Talanta 71 (2007) 136–140

Determination of trace metals by ICP-OES in plant materials after

preconcentration of 1,10-phenanthroline complexes on activated carbon
Barbara Mikuła ∗ , Bożena Puzio
Institute of Chemistry, Silesian University, 40-006 Katowice, Poland
Received 11 February 2004; received in revised form 14 February 2006; accepted 17 March 2006
Available online 8 May 2006

Abstract
In this work, 1,10-phenanthroline was used as a complexing agent for the separation and preconcentration of Cd(II), Co(II), Ni(II), Cu(II) and
Pb(II) on activated carbon. The metals were adsorbed on activated carbon by two methods: static (1) and dynamic (2). The optimal condition for
separation and quantitative preconcentration of metal ions with activated carbon for the proposed methods was for (1) in the static methods in
the pH range 7–9. The desorption was found quantitative with 8 mol dm−3 HNO3 for Cd(II) (92.6%), Co(II) (95.6%), Pb(II) (91.0%), and with
3 mol dm−3 HNO3 for Cd(II) (95.4%), Pb(II) (100.2%). The preconcentration factor was 100 with R.S.D. values between 1.0 and 2.9%. For (2),
the dynamic method (SPE), the pH range for the quantitative sorption was 7–9. The desorption was found quantitative with 8 mol dm−3 HNO3
for Cd(II) (100.6%), Pb(II) (94.4%), and reasonably high recovery for Co(II) (83%), Cu(II) (88%). The optimum flow rate of metal ions solution
for quantitative sorption of metals with 1,10-phenanthroline was 1–2 cm3 min−1 whereas for desorption it was 1 cm3 min−1 . The preconcentration
factor was 50 for all the ions of the metals with R.S.D. values between 2.9 and 9.8%.
The samples of the activated carbon with the adsorbed trace metals can be determined by ICP-OES after mineralization by means of a high-
pressure microwave mineralizer. The proposed method provides recovery for Cd (100.8%), Co (97.2%), Cu (94.6%), Ni (99.6%) and Pb (100.0%)
with R.S.D. values between 1.2 and 3.2%.
The preconcentration procedure showed a linear calibration curve within the concentration range 0.1–1.5 ␮g cm−3 . The limits of detection values
(defined as “blank + 3s” where s is standard deviation of the blank determination) are 5.8, 70.8, 6.7, 24.6, and 10.8 ␮g dm−3 for Cd(II), Pb(II),
Co(II), Ni(II) and Cu(II), respectively, and corresponding limit of quantification (blank + 10s) values were 13.5, 151.3, 20.0, 58.9 and 33.2 ␮g dm−3 ,
respectively.
As a result, these simple methods were applied for the determination of the above-mentioned metals in reference materials and in samples of
plant material.
© 2006 Elsevier B.V. All rights reserved.

Keywords: ICP-OES; 1,10-Phenanthroline; Activate carbon

1. Introduction aqueous solution by simply adjusting the pH to an adequate

The determination of elements is usually preceded by their
separation from the major components (matrix) of the sample,
and it involves simultaneous preconcentration of the trace com-
ponents.
Activated carbon is widely use a trace collector for multi-
element preconcentration in analysis of water, high-purity sub-
stances, vegetable sample, etc. There are two general approaches
to metal preconcentration using activated carbon, namely from
∗ Corresponding author. Fax: +48 32 599978.
E-mail address: bmikula@us.edu.pl (B. Mikuła).
value and by using a chelating agent.
A literature survey revealed that enrichment of heavy met-
als on actived carbon is usually carried out after chelation with
8-hydroxyquinoline [1–6], cupferron [7,8], dithiocarbamates
[9–12], dithizone [13,14], potassium ethylxanthate [15,16],
chrome azurol S [17] or the ammonium salt of dithiophospho-
ric acid O,O-diethyl ester [18]. Following desorption in a small
volume of nitric acid, the metal concentration are measured by
AAS or ICP-OES.
Zhang et al. [19] presents a method where by trace elements
are adsorbed in NH4 Cl–NH3 medium on activated carbon and
then determined by microwave plasma torch atomic emission
spectrometry.

0039-9140/$ – see front matter © 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.talanta.2006.03.041
 B. Mikuła, B. Puzio / Talanta 71 (2007) 136–140
1,10-Phenantroline has been used as a complexing reagent
for preconcentration trace metals [20–24].
Problems in using activated carbons for analytical work are
related to the large variations in the physical and chemical
properties of the different sources of carbon and difficulty in
obtaining full desorption of organic and inorganic analytes.
The aim of the present work was to investigate activated car-
bon for the preconcentration and separation of cadmium, copper,
nickel, cobalt and lead traces. 1,10-Phenantholine was used as
a complexing agent. The model system was used for the deter-
mination of heavy metals in plant materials.
2. Experimental
2.1. Apparatus and conditions
Mineralizer M-9 (WSL, Bytom); Mineralizer microwaves
UniClever (Plasmatronika); Spectroflame, ICP Model M (Spec-
tro Analytical Instruments).
The sequential spectrometer was used with following param-
eters: frequency, 27.12 MHz; power, 1.1 kW; demountable
quartz torch, Ar/Ar/Ar; coolant gas Ar, 14.0 l min−1 ; auxilliary
gas Ar, 0.5 l min−1 ; nebulizer gas Ar, 1.0 l min−1 ; nebulizer
pressure, 2.4 bar; glass spray chamber according to Scott, sam-
ple flow rate, 1.0 ml min−1 ; observation height 11 mm; holo-
graphic grating, 2400 grooves mm−1 ; dispersion of grating in
the first reciprocal order, 0.55 nm mm−1 ; wavelength range of
monochromator 165–460 nm; integration time, 3 s. The wave-
lengths for Cd, 226.50 nm; Pb, 220.35 nm; Ni, 352.45 nm; Co,
228.62 nm; Cu, 324.75 nm.
2.2. Reagents
Standard solutions Cd(II), Cu(II), Pb(II), Ni(II) and Co(II)
of concentration 1 mg dm−3 (Merck). Activated carbon (AC),
powder (J.T. Baker); 1,10-phenanthroline (POCH); conc. HNO3
(POCH); H2 O2 30% (POCH). All reagents used were of analyti-
cal or ultrapure grade. The water used for synthetic solutions was
doubly distilled in a quartz apparatus. The 1,10-phenanthroline
was prepared by dissolving 0.496(5) g of the reagent in 0.25 dm3
of doubly distilled water.
2.3. Preconcentration procedure
The procedure of the concentration of cadmium, copper,
nickel, cobalt and lead by adsorption on activated carbon with
the use of 1,10-phenanthroline was as follows.
Activated carbon powder (J.T. Baker) was kept in nitric acid
(1:1) solution for 24 h so as to remove the metal ions and other
impurities sorbed on it. Then it was filtered and rinsed with
doubly distilled water until it was free from acid. It was dried
in a drying furnace at 110 ◦ C. The complexing reagent and the
activated carbon were added to a beaker with the 50 cm3 model
solution containing 5 ␮g each Pb(II), Co(II), Cu(II), Ni(II) and
Cd(II). The pH of the solution was adjusted to desired value
(pH ≈ 7). The required pH of the solution was adjusted by
adding 0.1 mol dm−3 hydrochloric acid or 0.1 mol dm−3 sodium
hydroxide.
137
The activated carbon, after the metals sorption, was rinsed
with water and dissolved in 10 cm3 of 3 and 8 mol dm−3 . The
metals concentration was determined with ICP-OES.
2.3.1. Preconcentration of activated carbon by static
method
A 10 cm3 of the complexing reagent (0.01 mol dm−3 1,10-
phenanthroline solution) and 0.1 g activated carbon were added
to the sample and diluted to 50 cm3 . The mixture was stirred
with a magnetic bar for 25 min. Then the sample was prepared
in two ways.
In the first method, the sample was filtered through a fil-
ter paper, rinsed with water and dissolved in 10 cm3 of 3 and
8 mol dm−3 HNO3 .
In the second method, the mixture was filtered through a
small filter paper (Millipore). Then a filter paper covered with
activated carbon was mineralized by adding 3 cm3 of nitric acid
in a microwave mineralizer. The obtained solution was diluted
to the volume of 10 cm3 .
2.3.2. Column method
The 500 mg of activated carbon was packed in a column SPE-
PP (polypropylene-size 3 cm3 ).
The sample solution containing 5 ␮g Cd(II), Cu(II), Pb(II),
Ni(II) and Co(II) and 2 cm3 of 1,10-phenanthroline solution
(pH ≈ 7.0) was passed through the columns filled with acti-
vated carbon after adjusting its pH to an optimum value at a
flow rate of 1 cm3 min−1 used by BAKERBOND SPE system.
The metals were then desorbed from the column with 10 cm3 of
8.0 mol dm−3 nitric acid.
2.3.3. Mineralization of plant materials
The 1 g sample of potatoes of 1 mm grain size, dried previ-
ously to the constant air-dry mass was mineralized by adding
10 cm3 of HNO3 and H2 O2 (t ∼ = 190 ◦ C) in a mineralizer M-9.
Then the obtained solution was diluted to the volume of about
50 cm3 . The prepared samples were neutralized to pH 7–8 with
the sodium hydroxide solution.
3. Results and discussion
The application of activated carbon for enrichment of trace
elements in different materials is often presented in the analytical
procedures. However, better results are to be expected when
the metals are complexed with organic chelating agents before
adsorption on AC. For these reasons 1,10-phenathroline was
choosen in this work as a complexing agent for enrichment on
AC.
It was proved experimentally that nitric acid slightly influ-
enced the simultaneous determination of Pb(II), Co(II), Cu(II),
Ni(II) and Cd(II) by the ICP-OES method. Model standard
curves (for the solutions containing the matrix reagents) were
linear in the concentration range 0.1–1.5 ␮g cm−3 for Cd, Cu,
Ni, Co and 0.2–1.5 ␮g cm−3 for Pb.
In the literature there are two methods proposed. One of them
requires the complex compound to be added to the sample first
and then adsorbed on the activated carbon. In the second, the
138 B. Mikuła, B. Puzio / Talanta 71 (2007) 136–140

Table 1
Effect on the concentration of elution solutions on results of determination of
heavy metals after preconcentration on AC with 1,10-phenanthroline by the
static method
CHNO3 (mol dm−3 ) Recovery (%)

Cd Co Cu Ni Pb

3 95.4 81.4 45.2 21.4 100.2

4 95.2 94.2 50.8 21.8 99.4
5 94.0 86.3 69.8 22.0 98.6
6 93.6 90.0 70.4 35.4 96.0
7 93.2 93.2 67.6 36.0 93.0
8 92.6 95.6 78.4 42.6 92.6
9 86.8 93.8 74.1 41.2 90.0
10 84.4 93.6 70.5 46.6 85.6

pH 7–8; 10 cm3 eluent volume; ligand: 0.01 mol dm−3 1,10-phenanthroline.

Fig. 1. The effect of pH on the recovery of metals with 1,10-phenanthroline by
static method.
activated carbon is modified with a complexing reagent before
contact with the ions of the metal. In this work the first method
was applied.
In order to obtain quantitative recoveries of the metal ions
on the activated carbon, the preconcentration procedure was
optimized for the various analytical parameters such as sam-
ple preparation, pH, amount of activated carbon, complexing
reagent, factor preconcentration and the stirring time were stud-
ied.
The effect of pH on the separation of metal ions was stud-
ied in the range 2–10, keeping the other parameters constant.
As shown in Fig. 1, the optimum pH range for quantitative
recoveries of Cu, Ni, Pb, Cd and Co was above 7. The effect of
amount of activated carbon and 1,10-phenanthroline was exam-
ined in the range 50–300 mg and 5–20 cm3 of 0.01 mol dm−3
solution, respectively. In the proposed procedure, 100 mg AC
and 10 cm3 of 0.01 mol dm−3 1,10-phenanthroline were recom-
mended for quantitative sorption of metal ions. For the 300 mg
AC and above, the preconcentration was not quantitative. The
stirring time of the solution was tested in the range 10–40 min.
The result of the stirring time effect demonstrated that the sorp-
tion of the complex was quantitative after 25 min.
For the group desorption Pb(II), Co(II), Cu(II), Ni(II) and
Cd(II), 8 mol dm−3 of eluent (nitric acid) proved to be efficient.
However, for the desorption of Cd(II) and Pb(II), it was suffi-
cient to apply 3 mol dm−3 HNO3 as an eluent, obtaining almost
100% recovery of metals (Table 1). The results showed that des-
orption was not quantitative for nickel and copper. Therefore,
the activated carbon with adsorbed metals was mineralized with
3 cm3 of nitric acid. The results presented in Table 2 confirm
the efficiency of preconcentration of metals on activated car-
bon using 1,10-phenanthroline. Difficulties with the elution of
adsorbed metals are probably due to formation of metal com-
plexes strongly adsorbed on activated carbon.
This procedure was also applied to the preconcentration of
the investigated elements by the column method. The influ-
ence of the flow rate in the range 1.0–3.0 cm3 min−1 on the
sorption of metals into SPE and elution was studied. The pecon-
centration and elution flow rate was quantitative for this range
and hence 1.0 cm3 min−1 was choosen for preconcentration and
elution in the later studies. Table 2 shows the results of the
preconcentration of the complexes of metal ions with 1,10-
phenanthroline by the static and column method. The results
of the preconcentration in column method gave good R.S.D.
but recoveries of the elements were lower than in the static
method. Quantitative preconcentration and elution of metals
was obtained by increasing the dilution of 5 ␮g metal ions in
the range 25–500 cm3 (final volume: 10 cm3 ). The enrichm-
ment factor was found to be approximately 50. The limit of
detection values (defined as “blank + 3s” where s is the stan-
dard deviation of the blank determination) were 5.8, 70.8,
6.7, 24.6, and 10.8 ␮g dm−3 for Cd(II), Pb(II), Co(II), Ni(II)
and Cu(II), respectively. The corresponding limit of quantifi-
cation (blank + 10s) values were 13.5, 151.3, 20.0, 58.9 and
33.2 ␮g dm−3 , respectively.

Table 2
Results of analysis of metal ions by ICP-OES after preconcentration on AC
M Column method, elution Static method

Recovery (%) R.S.D. (%) Elution Mineralized AC

Recovery (%) R.S.D. (%) Recovery (%) R.S.D. (%)

Cd 100.6 2.9 92.6 2.9 100.8 3.1

Co 83.0 9.0 95.4 2.6 97.2 3.2
Cu 87.6 9.4 78.6 1.0 94.6 2.4
Ni 24.6 9.0 39.4 3.0 99.6 1.2
Pb 94.4 9.8 91.0 2.7 100.0 2.3

pH 7–8; eluent: 10 cm3 of 8 mol dm−3 HNO3 ; ligand: 0.01 mol dm−3 1,10-phenanthroline.
 B. Mikuła, B. Puzio / Talanta 71 (2007) 136–140 139

Table 3
Results of determining of Cd, Pb, Co, Ni and Cu in references material (oriental tobacco leaves, CTA-OTL-1) by ICP-OES methods after preconcentration of metals
with 1,10-phenanthroline on activated carbon
Metal Certified value (␮g g−1 ) Determined (␮g g−1 )

Column method, elution Static method

Elution Mineralize AC

Cd 1.12 ± 0.12 1.07 ± 0.13 1.05 ± 0.06 1.15 ± 0.07

Pb 4.91 ± 0.80 5.25 ± 0.1 5.31 ± 0.08 5.02 ± 0.01
Co 0.879 ± 0.039 0.70 ± 0.09 0.84 ± 0.06 0.89 ± 0.01
Ni 6.32 ± 0.65 1.28 ± 0.07 1.55 ± 0.08 6.25 ± 0.09
Cu 14.1 ± 0.5 14.1 ± 0.1 6.0 ± 0.1 13.9 ± 0.1

pH 7–8; eluent: 10 cm3 of 8 mol dm−3 HNO3 ; ligand: 0.01 mol dm−3 1,10-phenanthroline.

Different amounts of the metals were preconcentrated by Preconcentrating of heavy metals on activated carbon by
the proposed methods in the range 1.0–15 ␮g in 500 cm3 solu- the static and column methods, using elution with proper acid,
tion. The R.S.D. and the average recovery preconcentration were recovery of some metals was not qantitative. That is why
comparable (Table 2). mineralization of activated carbon with adsorbed metals was
In order to establish the validity of the proposed procedure, preferred.
the method has been applied to the determination of the content
of the studied elements in standard reference material-oriental 4. Conclusion
tobacco leaves (CTA-OTL-1). The results of the metal analyses
after preconcentration on activated carbon using two different The proposed static and column methods of the preconcen-
methods (the static and column methods) are reported in Table 3. tration of Co(II), Pb(II), Ni(II), Cd(II) and Cu(II) as complexes
The use of both methods gave good recovery for cadmium, lead with 1,10-phenanthroline with the use of activated carbon were
and cobalt. Only the recovery obtained for copper and nickel in found simple and accurate. The static method may be used for
the references material was significantly lower, but recovery of preconcentration and determination of Cd, Co and Pb. For pre-
metals was comparable with the values obtained for the model concentration of Cd and Pb, the static and column methods
solutions, and can also be applied to determine the approximate may be applied. However, for the group determination of the
contents of these metals. metals, mineralization of activated carbon with adsorbed met-
The AC mineralization method allowed to obtain about 100% als was proposed. It was found that there was no significant
recovery. difference between achieved results by proposed methods and
These results proved also that the procedure can be applied certified results. The methods of preconcentration of heavy met-
satisfactorily for the determination of metals in contaminated als can be used for their determination in plant materials by the
samples of plant materials. The preconcentration procedures ICP-OES.
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and Cu(II) in potatoes by ICP-OES (Table 4). The R.S.D. val-
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