Microchemical Journal 168 (2021) 106501

Contents lists available at ScienceDirect

Microchemical Journal
journal homepage: www.elsevier.com/locate/microc

Review Article

Analytical methods to detect adulteration of argan oil: A critical review

Faez Mohammed a, *, Dominique Guillaume b, *, Jon Warland a, *, Nada Abdulwali c
a
School of Environmental Sciences, University of Guelph, 50 Stone Road E, Guelph, ON N1G 2W1, Canada
b
ICMR, School of Medicine-Pharmacy, CNRS, UMR 7312, 51 RueCognacqJay, Reims 51100, France
c
Faculty of Education, Sana’a University, Sana’a, Yemen

A R T I C L E I N F O A B S T R A C T

Keywords: Argan oil is widely known as an edible, cosmetic, and pharmacologically active oil. It is also particularly
Analytical techniques expensive. Therefore argan oil adulteration with low price vegetable oils is frequent, making accurate, easy to
Authenticity use, and fast techniques to detect argan oil adulteration necessary. In this review, we present the advantages and
Fluorescence spectroscopy
disadvantages of a range of methods developed to detect argan oil adulteration. Though chromatography or
Vegetable oil
infrared spectroscopy present the advantage of being efficient, easy to use and accurate, these techniques are
Argan oil
time-consuming, expensive, and require somehow complexe sample preparation. At the present time, fluores­
cence spectroscopy appears to be the most efficient technique.

1. Introduction
Argan nuts contain one to three kernels. After careful nut breaking,
kernels can be collected and then cold-pressed to prepare argan oil [1].
Kernels that have been lightly roasted prior to pressing deliver a
hazelnut-flavored oil of edible grade, while raw (unroasted) kernels
deliver cosmetic argan oil. The argan oil extraction yield is around 50%
depending on tree genetic and/or phenotypic parameters [2].
The argan tree is only endemic in Southern Morocco. The vast area
covered by argan trees, named the argan forest, was designated a
UNESCO biosphere reserve in 1998 [3]. Eleven years later, argan oil was
internationally certified as a Protected Geographical Indication (PGI)
product. These two international recognitions are not only prestigious,
but they also guarantee the quality and stability of the biotope in which
argan trees grow, as well as the preparative process established to
extract argan oil [1]. Even though this protected process is semi-
automated, and hence more efficient than the ancestral extraction
method, it leads to the preparation of only 4 L of oil from 100 kg of dried
argan fruit after 20 person hours [4]. Argan oil’s dietary and dermo-
cosmetic properties are numerous and well-established [5–6]. There­
fore the main market for argan oil is in industrialized countries where,
due to its relative scarcity, it is frequently negotiated at more than $300/
L. Such a high price inevitably fuels the risk of fraud through intentional
mislabeling or falsification of argan oil by illicit addition of various
amounts of cheap or easily accessible vegetable oils [7].
To detect most types of fraud, the Moroccan authorities have enacted
a standard operating procedure for analysis [8] that uses the GC quan­
tification of campesterol, a sterol found in very minute quantities in
argan oil, although relatively abundant in most vegetable oils, as a
chemical marker [9].
Even though the different detection methods of argan oil adultera­
tion have been the topic of a recent review [7], the ever-growing eco­
nomic importance of argan oil prompts us to provide new assessment
and critical analysis of the current methods available for the detection of
argan oil adulteration with vegetable oils.
Several sophisticated techniques such as, inductively coupled
plasma-optical emission spectroscopy/atomic emission spectroscopy,
chromatography, vibrational spectroscopy (infrared, mid infrared,
visible and near infra-red, raman), nuclear magnetic resonance, elec­
tronic nose, voltammetric electronic tongue, and fluorescence spec­
troscopy (fusion of synchronous, laser), have been recently proposed to
determine argan oil purity. The aim of this review is to present the
techniques used to identify and quantify argan oil adulterations with
other vegetable oils, as well as critically analyze them in order to
identify a technique void of major disadvantages for the satisfaction of
consumers, producers, and manufacturers.
2. Analytical techniques to detect adulteration of argan oil
2.1. Application of chromatography techniques
Chromatography is the most popular technique to analyze the purity

* Corresponding authors.
E-mail addresses: faez@uoguelph.ca (F. Mohammed), dominique.guillaume@univ-reims.fr (D. Guillaume), jwarland@uoguelph.ca (J. Warland).

https://doi.org/10.1016/j.microc.2021.106501
Received 30 December 2020; Received in revised form 8 May 2021; Accepted 2 June 2021
Available online 6 June 2021
0026-265X/© 2021 Elsevier B.V. All rights reserved.
F. Mohammed et al.
Fig. 1. HPLC-ELSD chromatograms of argan oil, olive oil, sunflower oil, and soy bean oil [17].
of foods [10–11]. It offers the feature of short analysis period and high
reproducibility [12].
The use of quantitative campesterol gas chromatography (GC)-
analysis to detect argan oil adulteration with olive, sunflower, soybean,
rapeseed, apricot, sesame, hazelnut, and arachis oils has been suggested
as early as 2007 [9]. Results evidenced the accuracy and reliability of GC
to quantify the sterol content of edible oils. The study reported that GC
campesterol level determination is a precise, authoritative, and easy to
employ manner for the ascertainment of argan oil purity up to 98% [13].
Consequently, measuring campesterol level by GC-analysis was found to
be a highly efficient technique to confirm the purity argan oil; thus it is
the method officially selected to detect argan oil adulteration with other
vegetable oils [8].
Maata et al. attempted to use combined various chromatography
techniques to detect argan oil adulteration by vegetable oils (soy, sun­
flower, rapeseed, peanut, sesame, apricot, olive, and hazelnut oils),
based on linolenic acid, triglycerides, and stigmastadiene contents, in
2011 [14]. This study showed the possibility of detecting the adultera­
tion of argan oil after adding 5% vegetable oils with a high linolenic acid
content (rapeseed, soya). However, the detection of adulteration of
argan oil with vegetable oils low in linolenic acid (olive, sunflower,
peanut) has proven difficult. Triglyceride content did not allow the
detection of adulteration of argan oil by other vegetable oils below a 5%
level because of the triglyceride content in these oils is close to that in
argan oil. The stigmastadiene content determination allowed detection
2
Microchemical Journal 168 (2021) 106501
of the adulteration of argan oil by other refined vegetable oils at the 1%
level. In conclusion, the study evidenced that the accuracy of chroma­
tography techniques differs based on the type of adulterant and
measured minor components.
The use of gold nanoparticles (AuNPs) and spectrophotometry to
detect adulteration of argan oil with sunflower and olive oils, based on
the identification of total phenolic acids in virgin argan oil was reported
in 2011 [15]. The resultant redox reaction led to a color change
accompanied by powerful light absorption at 555 nm. Ferulic acid was
selected as an adulteration marker to evaluate the authenticity of virgin
argan oil because it represents more than 95% of the total phenolic acid
content of virgin argan oil. HPLC method was employed to validate the
efficiency of this technique and provided a detailed analysis of all
phenolic compounds found in the samples through analyzing pure and
adulterated argan oil. Results confirmed the efficiency of using gold
nanoparticles (AuNPs) and spectrophotometric analysis to detect argan
oil adulteration. Chromatography technique associated with AuNPs
demonstrated its effectiveness to detect adulterants in argan oil based on
identification of total phenolic acids of purities up to 94%.
The implementation of gas chromatography to detect argan oil
adulteration by edible vegetable oils, based on the content of fatty acids,
hydrocarbon fraction, 3,5-stigmastadiene, the alkyl esters of fatty acids,
and chlorophyllic pigments was proposed in 2012 [16]. Physical prop­
erties such as viscosity, density, and refractive index have also been
suggested to detect argan oil adulteration. This study showed that 3,5-
F. Mohammed et al. Microchemical Journal 168 (2021) 106501

Fig. 2. Voltammetric responses of Pt sensor immersed in samples of different percentage of sunflower oil added to (a) comestible and (b) cosmetic argan oil [38].

Table 1
Limits and practical information obtained using the different analytical methods to detect adulteration of argan oil.
Method Useful for adulteration with Minimum level of Detection limits Concentration Analysis time
adulterant detected (%) (μg/L) ranges (%) (min)

ICP-OES Olive, sunflower, and soyabean oil 5.88 0.03–220 30–70 10

ICP-AES – – 0.03–40 – 1–2
Gas chromatography Olive, sunflower, soybean, rapeseed, apricot, 2 – 0–5 15–30
sesame, hazelnut, and arachis oils
Liquid Chromatography Sunflower, soybean, and olive oil 5 4 x106 1–5 –
Visible and Near Infra-Red Cheap vegetable oils 0.35 5 x107 0–30 <0.017
Spectroscopy
Raman spectroscopy Olive oil – 354 x104 1–20 1.67x 10− 5

Nuclear magnetic resonance Sunflower oil 20 100 20–50 <30

(NMR)
E-nose and e-tongue Sunflower oil 10 – 0–70 10
Fluorescence spectroscopy Olive oil 0.43 5 x106 − 100 0–27 17x10− 4

x106

stigmastadiene, kaurene, and pheophytin-a were potential new markers
for detecting argan oil adulteration with refined sunflower, and virgin
olive oils at level of 5%. In contrast, fatty acids could possibly be used as
markers to detect argan oil adulteration only at levels higher than 10%,
a value too high to be acceptable to the food or cosmetic industry. The
refractive index presented a significant degree of variation when argan
oil was adulterated with 10% sunflower oil. Again, this is too high an
adulteration level to be acceptable by the food or cosmetic industry. Gas
chromatography technique showed a high effectiveness up to 95% pu­
rity to detect the adulteration of argan oil with refined sunflower, or
virgin olive oils based on the determination of 3,5-stigmastadiene,
kaurene, and pheophytin-a compared with the identification of adul­
terants by measuring of fatty acids with effectiveness up to 90%.
The application of high-performance liquid chromatography­
–evaporative light scattering detection (HPLC-RID) to detect argan oil
adulteration with vegetable oils was reported in 2014 [17]. Tri­
acylglycerol profiles were used as an indicator for the detection of
vegetable oils such as sunflower, soybean, and olive oil in argan oils.
Model chromatograms of argan, sunflower, olive, and soybean oil tri­
acylglycerols are shown Fig. 1. The technique detected argan oil adul­
teration with sunflower, soybean, and olive oil of up to 5%. Liquid
chromatography presented an agreeable efficiency to detect the adul­
teration of argan oil with vegetable oils based on measuring the tri­
acylglycerol content.
To evaluate the authenticity of argan oil sold in Bulgaria, a study
based on the combined analysis of oxidative stability (acid value,
peroxide value, conjugated dienes and induction period) and fatty acid,
triacyglycerol, sterol contents using chromatographic technique
together with principal component analysis (PCA) was reported in 2016
[18]. Results were compared with those collected with authentic cold-
pressed Moroccan argan oil. The study showed that the sterol compo­
sition of one sample was different from that of authentic argan oil, with
low oxidative constancy, which confirms that this sample was adulter­
ated with another vegetable oil. In contrast, the fatty acid, tri­
acylglycerol, and sterol contents were identical to those of the authentic
argan oil sample of high oxidative stability. The study confirmed that the
use of chromatographic technique with PCA showed an acceptable
effectiveness to detect the adulterants in argan oil by measuring the
sterol composition.
The triacylglycerol profile to detect the purity of argan oil using
HPLC-PDA-ESI-TOF/MS and HPTLC techniques was reported in 2018
[19]. Two simple methods to quickly analyze argan oil-based products
have been developed. nUHPLC-PDA permits the identification of pure
argan oil, whereas mass spectrometry (MS) is able to detect argan oil
within a product down to 0.03% concentration. This study showed that
chromatographic and mass spectrometry techniques complement each
other, indeed, when chromatographic analysis determines the purity of
argan oil in argan oil-products, mass spectrometry quantifies argan oil in

3
F. Mohammed et al. Microchemical Journal 168 (2021) 106501

Table 2 (OPLS-DA) regression model showed successful discrimination allowing

Summary of the analytical techniques for identifying the authenticity of argan detection of adulteration in argan oil at levels higher than 5% in the case
oil. of sunflower, olive, and soya oils, and higher than 15% in the case of
Number Adulterant Analytical technique Multivariate Reference corn oil. Chromatographic techniques coupled with chemometric multi-
of argan analysis data analysis could offer different effectiveness to predict the purity
oil argan oil according to the type of adulterants and tocopherols values.
samples
Chromatography is an efficient technique to predict the adulteration
ICP-AES/OES of argan oil with different vegetable oils based on the quantification of
5 ICP-OES [23]
– –
minor components. Chromatography is an acceptable technique in terms
17 Olive, ICP-OES HCA, PCA, [22]
sunflower,and DA, CHAID of selectivity, sensitivity, and cost. Unfortunately, it can not be consid­
soya oil ered environmentally friendly because it requires the use of toxic
– – ICP-AES – [27] chemicals during the preparation of the sample. Thus, there is a urgent
Chromatography technique need to reevaluate this technique or develop alternative sample prepa­
– Olive, Gas chromatography – [9] ration methods.
sunflower, In this section, we will discuss the use of ICP-OES/AES techniques to
soybean,
detect the adulteration of argan oil based on measuring elemental levels.
rapeseed,
apricot,
These techniques are of high accuracy for determination of element-
sesame, content in vegetable oils and in other foods.
hazelnut, and
arachis oils 2.2. Inductively coupled plasma optical emission spectrometry/
– Soy, GC – HPLC [14]
sunflower,
inductively/atomic emission spectrometry
rapeseed,
peanut, The elemental content of plant material is influenced by extrinsic
sesame, factors (e.g. environment, use of fertilizers, pollution) and intrinsic
apricot, olive
factors that depend on the species. The argan forest is a homogeneous
and hazelnut
oils. geological area, as is its soil metal content. Consequently, argan oil
19 Sunflower, Gold nanoparticles – [15] metal content undergoes little fluctuation [21]. This stability has led to
and olive oils (AuNPs) and suggest argan oil metal content determination as an efficient method to
spectrophotometric, distinguish argan oil from other vegetable oils unambiguously [22–24].
and HPLC-DAD/FD
– Refined, GC – HPLC. – [16]
Inductively coupled plasma optical emission spectrometry/induc­
sunflower and tively/atomic emission spectrometry (ICP-OES/AES) has been demon­
virgin olive strated to be a fast, accurate, and effective technique for identifying
oils. elemental concentrations in food [25]. It is a useful and accurate tech­
19 Sunflower, High-performance [17]
–
nique for trace analysis due to its high sensitivity and ability to simul­
soy bean, and HPLC-RID
olive oil taneously determine many elements at different spectral lines [26].
6 Vegetable oil Chromatographic [18] Gonzálvez initially reported the elemental content of argan oil using
technique inductively coupled plasma optical emission spectroscopy (ICP-OES) in
16 Vegetable oils UHPLC-PDA-ESI- – [19] 2010 [23]. This study demonstrated the levels of aluminum, calcium,
TOF/MS
16 Olive, An Online HPLC AF, OPLS-DA [20]
chromium, iron, potassium, lithium, magnesium, sodium, vanadium,
sunflower, and zinc to be different in argan oil from that found in other edible oils,
corn, and soya thus providing a possible new way to detect adulteration in argan oil.
oils This study was the first to exploit the ease of use of the ICP-OES tech­
Vibrational spectroscopy (infrared and Raman spectroscopy) nique to determine the purity of argan oil. ICP-OES technique showed its
82 Sunflower and Infrared Spectroscopy ATR, PLS [31] ability to measure the elemental levels in argan oil with high precision.
soybean oils The use of inductively coupled plasma optical emission measurement
192 Cheap Visible and Near PLS, RMSEP, [32]
(ICP-OES) in conjunction with chemometric tools (hierarchical cluster
vegetable oils Infra-Red SEP, PCA
Spectroscopy (Vis/ analysis (HCA), principal component analysis (PCA), classification trees,
NIRS) and discriminant analysis (DA)) to detect the adulteration of argan oil
90 Olive oil Raman spectroscopic RMSEV [35] with olive, sunflower, and soybean oil has been reported in 2010 [22]. If
Commercial Mid Infrared PCA, SVMR, [33]
–
the direct distinction between argan oil and soybean and olive oils based
oil Spectroscopy PLSR
on trace element composition is difficult to achieve, multivariate anal­
Other spectroscopic techniques ysis allowed a much better distinction between pure and adulterated
36 Sunflower oil E-nose and e-tongue PCA, DFA, [38]
argan oil samples. The Chi-squared Automatic Interaction Detector
SVM
56 Olive oil Fluorescence PCA [41] (CHAID) method achieved a detection rate of 94.12% for adulterated
technique argan oil by employing only the content of K, and DA analysis showed a
– Corn oil Fluorescence PLS [42] detection rate of 93.65%. The study clearly demonstrated that chemo­
spectroscopy (SFS) metric analysis is required in conjugation with ICP-OES technique to
47 Sunflower oil Nuclear magnetic – [49]
resonance (NMR)
achieve reliable detection of argan oil purity.
Recently, the efficiency of the inductively coupled plasma atomic
emission spectroscopy technique (ICP-AES) to certify the authenticity of
these products at up to 99.97% purity. argan oil has been confirmed [27–29]. Since tin content of argan oil is
Exploiting HPLC in conjunction with chemometric multi-data anal­ different from that of olive, sesame, mustard, corn, peanut, and sun­
ysis to detect adulterated argan oil with vegetable oils (olive, sunflower, flower oils, the study concluded that tin-content can be used as a specific
corn, and soya oils), based on tocopherol values, has been proposed in marker to certify the lack of these oils in argan oil. The study established
2019 [20]. The [γ-toc/α-toc] ratio was suggested as a new adulteration the ability of ICP-AES technique to detect argan oil adulteration by
factor. Orthogonal projections to latent structures- discriminant analysis specifically measuring the tin-level in questionable argan oil samples.

4
F. Mohammed et al. Microchemical Journal 168 (2021) 106501

Table 3
Comparison of the functioning principles, advantages, and disadvantages of different methods used to detect and quantify adulterated argan oil.
Functioning Principle Advantage Disadvantage

ICP-OES Measurement of emission light from excited atoms that 1. Low detection limits multiple
correspond to the photon wavelength 2. Elements, limited spectral
interferences
3. Good stability
4. Low matrix effects
5. It is environmentally friendly
ICP-AES 1. Multi-element technique
2. Large analytical range
3. High sample throughput
4. Low sample volume
5. Simple sample preparation
6. It is environmentally friendly
Gas Separation of a gaseous mixture into individual components 1. Robust technique
Chromatography (substances) on passing a gas flow through a thin silica column 2. Gold standard for both screening and
confirmation analysis
3. High specificity
4. It is not environmentally friendly
Liquid Separation of a liquid mixture into individual components on 1. Optimized for larger analytes
Chromatography passing a liquid through a steel column packed with different 2. Rapid separations
particles layer (particles sizes >2 µm) of stationary phase 3. Simpler sample separation
4. It is not environmentally friendly
Infrared Measurement of the vibrations of atoms and determination of the 1. Minimum or no sample preparation
Spectroscopy functional groups. 2. Nondestructive and rapid
determination
3. High reproducibility
4. Less adverse impact on
environmental
E-nose and e- 1. Assess aroma throughout the whole
tongue production process
2. Indirect food quality measurement
option
3. It has not a negative effect on
environmental
Raman Inelastic scattering of incident radiation through its interaction 1. Non-destructive
spectroscopy with vibrating molecules and probe the molecular vibrations 2. Minimal sample preparation.
3. Label-free, no dyes and toxic
wasteproducts.
4. High specificity.
5. Simultaneous detection of
macromolecules
6. Compatible with physiological
measurements due to weak water
interferences.
7. In vivofiber-optic applications
8. Less adverse impact on
environmental
Fluorescence Fluorophore absorbs energy in the form of light at a specific 1. High sensitivity.
spectroscopy wavelength and liberate energy in the form of emission of light at 2. High specificity.
a higher wavelength. 3. Minimal sample preparation.
4. It determine fluorescence intensity,
decay time, and the concentration of the
component.
5. Immune to the scattering of light.
6. It is environmentally friendly
1. Liquid samples only
2. Expensive technique
1. High detection limit
2. Equipment cost
3. High level of staff expertise
4. Laboratory set up costs
5. Expensive technique
1. Laborious sample preparation (e.g.
derivatization, cleavage of conjugates)
2. Limited utility for thermally stable
volatile species
3. Expensive technique
1. Higher maintenances
2. Matrix effect
1. Time-consuming data analysis and
construction of calibration models
2. Not expensive technique
1. Time-consuming
2. Expensive technique
3. Require skilled personnel
1. Autofluorescence (sample dependent)0.
2-Low sensitivity.
3. Raman signals lead to long acquisition
times. Slow imaging by point scanning.
4. Video rate imaging almost impossible due
to low scattering efficiency and long
measurement times.
5. Sophisticated data analysis often
6. Not expensive technique
1. All molecules are not fluorescent.
2. It has limitations related to loss of
recognition capability and photostability
3. It is susceptible to the auto-fluorescence
of the sample.
4. Potential toxicity
5. The short lifespan of fluorophores
6. Not expensive technique

Nevertheless, the use of elemental content determination to detect
adulteration of argan oil with other vegetable oils could present limi­
tations due to the possible similarity of argan oil mineral composition
with some other vegetable oils and the cost of technique execution.
Vibrational spectroscopy is a third technique that has been used to
determine the purity of argan oil. It requires little sample preparation
and is less expensive than the previously decribed techniques. This
section details several applications of vibrational spectroscopy to
detection of adulteration.
2.3. Vibrational spectroscopy (Infrared and Raman Spectroscopy)
2.3.1. Application of Infrared spectroscopy
Infrared spectroscopy is commonly employed for fast (typically
20–60 s per measurement) and non-destructive examination of both
industrial and natural substances in food products. It is also used in
suspected food fraud cases as it represents a fast, easy, and authoritative
detection method for these investigations. Infrared spectral measure­
ments supply the chemical bond information in the compounds [30].
The use of mid-infrared spectroscopy in coupling with attenuated
total reflectance (ATR) and partial least squares (PLS) to detect and
quantify argan oil adulteration with different edible oils was suggested
in 2012 [31]. PLS was used to predict soybean and sunflower oil levels as
adulterants in argan oil due to differences in spectral peaks between
pure and adulterated argan oil samples. Reults showed that PLS could
detect adulterant levels up to 30% w = w. The study showed that the
combination of mid-infrared spectroscopy with multi-variate analysis
(ART, PLS) is able to detect adulteration of argan oil.
The use of Visible and Near Infra-Red Spectroscopy (Vis/NIRS) as
non-destructive optical techniques combined with chemometric tools,
PLS, root mean square error of prediction (RMSEP), standard error of
prediction (SEP), and principal component analysis (PCA) to predict

5
F. Mohammed et al.
authenticity of argan oil, was proposed in 2019 [32]. The study focused
on detecting and quantifying the adulteration of argan oil in the spectral
ranges from 500 to 1000 nm and 1000 to 1700 nm. The results showed
that the Vis/NIRS technique is a rapid method to identify adulteration in
argan oil at a level of 0.35% in <1 s without needing to prepare or
destroy the samples. Visible and Near Infra-Red Spectroscopy is hence
an efficient technique to detect adulteration of argan oil at precision up
to 99.65%.
The determination of the purity of argan oil using Mid Infrared
Spectroscopy (MIR-TF), together with mathematical and statistical al­
gorithms, was recently reported [33]. Three pattern recognition
methods were used for data analysis: principal component analysis
(PCA), support vector machine learning regression (SVMR), and partial
least square regression (PLSR). Based on these mathematical analyses,
the percentage of adulteration with commercial oils was determined. A
strong relationship between the practical and expected values (PLSR)
was also observed and explained by the coefficient R2, which reach 0.99.
The use of Mid Infrared Spectroscopy (MIR-TF) together with mathe­
matical and statistical algorithms (PCA, SVMR, PLSR) contributed to
give clear detection of the adulterants in argan oil.
2.3.2. Raman spectroscopic analysis to detect olive oil mixtures in argan oil.
Raman spectroscopy is one of the essential techniques used to detect
adulteration of foods. This non-destructive technique provides chemical
information about the samples. Raman spectroscopy is helpful for both
solid and liquid samples [34]. Due to these advantages, it has gained
popularity compared with other analytical techniques.
Raman spectroscopy combined with the Hybrid Linear Analysis/
Goicoechea and Olivieri (HLA/GO) multivariate analysis technique, has
been used to detect adulteration of argan oil with olive oil in 2019 [35].
Raman spectra of 90 samples within the spectral range of 400–1500
cm− 1 were pretreated using standard normal variate (SNV) method to
evaluate the performance of the hybrid linear analysis methodology
developed by Goicoechea and Olivieri (HLA/GO). The study indicated
that calibration and validation models developed through the HLA/GO
analysis achieved a high accuracy of R2C = 0.98 and R2V = 0.97, and
low root-mean-square errors of calibration (RMSEC) of 0.41% and root-
mean-square error of validation (RMSEV) of 0.36% for eight concen­
trations of olive oil in argan oil. Compared with other vibrational
spectroscopy techeniques, Raman spectroscopy is a less-sensitive tech­
nique to predict the purity of argan oil, but the use of multivariate
analysis together with Raman spectroscopy greatly improve the preci­
sion of this technique to detect adulteration of argan oil.
The vibrational spectroscopy methods together with the multivariate
analysis have provided satisfactory results regarding the detection of
argan oil adulteration with sunflower, soybean, olive, commercial, and
cheap vegetable oils.
2.4. Other spectroscopic techniques
The use of other techniques such as fluorescence spectroscopy and
nuclear magnetic resonance have been of interest to detect adulteration
of argan oil. These techniques are rapid, and do not need sample prep­
aration or the use the chemo-metric tools. This section details the use of
these techniques to detect the purity of argan oil.
2.4.1. Application of electronic nose and voltammetric electronic tongue
Electronic-nose (e-nose) and electronic-tongue (e-tongue) can be
used to identify food quality properties, which are very helpful analyt­
ical tools in monitoring food treatment and detecting product authen­
ticity. E-nose and e-tongue users need to control sample preparation,
sampling, and data treatment [36]. E-nose and e-tongue do not supply
information on the nature of the underlying compounds but only pro­
vide a digital fingerprint about the food that can be examined by means
of statistical multivariate [37].
In 2014 [38], an e-nose system based on 5-TGS sensors and e-tongue
6
Microchemical Journal 168 (2021) 106501
formed by 7-voltammetric electrodes were used to quantify the per­
centage of sunflower oil adulterant in argan oil. The e-nose showed the
sensor response of TGS 842 decreased significantly, varying with the
percentage added sunflower oil as shown in Fig. 2. PCA and DFA results
showed that the e-nose data were acceptable for discrimination between
pure and adulterated argan oils. Moreover, SVM afforded acceptable
success ratios for comestible and cosmetic argan oil of 91.67%, and
83.34%, respectively. The effectiveness of e-nose and voltammetric e-
tongue was emphasized to distinguish argan oil adulteration with
different proportions of sunflower oil (10 to 70%).
A significant sample size is needed for each kind of validation using
e-nose or e-tongue. Because the amount of volatiles released from oil
depends on many factors such as humidity, pressure, and temperature,
sample preparation of e-nose and e-tongue is very challenging. Indeed, it
is necessary to avoid the liberation of volatiles from argan oil during the
preparation of the sample prior to e-nose and e-tongue analysis. There is
also a need for the development of technique-sensitivity for a small
sample size.
2.4.2. Using fluorescence spectroscopy to detect adulteration of argan oil
Fluorescence spectroscopy is used as an analytical tool to predict the
authenticity of foods. It is a non-destructive technique that can offer
quick and sensitive results [39,40]. This technique employs a light beam
(ultraviolet and laser beam) for excitation electrons, causing
fluorescence.
The application of the Laser-Induced Fluorescence technique and
chemometrics tools to detect argan oil adulterated with olive oil was
reported in 2016 [41]. The fluorescence spectra of many samples was
gauged employing a laser beam at 532 nm. Spectral data were treated to
obtain the best calibration model for quantification of olive oil in argan
oil. The study showed the possibility of adulteration detection of argan
oil with as low as 0.43% of olive oil (w/w). Laser-Induced Fluorescence
is hence an efficient tool to identify the presence of olive oil in argan oil.
The first use of synchronous fluorescence spectroscopy (SFS) to
identify the adulteration of argan oil with corn oil and its quantification
was reported in 2017 [42]. Fifteen one-class classification methods were
employed simultaneously over the 10 emission wavelengths (Δλ) groups
of SFS spectra to detect argan oil adulteration. Two calibration processes
were used with fusion 10 Δλ SFS spectral data groups for quantification
analysis. One was multivariate calibration by PLS. The other was a
univariate calibration approach by collecting SFS spectra at particular
SFS spectral ranges. This study aimed to detect corn oil content in argan
oil, and the study reported that adulteration prediction errors decreased
with fusion comparing with the calibration at individual Δλ intervals.
This method allowed to detect 4% adulteration. Synchronous fluores­
cence spectroscopy technique gave an acceptable effectiveness to detect
adulteration argan oil at purities up to 96%.
Fluorescence spectroscopy (Synchronous fluorescence or Laser-
Induced Fluorescence) is an accurate technique to predict the argan
oil adulteration with olive and corn oil at percentage up to 99.57% and
96%, respectively. It is a rapid technique, and there is no need to treat
the sample. Thus, fluorescence spectroscopy can be employed as a rapid
screening technique to predict argan oil authenticity with all types of
adulteration.
2.4.3. Using of benchtop 1H NMR
Nuclear magnetic resonance (NMR) can provide information about
the purity, quantitative analysis, geographic origin, structural clarifi­
cation, chemical profile, and prediction of food adulteration throughout
a short period of time [43–48].
Assessment of compositional parameters and reporting on the exis­
tence of fraud products in argan oil using NMR, occurred in 2020 [49].
The study proved useful in detecting adulterated argan oil by oils con­
taining elevated amounts of α-linolenic acid, which is almost absent
from pure argan oil. NMR technology is higly recommended to detect
such type of adulteration.
F. Mohammed et al.
NMR technique is considered a helpful alternative to detect adul­
teration of argan oil compared with the other techniques. It offers rapid,
simple, efficient, accurate screening analysis and the possibility of a
sample analyzing without previous treatment and without taking them
out of their original bottles, but this technique is still costly.
In summary, eleven oils (olive, sunflower, soybean, rapeseed,
apricot, sesame, hazelnut, arachis, soy, peanut, and corn oils) are
frequently used to adulterate argan oil. Therefore, several methods have
been developed to identify traces of these oils within argan oil. Using gas
chromatography, it is possible to detect the adulteration argan oil with
all kinds of vegetable oils containing campesterol whose content is only
0.4% in argan oil. Adulteration of argan oil with linolenic acid-rich oils
as rapeseed, corn, and soybean oils can be performed with an accuracy
up to 95%. However such method will not allow the detection of adul­
teration with olive, sunflower, and peanut oils. Triglyceride content
determination is mostly useful to detect the adulteration of argan oil
with olive oil, with a limit of 5%. The adulteration of argan oil with
refined sunflower and virgin olive oils was determined at level of 5% by
analyzing 3,5-stigmastadiene, kaurene, or pheophytin-a content. Using
triacylglycerol content, it is possible to detect the adulteration of argan
oil after the addition of up to 5% of sunflower, soybean, and olive oils.
Detection of the adulteration of argan oil based on tocopherol values
varies between a 5% limit level in the case of sunflower, olive, and soy
oils and only 15% in the case of corn oil due to it containing low to­
copherols values. The use of ICP-OES/AES is able to discriminate argan
oil from sunflower based on metal content, while the discrimination of
argan oil from olive, seeds and soyabean oils is difficult to achieve. In
addition to the efficiency of the techniques, the type and major com­
ponents of oils used for adulteration represents a challenge to determine
the purity of argan oil.
3. How to select the best method to certify argan oil autheticity
Tables 1 and 2 summarize the analytical techniques, functioning
principle, pros and cons of the different methods used to detect and
quantify adulterated argan oil. The difficulty in selecting an appropriate
method for the detection of argan oil adulteration is not simply its ac­
curacy. Obviously, the cost, the possibly necessary sample preparation
time, the toxicity of the reagents are additional hurdles that must be
considered by those willing to assess argan oil sample purity. Indeed, if
fluorescence spectroscopy is claimed to assess argan oil authenticity up
to 99.57% [41], the method still detects only fluorescent adulterants.
Therefore fraud using non-fluorescent adulterants could be undetected.
It is also susceptible to auto-fluorescence. Liquid chromatography can
evaluate argan oil purity up to 98–99% [9,14] based on campesterol
quantification, but this technique requires high maintenance and may
undergo matrix effect. E-nose and e-tongue technique have the ability to
confirm the purity of argan oil up to 90% [38], but it is time-consuming
and requires a skilled personnel. Hence, these techniques should be
improved with up to date technologies. Unfortunately, it is not possible
to use a unique analytical technique for the detection of the precise level
of each possible argan oil adulterant, those being to numerous. Never­
theless, for the affirmation of argan oil purity and for fast and easy
detection of possible argan oil frauds hand-held devices based on the
fluorescence spectroscopy or electronic tongue should be developed and
used. The method that could be run rapidly and considered as a routine
analysis is still missing and is still highly expected by the argan oil in­
dustry.Table 3.
4. Conclusion and future perspective
Argan oil quality control is a sensitive issue for its production.
Various techniques have been developed for the detection and quanti­
fication of argan oil adulteration. Furthermore, chemo-metric tools are
frequently required to evaluate the large amount of data generated by
the different analytical techniques. However, industrial and commercial
7
Microchemical Journal 168 (2021) 106501
sectors are still looking forward to modern, accurate, fast, inexpensive,
easy to use, and environmentally friendly techniques. New techniques
should also detect all the adulteration types in argan oil and have the
ability to quantify at the lowest level for any possible argan oil adul­
terant. Such a method still needs to be designed.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgements
This project is jointly supported from the University of Guelph and
the Institute of International Education’s Scholar Rescue Fund (IIE-SRF).
References
[1] Z. Charrouf, D. Guillaume. Ethnoeconomical, ethnomedical, and phytochemical
study of Argania spinosa (L.) Skeels, Journal of Ethnopharmacology. 67. 1999. 7-
14. 10.1016/S0378-8741(98)00228-1.
[2] S. Gharby, H. Harhar, B.E. Kartah, H. El Monfalouti, C. Denhez, M. Hilali,
D. Guillaume, Z. Charrouf, Can fruit-form be a marker for argan oil production ?
Nat. Prod. Commun. 8 (2013) 25–28, https://doi.org/10.1177/
1934578X1300800106.
[3] Z. Charrouf, D. Guillaume. The argan oil project: going from utopia to reality in 20
years, Oilseeds & Fats Crops and Lipids. 25. 2018. D209. 10.1051/ocl/2018006.
[4] Z. Charrouf, D. Guillaume, A. Driouich, The argan tree, an asset for Morocco,
Biofutur. 220 (2002) 54–57.
[5] Z. Charrouf, D. Guillaume, Argan oil: Occurrence, composition and impact on
human health, Eur. J. Lipid Sci. Technol. 110 (2008) 632–636, https://doi.org/
10.1002/ejlt.200700220.
[6] D. Guillaume, Z. Charrouf, Argan oil and other argan products; use in
dermocosmetology, Eur. J. Lipid Sci. Technol. 113 (4) (2011) 403–408, https://
doi.org/10.1002/ejlt.v113.410.1002/ejlt.201000417.
[7] D. Guillaume, D. Pioch, Z. Charrouf. Argan [Argania spinosa (L.) Skeels] oil :
extraction, composition, and uses. In Fruit oils : Chemistry and functionality.
Fawzy Ramadan, M. (Ed.), Springer Nature Switzerland AG (2019). 10.1007/978-
3-030-12473-1_16.
[8] Service de normalisation industrielle marocaine (Snima). Huiles d’argane.
Spécifications. Norme marocaine NM 08.5.090. Rabat. 2003.
[9] M. Hilali, Z. Charrouf, A.E.A. Soulhi, L. Hachimi, D. Guillaume, Detection of argan
oil adulteration using quantitative campesterol GC-Analysis, Journal of the
American Oil Chemists’ Society. 84 (8) (2007) 761–764, https://doi.org/10.1007/
s11746-007-1084-y.
[10] G.P. Danezis, A.S. Tsagkaris, F. Camin, V. Brusic, C.A. Georgiou, Food
authentication: Techniques, trends & emerging approaches, Trends Anal. Chem. 85
(2016) 123–132, https://doi.org/10.1016/j.trac.2016.02.026.
[11] G.P. Danezis, A.S. Tsagkaris, V. Brusic, C.A. Georgiou, Food authentication: State of
the art and prospects, Curr. Opin. Food Sci. 10 (2016) 22–31, https://doi.org/
10.1016/j.cofs.2016.07.003.
[12] F. Dionisi, J. Prodolliet, E. Tagliaferri, Assessment of olive oil adulteration by
reversed-phase high-performance liquid chromatography/amperometric detection
of tocopherols and tocotrienols, Journal of the American Oil Chemists’ Society. 72
(1995) 1505–1511, https://doi.org/10.1007/BF02577844.
[13] M. Hilali, Z. Charrouf, A.E. Aziz Soulhi, L. Hachimi, D. Guillaume, Influence of
origin and extraction method on argan oil physico-chemical characteristics and
composition, J. Agric. Food. Chem. 53 (6) (2005) 2081–2087, https://doi.org/
10.1021/jf040290t.
[14] N. Maata, B. Kartah, H. Harhar, S. Gharby, E.L.M. Benazzouz, D. Guillaume, Z.
Charrouf. Détection de l’adulteration de l’huile d’argane par des huiles végétales
vierges et raffinées, Actes du Premier Congrès International de l’Arganier. 2011.
Décembre Agadir. 15–17.
[15] M. Zougagh, R. Salghi, S. Dhair, A. Rios, Nanoparticle-based assay for the detection
of virgin argan oil adulteration and its rapid quality evaluation, Anal. Bioanal.
Chem. 399 (7) (2011) 2395–2405, https://doi.org/10.1007/s00216-010-4628-1.
[16] I. Ourrach, M. Rada, M.C. Pérez-Camino, M. Benaissa, Á. Guinda, Detection of
argan oil adulterated with vegetable oils: New markers, Grasas y Aceites. 63. 2012.
355-364. 10.3989/gya.047212.
[17] R. Salghi, W. Armbruster, W. Schwack, Detection of argan oil adulteration with
vegetable oils by high-performance liquid chromatography–evaporative light
scattering detection, Food Chem. 153 (2014) 387–392, https://doi.org/10.1016/j.
foodchem.2013.12.084.
[18] S.M. Momchilova, S.P. Taneva, R.D. Dimitrova, I.R. Totseva, D.V. Antonova,
Evaluation of authenticity and quality of argan oils sold on the bulgarian market,
Rivista Italiana Delle Sostanze Grasse XCIII(Apr.-Jun) (2016) 905–1103.
[19] G. Pagliuca, C. Bozzi, F.R. Gallo, G. Multari, G. Palazzino, R. Porrà, A. Panusa,
Triacylglycerol “hand-shape profile” of Argan oil Rapid and simple UHPLC-PDA-
ESI-TOF/MS and HPTLC methods to detect counterfeit Argan oil and Argan-oil-
F. Mohammed et al.
based products, J. Pharm. Biomed. Anal. 150 (2018) 121–131, https://doi.org/
10.1016/j.jpba.2017.11.059.
[20] S.E. Çelik, A. Asfoor, O. Şenol, R. Apak, Screening method for argan oil
adulteration with vegetable oils: an online HPLC assay with postcolumn detection
utilizing chemometric multidata analysis, J. Agric. Food. Chem. 67 (2019)
8279–8289, https://doi.org/10.1021/acs.jafc.9b03001.
[21] F. Mohammed, R. Bchitou, M. Boulmane, A. Bouhaouss, D. Guillaume, Modeling of
the distribution of heavy metals and trace elements in argan forest soil and parts of
argan tree, Nat. Prod. Commun. 8 (2013) 20–23, https://doi.org/10.1177/
1934578X1300800105.
[22] A. Gonzálvez, S. Armenta, M. de la Guardia, Adulteration detection of argan oil by
inductively coupled plasma optical emission spectrometry, Food Chem. 121 (3)
(2010) 878–886, https://doi.org/10.1016/j.foodchem.2009.11.091.
[23] A. Gonzálvez, M.E. Ghanjaoui, M. El Rhazi, M. de la Guardia, Inductively coupled
plasma optical emission spectroscopy determination of trace element composition
of argan oil, Food Sci. Technol. Int. 16 (1) (2010) 65–71, https://doi.org/10.1177/
1082013209353343.
[24] F.A.E. Mohammed, R. Bchitou, A. Bouhaouss, S. Gharby, H. Harhar, D. Guillaume,
Z. Charrouf, Can the dietary element content of virgin argan oils really be used for
adulteration detection? Food Chem. 136 (1) (2013) 105–108, https://doi.org/
10.1016/j.foodchem.2012.07.098.
[25] R.E.S. Froes, W.B. Neto, N.O.C.e. Silva, R.L.P. Naveira, Clésia.C. Nascentes, José.B.
B. da Silva, Multivariate optimization by exploratory analysis applied to the
determination of microelements in fruit juice by inductively coupled plasma
optical emission spectrometry, Spectrochim. Acta, Part B 64 (6) (2009) 619–622,
https://doi.org/10.1016/j.sab.2009.06.006.
[26] I.Juranović. Cindrić, M. Zeiner, M. Kröppl, G. Stingeder, Comparison of sample
preparation methods for the ICP-AES determination of minor and major elements
in clarified apple juices, Microchem. J. 99 (2) (2011) 364–369, https://doi.org/
10.1016/j.microc.2011.06.007.
[27] F. Mohammed, D. Guillaume, N. Abdulwali, B. Zabara, R. Bchitou, Tin content is a
possible marker to discriminate argan oil against olive, sesame, mustard, corn,
peanut, and sunflower oils, Eur. J. Lipid Sci. Technol. 121 (2019) 1–8, https://doi.
org/10.1002/ejlt.201800180.
[28] F. Mohammed, N. Abdulwali, D. Guillaume, N. Tenyang, R. Ponka, S. Al-Gadabi,
R. Bchitou, A.H. Abdullah, K.M. Naji, Chemical composition and mineralogical
residence of sesame oil from plants grown in different Yemeni environments,
Microchem. J. 140 (2019) 269–277, https://doi.org/10.1016/j.
microc.2018.04.011.
[29] F. Mohammed, D. Guillaume, N. Abdulwali, H. Harhar, H.J. Al-Jobory, Argan oil
element content is a powerful marker of the quality of the fruit used for its
preparation, Plant Foods Hum. Nutr. 75 (2) (2020) 230–235, https://doi.org/
10.1007/s11130-020-00797-0.
[30] R. Valand, S. Tanna, G. Lawson, L. Bengtström, A review of fourier transform
infrared (FTIR) spectroscopy used in food adulteration and authenticity
investigations, Journal Food Additives & Contaminants: Part A. 37 (2020) 19–38,
https://doi.org/10.1080/19440049.2019.1675909.
[31] A. Oussama, F. Elabadi, O. Devos, Analysis of argan oil adulteration using infrared
spectroscopy, Spectrosc. Lett. 45 (6) (2012) 458–463, https://doi.org/10.1080/
00387010.2011.639121.
[32] S. Farres, L. Srata, F. Fethi, A. Kadaoui, Argan oil authentication using visible/near
infrared spectroscopy combined to chemometrics tools, Vib. Spectrosc. 102 (2019)
79–84, https://doi.org/10.1016/j.vibspec.2019.04.003.
[33] A. El Orche, M. Bouatia, H. Labjar, M. Maaouni, M. Mbarki. Coupling Mid Infrared
Spectroscopy to mathematical and statistical tools for automatic classification,
qualification and quantification of Argan oil adulteration. 2020 IEEE 6th
International Conference on Optimization and Applications (ICOA). 10.1109/
ICOA49421.2020.9094456.
Microchemical Journal 168 (2021) 106501
[34] A. Kazlagić, E. Omanović-Mikličanin, Application of Raman Spectroscopy in Food
Forensics: A Review, IFMBE Proceedings. 73 (2019) 257–263, https://doi.org/
10.1007/978-3-030-17971-7_40.
[35] R. Joshi, B.K. Cho, R. Joshi, S. Lohumi, M. Akbar Faqeerzada, H.Z. Amanah, J. Lee,
C. Mo, H. Lee, Raman spectroscopic analysis to detect olive oil mixtures in argan
oil, Korean, J. Agric. Sci. 46 (2019) 183–194, https://doi.org/10.7744/
kjoas.20190008.
[36] J. Tan, J. Xu, Applications of electronic nose (e-nose) and electronic tongue(e-
tongue) in food quality-related properties determination: A review, Artificial
Intelligence in Agriculture. 4 (2020) 104–115, https://doi.org/10.1016/j.
aiia.2020.06.003.
[37] M.S. Cosio, D. Ballabio, S. Benedetti, C. Gigliotti, Geographical origin and
authentication of extra virgin olive oils by an electronic nose in combination with
artificial neural networks, Anal. Chim. Acta 567 (2) (2006) 202–210, https://doi.
org/10.1016/j.aca.2006.03.035.
[38] M. Bougrini, K. Tahri, Z. Haddi, K. Saidi, N. El Bari, B. Bouchikhi, Detection of
adulteration in argan oil by using an electronic nose and a voltammetric electronic
tongue, Journal of Sensors. 4 (2014) 1–11, https://doi.org/10.1155/2014/245831.
[39] T. Dramićanin, L. Lenhardt Acković, I. Zeković, M.D. Dramićanin, Detection of
adulterated honey by fluorescence excitation-emission matrices, Journal of
Spectroscopy. 8395212 (2018) 6, https://doi.org/10.1155/2018/8395212.
[40] G.M. Strasburg, R.D. Ludescher, Theory and application of fluorescence
spectroscopy in food research, Trends Food Sci. Technol. 6 (1995) 69–75, https://
doi.org/10.1016/S0924-2244(00)88966-9.
[41] S. Addou, F. Fethi, M. Chikri, A. Rrhioua, Detection of argan oil adulteration with
olive oil using fluorescence spectroscopy and chemometrics tools, Journal of
Materials and Environmental Science. 7 (2016) 2689–2698.
[42] T.D. Stokes, M. Foteini, B. Brownfield, J.H. Kalivas, G. Mousdis, A. Amine,
C. Georgiou, Feasibility assessment of synchronous fluorescence spectral fusion by
application to argan oil for adulteration analysis, Appl. Spectrosc. 3 (2017)
432–441, https://doi.org/10.1177/0003702817749232.
[43] R.M. Alonso-Salces, M.V. Holland, C. Guillou, 1H-NMR fingerprinting to evaluate
the stability of olive oil, Food Control 22 (12) (2011) 2041–2046, https://doi.org/
10.1016/j.foodcont.2011.05.026.
[44] Z. Barison, C.W.P. Silva, F.R. Campos, F. Simonelli, C.A. Lenz, A.G. Ferreira,
A simple methodology for the determinations of fatty acid composition in edible
oils through 1H NMR spectroscopy, Magn. Reson. Chem. 48 (2010) 642–650,
https://doi.org/10.1002/mrc.2629.
[45] G. Fang, J.Y. Goh, M. Tay, H.F. Lau, S.F.Y. Li, Characterization of oils and fats by
1
H NMR and CG/MS fingerprinting: classification, prediction and detection of
adulteration, Food Chem. 138 (2013) 1461–1469, https://doi.org/10.1016/j.
foodchem.2012.09.136.
[46] F. Longobardi, A. Ventrella, C. Napoli, E. Humpfer, B. Schütz, H. Schäfer, M.
G. Kontominas, A. Sacco, Classification of olive oils according to geographical
origin using 1H NMR fingerprinting combined with multivariate analysis, Food
Chem. 130 (2012) 177–183, https://doi.org/10.1016/j.foodchem.2011.06.045.
[47] R. Popescu, D. Costinel, O.R. Dinca, A. Marinescu, I. Stefanescu, R.E. Ionete,
Discrimination of vegetable oils using NMR spectroscopy and chemometrics, Food
Control 48 (2015) 84–90, https://doi.org/10.1016/j.foodcont.2014.04.046.
[48] C. Siciliano, E. Belsito, R. De Marco, M.L. Di Gioia, A. Leggio, A. Liguori,
Quantitative determination of fatty acid chain composition in pork meat products
by high resolution 1H NMR spectroscopy, Food Chem. 136 (2) (2013) 546–554,
https://doi.org/10.1016/j.foodchem.2012.08.058.
[49] Y. Gunning, A.J. Jackson, J. Colmer, F. Taous, M. Philo, R.M. Brignall, T. El Ghali,
M. Defernez, E.K. Kemsley, High-throughput screening of argan oil composition
and authenticity using benchtop 1H NMR, MRC. 58 (2020) 1177–1186, https://doi.
org/10.1002/mrc.5023.