 0 ( 0 0 ) 0 0 3 9 0 - 8

638

M. Shamsipur et al. / Talanta 52 (2000) 637643

However, due to the presence of lead in environmental samples at low levels, its separation from
other elements present and also the use of a
pre-concentration step prior to the lead determination is usually necessary.
Liquidliquid extraction and separation of
Pb2 + ion in the presence of classical [68] and
macrocyclic ligands [9 12] is frequently reported
in the literature. In order to reduce consumption
and exposure to hazardous organic solvents, disposal costs and extraction time, solid-phase extraction (SPE) can be used as an attractive
alternative for the classical solvent solvent extraction methods [13 15]. Recently, SPE disks
were successfully utilized for the extraction of
several organic [16 19] and inorganic analytes
[2023]. We recently modified octadecyl silica
membrane disks with some macrocyclic and classical ligands for the extraction and determination
of ultra trace amounts of barium [21], mercury
[22] and uranyl ion [23] by FAAS, CVAAS and
spectrophotometry, respectively. We now report
an efficient and relatively rapid method for the
selective extraction and concentration of Pb2 +
ions by octadecyl silica membrane disks modified
with a recently synthesized bis(anthraquinone)sulfide derivative (bis[1-hydroxy-9,10-anthraquinone-2-methyl]sulfide, BAS), as a highly selective
and stable reagent, from soil and water samples
and its determination with FAAS. To the best of
our knowledge, modified octadecyl silica membrane disks have not been employed previously
for the separation and concentration of lead ions
from aqueous samples. It is noteworthy that, we
have recently reported a lead-selective membrane
potentiometric sensor based on the anthraquinone
derivative used in this study [24].

2. Experimental

2.1. Reagents
All acids used were of the highest purity available from Merck chemical company and used as
received. All organic solvents used were of HPLC
grade from Merck. Analytical grade nitrate salts
of lead, cadmium, mercury, cobalt, nickel, copper,
zinc, magnesium, calcium, strontium, barium,
lithium, sodium and potassium (all from Merck)
were of the highest purity available and used
without any further purification except for vacuum drying over P2O5. Bis[1-hydroxy-9,10-anthraquinone-2-methyl]sulfide was synthesized
from commercially available initial reactants
(Merck or Fluka) in \90% yield [25,26] and used
after recrystallization from pure benzene and vacuum drying. Doubly distilled deionized water was
used throughout.

2.2. Instruments
The lead determinations were carried out on a
PerkinElmer 603 atomic absorption spectrometer with a hallow cathode lamp and a deuterium
background corrector, at a wavelength of 217 nm
(resonance fine) using an airacetylene flame. The
AAS determinations of all other cations were
performed under the recommended conditions for
each metal. The pH was determined with a Corning ion analyzer 250 pH/mV meter with a combined glasscalomel electrode. Extractions were
performed with 47 mm diameter0.5 mm thickness Empore membrane disks containing octadecyl-bonded silica (8-mm particle, 60-A, pore size, 3
M Co., St. Paul, MN) with a standard Millipore
47-mm filtration apparatus.

2.3. Sample extraction

After placing the membrane disk in the filtration apparatus, it was washed with 10 ml
methanol and then with 10 ml acetonitrile to
remove all contaminants arising from the manufacturing process and the environment. After dry-

M. Shamsipur et al. / Talanta 52 (2000) 637643

ing the disk by passing air through it for several min, a solution of 15 mg BAS dissolved
in 2 ml of chloroform was introduced to the
reservoir of the apparatus and was drown
slowly through the disk applying a slight vacuum until the ligand penetrated the membrane
completely. The solvent was evaporated at
50C.
After drying, the modified disk was washed
with 25 ml of water to pre-wet the surface of
the disk prior to the extraction of Pb2 + ions
from aqueous samples. Then 500 ml of the sample containing 5 mg of Pb2 + ions was passed
through the membrane (flow rate=20 ml
min 1). After the extraction, the disk was dried
completely by passing air through it for few
minutes. The extracted lead was then stripped
from the modified membrane disk using 10 ml
of 0.5 M solution of acetic acid (flow rate = 2
ml min 1). It is interesting to note that the
reagent BAS is quite stable in acidic solutions,
and it is sparingly washed out from the surface
of the disks with the eluent used. Thus, each
modified disk could sufficiently be used for at
least five times.

2.4. Lead ions in ri6er water and soil samples

[27,28]
Accurately weighed 1 g of soil samples (less
than 200 mesh, dried at 110C was poured into
a 250-ml beaker and 10 ml concentrated nitric
acid was added to it. The mixture was gently
heated under a hood until drying. After complete drying and cooling to room temperature, a
second 10-ml portion of concentrated nitric acid
was added and the procedure was repeated.
Then 10 ml concentrated hydrochloric acid was
added to the beaker and the mixture was gently
heated until complete drying. After cooling, the
residue was dissolved in 10 ml of 1 M HCl and
the solution was then filtered into a 100-ml calibrated flask, using a syringe filter (0.45 mm pore
sized). The sample was neutralized by proper
amounts of a 1 M NaOH solution and finally
diluted to the mark with water.

639

3. Results and discussion

It is well known that various hydroxy
derivatives of 9,10-anthraquinone are able to
form stable 2:1 (ligand-to-metal) complexes with
alkaline earth, transition and heavy metal ions
[2931], among which the resulting Pb2 +
complexes are of the most stable ones [29]. Due to
its negligible solubility in water and the existence
of two 1-hydroxy-9,10-anthraquinone groups and
a donating sulfur atom in its structure, we have
previously used BAS as a very suitable ion carrier
in construction of a Pb2 + ion-selective electrode
[24]. It should be noted that the log Kf value for
the formation of a 1:1 Pb2 + BAS complex in
acetonitrile solution, as estimated from the
conductance measurements [32], was found to be
\ 7. Thus, in this study we used the ligand as a
potential modifier for the SPE and determination
of Pb2 + ions by the membrane disks and FAAS.
Some preliminary experiments were carried out in
order to investigate the quantitative retention of
Pb2 + ions by the octadecyl silica membrane disks
in the absence and presence of BAS, after the
recommended washing, wetting and conditioning
procedures were performed. It was found that,
while the conditioned membrane disk itself does
not show any tendency for the retention of lead
ions, the membrane disk modified by BAS is
capable to retain Pb2 + ions in the sample solution
quantitatively (the test solution used contained 5
mg lead in 25 ml water).

3.1. Choice of eluent

In order to choose the most effective eluent for
the quantitative stripping of the retained Pb2 +
ions by the modified disks, after the extraction of
5 mg lead in 500 ml water, the lead ions were
stripped with varying volumes of 1 M solutions of
different acids and the results are summarized in
Table 1. As seen, among four different acid
solutions used, 5 ml of 1 M acetic acid (or 10 ml
of 0.5 M of the acid) can afford the quantitative
elution of lead from the disk. As is also obvious,
the lower the acetic acid concentration used, the
higher the volume necessary for the quantitative
elution of the retained lead ions. It is noteworthy

M. Shamsipur et al. / Talanta 52 (2000) 637643

640

that the acetate ion forms a highly stable complex

with Pb2 + ion [33].

bility of the hydrolysis of octadecyl silica in the

disks [22].

3.2. Effect of flow rate

3.4. Effect amount of BAS

The dependence of the uptake of Pb2 + ions by

the modified disk on the flow rate was studied, the
flow rate being varied from 1 to 30 ml min 1. It
was found that adsorption of the metal ion is
quantitative and reproducible in this range. Similar results for the extraction of organic [18,19] and
inorganic [21 23] species by octadecyl silica membrane disks have already been reported. The rate
was maintained at 20 ml min 1 throughout the
experiments. On the other hand, quantitative
stripping of Pb2 + ions from the disk was achieved
in a flow rate range of 0.5 4 ml min 1, using 5
ml of 1 M acetic acid. At higher flow rates (up to
20 ml min 1), quantitative stripping of lead
needed larger volumes of 1 M acetic acid. A flow
rate of 2 ml min 1 was chosen for further studies.

As the amount of loaded ligand on the membrane disk increases, the flow rate of the lead
solutions through the modified disk will decrease.
Thus, the least amount of BAS necessary for the
quantitative extraction of 5 mg Pb2 + from a 500
ml aqueous sample was studied by using varying
amounts of the reagent (i.e. from 5 to 25 mg). The
results indicated that the extraction of lead is
quantitative using above 15 mg of the ligand.
Hence, subsequent extraction experiments were
carried out with 15 mg of BAS.

3.3. Effect of pH
Lead ion solutions were adjusted to the required pH and passed through the modified disks.
Then the metal ions were eluted from the disks by
1 M acetic acid solution. Subsequent atomic absorption analysis resulted in the percentage recoveries of the eluted lead ions at various pH. The
pH range investigated was between 2 and 7. The
results revealed that the percentage recovery of
lead ions is nearly independent of pH. Higher pH
values (\ 7) were not tested because of the possi-

3.5. Analytical performance

The break-through volume of sample solution
was tested by dissolving 5 mg of lead in 25, 50,
100, 250, 500, 1000, 1500 ml water and the recommended procedure under optimal experimental
conditions was followed. In all cases, the extraction by the modified membrane disk was found to
be quantitative. Thus, the break-through volume
for the method should be greater than 1500 ml.
Consequently, by considering the final elution volume of 5 ml and the break-through volume of
1500 ml, an enrichment factor of 300 was easily
achievable.
The maximum capacity of the membrane disk
modified by 15 mg of BAS was determined by
passing 500 ml portions of an aqueous solution

Table 1
Percent recovery of lead from the modified membrane disks using different stripping acid solutionsa
Stripping acid solution

HNO3 (1 M)
HCl (1 M)
HBr (1 M)
CH3COOH (1 M)
CH3COOH (0.5 M)
a
b

% Recoveryb
5 ml

10 ml

15 ml

20 ml

25 ml

8
35
48
100
68

12
42
52
100
100

15
43
54
100
100

16
44
58
100
100

17
46
60
100
100

Initial samples contained 5 mg Pb2+ ion in 500 ml water.

RSDs obtained based on three replicate analyses were within 1.22.5.

M. Shamsipur et al. / Talanta 52 (2000) 637643

Table 2
Separation of lead from binary mixturesa
Diverse ion

Amount taken % Found

(mg)

Li+
Na+
K+
Mg2+
Ca2+
Sr2+
Ba2+
Co2+
Ni2+
Cu2+
Zn2+
Cd2+
Hg2+
Mn2+
Fe3+
Cr3+
Al3+
VO
3

2.1
2.3
2.0
1.9
1.8
2.7
3.0
2.9
2.6
2.4
2.2
1.6
3.0
2.4
2.6
1.8
3.0
2.1

NAPDb
NAPD
NAPD
NAPO
NAPD
3.7 (1.3)
NAPD
NAPD
NAPD
NAPD
NAPD
NAPD
NAPD
NAPD
NAPD
NAPD
NAPD

% Recovery of
Pb2+ ion
98.9
99.3
99.1
96.4
101.2
101.3
98.6
96.4
98.9
99.8
97.3
95.1
99.3
97.3
98.4
98.3
99.3
99.2

(1.4)c
(1.7)
(1.8)
(2)
(2.1)
(1.6)
(1.4)
(1.3)
(1.6)
(1.9)
(1.2)
(1.1)
(1.2)
(1.4)
(1.8)
(1.4)
(1.2)
(1.9)

a
Initial samples contained 5 mg Pb2+ and different amounts
of diverse ions in 500 ml water.
b
No adsorption, passes through disk.
c
Values in parentheses are RSDs based on three replicate
analyses.

Table 3
Determination of lead in water samples
Sample numbera

1
2
3
4
5

Lead concentration (ppm)

Proposed method

ICP

20.5
20.1
19.8
16.3
0.7

21.0 (1.8)
20.5 (1.4)
20.0 (1.4)

(1.8)
(1.4)
(1.8)
(1.2)
(1.4)

a
Samples were collected from Chaloos river at distances of
0.5, 0.7, 0.8, 2 and 15 km, respectively, from Alika lead mines.

containing 2000 mg lead through the disk, followed by determination of the retained metal ions
using FAAS. The maximum capacity of the disk
was found to be 476 mg of Pb2 + ions.
The limit of detection (LOD) of the proposed
method for the determination of lead was studied
under the optimal experimental conditions. The
LOD was obtained from CLOD =KbSbm 1

641

[34,35], where Sb is the S.D. of the blank measurements (ten replicates) and m is the slope of the
linear calibration graph and K is a confidence
factor equal to 3. The LOD of the method was
found to be 50 ng per 1000 ml. The reproducibility of the procedure was found to be at the most
2%.
In order to investigate the selective separation
and determination of Pb2 + ion from its binary
mixtures with diverse metal ions, an aliquot of
aqueous solution (500 ml) containing 5 mg Pb2 +
and milligram amounts of other cations was taken
and the recommended procedures was followed.
The results are summarized in Table 2. As seen,
the lead(II) ions in the binary mixtures are retained almost completely by the modified membrane disk, even in the presence of up to about 3
mg of diverse ions. It is interesting to note that,
with the exception of Sr2 + ions, the retention of
other cations by the modified disk is negligible
and they can be separated completely from the
Pb2 + ion. However, in the case of Sr2 + ion, its
retention by the disk is 3.7%.
In order to assess the applicability of the proposed method to real samples with different matrices containing varying amounts of a variety of
diverse ions, it was applied to the determination
of lead in water and soil samples taken from
Chaloos river (Chaloos, Iran) at different distances from Alika lead mines (Chaloos, Iran). The
results obtained for the water and soil samples by
the proposed method, after calibration by the
external standardization method, and those obtained by inductively coupled plasma-atomic
emission spectrometry (ICPAES) are summarized in Tables 3 and 4, respectively. As seen,
there is a satisfactory agreement between the results obtained by the proposed method and by
ICPAES. Moreover, as it is expected, the lead
content of both water and soil samples decreases
by increasing distance from the lead mines.

4. Conclusions
BAS was used as a highly selective reagent to
modify the octadecyl silica membrane disks for
the successful SPE of Pb2 + ions. In comparison

M. Shamsipur et al. / Talanta 52 (2000) 637643

642
Table 4
Determination of lead in soil samples
Sample numbera

1
2
3
4
5
6
7
8
9
10

Lead concentration in final solution (mg ml1)

Proposed method

ICP

21.4
11.5
4.0
1.8
1.6
1.3
1.1
1.0
0.9
0.2

21.5 (1.4)
11.3 (1.3)

(1.2)
(1.4)
(1.4)
(1.2)
(1.1)
(1.5)
(1.2)
(1.5)
(1.2)
(1.3)

Lead content of soil samples (mg g1)

2140
1150
400
180
160
130
110
100
90
20

Samples were collected from Chaloos river at distances of 0.5, 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0, 15 and 35 km, respectively, from
Alika lead mines.

with the previously reported organic reagents for

Pb2 + ions [6 12], BAS possesses a high selectivity
for Pb2 + ion over many other cations including
alkali, alkaline earth, transition and heavy metal
ions [24], it is quite stable at highly acidic media
and can be easily synthesized from commercially
available compounds at a high yield (i.e. \ 90%)
[25,26]. The method is relatively rapid as compared with previously reported procedures for the
separation and determination of lead [6 12]. The
time taken for the separation and analysis of lead
ion in 500 ml water samples is at the most 45 min.
The method can be successfully applied to the
separation and determination of lead in real
samples.

References
[1] T.E. Berman, Toxic Metals and Their Analysis, Heyden
and Son, London, 1980.
[2] C.D. Klassen, M.D. Amdur, J. Dull, Casarett and Dulls
Toxicology, third ed., Macmillan, New York, 1986.
[3] J.O. Nriagu (Ed.), The Biochemistry of Lead in the
Environment, Elsevier, Amsterdam, 1978.
[4] Z. Marczenko, Separation and Spectrophotometric Determination of Elements, Ellis Horwood, London, 1986.
[5] B. Welz, Atomic Absorption Spectrometry, VCH, Amsterdam, 1985.

[6] J. Mortatti, F.J. Krug, H. Bergamin, Energy Nucl. Agric.

4 (1982) 82.
[7] Methods for Chemical Analysis of Water and Waste,
EPA-600/4-79-020, Environmental Protection Agency, Research Triangle Park, NC, 1983.
[8] A. Arrebola Ramirez, D. Gazquez, I.M. de la Rosa, F.
Moreno, Anal. Lett. 27 (1994) 1595.
[9] W. Szezepaniak, B. Jskowiak, Anal. Chim. Acta 140
(1982) 261.
[10] Y. Sakai, N. Kawano, H. Nakamura, M. Takagi, Talanta
33 (1986) 407.
[11] E.A. Novikov, L.K. Shpigun, Yu.A. Zolotov, Anal. Chim.
Acta 230 (1990) 157.
[12] M. Kompani, M. Shamsipur, J. Sci. I. R. Iran 7 (1996) 13.
[13] R.E. Majors, LC-GC 4 (1989) 972.
[14] M. Moors, D.L. Massart, R.D. McDowall, Pure Appl.
Chem. 66 (1994) 277.
[15] R.M. Izatt, J.S. Bradshaw, R.L. Bruening, Pure Appl.
Chem. 68 (1996) 1237.
[16] E.R. Brawer, H. Lingeman, U.A.Th. Brinkman, Chromatographia 29 (1990) 415.
[17] K.Z. Taylor, D.S. Waddell, E.J. Reiner, K.A. MacPherson, Anal. Chem. 67 (1995) 1186.
[18] Y. Yamini, M. Ashraf-Khorasani, High Resolut. Chromatogr. 17 (1994) 634.
[19] Y. Yamini, M. Shamsipur, Talanta 43 (1996) 2117.
[20] L.B. Bjoklund, M. Morrison, Anal. Chim. Acta 343 (1997)
259.
[21] Y. Yamini, N. Alizadeh, M. Shamsipur, Sep. Sci. Technol.
32 (1997) 2077.
[22] Y. Yamini, N. Alizadeh, M. Shamsipur, Anal. Chim. Acta
355 (1997) 69.
[23] M. Shamsipur, A.R. Ghiasvand, Y. Yamini, Anal. Chem.
71 (1999) 4892.

M. Shamsipur et al. / Talanta 52 (2000) 637643

[24] H.R. Pouretedal, A. Forghaniha, H. Sharghi, M. Shamsipur, Anal. Lett. 31 (1998) 2591.
[25] H. Sharghi, A. Forghaniha, Iran. J. Chem. Chem. Eng. 14
(1995) 16.
[26] H. Sharghi, A. Forghaniha, J. Sci. I. R. Iran 7 (1996) 89.
[27] R.M. Harrison, D.P. Laxen, Water Air Soil Pollut. 8 (1977)
387.
[28] O. Hutzinger, The Handbook of Environmental Chemistry, vol. 3, 1980 Part A.
[29] G.A. Qureshi, G. Svehla, M.A. Leonard, Analyst 104
(1979) 705.
[30] P.L. Gutierrez, N. Nguyen, in: D. Dryhurst, K. Niki (Eds.),

[31]
[32]
[33]
[34]
[35]

643

Redox Chemistry and Interfacial Behavior of Biological

Molecules, Plenum, New York, 1988.
A.R. Fakhari, J. Ghasemi, M. Shamsipur, unpublished
results.
M.R. Ganjali, A. Rouhollahi, A.R. Mardan, M. Shamsipur, J. Chem. Soc. Faraday Trans. 94 (1998) 1959.
Ju. Lurie, Handbook of Analytical Chemistry, Mir,
Moscow, 1975.
ACS Committee on Environment Improvement, Anal.
Chem. 52 (1980) 2242.
J.D. Ingle, S.R. Crouch, Spectrochemical Analysis, Prentice Hall, Englewood Cliffs, NJ, 1988.