Microchemical Journal 85 (2007) 136 – 139

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Trace elemental characterization of edible oils by ICP–AES and GFAAS

Iva Juranovic Cindric a , Michaela Zeiner b,⁎, Ilse Steffan b
a
Laboratory of Analytical Chemistry, Faculty of Science, University of Zagreb, Horvatovac 102 a, HR-10000 Zagreb, Croatia
b
Institute of Analytical Chemistry, University of Vienna, Währingerstraβe 38, A-1090 Vienna, Austria

Received 17 January 2006; received in revised form 11 April 2006; accepted 11 April 2006
Available online 27 June 2006

Abstract

A method for the determination of the inorganic profile in edible oils is proposed. The quantification of selected metals in various oils (olive,
pumpkin seed, sunflower, sesame seed, hazelnut, grape, soya, rice oil) was carried out using microwave assisted digestion followed by ICP–AES
and GFAAS. The detection power of the ICP–AES technique was sufficient for the determination of Ca, Fe, Mg, Na, and Zn. Since the samples
contained very low amounts of Al, Cu, Co, Cr, K, Ni, Mn, and Pb, these elements were measured by GFAAS. Differences of metal concentrations
for edible oils obtained in this preliminary study represent a starting basis for the development of an additional analytical procedure applicable for
oil characterization.
© 2006 Elsevier B.V. All rights reserved.

Keywords: Edible oils; Trace elements; Characterization; ICP–AES; GFAAS

1. Introduction An alternative approach for adulteration detection and oil

Oil characterization is the basis for further nutritional and
food technological investigations such as adulteration detec-
tion [1]. The most common adulteration is an addition of a
cheaper vegetable oil to expensive oil (for example, because
of high viscosity of pumpkin seed oil, occasionally some
producers add sunflower seed oil to the pumpkin seed oil for
dilution). Authenticity is a very important quality criterion for
edible oils and fats, because there is a big difference in prices
of different types of oil and fat products. Adulteration
detection is possible by determining the ratio of the contents
of some chemical constituents and assuming these ratios as
constant for a particular oil. Analyses of flavoring compo-
nents of edible oils by chromatographic techniques (GC,
RPLC–GC, GC–MS) [2–4], isotopic assays [5], and
assessment of sterols and triglycerols with NMR [6,7], or
FT-IR [8–10] are recently proposed methods for the detection
of edible oil adulteration. However, some of these determina-
tions of authenticity for edible oils and fats are very time-
consuming and labor intensive.
⁎ Corresponding author. Tel.: +43 1 4277 52366; fax: +43 1 4277 9523.
E-mail address: michaela.zeiner@univie.ac.at (M. Zeiner).
0026-265X/$ - see front matter © 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.microc.2006.04.011
characterization is the application of spectroscopic methods
[11–19]. The determination of the inorganic profile of oils is
important because of the metabolic role of some elements in the
human organism. On the one hand, there is knowledge of the
food's nutritional value, which refers to major and minor
elements. On the other hand, there is the concern to verify that
the food does not contain some minerals in quantities toxic for
the health of the consumers, regardless whether this presence of
minerals is naturally occurring or is due to contamination during
the production processes. As regards to adulteration detection,
approaches based on atomic spectroscopy can be attractive
because detecting, e.g. a mixture of olive oil and hazelnut oil
represents a major challenge for food scientists because the fatty
acid and sterol composition and the oxidative stability of these
two oils are very similar [20].
In this report, the inductively coupled plasma atomic
emission spectrometry (ICP–AES) and graphite furnace atomic
absorption spectrometry (GFAAS) determinations of elements
in edible oils are described. A microwave assisted digestion was
applied for the dissolution of the samples. The metal contents of
eight different species of edible oils were determined. The
presented investigation represents a pilot study focused on the
type of oil analyzed and its inorganic profile.
 I.J. Cindric et al. / Microchemical Journal 85 (2007) 136–139 137

2. Experimental Table 2
Selection of lines, pretreatment and atomization temperatures for GFAAS
2.1. Reagents, standards and sample preparation Element Wavelength Pretreatment Atomization
(nm) temperature (°C) temperature (°C)
For the experimental work nitric acid (65 wt.% p.a.), Al 309.3 1200 2300
hydrogen peroxide (30 wt.% p.a.) and p.a. single element Co 242.5 1400 2400
Cr 357.9 1500 2300
standards (Merck, Darmstadt, Germany) were used.
Cu 324.8 1200 1900
For both ICP–AES and GFAAS, measurements were K 766.5 900 1500
accomplished by calibration using aqueous mixed standards Mn 279.5 1300 1900
prepared in HNO3 (1M). All calibration curves were based on Ni 232.0 1100 2300
five standards, including a blank. Standard stock solutions
(1g/L) were used. For the preparation of aqueous standard
solutions, appropriate dilutions of a 1 g/L multielement in the inorganic profile according to the different oil and that the
solution were applied. The calibration ranges were selected results are Gaussian distributed, 99.9% of the data are part of
according to the expected concentrations of the elements of one parent population.
interest and depending on the technique applied (ICP–AES or The LODs were calculated as the concentration equivalent to
GFAAS). three times the standard deviation (3σ) of the signal of the blank
The oil samples (3 to 5 different products each) were solution.
produced in Croatia, all commercially available except pumpkin
seed oil (homemade). The olive oil analyzed was extra-virgin. 3. Results and discussion
The samples of edible oils (0.5 g) were digested using a mixture
of nitric acid (4 mL) and hydrogen peroxide (2 mL) in a The relative standard deviations (RSD) were approx. 2% for
microwave digestion system. The oils were digested according the measurements performed by ICP–AES and 3–5% for those
to the following optimized program (power [W]/time [min]): by GFAAS for the determination of each analyte in one sample
250/2, 0/1, 250/2, 600/1, 400/5, ventilation 3.0 min and (three digests) and up to 6% or up to 8% for the means of each
measured by both ICP–AES and GFAAS. oil (3–5 samples) for data obtained by ICP–AES or GFAAS,
All glassware was cleaned with nitric acid prior to use. respectively.
Table 4 shows the results for the determination of the
2.2. Apparatus elements by ICP–AES. The detection power of this technique
was sufficiently high for the determination of Ca, Fe, Mg, Na,
The instruments used were a Perkin Elmer PE 4100 ZL and Zn in digested samples of edible oils. Concentrations of 3
atomic absorption spectrometer and an ARL 3580 ICP–AES. to 4μg Zn/g in all samples except the pumpkin seed oil
All instrument-operating parameters are summarized in Tables sample (13.5 μg/g) were measured. Pumpkin seed oil differs
1–3, a more detailed version can be found in a previous paper also from the other oils regarding the concentration of K
[21]. For microwave digestion of the samples a high (45.3 μg/g). For all other oils the concentration of K was
performance microwave digestion apparatus MLS-1200 below the LOD of the ICP–AES method. Pumpkin seed oil
MEGA with an EM-30 unit was used.
Table 3
2.3. Statistics Line selection and limits of detection (LOD) for the ICP–OES determination of
elements in olive oil
Results are presented as the mean of the mean values of each Element Wavelength/nm LOD (μg/g olive oil)
oil (three digests per sample/3–5 samples per oil). Standard
Al 396.1 1.04
deviations were calculated for each oil and are based on Ca 393.3 0.08
measurements in triplicate. Assuming that there is no difference Cd 226.5 0.05
Co 238.8 0.28
Cr 267.7 0.81
Table 1 Cu 327.3 0.32
Operating conditions for GFAAS Fe 259.9 0.41
Ka 766.5 0.29
Instrument PE 4100 ZL
Mg 279.5 0.06
Spectrometer Littrow-design Mn 257.6 0.08
Gratings 1800lines/mm Mo 202.0 0.19
Atomizing unit Transverse heated graphite tube Ni 341.4 0.26
Background correction Longitudinal Zeeman effect Pa 178.2 1.63
Magnetic field 0.9T Pb 220.3 0.22
Inert gas Argon Ti 337.2 0.07
Alternative gas Air V 310.2 0.15
Autosampler AS-71 Zn 206.2 0.09
Sample volume 20μL a
Elements measured by sequential mode ICP–OES.
 138
Table 4
Results for the determination of elements in edible oils by ICP–AES
Oil (n) ICP-AES
Ca Fe Ka Mg Na Zn
Olive (5) 2.0 1.9 2.2 1.8 2.2 14.9 15.8 14.2 16.6 16.4 <0.3 3.5 3.2 3.8 3.4 3.6 34.1 34.0 34.2 34.5 34.2 3.4 3.0 3.1 3.7 3.4
Mean 2.0 15.6 3.5 34.2 3.4
Pumpkin seed (5) 16.7 16.8 16.9 17.3 16.8 73.5 73.9 74.6 74.1 74.0 45.5 45.1 44.9 45.7 45.3 16.3 16.3 16.4 16.6 16.4 20.4 20.4 21.0 20.5 20.7 12.5 13.1 13.9 14.0 13.5
Mean 16.9 74.0 45.3 16.4 20.6 13.5
Sunflower (5) 0.4 0.5 0.4 0.7 0.5 15.0 15.1 15.0 15.8 15.3 <0.3 3.4 3.3 3.4 3.5 3.4 34.7 34.8 34.7 34.6 34.7 3.0 3.2 3.4 3.4 3.0
Mean 0.5 15.3 3.4 34.7 3.2
Sesame seed (3) 0.2 0.2 0.1 14.4 14.8 15.2 <0.3 3.8 3.8 3.5 33.4 33.5 33.3 2.8 3.0 3.5
Mean 0.2 14.8 3.7 33.4 3.1
Hazelnut (3) 14.5 15.4 14.9 15.4 15.5 15.4 <0.3 19.3 19.3 19.2 35.2 35.4 35.0 2.8 3.5 3.9
Mean 14.9 15.4 19.3 35.2 3.4
Grape (3) 4.1 4.1 3.8 14.8 15.0 15.0 <0.3 4.8 5.0 5.2 33.1 34.5 34.8 3.2 3.0 3.4

I.J. Cindric et al. / Microchemical Journal 85 (2007) 136–139

Mean 4.0 14.9 5.0 33.8 3.2
Soya (5) 0.1 0.3 0.2 0.2 0.7 23.5 23.4 23.1 23.3 23.3 <0.3 6.9 7.2 7.5 7.3 7.1 15.2 15.2 15.1 15.0 15.1 4.0 3.9 4.5 4.5 4.3
Mean 0.3 23.3 7.2 15.1 4.3
Rice (3) 0.3 0.4 0.5 14.5 14.1 14.3 <0.3 3.2 3.1 3.3 32.0 31.9 33.3 2.1 3.7 2.9
Mean 0.4 14.3 3.2 32.4 2.9
Results are given in μg/g (means of 3 to 5 oils each).
a
For ICP-AES determination of K the LOD in edible oil samples was 0.3 μg/g.

Table 5
Results for the determination of elements in edible oils by GFAAS
Oil (n) GFAAS
Al Co Cu Ka Mn Ni Cr, Pb
Olive (5) 0.15 0.12 0.10 0.11 0.14 1.15 1.12 1.12 1.14 1.13 0.03 0.04 0.04 0.05 0.04 0.07 0.07 0.02 0.06 0.1 0.09 0.11 0.13 0.11 0.2 1.1 1.6 1.8 1.9 1.7 <0.001
Mean 0.12 1.13 0.04 0.06 0.11 1.6
Pumpkin seed 1.5 1.2 1.5 1.6 1.7 <0.003 0.4 0.4 0.1 0.5 0.6 a <0.002 6.0 6.1 5.9 6.4 6.0 <0.001
(5)
Mean 1.5 0.40 6.1
Sunflower (5) 0.07 0.07 0.09 0.06 0.1 0.03 0.01 0.01 0.02 0.01 <0.004 0.60 0.59 0.62 0.69 0.65 <0.002 0.1 0.11 0.09 0.09 0.1 <0.001
Mean 0.08 0.01 0.63 0.1
Sesame seed (3) 0.10 0.10 0.14 0.09 0.11 0.13 0.51 0.59 0.56 0.07 0.09 0.1 <0.002 0.28 0.32 0.30 <0.001
Mean 0.12 0.11 0.56 0.08 0.30
Hazelnut (3) 0.27 0.26 0.27 0.09 0.12 0.08 0.54 0.48 0.48 <0.005 0.66 0.43 0.41 0.18 0.52 0.08 0.1 0.09 <0.001
Mean 0.27 0.09 0.50 0.42 0.09
Grape (3) 0.05 0.09 0.07 0.02 0.03 0.02 0.22 0.20 0.28 0.19 0.11 0.23 <0.002 0.08 0.08 0.09 <0.001
Mean 0.07 0.03 0.24 0.19 0.08
Soya (5) 0.11 0.12 0.11 0.10 0.12 0.01 0.02 0.02 0.02 0.03 <0.004 0.04 0.03 0.06 0.05 0.07 <0.002 0.21 0.22 0.25 0.22 0.24 <0.001
Mean 0.11 0.02 0.05 0.23
Rice (3) <0.005 <0.003 <0.004 0.19 0.15 0.17 <0.002 0.09 0.07 0.1 <0.001
Mean 0.17 0.08
Results are given in μg/g (means of 3 to 5oils each). For GFAAS determination all LODs in edible oils were in the range of 0.001 to 0.005μg/g.
a
The concentration of K in pumpkin seed oil was higher than 1μg/g.
 I.J. Cindric et al. / Microchemical Journal 85 (2007) 136–139
and hazelnut oil samples contain higher amounts of Mg (16 to
20 μg/g) and Ca (14 to 17μg/g) compared to the other edible
oils analyzed (0.2 to 4 μg/g). The concentration of Na of the
oils investigated was approx. 34 μg/g and differs only for
pumpkin seed oil (20.6 μg/g) and soya oil (15.1 μg/g). A
rather high amount of Fe was found in pumpkin seed oil
(74.0 μg/g). All other edible oils contained approx. 15 μg Fe/
g, except the soya oil sample (23.3 μg Fe/g). The concentra-
tions of Al, Cu, Co, Cr, K, Ni, Mn, and Pb were considerably
lower than the LODs obtained by ICP–AES (0.9 μg/g for Al,
0.3 μg/g for Co, Cu, and K, 0.2 μg/g for Ni).
Since the samples contained very low concentrations of Al,
Cu, Co, Cr, K, Ni, Mn, and Pb, these elements were measured
by GFAAS (Table 5). The concentrations of Al, Co, Cu, K, and
Ni were in the range of 0.1 to 1.5 μg/g. Pumpkin seed oil
samples contain higher amounts of Ni (6.1 μg/g) compared to
the other edible oils investigated (0.2 to 1.6 μg/g) and therefore
mixing with another oil causes a decrease in the Ni
concentration. Concentrations of Mn, Cr and Pb were below
the limit of detection of the GFAAS method.
Zn was found in the range of 2.9 to 3.5 μg/g in all edible
oil samples except the pumpkin seed oil (13.5 μg/g). Pumpkin
seed oil differs also from the other oils regarding its K
concentration (45.3 μg/g). Hazelnut and pumpkin seed oil
samples contain higher amounts of Mg (16 to 20 μg/g) and
Ca (14 to 16 μg/g) compared to the other oils (0.2 to 4 μg/g).
The concentration of Na is approx. 34μg/g and differs only
for pumpkin seed (20.6 μg/g) and soya oil (15.1 μg/g). A
high Fe concentration was found in pumpkin seed oil
(74.0 μg/g). Soya oil contains also a higher Fe amount
(23.3 μg/g) compared to all other oils (approx. 15 μg Fe/g).
The concentrations of Al, Co, Cu, K, Mn, and Ni were in the
range of 0.002 to 2.1μg/g.
4. Conclusion
The determination of trace elements in oil samples by ICP–
AES and GFAAS after microwave-assisted digestion repre-
sents a reliable and simple analytical method for oil
characterization. The findings of this preliminary study clearly
demonstrate the differences in the metal concentrations of
edible oils. The concentration of K and Ni in pumpkin seed oil
differs from the other oils. Consequently, determination of very
low concentrations of K and Ni by ICP–AES or GFAAS
method in pumpkin seed oil indicates a possible adulteration
by an another edible oil. Furthermore, pumpkin seed oil and
hazelnut oil samples contain higher amounts of Mg and Ca
compared to the other edible oils analyzed. Soya oil contains
also a higher Fe amount compared to all other oils. The
139
difference in the concentrations of Mg and Ca or Fe can be
used for adulteration determination.
For further investigations in this field, more samples of each
oil type should be analyzed to allow evaluation by multivariate
data analyses. In addition, more information for each sample
concerning the cultivar, the growing conditions, the year of
harvest and the way of production and storage should be taken
into account and used for data filtering.
Acknowledgements
This work was supported by OEAD (Austrian Academic
Exchange Service) scholarships (OEAD research scholarship
no. 1348-6/1999 and Ernst Mach scholarship no. 807-9/2000)
in the course of a co-operation between Croatia and Austria
(Croatian Ministry of Science and Technology and Austrian
Culture Institute).
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