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Solid phase extraction of gold by sorption

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DOI: 10.1016/S0039-9140(03)00136-X Source: PubMed

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 Talanta 60 (2003) 839
/844
www.elsevier.com/locate/talanta

Solid phase extraction of gold by sorption on octadecyl silica

membrane disks modified with pentathia-15-crown-5 and
determination by AAS
Marzieh Bagheri, Mohammad Hossein Mashhadizadeh *, Saeid Razee
Chemistry Department, Shahid Bahonar University, 22-Bahman, Kerman 76169133, Iran

Received 19 September 2002; received in revised form 25 February 2003; accepted 26 February 2003

Abstract

A simple and selective method for rapid and efficient concentration and determination of mg l1 levels of Au(III) ions
in aqueous solution using octadecyl silica membrane disks modified by pentathia-15-crown-5 and flame atomic
absorption spectrometry is presented. The influence of flow rates of eluent and sample solution, amount of ligand, types
and least amount of eluent for elution of Au from disks were investigated. Break through volume and limit of detection
of the membrane disks modified by 5 mg of the thiacrown ether was found to be 2.0 l and 1.0 mg l 1, respectively. The
effects of various cationic interferences on percent recovery of gold were studied. The method was successfully applied
for the determinations of gold in some pharmaceutical samples and for the recovery of trace Au3 ions from synthetic
and water samples.
# 2003 Elsevier Science B.V. All rights reserved.

Keywords: Preconcentration; Gold (III); Pentathia 15-crown-5; Octadecyl silica; Membrane disk; Atomic absorption spectroscopy

1. Introduction available techniques. These include the liquid and

The separation, preconcentration and determi-
nation processes of trace metal ions from different
matrices especially water samples are mainly based
on the utilization and application of a number of
* Corresponding author. Tel.: /98-341-322-2033; fax: /98-
341-322-1452.
E-mail address: mashhadizadeh@mail.uk.ac.ir (M.H.
Mashhadizadeh).
0039-9140/03/$ - see front matter # 2003 Elsevier Science B.V. All rights reserved.
doi:10.1016/S0039-9140(03)00136-X
solid phase extraction (SPE), ion-exchanger and
co-precipitation by metal hydroxides [1,2]. The
preconcentration procedure is an essential step for
the accurate measurement and analysis of the
various metal species, especially those present in
trace level (mg l 1 and ng l 1) in order to match
with the detection limits of the major instrumenta-
tions (AAS and ICP-OES) [3,4].
Liquid
/liquid extraction (LLE) of different
metal ions has been widely employed in chemistry
and industry for many years [5]. Disadvantages of
840 M. Bagheri et al. / Talanta 60 (2003) 839
/844
LLE methods are emulsion formation, different
extraction efficiencies for various compounds with
various extracting agents, and low sensitivity. The
sensitivity of LLE methods can be increased by
removing part of the extracting solvent by heat or
by a stream of an inert gas. This step, however, can
lead to losses of analytes, and safety hazards
involved in handling toxic and inflammable sol-
vents are not negligible. Frequently, the whole
LLE procedure is tedious, time consuming and
costly [6]. Thus, much interest has been recently
focused in repairing conventional solvent extrac-
tion methods for isolating environmental pollu-
tants with SPE techniques.
The synthetic methods of solid phase extractors
and preconcentrators are mainly based on the
surface modification of the solid supports by either
the chemical immobilization or physical adsorp-
tion approaches [7,8]. The modified solid sorbents
are then used and applied in the fields of normal or
selective SPE of the target species [9,10]. Such
variations in the behavior of the modified solid
sorbents are mainly dependent on the presence of
some active donor atoms or groups such as O, N, S
and P into the incorporated organic modifier.
The complexing properties of macrocyclic poly-
thioethers (thiacrown ethers) have been studied
and metal complexes with thiacrown ethers have
been isolated and characterized [11,12]. Thiacrown
ethers have also been studied as analytical re-
agents, which are selective for soft metal ions
[13,14].
We have recently used some thiacrown ethers
and mercapto compounds as neutral carriers in
liquid membrane transport and PVC membrane
electrode studies of some heavy metal ions [15
/
20].
The aim of this work is to develop a rapid and
efficient method for the selective extraction, con-
centration of mg l 1 levels of Au (III) in aqueous
solution using octadecyl silica membrane disks
modified by pentathia-15-crown-5 (PT15C5, I)
and determination using flame atomic absorption
spectrometry (FAAS). The influence of flow rates
of eluent and sample solution, amount of ligand,
types and minimum amount of eluent for elution
of Au from disks was investigated.
2. Experimental
2.1. Apparatus
The determinations of gold were performed on a
Shimadzu AA-760 atomic absorption spectro-
meter equipped with a hollow cathode lamp
(HCL). The absorbance wavelength was set at
242.8 nm (resonance line) and the spectral band-
width at 0.5 nm. The determination of all other
cations were carried out with a Shimadzu AA-760
atomic absorption spectrometer under recom-
mended conditions for each metal ion. A digital
pH meter, Metrohm model 632, equipped with a
combined glass calomel electrode was used for the
pH adjustments.
2.2. Reagents
Analytical grade chloride salts of gold, magne-
sium, calcium, cobalt, copper, nickel, zinc, cad-
mium, mercury, potassium and sodium (all from
Merck) were of the highest purity available and
used without further purification except for va-
cuum drying over P2O5. Reagent grade pentathia-
15-crown-5 (PT15C5, Aldrich) was used as re-
ceived. Methanol and acetonitrile (both from
Merck) were of extra pure grade and used as
received. The standard stock solution of gold (III)
was prepared by dissolving appropriate amount of
tetrachloroauric(III) acid in 0.001 M hydrochloric
acid solution. Working solutions were prepared by
appropriate dilution of the stock solution with
water.
 M. Bagheri et al. / Talanta 60 (2003) 839
/844
2.3. General procedure
Extractions were performed with 47 mm dia-
meter/0.5 mm thickness 3M EmporeTM mem-
brane disks containing octadecyl-bonded silica (8
mm particle size, 60 A pore size) distributed by
Varian. The disks were used in conjunction with a
standard Sartorius 47 mm filtration apparatus.
After placing the membrane disk in the filtration
apparatus, it was washed with 10 ml methanol and
10 ml acetonitrile to remove all contaminants
arising from the manufacturing process and the
environment. After drying the disk by passing air
through it for several minutes, it was dried inside
an oven at 60 8C. Then a solution of 5.0 mg
PT15C5 dissolved in 5 ml acetonitrile was intro-
duced to the reservoir of the apparatus and was
washed with 25 ml water and then 5 ml methanol
and finally dried by passing air through it. In this
step membrane disk modified by the thiacrown
ether was ready for sample extraction.
The general procedure for the extraction of
Au3 ions on the membrane disk was performed
as follows: The modified disk was first washed
with 2 ml methanol followed by washing with 25
ml water. This step prewets the surface of the disk
prior to the extraction of Au3 ions from water. It
is practically important to wet the surface of the
disk with methanol during the extraction of gold
(III) ions was underway. Then 500 or 1000 ml of
the sample solutions containing mg amounts of
Au3 was passed through the membrane at a flow
rate of 20
/30 ml min 1. With this procedure,
Au3 ions in water samples was quantitatively
adsorbed on the modified disk and consequently
were eluted by four 5.0 ml portions of 0.5 M
thiosulfate solution at a flow rate of 5 ml min 1.
Each portion was collected in a 10 ml volumetric
flask and diluted to the mark with water and the
amount of gold (III) was then determined by AAS.
3. Results and discussion
Thiacrown ethers have the characteristics of
polythioethers, and hence formation of their com-
plexes with metal cations may be primarily attrib-
841
uted to the affinity of the metal ion for sulfur
atoms. Of course, the relative sizes of the metal ion
and the cavity of the macrocyclic ligand can also
play an important role in the selectivity of the
resulting complex [12].
Ligands for use, as ionophore in a disk modified
SPE for Au3 ions should fulfil certain conditions.
They should be selective for Au3 over other
metal ions. They should have rapid exchange
kinetics and should be sufficiently lipophilic to
prevent leaching of the ligand into the solutions of
sample and eluent.
Chelating agents with soft coordination sites
like sulfur seem to generate great affinity toward
soft metal ions such as Au. Thiacrown ethers are
macrocyclic rings containing sulfur donor atoms,
which have high bonding affinities with soft metal
ions such as Cu, Ag , Hg2, and Au3 ions
[11,21
/24]. These macrocyclic ligands are free of
any protonation consideration and hardly soluble
in water.
The equilibrium constant for the reaction of the
tetrachloro complex with the thiamacrocycle to
give the macrocycle-cation complex plus four
anions is very high for Au (III) [24]. Thus,
considering the stability trend as well as the high
lipophilicity of the thiacrown ethers, we investi-
gated to use of PT15C5 as a suitable modifier for
the selective concentration and extraction of Au3
ions by the octadecyl silica membrane disks.
Some preliminary experiments were carried out
in order to investigate the quantitative retention of
Au3 ions by the octadecyl silica membrane disks
in the absence and presence of PT15C5. It was
found that, while the membrane disk itself does
not show any tendency for the extraction of gold
ions, the disks modified by PT15C5 are capable to
quantitatively retain Au3 ions in the sample
solution (the test solutions contained 5.0 mg
Au3 in 500 ml water). The optimal amount of
the thiacrown ether which must be loaded on the
octadecyl silica membrane disks for the quantita-
tive recovery of 5.0
/50 mg Au3 ion from aqueous
sample solutions was found to be approximately
5.0 mg or more. The use of less than 5.0 mg of the
ligand, resulted in considerable decrease in the
recovery of Au3 ions.
842 M. Bagheri et al. / Talanta 60 (2003) 839
/844

3.1. Choice of eluent The influence of the pH of test solutions on the

In order to choose a proper eluent for the
retained Au3 ions, after the extraction of 5 mg
gold from 100 ml water by the modified disks with
5 mg PT15C5, the gold ions were stripped with
four 5 ml portions of various potential stripping
agents. The results are summarized in Table 1. It is
immediately obvious that, different stripping
agents examined, thiosulfate is the most promising
one. The effect of varying concentration of S2O23
ion on the recovery of gold ion was also studied
and the results are included in Table 1. As seen, 20
ml of 0.5 M S2O2 3 solution can accomplish the
quantitative elution of gold from the modified
membrane disk.
recovery of 5 mg Au3 from 500 ml solutions was
studied in the pH range 1.0
/9.0. The pH was
adjusted by using 1 M hydrochloric acid or 0.1 M
NaOH. The results shown in Fig. 1 indicate that
the Au3 ion can be retained quantitatively in the
pH range 4.5
/7.0. The pronounced decreased in
the Au3 recovery in solutions of pH B/4.5 are
due to the possible decomposition of thiosulfate in
acid solution. However, decreased in the Au3
recovery in solutions of higher pH values (/7) are
due to the hydrolysis of Au3 and possibility of
the hydrolysis of octadecyl silica in the disks.
The maximum capacity of the membrane disk
modified by 5.0 mg of PT15C5 was determined by
passing 10 ml portions of an aqueous solution

3.2. Effect of flow rate and pH

The effect of flow rates of sample and stripping

solutions from the modified membrane disk on the
retention and recovery of Au 3 ion was studied.
It was found that, in the range of 10
/100 ml
min 1, the retention of gold by the membrane disk
is not very affected by the sample solution flow
rate considerably. On the other hand, quantitative
stripping of gold ions from the disk was achieved
in a flow rate range of 1.0
/5.0 ml min 1, using
10
/20 ml of 0.5 M S2O2
3 . At higher flow rates (up
Fig. 1. Effect of pH on recovery of gold (III) ion from
to 5 ml min 1) quantitative stripping of gold
membrane disks modified with PT15C5.
needed larger volumes of S2O2 3 .

Table 1
Percent recovery of gold from the modified membrane disk as a function of stripping solutions and volume of eluenta

Stripping agent Volume of eluent

First 5 ml Second 5 ml Third 5 ml Fourth 5 ml Total

HBr 15 5 4 2 26
Thiourea 27.1 23 17.5 8.8 76.4
HNO3 5.2 1.9 1.6 0.9 9.6
HCl 15.7 9.5 7 5.9 38.1
EDTA 5.5 4.8 3.6 2.7 16.6
Na2S2O3 (0.01 M) 25 7.5 3.5 3.5 39.5
Na2S2O3 (0.05 M) 48 20.5 3.5 2 74
Na2S2O3 (0.1 M) 50 31 3.2 2 86.2
Na2S2O3 (0.5 M) 52.5 30 15.5 2 100
Na2S2O3 (1.0 M) 55.2 29.3 13.7 1.8 100
a
Initial samples contained 5.0 mg Au3 ion in 500 ml water.
 M. Bagheri et al. / Talanta 60 (2003) 839
/844 843

containing 5 mg gold, followed by the determina- Table 2

tion of the retained Au3 ions using AAS. The Separation of gold from binary mixturesa
maximum capacity of the disk was found to be 750 Diverse Amount taken % % Recovery of Au3
mg of gold ion on the disk. ion (mg) Found ion
The reuse of a modified disk was tested for its
ability to perform the SPE for more than one Ni2 5.87 NADPb 102.5 (0.5)c
K 60.5 NADP 101.1 (0.5)
sample. It was found that the use of the same disk Na 61 NADP 100.1 (0.4)
modified with 5 mg PT15C5 for at least ten times Cd2 3.5 0.3 (0.8) 98.2 (0.6)
resulted in no change in the recovery of Au3 ion. Co2 15.8 NADP 99.7 (1.0)
However, for the SPE of trace amounts of gold Zn2 4.3 NADP 99.8 (0.8)
from real samples, it is recommended to use a new Ag  5 NADP 98.5 (0.9)
Mg2 85 NADP 99.3 (1.2)
modified disk for every sample to protect the Ca2 72 NADP 99.6 (2.1)
samples from possible contaminations. Cu2 6.2 0.2 (1.2) 99.1 (1.3)
Hg2 3.1 20 (1.2) 89.7 (1.1)
3.3. Analytical performance Hg2 3.1 3.0 (0.5) 99.5 (1.2)d
a
Initial samples contained 5.0 mg Au3 and different
The break through volume of sample solutions amounts of divers ions in 500 ml water.
was investigated by dissolving 5 mg of gold in 100, b
No adsorption passes through disk.
c
200, 500, 1000, 1500, 2000 and 2500 ml water and Values in parentheses are R.S.D. based on four replicate
the proposed procedure was followed. The Au ions analyses.
d
At the presence of 0.01 M EDTA.
were quantitatively retained from 2000 ml and
smaller volumes. Thus, the break through volume
for the proposed SPE method was 2000 ml. Table 3
The repeatability of extraction of gold ion with Recovery of gold added to 500 ml solution of the synthetic and
water samplesa
membrane disk was investigated and the percent of
metal ion (5.0 mg Au3 in 500 ml water) obtained Sample % Recovery of
at optimum conditions from ten replicate experi- Au3 ionb
ments was found to be 99.79/1.0%.
Synthetic sample 1 (Mg2 ,Na  and 99.8 (0.8)
In order to study the selective separation and Ca2 , 5 mg of each cation)
determination of gold ion from its binary mixtures Synthetic sample 2 (Mg2 , Ca2 , Na , 5 103.2 (0.8)
with diverse metal ions, an aliquot of aqueous mg of each cation and Co2 , Ni2 ,
solutions (500 ml) containing 5.0 mg Au3 and mg Cu2 , Zn2 , Hg2 , Ag  , 1 mg of each
amounts of other cations was taken and the cation)
Tap water 99.6 (0.7)
proposed procedure was followed. The results are River water (Karoun) 101.1 (0.9)
summarized in Table 2. The results show that the River water (Maragheh) 102.1(0.6)
modified membrane disk, even in the presence of Laboratory water 100.3 (1.9)
up to about 5.0 mg of diverse ions retains the gold a
Each sample contains 5.0 mg Au3 .
(III) ions in the binary mixtures almost completely. b
Values in parentheses are R.S.D. based on four replicate
In order to test the accuracy and applicability of analyses.
the proposed method to the analysis of the real
samples, with different matrices, it was applied to
the separation and recovery of Au3 ions from a
synthetic sample. The result, as the average of four results are summarized in Table 3. And show
separate determinations is shown in Table 3. In that, in all cases, the gold recovery is almost
view of the application of the method to the quantitative. In addition, the proposed method
determination of gold in water, standard solutions was also used for separation and determination of
containing Au3 were added to tap water, river gold from some pharmaceutical preparations. The
water, spring water and synthetic water. The results are shown in Table 4. As seen, the
844 M. Bagheri et al. / Talanta 60 (2003) 839
/844

Table 4
Determination of gold in pharmaceutical preparations

Sample Nominal amount (mg)a Found amount by AAS (mg) Found by this method (mg)b Recovery (%)

Auranofin (tablet) 0.87 0.871 0.881 (0.003) 101.1

Gold sodium thiomaleate 4.83 4.824 4.815 (0.004) 99.8
(injection)
a
Drug content, mg per tablet or mg per injection.
b
Values in parentheses are R.S.D. based on five replicate analyses.

recoveries of gold from each sample were about
99
/101%.
4. Conclusions
The proposed SPE method based on octadecyl
silica membrane disks modified with PT15C5 is a
simple, rapid, highly selective and reproducible
method for the separation, concentration and
determination of gold ions. The time taken for
the separation and analysis of gold is at most 40
min. The method can be successfully applied to the
separation and determination of gold in real
samples. The reproducibility of the method is at
the most 2.1%.
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