Journal of Trace Elements and Minerals 1 (2022) 100003

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Journal of Trace Elements and Minerals

journal homepage: www.elsevier.com/locate/jtemin

Fast determination of trace metals in edible oils and fats by inductively

coupled plasma mass spectrometry and ultrasonic acidic extraction
Roseli M. de Souza b, Carlos A.T. Toloza c, Ricardo Q. Aucélio a,∗
a
Departamento de Química, Pontifical Catholic University of Rio de Janeiro (PUC-Rio), Rio de Janeiro, Brazil
b
Institute of Chemistry, Rio de Janeiro Federal University, Rio de Janeiro, Brazil
c
Department of Natural and Exact Sciences, Universidad de la Costa, Barranquilla, Colombia

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

Keywords: Trace elements play an important role in humans as some are essential for the proper functioning of the body
ICP-MS while others may have negative impact in health. Inductively coupled plasma mass spectrometry (ICP-MS) has
Edible oils and fat been used for the determination of nine elements (Cd, Cr, Cu, Fe, Mn, Ni, Ti, V e Zn) in olive oil, soy oil and
Trace-elements
margarine. Samples were treated with nitric acid solution (10 % v/v) and heated at 50 °C for 30 min. This mixture
Ultrasonic acidic extraction
was placed in an ultrasonic bath for 20 min, in order to obtain quantitative extraction of trace-elements into the
acid solution, which was directly aspirated into the ICP-MS to be quantified, using analytical curves constructed
with aqueous standards. This simple sample preparation procedure along with an efficient sample introduction
strategy (using a Meinhard K3 nebulizer and a twister cyclonic spray chamber) facilitated the overall analytical
process. Internal standardization with Rh was used to correct matrix effects and signal fluctuations. Limits of
detection in the ng g−1 range were achieved for all elements and were appropriate for the intended application.
The method was tested by the analysis of samples before and after fortification with metalo-organic standards
and recoveries between 88 and 117% were achieved. The method was found to lead to reliable results using a
fast and simple procedure.

Introduction of different techniques: voltammetry [10], inductively coupled plasma

Freshness and storability of edible fats and oils can be affected by
the presence of trace-metals [1]. Metals contamination of fatty foods
occurs mainly during industrial processing such as refining, bleaching
and deodorization but some metal contaminants come from the environ-
ment, for instance, olive oil may be contaminated due to the presence
of metals in the soil, water and in the air [2].
Contaminations with Fe, Cu, Ca, Mg, Co, Ni and Mn are known to
increase the rate of oil oxidation. For instance, trace amounts of Cu (0.1–
1 μg g−1 ) and Fe (1 μg g−1 ) are known to cause the rancidity of fats,
since they serve as catalysts for oxidation of unsaturated bonds in lipids,
causing the rapid deterioration of cooking oil and fat-containing foods
[3–5]. Other elements, such as of Pb, Cd and Zn, are of concern [6] on
the account of their toxicity and deleterious effects on metabolism [3] as
their presence in edible oils is linked to the growing use of sewage sludge
and other wastes as fertilizers in agricultural lands [7].
In terms of the analysis of oily samples, there is extensive literature
concerning lubricating oils [8,9] but considerably less information and
reports regarding the analysis of edible oils and fats. Edible oils have
been analyzed for different elements at sub-𝜇g g−1 levels using a number
optical emission spectrometry (ICP OES) [11–13] or mass spectrome-
try ICP-MS [14–17], although the most frequently used methods in the
literature are based on atomic absorption spectrometry (AAS) [18–21],
which includes some official methods [18]. Most of the analytical meth-
ods require sample treatments to allow quantitative analysis. The most
common procedures employed the destruction and/or dilution of the or-
ganic matter by previous sample calcination followed by acid dissolution
[22], extraction [23], solubilization [5], dilution with organic solvent
[24], sample microwave assisted digestion [14] and sample emulsifica-
tion [25]. All of these procedures also imply in larger dilution factors.
Thus the development of a simple but accurate analytical method
for direct trace-element determination in edible fat and oils is desir-
able although it has been a challenge due to the physical properties of
these samples and because of the diversity of chemical species that they
contain. Apart from the challenges imposed by sample physical char-
acteristics, one of the main problems with quality control and edible
oil analysis is the low metal content usually found, which requires very
sensitive techniques and low sample dilution factors. ICP-MS is an an-
alytical technique suitable for such type of analysis as it easily allows
multi-elemental determination at ng g−1 levels or less also allowing the

∗
Correspondent author.
E-mail address: aucelior@puc-rio.br (R.Q. Aucélio).

https://doi.org/10.1016/j.jtemin.2022.100003
Received 2 May 2022; Received in revised form 10 June 2022; Accepted 11 June 2022
Available online 13 June 2022
2773-0506/© 2022 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/4.0/)
R.M. de Souza, C.A.T. Toloza and R.Q. Aucélio
choice of monitoring suitable isotopes to improve selectivity in analy-
sis, bringing clear advantages over atomic absorption or optical emission
techniques.
The drawbacks of the direct introduction of organic samples into
ICP plasmas are well known [23]. The presence of solvent vapor in
the plasma causes carbon deposition on the cooler surfaces of the sam-
pler/skimmer and on the ion lenses, affecting the transport efficiencies
of ions. In addition, polyatomic interferences caused by carbon-argon
species seriously limit the quantification of some elements [26]. Another
negative effect is the blocking of the injector due to carbon formed from
the incomplete oxidation of the organic matrix. These problems have
been solved by the addition of a small proportion of oxygen into the
plasma gas mixture and reduction of temperature of the nebulization
chamber [26], using ultrasonic nebulizer with membrane de-solvation,
which reduces the amount or organic vapor reaching the plasma [27].
Another alternative has been the use of a heated V-groove nebulizer,
which permits a reduction of sample viscosity [27]. Most recent alter-
native for reduction of organic load is the coupling of electrothermal
vaporizer to the ICP-MS for the determination of Zn, Cd and Pb in veg-
etable oils, or the use of laser ablation as a method to vaporize oils,
carrying out into the ICP time-of-flight mass spectrometer [28].
In the present work, a method for the determination of Cd, Cr, Cu,
Fe, Mn, Ni, Ti, V and Zn in olive oil, soy oil and margarine by ICP-MS is
proposed. Samples were introduced as aqueous solutions obtained from
the ultrasonic analyte extraction into an acidic aqueous medium. The
principal variables that affect the extraction procedure and the sample
introduction into the ICP-MS (nitric acid concentration, heating time
and the exposure time to ultrasound) were chosen aiming short sam-
ple preparation time and high sensitivity in signal measurements. Ultra-
sound extraction in acidic medium enables extraction of metallo-organic
species in sample into the aqueous solution, implying in low dilution fac-
tors and minimizing oil matrix components introduced into the ICP-MS.
Experimental
Instrumentation
An Elan 5000A quadrupole inductively coupled plasma mass spec-
trometer (Perkin-Elmer-Sciex, Ontario, Canada) was used. The instru-
ment was equipped with a pneumatic concentric nebulizer (Meinhard
TR-30-K3) and a glass twister cyclonic spray chamber (both from Glass
Expansion, Hawthorn, Australia) of 0.75 mm internal diameter and
Table 1
Instrumental parameters for the ICP-MS measurements.
Parameter
RF power (W)
Ar plasma (L min−1 )
Ar outer (L min−1 )
Ar nebulizer (L min−1 )
Injector diameter (mm)
Sampler and skimmer cones
Signal measurement
Resolution
Sweeps per reading
Dwell time
Sweep per reading
Auto lens
Isotopes (%abundance)
Signal acquisition
Solution uptake rate (mL min−1 )
2
Journal of Trace Elements and Minerals 1 (2022) 100003
20 mL volume. A peristaltic pump was used to feed the nebulization sys-
tem with sample solution and standard solutions. Important optimized
instrumental parameters are listed in Table 1. A time programmable ul-
trasonic cleaner bath USB 124 (Brazil), operating with a frequency of
40 kHz, was used. The ultrasonic bath has a total volume of 2 L (the
volume of water used was 1 L) and a single transducer at the center of
the device. Erosion tests with aluminum foil and extraction tests using
standard reference material [26] indicated that this only transducer ir-
radiates ultrasound in a homogeneous way. Water temperature inside
the ultrasonic bath did not surpass 40°C after 1 h operation.
Reagents and solutions
All reagents used were of analytical-reagent grade, except HNO3 ,
which was previously purified in a quartz sub-boiling still. High pu-
rity de-ionized water (resistivity 18.2 MΩ cm), obtained using a Milli-
Q water purification system (Millipore, Bedford, MA, USA), was used.
Metallo-organic multielement standard (Conostan S-21- Conoco Inc.,
Texas, USA) was used to fortify the original samples as there are not
standard reference materials to these matrixes for the validation of the
proposed method. Multielement aqueous standard stock solutions con-
taining 1000 mg L−1 of each element (Merck-23) were obtained from
Merck (Darmstadt, Germany). Argon (99%) was used for plasma opera-
tion and it was obtained from Messer, Rio de Janeiro, Brazil. Xylene was
also from Merck. Soy oil (100 % soy oil), olive oil (pure olive oil) and
margarine were obtained from local vendors. All solutions were stored in
high-density polyethylene bottles. Analytical standards were prepared
by suitable serial dilutions of multielement stock solutions in HNO3 (10
% v/v). National Institute for Standards and Technology (NIST) standard
materials NIST 1634c and NIST 1084a were used to evaluate extraction
efficiencies.
Sample preparation
Analytes were extracted from samples by sonication in HNO3 (10
% v/v) aqueous solution according to the following procedure: Samples
(about 5.000 ± 0.005 g) of olive or soy oil or margarine (0.5000 ± 0.005
g) were accurately weighted in 15 mL centrifuge tubes. Xylene (0.5 mL)
was added in order to make the sample more fluid, helping to disperse
it into the 10 mL HNO3 acid aqueous solution that was further placed
into the tube. Samples were fortified with 10 μL of Rh standard aqueous
solution (1000 μg g−1 ) in order to act as internal standard. Rhodium was
Settings
1400
15.0
1.0
0.8
2.0
Pt
Peak area
0.7 a.m.u. (10% of the peak height)
1
25 ms
100
on
114
Cd (28.86), 52 Cr (83.76), 53 Cr (9.55),
63
Cu (69.17),
65
Cu (30.91), 57 Fe (2.19), 55 Mn (100),
60
Ni (26.23),
62
Ni (3.66), 51 V (99.76), 66 Zn (27.81)
Resolution: normal; scanning mode: peak
hop; dwell time = 100 ms; time /
replicate = 100 ms; number of
replicates = 4; readings per replicate = 1
1.2
R.M. de Souza, C.A.T. Toloza and R.Q. Aucélio Journal of Trace Elements and Minerals 1 (2022) 100003

Table 2
Average recovery based on the spiked concentrations considering different concentration levels alto-
gether (n = 3 for each concentration level).

Analyte Olive oil (Percent recovey %) Soy oil (Percent recovey %) Margarine (Percent recovey %)

Cd 92 ± 2 95 ± 5 93 ± 8
Cu 91 ± 2 102 ± 2 100 ± 6
Cr 106 ± 3 104 ± 2 91 ± 2
Fe 88 ± 4 87 ± 7 88 ± 8
Mn 101 ± 4 109 ± 4 97 ± 8
Ni 102 ± 8 105 ± 2 91 ± 3
V 95 ± 2 90 ± 5 99 ± 6
Zn 106 ± 6 117 ± 6 102 ± 3

Table 3 Table 4
Analytical curve parameters. Trace elements original concentrations (μg g−1 ) in olive
oil, soy oil and margarine calculated by the recovery tests
Analyte Calibration function R2
(n-4) using multiple standard additions.
Cd y = 1047.4x + 979,5 0.9991
Analyte Olive oil Soy oil Margarine
Cu y = 1750.3x + 55.3 0.9998
Cr y = 1294.5x + 43.1 0.9998 Cd < LD < LD < LD
Fe y = 3682.1x + 328.4 0.9995 Cu 0.091 ± 3 0.095 ± 3 0.024 ± 4
Mn y = 2017.9x + 522.7 0.9997 Cr < LD < LD < LD
Ni y = 923.1x + 59 0.9999 Fe 5.05 ± 3 4.98 ± 4 4.92 ± 6
V y = 4085.6x + 265.4 0.9995 Mn 0.37 ± 2 0.055 ± 4 0.33 ± 2
Zn y = 2969.5x + 247 0.9980 Ni 1.64 ± 5 1.23 ± 5 1.65 ± 4
V < LD < LD < LD
m in cps g 𝜇g−1 and b in counts per second (cps).
Zn 0.039 ± 3 0.032 ± 5 0.38 ± 3

chosen as the internal standard since it is a noble metal (ion less probe
to reactions in plasma conditions) also presenting m/z ratio close to that
of the group of chosen analytes. The mixture mixed, with the help of a
vortex, for 2 min agitation. Then, the tube was partially immersed in
thermostatic bath (set at 50°C) for 20 min. After heating, the tubes were
right away placed in an ultrasonic bath (containing sufficient water to
cover half of the tube height) to be sonicated for 20 min. No cooling
between heating and sonication was needed. A two phase system, con-
taining a transparent solution in the bottom with an oil phase floating
on the top, was achieved. A volume of 5 mL of the clear aqueous phase
was removed and transferred to a volumetric flask. The ultrasonic bath
employed allowed the simultaneous preparation of eight samples. Total
sample preparation time was about 45 min.
Results and discussion
Critical experimental variables for ultrasonic-assisted acid extraction
Many authors have demonstrated that ultrasonic-assisted procedures
are very efficient and simple way to extract trace-metals into aqueous so-
lutions. The success of such procedures relies on the proper optimization
of the parameters and on the use of effective ultrasonic apparatuses. The
use of the ultrasonic probe allows more efficient extractions in reduced
times mainly because of the higher radiances achieved with such devices
[29]. Nevertheless, the ultrasonic bath is the most widely available and
cheapest source of ultrasonic irradiation. It is also more appropriate for
working with acid medium because the liquid solution to be sonicated
is never in direct contact with the ultrasonic device, avoiding sample
contamination with elements of interest, some of them also present in
the probe material. Extractions from oils may also impose difficulties
for using probes since the oil sticks on its surface increasing the risk of
cross contaminations.
The efficiency of the ultrasonic extraction of analytes into acid solu-
tions is dependent upon critical factors such as the need for sample pre-
heating, the exposure time to ultrasonic radiation and acid concentra-
tion. The former factor (in this case, the concentration of HNO3 ) directly
affects the performance of ICP-MS measurements and therefore must be
carefully chosen. Many studies indicate the use of only a strong oxidant
mineral acid, such as HNO, to perform element extractions [30] and also
describe different ultrasonic exposition times in order to achieve com-
plete extractions for different samples [25]. Acidic extractions enable
the removal of even metallo-organic analyte species present in samples
into the aqueous solution. The three main experimental factors that in-
fluence the ultrasonic assisted extraction (acid concentration, heating
time and ultrasound exposition time) were studied using a univariate
approach followed by a 23 factorial design in order to find best condi-
tions for the extraction of refractory elements in petroleum prior to ICP
OES determination [28]. It was found that pre-heating of solution was
the most relevant parameters and there is no relevant mutual interaction
between them. Ultrasonic time was also important but it was a robust
parameter if employed within 15 and 20 min [28]. These values were
taken as reference in this present work in order to explore conditions
to perform extraction using more diluted acidic solutions. For the ex-
traction solution, only one concentration of nitric acid was used (10%
v/v) since the use of concentrated acid may impose interferences in the
ICP-MS measurements.
The optimization was made through recovery tests using oil samples
fortified with metallo-organic standards (Conostan S-21) of the analytes.
The extraction of elements into aqueous solution was improved as the
heating time increased. It was found that the temperature must be set to
at least 50°C. Higher temperatures seem not to improve results. Analyte
recoveries using less than 10 min heating time were below 60 % for all
the elements (Cd, Cr, Cu, Fe, Mn, Ni, Ti, V and Zn). For vials heated for
15 or 20 min, all recoveries were found in the 90 – 110 % range. Longer
heating times did not affect significantly these recoveries. Sonication
time was also found to be critical and best results were found using 15
to 20 min. The application of longer sonication times (above 30 min)
seems either not to affect recoveries or deteriorate them.
Analytical performance
The major constituents of food matrices (C, Ca, Cl, P, K, Na and S)
are also the main sources of spectral interferences in ICP-MS analysis.
For instance, C, Ca and Cl can cause interferences for the determination
of 51 V (35 Cl16 O), 52 Cr (40 Ar12 C), 60 Ni (44 Ca16 O). Such isobaric inter-
ference may be eliminated by selecting a suitable isotope, or may be
corrected or reduced by applying correction equations. Tests were per-

3
R.M. de Souza, C.A.T. Toloza and R.Q. Aucélio Journal of Trace Elements and Minerals 1 (2022) 100003

Table 5
Trace element analysis in edible oils using different preparation methods.

Samples Analytes Procedures technique LOD Recovey % Reference

−1
Olive oils Cu, Cd, Cr, and Ni Microwave assisted acid ICP-MS 0.8 to 40 ng g ∼ 87 [14]
dissolution with HNO3
Vegetable oils Cd, Fe, Cr, Mn and Ni Microwave assisted ICP-MS with DRC 0.009 to 10.2 ng g−1 91–119 [15]
acid dissolution with HNO3
Vegetable oils Cr, Cu, Microwave assisted ET AAS 0.001 to 0.005 𝜇g - [12]
Mn, Fe acid dissolution with ICP OES g −1
and HNO3 in the presence of H2 O2 0.06 to 0.41 𝜇g g−1
Zn
Olive oil Zn, Cd, Fe Microwave assisted ET AAS 0.1 to 12.0 ng g–1 - [31]
and Cu acid dissolution with
HNO3 in the presence of H2 O2
Olive oil Ni and Cu Microwave assisted ET AAS 0.001 Cu and 0.002 - [32]
acid dissolution with HNO3 Ni 𝜇g g−1
Olive oil Mn, Cu, Cd, Dilution ET AAS 0.02 to 0.10 𝜇g g−1 - [24]
Ni, Cr and Fe with
(1,4, dioxane)
Olive oil Mn, Cd, Cr, Emulsification using TritonX-100 ICP-MS 0.25 to 0.50 ng g−1 . 90-120 [16]
Cu, Ni
Olive oil Cd, Cr, Cu, Fe, Mn, Ni, Acid dissolution with HNO3 in a ICP-MS 0.07 to 20.0 ng g−1 93-112 [17]
Ti, V water bath at 95 °C.
Olive oil Cd, Cr, Cu, Fe, Mn, Ni, Ultrasonic assisted extraction in ICP-MS 1.5 to 40.0 ng g−1 88-117 present work
And margarine Ti, V e Zn acidic medium with HNO3
ICP-MS: Inductivelly Coupled Plasma Mass Spectrometry.
DRC: Dynamic reacto Cell.
ET AAS: Electrothermal Atomic Absorption Spectrometry.

formed with samples analyzed after fortification with the reference val-
ues to check for possible isobaric interferences. The primary isotope for
each element was used for this study and adequate recoveries were ob-
tained for all of the elements Table 2. Moreover, for chromium, better
results were observed using 53 Cr than 52 Cr. Recoveries were in the 88
% – 117% range.
The method limit of detection (LOD) obtained for Cd, Cr, Cu, Fe,
Mn, Ni, Ti, V and Zn were 1.5, 6, 1.2, 39, 9, 3, 40, 3, 18 ng g−1 , respec-
tively, in olive and soy oils, and 15, 60, 12, 390, 90, 30, 400, 30, 180
ng g−1 , respectively, in margarine. The LOD values were determined
as 3 times the standard deviation of the 20 consecutive measurements
of the reagent blanks multiplied by the dilution factor used for sample
preparation (3 times in oils and 30 times in margarine). The parameters
of the analyte curves prepared with aqueous standards are indicated in
Table 3. Linear responses were achieved in the 0.01 – 50 μg g−1 analyte
concentration range.
Recovery tests were made with samples fortified with metallo-
organic standards at three different concentration levels in order to get
the recoveries in relation to the fortified concentration also to allow esti-
mation of the real analyte content in the samples (Table 4). The original
analyte content in samples varied from 0.004 μg g−1 (V) to 5.05 μg g−1
(Fe) with no detectable values for Cd, Cr and V. The between- and
within- extraction batch precision of for all of the analyzed elements
were lower than 6 % and 2 %, respectively.
Analytical figures of merit of methods reported in literature for edi-
ble oils are listed in Table 5, along with the ones reported in the present
work. Limits of detection found are in general comparable and influ-
enced by instrument, sample amount and sample dilution factors during
sample treatment and prior to analysis. The ones that report percent re-
coveries, their values shown adequate performance considering the con-
centration levels determined. The major difference arises in terms of ex-
perimental procedures concerning complexity of sample treatment and
their consequences in measurement. Methods based on decomposition
of samples (in open and in closed vessels) are time intensive and prone
to contamination and losses, however, sample is completely mineralized
to be introduced into ICP-MS. Emulsification of sample using surfactants
is a viable alternative but requires low amount of oil to achieve homo-
geneous dispersion and organic load is high when introduced in the
ICP-MS, affecting background and operation due to carbon deposits in
torch and cones. In this sense, the proposed method is straightforward
as sonication provides efficient analyte extraction to the aqueous phase
that is compatible to the ICP-MS.
Conclusions
The proposed method showed to be reliable for the determination
of nine elements (total content) in edible oils (olive oil and soy oil) and
fat (margarine) by ICP-MS. The good agreement between found values
and the expected values indicated effective recoveries for analytes af-
ter acid extraction and subsequent accurate determination. Ultrasonic
extraction in acidic medium probably ensured effective conversion of
metallo-organic species into metal ions is aqueous solution. Considering
the time required for sample preparation, the proposed method is very
attractive also due to a minimum use of reagents, and reduced labor-
intensity. Moreover, ICP-MS allowed multi-elemental determinations at
low concentration levels. The developed method may be considered as
a practical alternative for the quality control of oily and fatty foodstuff
samples as other food-related products may be processed in the same
way before analysis.
Declaration of Competing Interest
The authors declare the following financial interests/personal rela-
tionships which may be considered as potential competing interests.
CRediT authorship contribution statement
Roseli M. de Souza: Investigation, Methodology, Formal analysis,
Writing – original draft. Carlos A.T. Toloza: Writing – review & edit-
ing. Ricardo Q. Aucélio: Funding acquisition, Methodology, Writing –
review & editing.
Acknowledgements
This work was partially financed by Coordenacao de Aperfeicoa-
mento de Pessoal de Nivel Superior (CAPES-Brazil) – Finance Code
001. Aucelio thanks scholarships from Brazilian agencies FAPERJ (E-
26/200.810/2021) and CNPq (306108/2021-6). Carlos Toloza Tanks

4
R.M. de Souza, C.A.T. Toloza and R.Q. Aucélio
CAPES (CAPES-Print/PUC-Rio). The dedication and skill of Alvaro J.
Pereira in ICP-MS measurements is acknowledged.
Ricardo Queiroz Aucelio reports financial support was provided by
National Council for Scientific and Technological Development (CNPq).
Ricardo Queiroz Aucelio reports financial support was provided by Car-
los Chagas Filho Foundation (FAPERJ) for Research Support of Rio de
Janeiro State. Ricardo Queiroz Aucelio reports financial support was
provided by Coordination of Higher Education Personnel Improvement
(CAPES).
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