Journal of Hazardous Materials 142 (2007) 272–278

Simultaneous preconcentration and determination of copper, nickel,

cobalt and lead ions content by flame atomic absorption spectrometry
Mehrorang Ghaedi ∗ , Farshid Ahmadi, Ardeshir Shokrollahi
Chemistry Department, Yasouj University, Yasouj 75914-353, Iran
Received 20 May 2006; received in revised form 9 August 2006; accepted 10 August 2006
Available online 12 August 2006

Abstract
A sensitive and simple method for the simultaneous preconcentration of nutritionally important minerals in real samples has been reported. The
method is based on the formation of metal complexes by 4,6-dihydroxy-2-mercaptopyrimidine (DHMP) loaded on activated carbon. The metals
content on the complexes are then eluted using 5 mL 2 M HNO3 in acetone, which are detected by AAS at resonance line. In this procedure,
minerals such as Cu, Ni, Pb and Co could be analyzed in one run by caring out the simultaneous separation and quantification of them. At optimum
condition the response are linear over concentration range of 0.04–1.1 ␮g mL−1 for Ni2+ and 0.04–1.0 ␮g mL−1 for Cu2+ , Pb2+ and Co2+ . The
detection limits of each element are expressed as the amount of analytes in ng mL−1 giving a signal to noise ratio of 3 are equal to 3.5, 3.4, 2.9 and
8.4 for Ni2+ , Co2+ , Cu2+ and Pb2+ . The sorption capacity was determined by saturating 0.5 g solid phase. The loading capacity are 0.54, 0.53, 0.63
and 0.45 mg g−1 for Ni2+ , Co2+ , Cu2+ and Pb2+ . The ability of method for repeatable recovery of trace ion are 99.0, 98.9, 99.2 and 98.8 with R.S.D.
of 1.4, 1.3, 1.2 and 1.4 for Ni2+ , Co2+ , Cu2+ and Pb2+ . The low detection limits of these elements in this technique make it a superior alternative to
UV–vis and in several applications, also an alternative to ICP-MS techniques. The method has been successfully applied for these metals content
evaluation in some real samples including natural water, leaves of spinach and cow liver.
© 2006 Elsevier B.V. All rights reserved.

Keywords: Heavy metal; 4,6-Dihydroxy-2-mercaptopyrimidine (DHMP); Atomic absorption spectrometry; Activated carbon

1. Introduction instrument. However, the low level of trace elements in drink-

ing waters is not compatible with the detection limit of AAS.
In the analysis of trace metal ions present in various samples Preconcentration can solve the above two problems and leads to
such as natural and waste water, biological and alloy samples, simplified heavy metal determination.
the direct determination with various instrumental methods is There are many methods of preconcentration, including co-
not possible owing to matrix effect and low concentration of precipitation, solvent extraction, electrochemical deposition,
metal ions in a sample. In trace analysis, therefore, a preconcen- membrane extraction, and solid phase extraction.
tration and/or separation of trace elements from the matrix are Solid phase extraction has several advantages over other sep-
frequently necessary to improve the detection limit and selec- aration techniques in view of: (i) trace and major concentrations
tivity. of trace ions present in hazardous samples can be removed
Various techniques have been applied for the determination with equal ease; (ii) higher enrichment factors; (iii) reusabil-
of trace heavy metals in aqueous samples. Direct instrumental ity of the adsorbent; (iv) absence of emulsion; (v) minimal
analysis of these samples is difficult because of complex forma- costs due to low consumption of reagents; (vi) ease of automa-
tion and significant matrices, which invariably influence normal tion; (vii) environmental friendly; (viii) safety with respect to
instrumental analysis. In addition, some metals have low con- hazardous samples. Accordingly, several solid phase extrac-
centrations, which are near or below the limit of detection of the tants have been employed for enrichment of traces of elements
from dilute solutions. A number of supports and chelating lig-
ands have been widely used in the design of chelating resins
∗ Corresponding author. Tel.: +98 741 2223048; fax: +98 741 2223048. for the preconcentration and separation of trace metal ions
E-mail address: m [email protected] (M. Ghaedi). from various matrices. The most prominent among the sup-

0304-3894/$ – see front matter © 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.jhazmat.2006.08.012
 M. Ghaedi et al. / Journal of Hazardous Materials 142 (2007) 272–278 273

while oxygen atoms of the ligands mostly interact with this ion
as a soft acid through ion–dipole interactions and soft atoms
such sulfur and nitrogen through soft–soft interaction, while all
resulting in fast complexation and higher sensitivity.
Here authors report a method for preconcentration of trace
elements, viz., Co, Ni, Cu, and Pb on a activated carbon modi-
Scheme 1. Schematic diagram of 4,6-dihydroxy-2-mercaptopyrimidine struc- fied with DHMP. The sorbed elements were eluted with 5 mL,
tures. 2 mol L−1 HNO3 . The effluents were further analyzed by AAS
for evaluating their metals content.

ports used are Amberlite XAD resins [1], activated carbon, [2], 2. Methods and materials
SDS coated alumina [3], modified chromosorb [4] and sepiolite
[5]. 2.1. Reagents
Among them activated carbon, which are characterized by
high adsorption capacity, allowing application under broad pre- Acids and bases were of the highest purity available from
concentration conditions has widespread application for trace Merck and used as received. Doubly distilled deionized water
element preconcentration. Metal ions to be preconcentrated on was used throughout. Analytical grade nitrate salts of lead,
activated carbon as a hydrophobic adsorbent need to be trans- cadmium, mercury, cobalt, nickel, copper, zinc, magnesium, cal-
formed corresponding metal chelates or precipitate [6–12] or cium, barium, sodium and potassium (all from Merck) were of
metal hydroxides [13], which could be adsorbed on activated the highest purity available and used without any further purifica-
carbon. Metal chelates could provide higher selectivity and tion. The ligand 4,6-dihydroxy-2-mercaptopyrimidine (DHMP)
high enrichment factors for such a preconcentration and sep- was purchased from Merck Company. The pH 6.0 was adjusted
aration. The mechanism involved in the adsorption of ions as by addition of appropriate amount of dilute nitric acid or potas-
trace compounds by activated carbon is not completely known. sium hydroxide to solutions. Activated carbon powder (Merck)
The mechanism of sorption is still under investigation and the was treated with 20% nitric acid, washed with de-ionized water
adsorption of heavy metals on AC could be explained using and oven-dried at 110 ◦ C.
Langmuir and Freundlich equations. It was assumed that the
sorption is quantitative when the chelate contains systems of ␲- 2.2. Instruments
electrons in the molecule and when the centers for binding on
carbon and those for the metal ions are spatially separated so that The evaluation of ions content were carried out on a Shimadzu
their orbital do not have a substantial influence [14]. The major 680 A or a Perkin-Elmer 603 atomic absorption spectrometer
advantage of these models is their simplicity; however, the mod- with a hallow cathode lamp and a deuterium background cor-
els fail to describe accurately the adsorption equilibrium under rector, at respective resonance line using an air–acetylene flame.
varying conditions, such as pH and ionic strength. The adsorp- The conditions for FAAS determination of these ions are pre-
tion equilibrium studies have revealed that pH is the dominant sented in Table 1. A Metrohm 691 pH/Ion meter with a combined
parameter controlling the adsorption [15]. Therefore, activated glass–calomel electrode was used for adjustment of test solution
carbon (AC) has been used as a collector, permitting the pre- pH. A Shimadzu UV–vis 160 spectrophotometer has been used
concentration and separation of low levels of analytes in several for measuring spectrophotometric data.
matrices [16–24]. As shown in Scheme 1, due to the existence of
a donating nitrogen atom as well as S (SH) group and O (OH) 2.3. Preparation of DHMP coated activated carbon
group and NH group in DHMP was expected to increase both
the stability and selectivity of its complex toward ions includ- SPE tubes and frits were soaked in 1% nitric acid overnight
ing copper, nickel, cobalt and lead ion over other metal ions, and then washed with water. A Pyrex glass column contain-
especially alkali and alkaline earth cations. It is occurred to us ing 0.5 g of activated carbon in water suspension was 40 cm
that the presence of some constituents with non-cyclic sulfur- long and 0.75 cm in internal diameter. The bed height in the
containing ligand in addition to nitrogen and oxygen in addition column was approximately 1 cm. The AC (500 mg) was impreg-
to the ␲-electrons results in selective interaction with these ions nated with DHMP by percolating 2 mL of 1% (w/v) DHMP

Table 1
Hollow cathode lamp conditions and flame conditions for FAAS
Element Slit (nm) Wavelength (nm) Lamp current (mA) Flow rate of flame gases (L min−1 )

Air Acetylene

Cu 0.5 324.8 3 8.0 1.8

Co 0.2 240.7 8 8 2.2
Ni 0.2 232.0 4 8 1.7
Pb 1.0 283.3 5 8.0 2.0
274 M. Ghaedi et al. / Journal of Hazardous Materials 142 (2007) 272–278

(20 mg) solution through the column packed with AC at a Appearance of white fume of perchloric acid in 1 mL solution
flow rate of 0.2 mL min−1 . The filtrate was collected and ana- is an indication of complete digestion.
lyzed for un-adsorbed DHMP with the UV–vis spectropho-
tometer at 280 nm. The column was then washed twice with 2.5. Preconcentration procedure
5 mL water and the filtrates were analyzed for DHMP that was
released. The retained amount of DHMP on the AC column was The pH of the solution (500–1000 mL) was adjusted to ∼6.0
110 mg g−1 . with hydrochloric acid and passed through the DHMP loaded-
AC column at a flow rate of 6 mL min−1 with the aid of a suction
2.4. Pretreatment of real samples pump. The analyte was then eluted with 5 mL of 2 M nitric acid
in acetone. The metal ions content of the eluent was measured by
2.4.1. Digestion of leaves of spinach flame-AAS. The same eluate was used to determine all analytes,
Leaves of spinach were purchased from Gachsaran Iran. while the eluate introduced into the chamber by discrete injec-
Afterwards, they dried and were taken in small mesh. A 40 g tion. The metals quantified one each time. The effects of sample
leaves of spinach was heated in silica crucible for 3 h on a hot volume, amount of DHMP, AC, pH and working solution ionic
plate and the charred material was transferred to furnace for strength on the recoveries of metal ions were investigated.
overnight heating at 650 ◦ C. The residue was cooled, treated
with 10.0 mL concentrated nitric acid and 3 mL 30% H2 O2 again 3. Results and discussion
kept in furnace for 2 h at the same temperature so that no organic
compound traces are left. The final residue was treated with 3 mL In order to show that complexation between ions and DHMP
concentrated hydrochloric acid and 2–4 mL 70% perchloric acid is responsible for selective, sensitive and reversible preconcen-
and evaporated to fumes, so that all the metals change to respec- tration of mention ions, the copper complexation with ligand,
tive ions. The solid residue was dissolved in water, filtered and as model has been investigated. Since these mention ions have
by keeping the pH at 6.0 made up to 250 mL by addition of similar property, similar results for them can be achieved. In
diluted KOH. The dissolved solution was suitably diluted and preliminary experiments typical complexation between copper
metals concentration was determined after suitable preconcen- ion and DHMP was examined using spectrophotometry, and the
tration using AAS. nature of respective complex was investigated using the mole
ratio method under the established experimental conditions by
2.4.2. Determination of metal ions in water samples Kin fit program [25]. In order to confirm this result and ascer-
Water samples were collected from spring water Tangari tain the nature and structure of the extracted species, to the fixed
spring, Yasouj, Iran and Beshar River, Yasouj, Iran; tap water amount of DHMP different mole ratio of copper ion was added
and wastewater are collected from Gachsaran, Iran. Before the and corresponding data are presented in Figs. 1 and 2. At mole
analysis, the samples were filtered through a cellulose membrane ratio of 2, indicating the association of two DHMP molecules
filter (Millipore) of pore size 0.45 ␮m. The organic content of the with the one molecule of copper ion. The stability constant of
water samples were oxidized in the presence of 1% H2 O2 and copper ion and DHMP has been investigated using spectropho-
addition of concentrated nitric acid. After acidification to 1% tometry as a general accurate and powerful method. According
with concentrated nitric acid, they were stored in polyethylene to the results of Table 2, it can bee seen that the DHMP is a
bottles. For the preconcentration procedure, pH of the 800 mL suitable sorbent with reversible sorption/desorption (medium
of water samples was adjusted to 6 and the sample passed formation constant), which facilitate both process is superior
through the column at flow rate of 6 mL min−1 . The metals, to those modified activated carbon.
which retained on activated carbon by complexation with DHMP
loaded on AC, were eluted with 5 mL of 2 mol L−1 HNO3 in ace-
tone. The effluent was sent to FAAS for evaluation of their metal
content evaluation.

2.4.3. Digestion of the liver sample

A 50 g of liver were taken and dried for 48 h in an oven at
120 ◦ C to remove the water content and to obtain a constant
weight (about 68% water). Dried liver sample transferred into
a glass flask. For the digestion of the sample, a concentrated
acid mixture of 3 mL H2 SO4 , 15 mL HClO4 , 15 mL HNO3 was
added and left to stand over night. The solution was kept in an oil
bath at 50 ◦ C until the foaming stopped. Then the temperature
was increased to 150 ◦ C and heating was continued until the
evolution of brown fumes of nitrogen oxides ceased. When a
dark brown in mixture was appeared, the flask was cooled for
about 2 min then a 5 mL of nitric acid had to be added. Heating Fig. 1. Spectra of complex of DHMP (1 × 10−3 M) with copper ion
was continued until nitrogen oxides fumes were longer given off. (1 × 10−3 M) in acetonitril in different mole ratio.
 M. Ghaedi et al. / Journal of Hazardous Materials 142 (2007) 272–278 275

Fig. 2. UV–vis spectra of 1 × 10−3 M of DHMP in acetonitrile and various Fig. 3. Effect of pH on recovery of metal ions at optimum conditions according
concentration of Cu2+ 1 × 10−3 M, mole ratio plot. to Table 5.

Table 2
amount of the sorbent also prevents the quantitative elution of
Logarithm of stability constants assembling for the interaction of Cu2+ with
DHMP in acetonitrile the retained metals by a small volume of eluent. For this rea-
son, the effect of the amount of activated carbon and the eluent
Complex nature log β
volume were examined. The effects of the amount of activated
Cu2+ DHMP carbon at fix value of DHMP on the sorption of metal ions at
1 1 5.000 ± 0.004 pH 6 were examined in the range of 100–800 mg. The results
1 2 8.001 ± 0.003 demonstrated that, quantitative recoveries ( > 95%) of the work-
ing elements were observed in the range of 400–500 mg. Above
500 mg, the recoveries were below 95% with 10 mL of the elu-
The efficiency of the DHMP-AC column for the sorption of ent. In the proposed procedure, 500 mg of activated carbon is
metals was studied by using 500 mg of DHMP-AC in compari- recommended.
son with 500 mg of AC for preconcentration of metals in a model As is well known, pH value of the solution has significant
solution, starting with 50 ␮g of each metal ions in 250 mL of influence on the overall performance of the retention of the
solution, the quantity of metals ion in the eluent was determined metal ions on activated carbon. The effect of pH on the precon-
by FAAS. The percentage sorption of the metals retained on the centration of metals on AC loaded with DHMP was studied by
sorbents was calculated from the difference between the starting determination of individual elements. Fifty micrograms (250 mL
amount of each metal (␮g) (Ns ) and the amount of metal (␮g) 0.2 ␮g mL−1 ) of each element were preconcentrated in the pH
left in the sample (Nf ) according to Eq. (1). range of 2.0–8.0 (by addition of diluted KOH or HCl) by intro-
Ns − N f ducing 20 mg of DHMP on the activated carbon. The elution
sorption (%) = × 100 (1) was performed with 5 mL of 2 mol L−1 HNO3 in acetone. The
Ns
data corresponding to each element was shown in Fig. 3. The
The DHMP-AC can retain all the metal ions while the untreated results obtained indicated that the ions could be retained quan-
AC cannot quantitatively retain Co, Ni, Cu and Pb. Evidently; titatively by the modified activated carbon at the pH 6.0. So the
the preconcentration of the metals with the untreated AC is not pH 6.0 ± 0.1 has been selected for the determination of metals
suitable for Co, Ni, Cu and Pb. Therefore, DHMP-AC seems content. The decrease in signal at pH > 6.0 is probably due to
to be a better sorbent in simultaneous sorption of the studied the precipitation of ions as their related hydroxide and at pH < 6
elements. The purpose of this work is to investigate the feasibility may be due to competition of hydronium ion toward complex-
of absorption of these ions on activated carbon modified with ation with PUT, which lead to the decrease in the recovery. To
DHMP. For obtaining maximum signal for evaluation of these achieve high efficiency and good selectivity, a pH of ∼6.0 was
ion contents, the effective parameters viz. pH of sample, amount selected for subsequent work.
of ligand and solid phase, type and concentration of eluting agent The elution of a group of analytes could be sometimes trou-
and flow rate must be optimized. blesome owing to irreversible binding of some elements. In
addition, desorption step leads to sample dilution and causes
3.1. Optimization of variables decrease of the analyte enrichment factor. An appropriate elu-
ent for metal desorption was selected by taking into account the
In optimization of variables 250 mL of 0.2 ␮g mL−1 of ions following considerations: (i) the eluent should desorb the metals
are used as sample solution. In the adsorption step, an appropri- or chelate complexes, (ii) should be suitable for the subsequent
ate amount of activated carbon should be used in order to obtain determination technique. Organic solvents and inorganic acids
quantitative retention of metals. On the other hand, an excess have been found to meet the requirements. In a set of simi-
276 M. Ghaedi et al. / Journal of Hazardous Materials 142 (2007) 272–278

Table 3
Effect of type and concentration of eluting agent on ions recovery
Eluent Recovery (%)

Co2+ Ni2+ Pb2+ Cu2+

5 mL 4 M HCl 69.4 54.6 55.6 59.4

5 mL 4 M HNO3 99.7 99.1 98.8 99.2
5 mL 4 M H2 SO4 64.3 68.3 62.3 61.3
5 mL 4 M H3 PO4 41.4 39.3 40.8 43.6
5 mL 1 M HNO3 a 72.3 79.2 78.9 80.6
5 mL 2 M HNO3 a 98.8 99.1 98.9 99.0
5 mL 3 M HNO3 a 98.9 99.2 99.4 99.3
3 mL 2 M HNO3 a 85.6 87.6 89.7 87.1
4 mL 2 M HNO3 a 94.6 95.4 96.2 97.3
6 mL 2 M HNO3 a 99.6 98.3 98.6 98.5
a Solution were prepared in acetone.

lar experiments, the standard solution for preconcentration was Fig. 4. Effect of amount of DHMP on recovery of metal ions at optimum con-
0.2 mg L−1 of above mention ions (pH 6, 250 mL). The eluents ditions according to Table 5.
chosen were 4 M sulfuric acid, phosphoric acid, hydrochloric
acid, nitric acid and 1–3 M nitric acid in acetone. The effective-
ness of metal desorption from DHMP-AC was evaluated from significant effect on the recoveries of the investigated elements.
the recovery (%) of ions. The recovery (%) in this section was All subsequent experiments were performed at 4 mL min−1 flow
calculated from the amount of metals (mg) in the starting solu- rate.
tion (Ns ) and the amount of metals (mg) eluted from the column In order to explore the possibility of enriching low concen-
(Nf ) according to Eq. (1). The results are summarized in Table 3. trations of the analytes from the large sample volume, the effect
According to Table 3, solvents could elute ions with recover- of the sample solution volume on the metal sorption was studied
ies (%) ranging from 39.3–99.6%. It is clear that 2 M nitric acid by passing 250–1600 mL volumes through the activated carbon
in acetone was the best eluent allowing 98.8–99.0% recovery column at a 4 mL min−1 flow rate. In this work, the amounts of
and 1.6–1.9% R.S.D. Thus, this solvent mixture was chosen for analyte added were constant. The results were given in Fig. 3.
desorption of all heavy metals studied in further experiments. The adsorption of the metal ions with 500 mg activated car-
The recovery of Co, Cu, Ni and Pb was investigated. Two hun- bon was not affected by sample volume below 1300 mL. Above
dred and fifty millilitres of solution was percolated through the this volume the percent sorption decreased for the analytes.
column with a flow rate of 4 mL min−1 . The elution step was In the present study 1300 mL of sample solution was adopted
performed using a flow rate of 0.6 mL min−1 . The recoveries for the preconcentration of the investigated ions from drinking
of Co, Cu, Ni and Pb using 2 M nitric acid in acetone as elu- water samples, the adsorbed metals can be eluted with 5 mL of
ent are shown in Table 3. The results show that the recoveries 2 M HNO3 in acetone and a preconcentration factor of 260 is
higher than 98.5% with R.S.D. values less than 2% with low achieved by this technique (Fig. 4).
blank value could be obtained for all metal ions, while using Common cations such as sodium, calcium, and magnesium
acids with further concentration lead to higher blank value and are always found in water samples and have the capability to
higher detection limit. compete with many metal ions to complex with ligands, and
The volume of the eluent was varied from 2 to 6 mL. In the common anions such as nitrate and chloride have the ability to
case of 500 mg of DHMP-AC, the volume of eluent >5 did bind with metal ions. Therefore, in their presence the efficiency
not affect the recoveries of the metals. In this study, 500 mg of the impregnated ligand to bind metal ions may be reduced
of DHMP-AC and 5 mL of eluent are ideal for the preconcentra- resulting in a reduction of the recovery.
tion of metal at a concentration of 50 ␮g or less in the solution The effects of matrix ions in water samples on the recovery
having volumes up to 1300 mL. of Cu, Co, Pb and Ni were also investigated (Table 4). There are
In order to determine the concentration of the DHMP required
for quantitative recoveries, the proposed method was applied, Table 4
changing the DHMP concentration from 5 to 25 mg per 500 mg Effects of the matrix ions on the recoveries of the examined metal ions (n = 3)
AC. It was found that, the recovery of the metal ions increased Ion Added as Tolerance limit ion (mg L−1 )
with increasing concentrations of DHMP added and reached a
Na+ NaCl 1000
constant value with at least 20 mg. On this basis, studies were K+ KCl 1000
carried out at a DHMP concentration of 20 mg. This concen- Cl− NaCl 1000
tration of ligand is enough for the preconcentration procedure Mg2+ MgCl2 600
because of the very low level of the investigated metal ion con- HCO3 − NaHCO3 1000
centrations in natural waters. PO4 3− Na3 PO4 500
Zn2+ , Cd2+ , Ba2+ , Ca2+ , Nitrate salt 100
The influence of flow rate on the adsorption of trace metals Ag+ , Al3+ , Cr3+ , Hg2+
was studied. Flow rate in the range of 2–4 mL min−1 had no
 M. Ghaedi et al. / Journal of Hazardous Materials 142 (2007) 272–278 277

Table 5 Table 7
Optimum value of method Recovery of trace elements from spiked liver sample after preconcentration on
activated carbon modified with DHMP (n = 3)
Parameter Optimum value
Analyte Added (␮g g−1 ) Found (␮g g−1 ) R.S.D. (%) Recovery (%)
pH 6.0
Amount of DHMP (mg) 20 Co 0 1.45 1.5 –
Amount of AC (g) 0.5 5 6.62 1.0 103.4
Eluting agent 5 mL of 2 mol L−1 HNO3 in acetone
Ni 0 1.57 1.7 –
Flow rate (mL min−1 ) 4
5 6.68 1.1 102.2
Volume of sample (mL) 250
Cu 0 6.9 0.9 –
5 12.1 0.6 104.0
Pb 0 0.73 1.4 –
no interferences in the presence of large amounts of alkaline, 5 5.78 1.0 101.0
alkaline earth metals and main anions in the water samples. The
matrix metal ions are not retained on the column because of their
Table 8
very low stability constants of DHMP complexes. The optimum
Recovery of trace elements from spiked spring water sample after preconcen-
conditions of method are presented in Table 5. tration on activated carbon modified with DHMP
At optimum condition the response are linear over concentra-
Analyte Added (␮g L−1 ) Found (␮g L−1 ) R.S.D. (%) Recovery (%)
tion range of 0.04–1.1 ␮g mL−1 for Ni2+ and 0.04–1.0 for Cu2+ ,
Pb2+ and Co2+ . The sorption capacity was determined by satu- 0 BL – –
rating 1 g of solid phase in bath method. The loading capacities Co 50 63.4 1.4 –
75 90.0 0.9 111.9
are 0.54, 0.53, 0.63 and 0.45 mg g−1 for Ni2+ , Co2+ , Cu2+ and
Pb2+ . The ability of method for repeatable recovery of trace ion 0 BL – –
are 99.0, 98.9, 99.2 and 98.8 with R.S.D. of 1.4, 1.3, 1.2 and Ni 50 83.4 1.5 –
75 109.2 1.0 102.4
1.4 for Ni2+ , Co2+ , Cu2+ and Pb2+ . The method detection limits
were calculated by three times the standard deviation (n = 15) 0 43.2 – –
Cu 50 94.5 1.3 102.6
of the blank. The values were 3.4 ␮g L−1 for Co, 2.9 ␮g L−1 for
75 120.2 0.9 102.8
Cu, 3.5 ␮g L−1 for Ni and 8.4 ␮g L−1 for Pb. These limits were
based on 50 mL of blank undergoing the preconcentration. They 0 BL 2.0 –
Pb 50 72.3 1.5 –
can be improved by increasing the sample volume. 75 98.3 0.9 104

BL: below linear range.

3.2. Recovery of spikes from real samples
4. Conclusion
The recoveries of the trace metal ions from a water samples
were studied. As can be seen in Tables 6–8, satisfactory results
DHMP loaded on activated carbon is a sensitive and accu-
were obtained for the elements examined. These results confirm
rate method for the determination of Co (II), Cu (II), Ni (II), and
the validity of the proposed method for the preconcentration of
Pb (II) in low concentrations. The results presented (Tables 1–8)
the investigated ions. The proposed method was applied for the
have confirmed its applicability to the separation and preconcen-
determination of Co, Cu, Ni, and Pb in natural water samples,
tration of these ion contents. This method is simple and there is
leaves of spinach and liver samples. The results are given in
no need for an elaborate cleanup procedure, since the adsorbed
Tables 6–8. The recoveries of the metal ions were in the order
metals are simply eluted with 5 mL of 2 mol L−1 HNO3 in ace-
of 98–104%. The R.S.D. values were less than 3%.
tone. The adsorbent for Co (II), Cu (II), Ni (II), and Pb (II)
preconcentration can be used for at least five successive analyses
without a considerable change. The method due to advantages
Table 6 such as high reliability, reproducibility, sensitivity, and high
Recovery studies of trace metal ions in leaves of spinach
tolerance limit of common ions and low detection limit is a pow-
Analyte Added (␮g g−1 ) Found (␮g g−1 ) R.S.D. (%) Recovery (%) erful tool for rapid and sensitive determination of these ions ion
Co 0 56.3 2.2 – in various media. The accuracy and precision of the proposed
75 132.3 0.9 101.3 SPE method was reported in term of recovery (%) ranging from
Ni 0 80.6 1.4 – 98 to 104%, and R.S.D. (%) ranging from 0.6 to 3.0%.
75 154.6 0.8 98.7
Cu 0 70.3 1.6 – References
75 144.1 0.9 98.4
Pb 0 45.6 1.8 – [1] S.L.C. Ferreira, C.F. Brito, A.F. Dantas, N.M.L. Araujo, A.C.S. Costa,
75 121.9 1.0 101.75 Nickel determination in saline matrices by ICP-AES after sorption on
Amberlite XAD-2 loaded with PAN, Talanta 48 (1999) 1173–1179.
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