Food Chemistry 147 (2014) 302–306

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Food Chemistry
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Analytical Methods

Preconcentration of heavy metals on activated carbon and their

determination in fruits by inductively coupled plasma optical
emission spectrometry
Barbara Feist ⇑, Barbara Mikula
Department of Analytical Chemistry, Institute of Chemistry, University of Silesia, 40-006 Katowice, Szkolna 9, Poland

a r t i c l e i n f o a b s t r a c t

Article history: A method of separation and preconcentration of cadmium, cobalt, copper, nickel, lead, and zinc at trace level
Received 27 April 2012 using activated carbon is proposed. Activated carbon with the adsorbed trace metals was mineralised using
Received in revised form 17 September a high-pressure microwave mineraliser. The heavy metals were determined after preconcentration by
2013
inductively coupled plasma optical emission spectrometry (ICP-OES). The influence of several parameters,
Accepted 1 October 2013
Available online 10 October 2013
such as pH, sorbent mass, shaking time was examined. Moreover, effects of inorganic matrix on recovery of
the determined elements were studied. The experiment shows that foreign ions did not influence recovery
of the determined elements. The detection limits (DL) of Cd, Co, Cu, Ni, Pb, and Zn were 0.17, 0.19, 1.60, 2.60,
Keywords:
Simultaneous determination
0.92 and 1.50 lg L1, respectively. The recovery of the method for the determined elements was better than
Multi element preconcentration 95% with relative standard deviation from 1.3% to 3.7%. The preconcentration factor was 80. The proposed
Activated carbon method was applied for determination of Cd, Co, Cu, Ni, Pb, and Zn in fruits materials. Accuracy of the pro-
Inductively coupled plasma optical emission posed method was verified using certified reference material (NCS ZC85006 Tomato).
spectrometry Ó 2013 Elsevier Ltd. All rights reserved.
Fruits

1. Introduction none)ethylenediimine (Ghaedi et al., 2009), ammonium

pyrrolidinedithiocarbamate (Daorattanachai, Unob, & Imyim,
Contemporary instrumental techniques, such as inductively 2005), methyl thymol blue (Ensafi & Ghaderi, 2008), bis-(salicylal-
coupled plasma optical emission spectrometry (ICP-OES) or atomic dehyde)-propane-1,3-diimine (Ghaedi et al., 2008), pyrocatechol
absorption spectrometry (AAS) allow for simultaneous or sequen- violet (Narin, Soylak, Elci, & Dogan, 2000), 8-hydroxyquinoline
tial determination of a large number of elements. Unfortunately, (Cerutti, Silva, Gasquez, Olsina, & Martinez, 2003), O,O-diethyldi-
concentrations of heavy metals in fruits are usually bellow detec- thiophosphate (Quinaia, De Silva, Rollemberg, & Curtius, 2001),
tion limits. Therefore, the trace metals have to be preconcentrated thiourea and bromide ion (Madrakian, Afkhami, & Esmaeili, 2003),
before the measurement. 1-(2-thiazolylazo)-2-naphtol (Starvin & Rao, 2004a, diarylazobi-
Activated carbon is still the most important sorbent due to its sphenol (Starvin & Rao, 2004b), pyrogallol red (Ensafi, Khayamian,
large surface area, high adsorption capacity, porous structure and & Karbasi, 2003), zinc-piperazinedithiocarbamate (Cesur, Macit, &
selective adsorption. Activated carbon has been widely used for Bati, 2000), and ethylenediamine (Li, Chang, Zou et al., 2009).
many purposes both in the laboratory and industrial settings. This The aim of this paper was to investigate the performance of
is due to its ability to adsorb organic compounds and organic metal activated carbon in absence of a complexing reagent in preconcen-
complexes. Since its introduction in analytical chemistry, enrich- tration and separation of cadmium, copper, nickel, cobalt, lead, and
ment of trace metals using unmodified and modified activated car- zinc traces. Activated carbon with the adsorbed trace metals was
bon has been carried out with very high preconcentration factors mineralised using a high-pressure microwave mineraliser and me-
in various matrices, e.g. of water, vegetable sample, sediment, fish, tal ions were determined using ICP-OES technique.
meat, etc. (Cerutti et al., 2003; Chakrapani, Mahanta, Murty, &
Gomathy, 2001; Jankowski, Jackowska, & Łukasiak, 2005; Jankow-
ski, Yao, Kasiura, Jackowska, & Sieradzka, 2005; Su et al., 2003). 2. Experimental
A literature survey revealed that enrichment of heavy metals on
activated carbon can be carried out after chelation with 1,10-phe- 2.1. Apparatus
nanthroline (Mikula & Puzio, 2007), bis(2-hydroxyacetophe-
An optical emission spectrometer, ICP Model M (Spectro Analyt-
⇑ Corresponding author. Tel.: +48 322592115; fax: +48 322599978. ical Instruments, Germany) was used for determination of Cd, Co,
E-mail address: [Link]@[Link] (B. Feist). Cu, Ni, Pb, and Zn. The sequential spectrometer was used with fol-

0308-8146/$ - see front matter Ó 2013 Elsevier Ltd. All rights reserved.
[Link]
 B. Feist, B. Mikula / Food Chemistry 147 (2014) 302–306 303

lowing parameters: frequency, 27.12 MHz; power, 1.1 kW; The fruit material was stored in labelled, tightly sealed polyethyl-
demountable quartz torch, Ar/Ar/Ar; coolant gas Ar, 14.0 L min1; ene containers.
auxiliary gas Ar, 0.5 L min1; nebulizer gas Ar, 1.0 L min1; nebu- The fruit sample was mineralised in the following way: 0.5 g of
lizer pressure, 2.4 bar; glass spray chamber according to Scott, the sample was digested in 6 mL of concentrated nitric acid using a
sample flow rate, 1.0 mL min1; observation height 11 mm; holo- microwave pressure mineraliser. The following program was ap-
graphic grating, 2400 grooves mm1; dispersion of grating in the plied: step 1 (time: 3 min, power: 60%), step 2 (time: 5 min, power:
first reciprocal order, 0.55 nm mm1; wavelength range of the 80%), and step 3 (time: 7 min, power: 100%). Then, the obtained
monochromator 165–460 nm. The wavelengths (integration time) solution was diluted to a volume of about 50 mL. Next, the sample
were 228.80 nm (3 s), 228.62 nm (4 s), 324.75 nm (3 s), was prepared using the preconcentration procedure. The same pro-
221.65 nm (5 s), 220.35 nm (5 s), 213.87 (4 s) for Cd, Co, Cu, Ni, cedure was used for the blank solutions.
Pb, and Zn, respectively. In the case of certified reference material (NCS ZC85006 Toma-
A UniClever microwave mineraliser (Plazmatronika BM-1z, Po- to), 0.5 g of the sample was digested in 6 mL of concentrated nitric
land) was used for dissolution of the fruits and tomato samples. An acid using a microwave pressure mineraliser and the program de-
N-1570 pH-metre (Mera-Elwro, Poland) with a glass ESAgP-309 scribed above.
electrode was employed for measurement of pH values in the
aqueous phase. A Pulverisette 14 variable speed rotor mill (Fritsch,
Germany) was used to obtain a homogeneous sample.
3. Results and discussion

2.2. Reagents and solutions 3.1. Effect of pH

All chemicals were of analytical grade. All reagents were dis- The influence of pH on the recovery was studied in the range
solved and diluted with high purity water obtained from Milli-Q from 2 to 11. The effect of pH on the recoveries of the studied ions
system. The following reagents were used in the experiment: acti- is shown in Fig. 1. It can be seen that all the metal ions were ad-
vated carbon (AC), powder (J.T. Baker, Phillipsburg, USA), nitric sorbed poorly at pH < 3. A quantitative recovery (>90%) for the
acid, hydrochloric acid, hydrogen peroxide, sodium hydroxide, ni- studied ions was obtained in the pH range of 6–11 for Cd, Co and
trates (V) of sodium, potassium, magnesium, calcium, strontium, Ni, 5–11 for Cu, 4–6 and 10–11 for Pb and 6–7 and 10–11 for Zn.
barium, aluminium, iron(III), manganese(II) (all from POCh, Gliw- So, a pH of 6.0 was selected as the compromising condition. The
ice, Poland), stock standard solutions of cadmium, cobalt, copper, adsorption experiments were performed in triplicates.
nickel, lead, and zinc with concentration of 1000 mg L–1 (Merck,
Darmstadt, Germany). Potassium phthalate buffer solution was
prepared by adding an appropriate amount of potassium phthalate
to sodium hydroxide solution until pH 6 was obtained. Activated 3.2. Effect of the mass of sorbent
carbon was kept in nitric acid (1:1) solution for 24 h so as to re-
move the metal ions and other impurities sorbed on it. Then it The effect of mass of the sorbent activated carbon on the sorp-
was filtered and rinsed with deionized water until it was free from tion of cadmium, cobalt, copper, nickel, lead, and zinc was tested in
acid. It was dried in a drying furnace at 110 °C. The accuracy of the the range of 25–150 mg. The results showed that a quantitative
method was assessed by analysing the certified reference material adsorption for metal ions was obtained in the range of 25–
(CRM): NCS ZC85006 Tomato (China National Analysis centre for 150 mg. In the subsequent experiment, 50 mg of AC were used.
Iron & Steel 2000).

2.3. Procedures 3.3. Effect of stirring time

2.3.1. Preconcentration of activated carbon by static method In this work, different stirring time (range from 10 to 120 min)
50 mg of activated carbon were added to 100 mL of solution was studied for the extraction of Cd, Co, Cu, Ni, Pb, and Zn by acti-
containing 1 lg of Cd and Co, 5 lg of Pb and Ni, and 10 lg of Cu vated carbon. It was found that the recovery of the metal ions is
and Zn. The pH value of the obtained solution was adjusted to 6 close to 100% even if adsorption process was performed for
using the phthalate buffer. Then, the solution was stirred for 20 min. Therefore, the stirring time of 20 min was chosen as the
20 min to facilitate adsorption of the metal ions onto the sorbent. adsorption equilibrium time. It indicated that kinetics of equilib-
Next, the solution was filtered through a paper filter. The paper fil- rium is very fast.
ter covered with activated carbon was mineralised by adding 3 mL
of nitric acid in microwave mineraliser in the conditions which are
described in Section 2.3.2. The solution was diluted to 5 mL with 120
water (final volume) and analysed. The concentration of metals
100
was determined by ICP-OES. The calibration samples were pre-
pared using 100 mL of the standard solution containing analytes Cd
Recovery (%)

80
in the ranges: 0.1–2 lg of Cd and Co, 0.5–10 lg of Ni and Pb, 1– Co
20 lg of Cu and Zn. In the next step, calibration samples were pre- 60
Cu
pared using preconcentration procedure described above. 40 Ni

2.3.2. Preparation of the plant material for the investigations 20 Pb

Apple and pear were selected for the analysis. The analysed 0 Zn
material was cleaned, broken up and dried in a laboratory drier 2 3 4 5 6 7 8 9 10 11
at a temperature of 50 °C for 48 h. Dried apple and pear were
pH
ground in a high-speed rotor mill (Fritsch, Germany), in order to
obtain a homogeneous sample with grain diameter of 0.5 mm. Fig. 1. Effect of pH on adsorption of the elements studied.
304 B. Feist, B. Mikula / Food Chemistry 147 (2014) 302–306

3.4. Maximum sample volume and enrichment factor These limits were based on using 100 mL of blank undergoing
the preconcentration.
In order to explore the possibility of enriching low concentra- Detection limits for ICP-OES technique were determined using
tions of analytes from large volumes, the effect of sample volume the following formula:
on the retention of the metal ions was also investigated. For this c
purpose, 50, 100, 200, 400, and 500 mL of sample solutions con- LOD ¼  IT  Sr  3=100;
ILþT  IT
taining 2 lg of Cd and Co, 10 lg of Pb and Ni, and also 20 lg of
Cu and Zn were investigated. It was found that quantitative recov- where c is the concentration of the element being determined in the
eries (>90%) were obtained for sample volumes up to 400 mL for standard, IL+T is the intensity of signal generated by the standard, IT
the studied ions. Above 400 mL, the recoveries of the analytes de- is the intensity of signal generated by the blank test, and Sr is the
creased slightly. The solution after mineralisation was diluted to relative standard deviation of the blank test.
5 mL with water (final volume), so the enrichment factor using this The relative standard deviations (RSD) of the eight replicate
method was 80. The effect of sample volume on adsorption is determinations are lower than 3.8% (3.0% Cd, 3.7% Co, 1.4% Cu,
shown in Fig. 2. 1.3% Ni, 2.1% Pb, and 1.3% Zn) what indicates that the method
has a good precision for the analysis of traces of Cd, Co, Cu, Ni,
3.5. Adsorption capacities Pb, and Zn in solution samples.
The characteristic performances of method presented in Table 1
The capacity of the adsorbent is an important factor to deter- show a good linearity range, low detection limits, high reproduc-
mine the amount of sorbent required for a quantitative adsorption ibility and low relative standard deviation for all elements. Satis-
of a specific amount of a metal ion from a solution. The sorption factory recoveries were obtained for the spiked analyte ions. The
process was performed for 1 h. In order to reach the ‘‘saturation’’, recoveries were higher than 95%, thus confirming the accuracy of
the initial concentrations of metal ions were increased till the pla- the proposed procedure.
teau values (adsorption capacity values) were obtained. The max-
imum adsorption capacity has been found to be 1.30, 1.20, 1.33, 3.8. Certified reference material analysis
1.78, 2.36, and 2.4 mg g1 for Cd, Co, Cu, Ni, Pb, and Zn, respec-
tively. The maximum adsorption capacities were determined for In order to check the accuracy of the ICP-OES measurements,
each ion individually. certified reference material (NCS ZC85006 Tomato) was analysed.
As it can be seen from Table 2, the accuracy of the determination
method is satisfactory. The results are in a good agreement with
3.6. Effect of foreign ions
the certified values. The only exclusion is lead, for which the ob-
tained result diverges from the certified value by 15%.
To verify the possibility of analytical applications for the pro-
posed method, the effects of some foreign ions, which can interfere
3.9. Analysis of fruit samples
with the determination of Cd, Co, Cu, Ni, Pb, and Zn, were exam-
ined under the optimised conditions. Solutions of 1.0 lg mL–1 of
The proposed method was applied to the determination of met-
Cd, Co, Cu, Ni, Pb, and Zn ions, and interference ions were analysed.
als in fruit samples (apple and pear). For the analysis of fruit sam-
The tolerance limit was set as the amount of ions causing recover-
ples, the standard addition method was used. The analytical results
ies of the examined elements to be less than 90%. The results show
are given in Table 3. As it can be seen, the recoveries of analytes
that 2000-fold K, Na, Ca, 1000-fold Mg, 500-fold Al, Fe, and 100-
were in the range of 96.7–101%. The results indicate that the pro-
fold Ba, Sr, Mn, Cr ions have no significant influence. Therefore,
posed method is reliable. Copper and zinc were present at higher
the tolerance limits of the foreign ions are very high.
concentrations and nickel at lower concentrations in the pear.
Samples of activated carbon with the adsorbed trace metals and
3.7. Detection limit and analytical precision sample fruit were mineralised using a high-pressure microwave
mineraliser. While preconcentrating heavy metals on activated
Under the selected conditions, eight portions of standard solu- carbon by the static methods, using elution with proper acid,
tions were enriched and analysed simultaneously following the recovery of some metals was not quantitative. If possible, the best
general procedure. In accordance with the definition of IUPAC, solution is the elimination of the elution step. The elution step or
the detection limit of the method was calculated based on three dissolving the main precipitate may have some drawbacks and
times the standard deviation of eight runs of the blank solution. risks due to incomplete and/or irreproducible extraction yield
The detection limits (3r) were found to be 0.17, 0.19, 1.60, 2.60, causing poor recoveries and precisions, irreproducible blank values
0.92, and 1.50 ng mL1 for Cd, Co, Cu, Ni, Pb, and Zn, respectively. from eluents, pollution of laboratory atmosphere and environment
especially due to acidic eluents (Mikula & Puzio, 2007). That is why
100
the mineralisation of activated carbon with the adsorbed metals
95 was preferred. In recent years, microwave ovens have been used
90 for acidic digestion of many types of food samples as an effective
Cd
Recovery (%)

85 alternative to classical digestion procedures. Thus, microwave

Co ovens are less easily contaminated, minimize losses of volatile ana-
80
Cu lytes, use small amounts of acids and shorten digestion times sub-
75 stantially in comparison with traditional methods (Bakkali, Martos,
Ni
70 Souhail, & Ballesteros, 2009).
65 Pb

60 Zn 3.10. Comparison with other method

50 100 200 400 500
Comparative information from some studies on preconcentra-
Volume (mL)
tion of metal ions by various methods for the significant digits
Fig. 2. Effect of sample volume on adsorption. are given in Table 4. As it may be seen from the data, the proposed
 B. Feist, B. Mikula / Food Chemistry 147 (2014) 302–306 305

Table 1
Specification of presented method at optimum conditions for each element (n = 8) and results of multi-elemental analysis ICP-OES method after preconcentration. Samples spiked
with 1 lg Cd and Co, 5 lg Pb and Ni, 10 lg Cu and Zn (p = 0.95).

Parameters Cd Co Cu Ni Pb Zn
Determined (lg) 1.00 ± 0.01 0.95 ± 0.01 9.85 ± 0.03 5.05 ± 0.04 4.83 ± 0.02 9.45 ± 0.03
Recovery (%) 100 95 98 101 97 95
RSD (%) 3.0 3.7 1.4 1.3 2.1 1.3
Calibration range (mg L1) 0.02–0.4 0.02–0.4 0.2–4 0.1–2 0.1–2 0.2–4
DL (lg L1) 0.17 0.19 1.60 2.60 0.92 1.50
Adsorption capacity (mg g1) 1.30 1.20 1.33 1.78 2.36 2.40

4. Conclusions
Table 2
Analysis of certified reference material NCS ZC85006 Tomato by ICP-OES. Results in The adsorption method with activated carbon in absence of a
mg kg1 (n = 4, p = 0.95).
complexing reagent can be successfully applied for determination
Metal Certified value ICP-OES Relative differences (%) of Cd, Co, Cu, Ni, Pb, and Zn in food samples. The preconcentration
Cd 0.82 ± 0.09 0.81 ± 0.07 1.2 factor of 80 was achieved. The recoveries of Cd, Co, Cu, Ni, Pb, and
Co 0.67 ± 0.04 0.62 ± 0.09 7.5 Zn in the presence of the matrix components containing the alka-
Cu 21.1 ± 2.5 20.8 ± 0.3 1.4 line and alkaline earth metal ions were good. The proposed meth-
Ni 2.23 2.09 ± 0.14 6.3
ods have good recovery and low detection limit values.
Pb 4.97 ± 0.54 4.23 ± 0.19 14.9
Zn 36.2 ± 3.1 35.7 ± 0.5 1.4 Consequently, the proposed procedures are fast, precise, reliable
and economic.
The presented method can be successfully applied to the pre-
method developed using non-modified AC has a relatively high
concentration and determination of analyte ions in food samples.
capacity and a low DL compared to other methods.

Table 3
Analysis of fruits and samples spiked with 1.0 mg kg1 of Cd and Co, 2.0 mg kg1of Cu and Pb and 3.0 mg kg1 of Zn and Ni (n = 6, p = 0.95).

Element Apple Pear

Found (mg kg1) Spiked fruits (mg kg1) Recovery (%) Found (mg kg1) Spiked fruits (mg kg1) Recovery (%)
Cd 0.32 ± 0.01 1.32 ± 0.02 100 0.33 ± 0.02 1.33 ± 0.03 100
Co 0.43 ± 0.01 1.42 ± 0.03 99 0.35 ± 0.01 1.36 ± 0.06 101
Cu 2.51 ± 0.05 4.48 ± 0.07 98.5 4.1 ± 0.1 6.09 ± 0.04 99
Ni 3.25 ± 0.07 6.35 ± 0.05 103 2.3 ± 0.1 5.30 ± 0.02 101
Pb 1.55 ± 0.05 3.50 ± 0.02 97.5 1.51 ± 0.06 3.48 ± 0.08 98.5
Zn 3.79 ± 0.08 6.7 ± 0.1 96.7 6.6 ± 0.3 9.6 ± 0.3 98.3

Table 4
Comparative data from studies about adsorption of heavy metals on activated carbon.

Chelating reagent Analyte Sorption DL (lg L1) PF Detection Sample References

capacity (mg method
g1)
Triethylenetetraamine TETA Cr, Fe, Pb 34.6, 36.5, 51.9 0.71, 0.35, 0.45 ICP-OES CRM – river sediment Zhang, Chang, Li, and He
(2010)
Ethylenediamine EDA Cr, Fe, Hg, 39.4, 28.9, 60.5, 0.28, 0.22, 0.09, 133.3 ICP-OES CRM – river sediment, Li, Chang, Hu et al. (2009); Li,
Pb 49.9 0.17 river water Chang, Zou et al. (2009)
1-(2-Formamidoethyl)-3-phenylurea FEP Cr, Cu, Fe, 39.3, 39.9, 77.8, 0.15, 0.41, 0.27, 100 ICP-OES CRM – river sediment, Tu et al. (2009)
Pb 17.3 0.36 river water
N,N0 -etylenebis-(etansulfonamide) ESEN Fe, Cr, Ni 0.38, 0.31, 0.06 10 ICP-OES Stream and cap water Karacan and Aslantas (2008)
Zincon Pb, Cr 17.9, 26.7 0.91, 0.65 150 ICP-OES CRM – river sediment, pig Li, Chang, Hu et al. (2009)
liver
1-Acylthiosemicarbazide Hg, Pb, Cu 67.8, 48.6, 78.2 0.12, 0.45, 0.20 100 ICP-OES CRM – river sediment, Gao et al. (2009)
river, lake, tap water
2-((2-Aminoethylamino) methyl)phenol Cu, Fe, Pb 12.1, 67.1, 16.2 0.27, 0.41, 0.16 50 ICP-OES CRM – peach leaf, tap, He et al. (2010)
lake water
4,6-Diydroxy-2-mercaptopyrimidine Ni, Co, Cu, 0.54, 0.53, 0.63, 3.5, 3.4, 2.9, 8.4 260 FAAS Spinach, liver, water Ghaedi, Ahmadi, and
DHMP Pb 0.45 Shokrollahi (2007)
Dithioxamide (rubeanic acid) DTO Cu, Ni, Co 0.56, 0.50, 0.47 0.5, 0.75, 0.80 330 FAAS River, tap and waste Ghaedi, Ahmadi, and Soylak
water, spinach, soil, blood (2007)
Bis salicyl aldehyde, 1,3-propan diimine Fe, Cu, Ni, 2.1 0.28, 0.27, 0.29, 175 FAAS Fish, spinach, meat, liver Ghaedi et al. (2008)
BSPDI Co, Cr, Zn 0.30, 0.28, 0.33
BHAPED Bis(2-hydroxy Fe, Cu, Ni, 2.1 0.28, 0.27, 0.29, 219 FAAS Milk, meat, fish, spinach, Ghaedi, Shokrollahi, Kianfar,
acetphenone)ethylendiimine Co, Cr, Zn 0.30, 0.28, 0.33 liver, water and Pourfarokhi (2009)
This work Cd, Co, Cu, 1.30, 1.20, 1.33, 0.17, 0.19, 1.6, 80 ICP-OES Fruit This paper
Ni, Pb, Zn 1.78, 2.36, 2.4 2.6, 0.92, 1.5
306 B. Feist, B. Mikula / Food Chemistry 147 (2014) 302–306

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