Trends in Analytical Chemistry 138 (2021) 116238

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Trends in Analytical Chemistry

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Gas chromatography ‒ mass spectrometry for characterisation,

assessment of quality and authentication of seed and vegetable oils
Maria Fernanda S. Mota a, b, 1, Habtewold D. Waktola a, Yada Nolvachai a, 1,
Philip J. Marriott a, *
a
Australian Centre for Research on Separation Science, School of Chemistry, Monash University, Wellington Road, Clayton, VIC, 3800, Australia
b
Universidade Federal do Rio de Janeiro, Escola de Química. Av. Athos da Silveira Ramos 149, CT Bl E, 21941-909, Rio de Janeiro, Brazil

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

Article history: Seed and vegetable oils are complex mixtures of components, with the major classes including mono-,
Available online 22 February 2021 di- and triacylglycerols, fatty acids, phytosterols, tocopherols and tocotrienols. An overview of recent
advances in the analysis of seed and vegetable oils by both one-dimensional (1D) and multidimensional
Keywords: gas chromatography (MDGC) methodologies is presented. Authenticity of food oils continues to be
Comprehensive two-dimensional gas important, and use of various classes of compounds as markers for adulteration are highlighted. Selected
chromatography
applications of contaminants analysis, including pesticides, hydrocarbons and plasticisers, are emphas-
Food
ised. A brief comparison of the separation technologies gas chromatography (GC) and liquid chroma-
GC
GC
GCeMS
tography (LC) is also included. The review concludes by highlighting recent advances and future trends.
Mass spectrometry © 2021 Elsevier B.V. All rights reserved.

1. Introduction
Seed and vegetable oils are essential for food formulation,
adding flavour and texture to the food. Moreover, these oils are
important nutrients for human health, being a source of energy,
essential fatty acids (FAs) (linoleic acid and linolenic acid) and
carriers for fat-soluble vitamins (i.e., A, D, K and E) [1]. Seed and
vegetable oils are complex, composed of a mixture of tri-
acylglycerols (TAGs) as a major component. The variation in TAGs
and their composition are responsible for the physical and chemical
characteristics of the oil [1,2]. The TAG composition in edible oils
varies according to the plant species, plant maturity, environmental
factors (e.g., soil quality and climate conditions) and processing
technology applied for oil production [1,3].
Other components of the oils include free FAs, mono-
acylglycerols, diacylglycerols, phospholipids, tocopherols, sterols,
resins and pigments, and minor volatile compounds which may
contribute to sensory attributes. Although the minor compounds
comprise of only 2e5% of the vegetable oils composition, they play
an important role in the quality, stability, aroma and health benefits
of the oils [4,5]. These compounds may be exploited to confirm
adulteration and degradation [6e8].
* Corresponding author. Fax: þ61 3 99058501.
E-mail address: Philip.Marriott@monash.edu (P.J. Marriott).
1
These authors contributed equally to this work.
Whilst gas chromatography (GC) has been a mainstay tool for
many years for analysis of many constituents of oils, one of the
problems in one-dimensional (1D) GC analysis is coelution of
components that limits correct identification and quantification of
the individual analytes. Multidimensional gas chromatography
(MDGC) subjects the sample to two or more independent separa-
tion steps. Components from the first dimension (1D) column are
re-analysed by the second dimension (2D) column of different
stationary phase selectivity [9], with an aim to significantly increase
peak capacity, i.e., the number of theoretical peaks that can be fitted
in the separation space (chromatogram). The technique is capable
of improving the separation performance by increasing peak ca-
pacity, ideally solving coelution problems, removing underlying
matrix or interfering compounds, and determining compounds
present at small abundance through cryofocusing enhancement
[10,11]. Two variants of MDGC are conventional heart-cut (H/C)
MDGC and comprehensive two-dimensional gas chromatography
(GC
GC) [12]. H/C MDGC is a targeted analysis, where small por-
tion(s) of the flow from a 1D column is(are) transferred to and re-
analysed on a 2D column. GC
GC is an untargeted analysis, where
compounds eluted from a 1D column are continuously re-analysed
in the 2D column, allowing full profiling of the sample. A modulator
is required to collect fractions from 1D and pass them ‘instanta-
neously’ to the 2D column. A cryogenic modulator creates a
compression zone between the two dimensions that increases the
height of the peak (cryofocusing) [13].

https://doi.org/10.1016/j.trac.2021.116238
0165-9936/© 2021 Elsevier B.V. All rights reserved.
M.F.S. Mota, H.D. Waktola, Y. Nolvachai et al.
GC is often coupled with the mass spectrometry (MS) detector.
The major advantage of this detector is that it allows identification
of the compounds based on mass-to-charge (m/z) ratios and rela-
tive abundances of the molecular and fragment ions, arising from
electron ionisation (EI), commonly at 70 eV. Thus, compound
identification can be suggested by analysing the MS spectrum and
comparing this with a commercial MS library such as NIST and
Wiley [12], although in absence of supporting identification, this is
considered a tentative identification.
Over the years, significant effort has been made to determine a
complete profile of the vegetable oil components, as well as to
uncover the presence of adulteration and/or contaminants in the
edible oil, in order to guarantee its authenticity and quality. Various
separation techniques have been explored and employed for this
task, such as gas chromatography (GC), high performance liquid
chromatography (HPLC), thin layer chromatography (TLC), and
supercritical fluid chromatography (SFC); further evaluation tech-
niques include mass spectrometry (MS), nuclear magnetic reso-
nance spectroscopy (NMR) [14e17], and other spectroscopic
methods [18]. GC coupled with MS (GCeMS) is largely used for
characterisation of FAs, TAGs, volatile compounds, and phytosterols
[5,19e21]. The present review mainly focuses on newer de-
velopments in edible seed and vegetable (which includes pro-
cessed) oil analysis using MS detection combined with both 1DGC
and MDGC. This includes the analysis of major and minor oil
components, contaminants, as well as markers for the determina-
tion of authenticity and adulteration. A comparison with LC tech-
nique, as another common technique for edible oil analysis, will
also be mentioned.
2. Gas chromatography (GC) and liquid chromatography (LC)
Vegetable oils comprise of a wide range of compound classes
that vary in their physicochemical properties such as molar mass
and vapour pressure. GC and LC techniques are often used for the
analysis of the vegetable oil composition. In terms of compound
type, GC is more suitable for the analysis of smaller, volatile com-
pounds, while LC is more robust for larger and less/non-volatile
compounds. Less volatile compounds can sometimes be analysed
by GC, commonly requiring derivatisation prior to analysis,
resulting in more volatile and stable products, although it increases
the method complexity and lengthens sample preparation. The
availability of derivatisable groups and their steric hindrance in the
analyte, and stability of the derivatised compounds should also be
considered. For volatile compounds, gas sampling techniques such
as headspace (HS) and solid-phase microextraction (SPME) are
available for GC, allowing simple sample preparation steps with
minimum sample clean-up, although quantitative analysis of all
components in a sample can be complicated for SPME [22]. While EI
is the most common ionisation mode for GC‒MS, ionisation modes
Fig. 1. Compound classes identified using different chromatographic platforms. (A) Venn diagram showing total compounds identified from different techniques. (B) Total
composition of the compound subclasses detected by different techniques shown in pie chart format. Adapted from Ref. [23]. Copyright (2018) MDPI.
2
Trends in Analytical Chemistry 138 (2021) 116238
available for LCeMS include atmospheric pressure chemical ion-
isation (APCI) and electrospray ionisation (ESI) in positive and
negative mode, however no standardised commercial database is
available for LC.
Both GC and LC techniques can be used in conjunction for
comprehensive profiling analysis. A comprehensive study of virgin
olive oil has shown that 94 compounds were exclusively identified
by LCeMS, with 11 by GCeMS, many more (47) were mutually
identified by both GC and LC methods (Fig. 1A) [23]. In this work,
GCeMS was operated in APCI mode, where its advantage over EI is
preservation of molecular ion information, at the expense of frag-
mentation and detailed library searching capability. Among 58
compounds identified, GCeAPCI-MS is preferred for identifying FAs
(38%), sterols (31%) and secoiridoids (17%) (Fig. 1B). LCeESI-MS is
capable of detecting more of the secoiridoids content, while
LCeAPCI-MS is able to detect a greater number of organic acids,
coumarins and free FAs (negative mode), and sterols (positive
mode).
In general, FAs, hydrocarbons, tocopherols, sterols and triterpenic
alcohols are suited to GC analysis, while LC methods are suitable for
simple phenols, secoiridoids, flavonoids, lignans and triterpenic
acids [24], although this distinction is not absolute, since for instance
flavonoids can be readily derivatised and analysed by GC.
3. GC‒MS analysis of different compound classes in vegetable
oils
3.1. Fatty acids (FAs)
The FA composition of vegetable oils determine the physical,
chemical and health attributes of the oil [25]. Whilst free FAs may
occur at low concentrations, they are generally derived from their
parent TAG (see later). FAs consist of hydrocarbon chains termi-
nated by a carboxyl acid group. In vegetable oils, FAs usually contain
an even carbon number (CN) with a hydrocarbon chain that may
vary from 8 to 24 carbons; CN 14 to 24 are the most prevalent, and
vary in their degree of saturation as the most common modification
[26,27].
The FA composition is normally determined after derivatisation
to their fatty acid methyl esters (FAMEs), transforming them into a
volatile form suitable for GC analysis. Acid catalysed esterification
and transesterification, and base catalysed transesterification are
widely applicable methods for FAME derivatisation [28]. The choice
of derivatising agent often revolves around its nuances in MS
fragmentation and has been recently reviewed [29].
Generally, FAME analysis in vegetable oils is conducted using a
single column GC (1DGC). Low polarity column phases do not
exhibit good selectivity towards separation of saturated and un-
saturated FA of a given CN, with saturated FA eluting marginally
later. However, polar phases such as poly(ethylene) glycol (PEG),
M.F.S. Mota, H.D. Waktola, Y. Nolvachai et al.
ionic liquid (IL) and cyanopropyl-substituted polysiloxanes
improve separation selectivity of a given CN based on the degree of
unsaturation, with saturated FA now eluting earlier than unsatu-
rated FA of the same CN [30e33]. However, coelution still arises for
FAMEs, and especially minor FAs that can be difficult to detect. To
enhance sensitivity and separation efficiency for GC analysis of
FAMEs, MDGC is an effective technique to address these issues
[5,34].
Kamatou and Viljoen [5] analysed FAME prepared from palm
and palm kernel oils using GCeMS/FID and GC
GCeTOFMS, aiming
to determine differences in FA composition. Five samples of palm
oil and two of palm kernel oil from different regions were studied.
The GCeMS/FID analysis was performed using a non-polar (5%
phenyl)-methylpolysiloxane column, while GC
GCeTOFMS anal-
ysis employed a polar PEG column in the first dimension (1D) and a
non-polar 1,4-bis(dimethylsiloxy)phenylene dimethylpolysiloxane
column in 2D. The number of FAMEs reported was doubled when
using GC
GC, providing a higher separation capacity and sensi-
tivity compared with GCeMS/FID. This improvement in GC sepa-
ration is most likely due to both using the GC
GC technique that
improves the resolution and sensitivity, as well as a more polar
phase (PEG) for the 1D column. Some minor FAMEs were found to
be region specific and demonstrated that GC
GC can differentiate
palm oils from different origins. Vyviurska et al. [35] applied
GC
GC‒TOFMS for characterisation of FA profiles of 8 vegetable
oils, including sunflower oil, sesame oil, mustard oil, hempseed oil,
olive pomace and extra virgin olive oils (EVOO), using a polar FFAP
(nitroterephthalic-acid-modified PEG) 1D and mid-polar 50%
phenyl-polysilphenylene-siloxane 2D columns. This led to suc-
cessful quantification of trace level medium-chain FAs and odd CN
FAs. Unsaturated FAs that may coelute in 1DGC such as
C21:0eC20:3 u6, C20:3 u3eC20:4 u6 and C20:5 u3eC22:0 were
baseline separated. Nosheen et al. [34] developed a fast GC
GC
method for FAME separation and quantification in safflower oil and
linseed oil. Using a dual IL column combination of 1,5-di(2,3-
dimethylimidazolium)pentane bis(trifluoromethylsulfonyl)imide
with 1,12-di(tripropylphosphonium)dodecane bis(trifluorometha
nesulfonyl)imide, FAME separation can be achieved within 16 min,
including the detection of C15:0 and C17:0 FAs in safflower oil.
Zhu et al. [36] developed a GC
GC‒MS method for profiling free
FAs in edible oil using magnetic dispersive extraction [37]. A 100%
dimethyl polysiloxane and 50% phenylpolysilphenylene siloxane
columns were used as 1D and 2D (non-polar/mid-polar) respec-
tively. A total of 64 free FAs were tentatively identified in peanut oil,
corn oil, olive oil, rapeseed oil, flaxseed oil, soybean oil, sesame oil,
and sunflower oil. The method was suggested to be useful for free
FA fingerprinting or discovery of free FA markers to guide pro-
cessing, storage, and authentication of edible oils.
Pojjanapornpun et al. [17] reported a GC
GC method for FAME
separation of canola oil, employing an inert highly polar IL phase as
1
D and less polar IL phase as 2D columns, providing a FA profile
similar to the literature for a polar/less-polar column set. In com-
parison with the conventional IL phase, the inert IL showed
significantly less column bleed. The application of GC and MS for FA
analysis was reviewed recently [29].
3.2. Triacylglycerols (TAGs)
TAGs are the major component of vegetable oils. TAG consist of
three FAs esterified to a central glycerol moiety. The composition of
FAs and their positional distribution on the TAG molecule influence
biological, chemical and physical proprieties of the vegetable oil
[2,25]. It is common to analyse FAs (measured as FAMEs) for an
indirect knowledge of TAG composition, since FAME analysis is
considerably simpler. However, this requires making assumptions
3
Trends in Analytical Chemistry 138 (2021) 116238
on how the FAs are distributed in the TAG molecules, which in-
fluences oil properties, such as crystallisation, oxidative stability
and melting point [2,38,39].
Identification of TAGs in edible oil is difficult because sufficient
selectivity for many different TAG molecules, which have similar
physicochemical characteristics (e.g., molecular mass or CN, and
degree of unsaturation), is lacking. Two common techniques for
TAG analysis are high temperature GC (HTGC) and high-
performance LC (HPLC) [21,31,39,40].
In HTGC, a high final oven temperature of up to 350 C or more,
depending on the molar mass of TAGs, is required. In order to elute
TAGs at the lowest possible temperature, the column length and
the film thickness should be minimised (or maximised phase ratio)
with a relatively high column flow velocity [41]. On a non-polar
column, TAG elution order is based on CN, meanwhile a mid-
polar column allows some measure of TAG separation according
to both CN and degree of unsaturation [21,39]. The 50e65% phenyl
capillary columns with high thermal stability, such as 50%-diphe-
nyldimethylpolysiloxane, and 65%-phenyl-35%-methylpolysilox-
ane, are commonly used for 1D HTGC analysis of TAGs [39,41,42].
These columns have a maximum operating temperature of about
360e370 C. During GC analysis of TAGs, the separation of free FAs,
monoglycerols and diglycerols is also possible [21,43,44], arising
usually from incomplete biosynthesis or hydrolysis of the TAG
molecules.
TAG identification by GC requires either retention time match-
ing with authentic TAG standards (not readily available for many
TAGs, and coelution is still a concern), and/or through interpreta-
tion of the mass spectrum. Using the molecular ion and charac-
teristic fragment ions, such as [MeRCO2]þ, [RCOþ128]þ, [RCOþ74]þ
and RCOþ, where R is the aliphatic hydrocarbon chain, individual
TAG can be tentatively identified and coelution can be indicated
[21,45]. Separation of TAGs in 1DGC is usually incomplete, and TAGs
with similar CN and degree of unsaturation often coelute.
Small abundance TAGs present a particular problem. Ruiz-
Sambla
s et al. [39] applied HTGC‒ion trap-MS to characterise TAG
profiles of various varieties of EVOO. Eight major TAG species were
identified in all olive oil samples studied (PPO, PPL, PSO, OOP, POL,
OOS, OOO and OOL), which contain only four of the major FAs
present in olive oil, namely: palmitic (P), oleic (O), linoleic (L) and
stearic (S) acids. Thus, FA analysis does not represent the TAG
heterogeneity. The same authors also studied the quantification of
blended olive oil and edible oils such as sunflower, corn, sesame
and soya oils by TAG fingerprinting using HTGCeMS and chemo-
metrics tools [46].
A review of TAG analysis in vegetable oils and foods using HTGC
was reported in 2015 [41]. In addition, recent advances in TAG
analysis, including MDGC for improved TAG separation, was pub-
lished recently [29].
3.3. Volatile organic compounds (VOCs)
Volatile organic compounds (VOCs) are commonly responsible
for the aroma of vegetable oils. VOCs found in different vegetable
oils can originate in the plant, and/or be formed during oil pro-
cessing and storage [47e49]. The aroma of vegetable oils has sig-
nificant impact on their acceptability. Virgin vegetable oils, such as
EVOO and sesame oil, which do not undergo refining, preserve their
original odours among other qualities. Among various VOCs, only
some key odorants influence the overall aroma of edible oils. The
knowledge of these compounds are important for edible oil pro-
cessing, aiming to enhance desirable compounds while decreasing
undesirables [49]. Vegetable oil VOCs are commonly analysed using
either GC‒MS or GC
GC‒MS [48,50e52], with sensory detection
(olfactometry) providing additional odour assessment [53].
M.F.S. Mota, H.D. Waktola, Y. Nolvachai et al. Trends in Analytical Chemistry 138 (2021) 116238

3.3.1. Sample extraction methods
Prior to GC injection, VOCs are extracted using techniques
such as solvent extraction, solvent-assisted flavour evaporation
(SAFE), headspace sorptive extraction (HSSE) or headspace solid-
phase microextraction (HS SPME) [49,54]. For the latter, a range
of coated fibres are commercially available to preferentially
extract different compound classes of VOCs from different sam-
ples [53], as each coating material has a measure of different
affinity towards various compound classes. For characterisation of
VOCs, HS SPME is often preferred due to its operational simplicity,
and low set-up cost, and has been employed for routine quality
control [55], despite its complex quantification. Some commonly
used SPME fibres are 100 mm polydimethylsiloxane (PDMS) and
50/30 mm divinylbenzene/carboxen/polydimethylsiloxane (DVB/
CAR/PDMS) (Table 1).
3.3.2. GC‒MS analysis of VOCs
Unsurprisingly, GC‒MS is the most common hyphenation of GC
for VOC analysis in vegetable oils with selected examples shown in
Table 1, focussing on HS SPME GC‒MS technique. Study objectives
include profiling, differentiation of cultivar and/or geographical
origin, detection of adulteration, investigating changes attributed
to processing and storage conditions, investigating traceability, and
sensory quality of the oil.
Pouliarekou et al. [60] classified olive oil samples according to
geographical origin and cultivar based on the analysis of VOCs. The
study achieved a classification rate of 87% and 74% by origin and
cultivar respectively. Similarly, almond cultivars were classified
based on VOC composition [64]. Xu et al. [48] investigated changes
in key VOCs in edible oils under various oxidation processes during
ambient storage conditions, showing that the concentration of
several VOCs progressively increased during oxidation, and the key
volatile oxidation compounds formed at ambient temperatures
differ from those generated at higher temperatures. These reports
used non- and mid-polar capillary columns with a length of
30e60 m. Many studies applied chemometric methods, such as
principal component analysis (PCA), linear discriminant analysis
(LDA) and cluster analysis (CA), for data analysis (Table 1).
3.3.3. GC
GC‒MS analysis of VOCs
GC
GC‒MS is an alternative approach for the analysis of VOCs
in vegetable oils although still represents a limited number of
studies. The stated preference for GC
GC over 1DGC applied to
VOCs is that it reveals many minor and overlapping peaks due to
increase in peak capacity from the additional separation dimension,
as well as improved resolution and sensitivity from the cry-
ofocusing effect. 1DGC is appropriate to analyse VOCs in oil samples
where the focus is on major compounds, and those that are well
resolved, to differentiate between oils of different varieties. Luki

c
et al. [67] studied EVOO using both GC‒TOFMS and GC
GC‒TOFMS
after HS SPME extraction. The study reported <30 compounds
detected and identified using 1DGC method, whereas up to 1000
compounds were detected and about 256 compounds were
tentatively identified using GC
GC. A further study of VOCs in
EVOO using GC
GC‒MS, reported about 119 compounds [51]. VOCs
are largely identified by comparing their MS data to selected MS
library entries (tentative identification) [64,68]. Further identifi-
cation uses comparison of retention indices and mass spectra with
authentic standards or samples [54,67]. The purposes of GC
GC‒
MS analysis of VOCs in vegetable oils are similar to those for GC‒
MS; Table 2 shows selected applications of GC
GC‒MS for VOCs in
vegetable oils.

Table 1
Selected applications of HS SPME GC‒MS for the analysis of VOCs in vegetable oils.

Study purpose SPME fibre used Column Phase Type (Dimensions)a Data Prob Ref

Olive oil
Traceability of olive oil based on volatiles 50/30 mm DVB/CAR/PDMS A: (30 m
0.25 mm
0.25 mm) PCA, LDA, ANN-MLP [56]
pattern
Quantification of the volatile profile to 50/30 mm DVB/CAR/PDMS A: (50 m
0.2 mm
0.4 mm) LDA, PCA [57]
support the panel test in their classification
Natural variation (genetic) of VOCs in virgin 50/30 mm DVB/CAR/PDMS A: (60 m
0.25 mm
0.25 mm) FA, PCA [58]
OO
Investigation of changes in volatiles in terms 50/30 mm DVB/CAR/PDMS B: (50 m
0.2 mm
0.55 mm) PCA [59]
of cultivar, harvest year, and geographic
regions
Characterisation and classification according 50/30 mm DVB/CAR/PDMS C: (60 m
0.32 mm
1 mm) ANOVA, LDA, PCA [60]
to cultivar and geographical origin
Volatile profiles in different heating 100 mm PDMS C: (30 m
0.25 mm
0.25 mm) ANOVA [61]
conditions
Differentiation according to cultivar 50/30 mm DVB/CAR/PDMS C: (60 m
0.32 mm
1 mm) MANOVA, LDA [50]
Comparative analysis of volatiles using SPME 50/30 mm DVB/CAR/PDMS C: (30 m
0.25 mm
0.25 mm) ANOVA, CA [62]
and SAFE A: (30 m
0.25 mm
0.25 mm)
Varietal and processing effects on the volatile 100 mm PDMS C: (30 m
0.25 mm
0.25 mm)) CA [63]
profile
Almond oil
Classification of almond cultivars 50/30 mm DVB/CAR/PDMS C: (30 m
0.25 mm
0.25 mm) LDA [64]
Sesame oil
Differentiation of volatiles of sesame oils 65-mm PDMS/DVB C: (30 m
0.25 mm
0.25 mm) ANOVA, PCA [65]
prepared with diverse roasting conditions
Peanut, soybean, rapeseed, and linseed
Monitoring oxidative stability and changes in 50/30 mm DVB/CAR/PDMS D: (60 m
0.25mm
0.25 mm) [48]
key VOCs in edible oils during ambient
storage
Sunflower, rapeseed and olive oil
Differentiation between edible oils and waste 65-mm PDMS/DVB C: (30 m
0.25 mm
0.25 mm) PCA, CA [66]
cooking oil
a
A: Poly(ethylene)glycol; B: 100% Dimethylpolysiloxane; C: (5%-Phenyl)-methylpolysiloxane; D: (50%-Phenyl)-methylpolysiloxane. Column dimensions are given as length

I.D.
film thickness
b
Data processing: ANOVA, analysis of variance; ANN-MLP, artificial neural networks with multilayer perceptrons; CA, cluster analysis; FA, factor analysis; LDA, linear
discriminant analysis; PCA, principal component analysis; MANOVA, multivariate analysis of variance.

4
M.F.S. Mota, H.D. Waktola, Y. Nolvachai et al. Trends in Analytical Chemistry 138 (2021) 116238

Table 2
Selected applications of GC
GC‒MS for the analysis of VOCs in vegetable oils.

Oil type Study purpose Sampling Modulator Column Phase Type (Dimensions)a Data Prob Ref
technique

Olive oil
1
Combined targeted and untargeted profiling HS SPME Quadjet dual-stage thermal D: A: (30 m
0.25 mm
0.25 mm) ANOVA, PCA, SLDA [67]
2
of VOCs for differentiation, according to modulator D: B: (1.50 m
0.15 mm
0.15 mm)
variety and geographical origin
1
Combined untargeted and targeted HS SPME Two-stage KT 2004 loop- D: A: (30 m
0.25 mm
0.25 mm) PCA [51]
2
fingerprinting for volatiles and ripening type thermal modulator D: C: (1 m
0.1 mm
0.10 mm)
indicators in olive oil
Defining a chemical blueprint of virgin olive HS SPME Set up 1: non-polar
polar Set up 1: non-polar
polar PCA, PLS-DA, OPLS-DA [69]
1
oil volatiles to be correlated to the product A loop-type single-jet D: D: (30 m
0.25 mm
0.50 mm)
2
sensory quality prototype cryogenic D: A: (1.2 m
0.1 mm
0.10 mm)
modulator developed at the Set up 2: polar
non-polar
1
University of Udine D: A: (30 m
0.25 mm
0.25 mm)
2
Set up 2: polar
non-polar D: C: (1 m
0.1 mm
0.10 mm)
Two-stage KT 2004 loop
thermal modulator
1
Traceability of olive oil based on volatile HS SPME GC
GCeTOFMS, cryogenic D: A: (30 m
0.25 mm
0.25 mm) PCA, LDA, ANN [56]
2
pattern modulator (N2 jetsehot air D: B: (1.25 m
0.1 mm
0.1 mm)
jets technology)
1
Fingerprint pattern recognition in olive oil HS SPME Longitudinally modulated D: D: (30 m
0.25mm
0.25 mm) ANOVA, PCA [70]
2
produced by two different techniques cryogenic system (LMCS) D: A: (1.5 m
0.1mm
0.1 mm)
Cold-pressed rapeseed oil
1
Identifying the differences between oils HS SPME Cryogenic modulator D: D: (30 m
0.25 mm
0.5 mm) PCA [52]
2
obtained from peeled seeds, whole seeds, D: A: (0.75 m
0.1 mm
0.1 mm)
flakes and roasted flakes
Sesame and peanut oils
1
Detection of adulteration in soybean oil HS Cryogenic modulator (N2 D: D: (30 m
0.25 mm
0.25 mm) PCA, CA [71]
2
jetsehot air jets D: B: (1.6 m
0.1 mm
0.15 mm)
technology)
Sesame oil
1
Identification of key aroma-active compounds HS SPME GC
GCeTOFMS, modulator D: D: (30 m
0.25 mm
0.25 mm) ANOVA [47]
2
in sesame oil from microwaved seeds not mentioned D: B: (1.9 m
0.1 mm
0.15 mm)
Soybean, peanut, rapeseed, and sunflower seed oils
1
Characterisation of volatile components HS Cryogenic modulator D: D: (60 m
0.25 mm
0.1 mm) PCA, HCA, RF [72]
2
D: B: (2 m
0.15 mm
0.15 mm)
a
A: Poly(ethylene) glycol; D: (5%-Phenyl)-methylpolysiloxane; B: (50%-Phenyl)-methylpolysiloxane; C: 14%-Cyanopropylphenyl-methylpolysiloxane. Column dimensions
are given as length
I.D.
film thickness
b
Data Processing: ANN, artificial neural networks; CA, cluster analysis; HCA, hierarchical clustering analysis; LDA, linear discriminant analysis; RF, random forests; SLDA,
stepwise linear discriminant analysis; PCA, principal component analysis; PLS-DA, partial least square discriminant analysis; OPLS-DA, orthogonal partial least square
discriminant analysis.

Combined targeted and untargeted profiling of VOCs in olive oil
with HS SPME GC
GC‒MS was used to study differentiation of olive
oils according to variety and geographical origin; through multi-
variate analysis, VOCs were reported to discriminate the samples
[67]. Similarly, a GC
GC‒MS method for fingerprinting of VOCs in
EVOO harvested at different maturation stages was developed [51].
Classification of four edible oils (soybean, peanut, rapeseed, and
sunflower seed oils) based on VOC profiles using HS GC
GC‒
TOFMS was reported [72]. Gracka et al. [52] reported the differ-
ences in VOC composition of cold-pressed rapeseed oils processed
by different methods, using HS SPME GC
GC‒TOFMS, comparing
oils obtained from peeled seeds, pressing whole seeds, flakes and
roasted flakes. PCA of VOCs showed that peeled seed oil is the most
similar to whole seed oil from the second pressing. It was also re-
ported that the sensory analysis of the oils differed from those of
VOC analysis. With sensory analysis, peeled seed oil was the most
similar to whole seed oil from the first pressing. Zhao et al. [71]
studied adulteration of sesame and peanut oils with soybean oil,
using HS GC
GC‒TOFMS analysis of VOCs. They were able to
differentiate minimum adulteration levels of 5% and 10% of soybean
oil, in peanut and sesame oils respectively.
Various compound classes constitute the VOC composition of
vegetable oils. These include alcohols, aldehydes, ketones, esters,
heterocyclic compounds, pyrazines, furans, furfurals, acids and
others. The distribution of VOCs in the oil samples depends on
whether there is a pre-treatment before extraction, such as oils
extracted from roasted seeds, or extraction of cold-pressed oils
from fresh materials [65,72]. Some compounds such as heterocyclic
and sulfur compounds, and aldehydes, are produced or increased in
concentrations with roasting or heating of the seeds during
extraction [47]. A particular vegetable oil from different sources
may have different VOC compositions, and many VOCs in unrefined
vegetable oils are key aroma compounds and have characteristic
odour quality [49].
The VOC composition of EVOO was described by Stilo et al. [54]
based on GC
GC‒TOFMS analysis. The study displayed the 2D
structured separation pattern based on volatile compound chemi-
cal class, typical of GC
GC (Fig. 2A). The lipoxygenase (LOX)
signature compounds (Fig. 2B) were considered the most important
class of informative VOCs. These include hexanal, (Z)-3-hexenal,
(E)-2-hexenal, (Z)-3-hexenol, (E)-3-hexenol, (E)-2-hexenol and (E,
Z)-2,4-hexadienal, related to the fresh-green and fruity notes. Ho-
mologous series of linear saturated and unsaturated aldehydes and
ketones were identified (Fig. 2C). This group of volatiles are said to
provide information on shelf life evolution and are related to fatty
and waxy notes, and include heptanal, octanal, nonanal, decanal,
undecanal, (E)-2-heptenal, (E)-2-octenal, (E)-2-nonenal and (E)-2-
decenal. A group of branched unsaturated hydrocarbons that
elute later in the 2D plot is shown in Fig. 2D, which are related to
olives at early stage ripening.
Hu et al. [72] studied the VOC composition of four edible oils e
soybean, peanut, sunflower seed and rapeseed oils. From the 114
tentatively identified VOCs, only 37 VOCs were common to all four
edible oils. Some components were detected only in one of the

5
M.F.S. Mota, H.D. Waktola, Y. Nolvachai et al.
Fig. 2. (A) 2D pattern of EVOO together with some informative patterns of volatiles, (B) lipoxygenase (LOX; C6) signature components, (C) linear saturated and unsaturated al-
dehydes, (D) enlarged area of branched unsaturated hydrocarbons correlated to olive fruit freshness. Adapted from Ref. [54]. Copyright (2019) MDPI.
edible oils investigated. Rapeseed oil was reported to have 16 VOCs,
some of which are thiocyanic acid methyl ester, N-methylene-
ethenamine, dimethyl disulfide and 3-pentenenitrile. 2-Undecenal,
2-methoxy-4-vinylphenol, and 1-butyl-2-cyclohexen-1-ol were
exclusively found in peanut oil, while 2-methyl-cyclopentanol and
dihydro-4-methyl-2(3H)-furanone are in sunflower seed and soy-
bean oils respectively.
3.4. Other minor compounds
Minor components of vegetable oils are important for the
knowledge of quality, health benefits, botanic origin and authen-
tication of the oil. Examples include phytosterols, tocopherols and
tocotrienols. Their analysis may require extra steps of extraction,
preconcentration and/or derivatisation of the target compounds,
which may demand additional solvents, reagents and time [8]. Due
to this, some studies have attempted to achieve the analysis of
these minor compounds in a single analysis using GCeMS.
3.4.1. Phytosterols
Phytosterols comprise different triterpene compounds with
important structural function in the plant membranes [73].
Numerous phytosterols are found in vegetable oils, which present
several health benefits such as lowering total blood cholesterol and
reduced risk of coronary heart disease [73e75]. The determination
of plant sterols can be achieved using GC with or without previous
extraction and derivatisation [76].
Tan et al. [77] avoided time-consuming sample preparation with
their validated method using GCeMS with selected ion monitoring
(SIM) for analysis and quantification of phytosteryl esters (cam-
pesteryl oleate, stigmasteryl oleate and b-sitosteryl oleate) without
saponification and extraction. Corn germ oil, rice bran oil and
wheat germ oil were simply dissolved in n-hexane prior to GCeMS
analysis. The selected ion m/z for identification of campesteryl
oleate were m/z 382, 147, and 81; stigmasteryl oleate m/z 394, 255,
and 81; and b-sitosteryl oleate m/z 396, 213, and 43. This technique
provided good separation of the target compounds in 10 min, with
the benefit of minimising sample preparation and fewer chemical
reagents, without extraction or derivatisation.
Xu et al. [78] compared GC
GCeTOFMS (non-polar/mid-polar
column set) with single column GCeFID for analysis of sterols in
safflower seed, soybean, rapeseed, sunflower seed and peanut oils.
6
Trends in Analytical Chemistry 138 (2021) 116238
Solid phase extraction and derivatisation were carried out prior to
GC analysis. Compared to GCeFID, GC
GCeTOFMS allowed com-
pounds to be identified and quantified down to trace level, plus
separation of compounds that otherwise coeluted in 1D separation.
GC
GCeTOFMS provided accurate quantification of sterol com-
pounds due the improved component separation.
3.4.2. Vitamin E
Vitamin E consists of 4 tocopherols and 4 tocotrienols isomers
(a, b, g and d; depending on the number and position of methyl
groups on the chromanol ring). Tocopherols have a saturated side
chain and the tocotrienols have an unsaturated one. Vitamin E is a
natural antioxidant with an important role in the quality and taste
of vegetable oil, and preventing oxidation [2]. It is an essential
human nutrient, exclusively obtained from the diet, prevents
oxidative stress, protects cell membranes, regulates gene expres-
sion, with potential prevention against some diseases such as car-
diovascular diseases, cancer, cataracts and Alzheimer's disease [79].
Determination of tocopherols and tocotrienols in vegetable oils is
usually achieved using reversed-phase HPLC (RP-HPLC); however,
GC approaches have also been reported [80,81].
GCeMS analysis of tocopherols and tocotrienols usually requires
derivatisation to ‘cap’ the eOH group, and increase the volatility of
the compounds; however, avoiding this step is faster and more
environmentally friendly. Zhang et al. [20] developed and validated
a GCeMS method for the simultaneous determination of a-, b-, g-
and d-tocopherols and a-, b-, g- and d-tocotrienols in vegetable oils
with neither saponification nor derivatisation. They were isolated
using ultrasonic extraction with methanol. A relatively high
maximum GC oven temperature (300 C) with a 5% phenyl-95%
polydimethylsiloxane column was used for GCeMS analysis,
providing adequate separation of a-, b-, g- and d-isomers of to-
copherols and tocotrienols in only 14 min. This method was tested
using olive, sunflower, sesame, soybean, corn, peanut, rapeseed,
palm and grapeseed oils, illustrating a fast and simple method for
simultaneous determination of tocopherol and tocotrienol isomers
in vegetable oils.
3.4.3. S-(E)-Elenolide and policosanol
Edible oils from plants may contain other bioactive compounds,
with some reported to be analysed by GCeMS. S-(E)-Elenolide is a
potential antihypertensive agent, belonging to the secoiridoid
M.F.S. Mota, H.D. Waktola, Y. Nolvachai et al. Trends in Analytical Chemistry 138 (2021) 116238

derivative compound class and found in the fresh oil of unripe ol-
ives arising from low water usage during malaxation [82]. The
compound was first isolated and characterised from EVOO [82]; its
structure was confirmed by both NMR and GCeMS.
Policosanol is a mixture of long-chain (C20eC36) aliphatic pri-
mary alcohols that reportedly exhibits antioxidant and anti-
arthritic properties; the compound has been analysed in milk
thistle plant oil using GC‒MS [83]. Identification of both S-(E)-ele-
nolide and policosanol employs a simple 1DGC configuration with a
standard non-polar polysiloxane column.
3.4.4. Comprehensive studies of minor compound classes
In order to minimise analysis time and cost, some studies aim to
analyse multiple classes of compounds in a single analysis. While
1DGC is a common choice due to its simplicity and availability,
MDGC and GC
GC offer improved capability to separate complex
samples owing to significantly greater peak capacity, sensitivity,
and group type analysis [12].
1DGC is often used for analysis of the target minor compounds
in edible oil. Olmo-Garcia et al. [84] reported use of GCeMS for
analysis of a minor compound fraction of EVOO. Minor components
were liquid-liquid extracted with ethanol/water, prior to derivati-
sation using N,O-bis(trimethylsilyl)trifluoroacetamide (BSTFA) and
trimethylchlorosilane (TMCS). A non-polar column was used for the
GCeMS separation. Despite the complexity of the GC separation
(Fig. 3), the technique was useful for obtaining important infor-
mation about minor compounds such as tocopherols, sterols, free
FAs, and phenolic and triterpenic compounds. This technique

Fig. 3. GC‒MS total ion chromatograms (TICs) of trimethylsilyl (TMS) derivatised extracts from (A) Frantoio, (B) Kalamon, and (C) Cayon virgin olive oil, using a 5% phenyl-95%
polydimethylsiloxane column (30 m
0.25 mm I.D.
0.25 mm df). Peak identification numbers: 1, Van; 2,TY; 3, HTY; 4, AcHTY; 5, EA I; 6, Qui; 7, p-Cou; 8, EA II; 9, C16:1; 10,
C16:0; 11, Fer; 12, C18:2; 13, C18:1; 14, C18:0; 15, DLA; 16, DOA; 17, LigAgly I; 18, squalene; 19, LigAgly II; 20, d-Toc; 21, LigAgly III; 22, OleAgly I; 23, b-Toc; 24, g-Toc; 25, OleAgly II;
26, OleAgly III; 27, a-Toc; 28, Api; 29, Cam; 30, Sti; 31, Lut; 32, b-Sit; 33, Pin; 34, D5-Ave; 35, AcPin; 36, CyArten; 37, MeCyArtan; 38, ER; 39, Cit; 40, OA; 41, BA; 42, MA. Full
abbreviation list refer to Ref. [84]. Reproduced with permission from Ref. [84]. Copyright (2019) Elsevier.

7
M.F.S. Mota, H.D. Waktola, Y. Nolvachai et al.
supported identification of 41 compounds, including 7 sterols
(campesterol, stigmasterol, b-sitosterol, D5-avenasterol; cyclo-
artenol, methylencycloartanol and citrostadienol); vitamin E iso-
mers (a-, b-, g- and d-tocopherols) and 19 phenolic compounds.
Among these phenolic compounds, there were 7 simple phenols
[vanillin (Van), tyrosol (TY), hydroxytyrosol (HTY), acetylated HTY
(AcHTY), quinic acid (Qui), p-coumaric acid (p-Cou) and ferulic acid
(Fer)], 8 secoiridoid derivatives [ligstroside aglycone (LigAgly) I, II
and III, oleuropein aglycone (OleAgly) I, II and III, decarboxymethyl
ligstroside aglycone (DLA) and decarboxymethyl oleuropein agly-
cone (DOA)], 2 flavonoids [apigenin (Api) and luteolin (Lut)] and 2
lignans [pinoresinol (Pin) and acetoxypinoresinol (AcPin)]. The LOD
and LOQ ranges were 0.04e0.79 mg/L, and 0.14e2.63 mg/L,
respectively.
Alberdi-Cedeno et al. [7] described an immersion SPME fibre
(PDMS/DVB) method for an oil matrix as an environmentally
friendly alternative to replace conventional derivatisation for minor
compound analysis using GCeMS. This approach could detect to-
copherols, tocotrienols and more than 25 sterols in edible oils
(soybean, corn, sunflower and linseed oils). Moreover, identifica-
tion of major compounds, including hydrocarbons, some volatile
compounds, monoglycerides and compounds related to oil oxida-
tion was possible.
Due to their relatively low concentrations, analysis of minor
compounds would generally lead to a complex chromatogram in
the presence of major abundance compounds, with low peak res-
olution. To achieve better separation, GC
GC allows access to a
greater separation space, with cryofocusing improves detectability.
A non-polar
mid-polar column set achieved good separation for
analysis of minor compounds in edible oils [10,85]. Tranchida et al.
[10] applied GC
GC with parallel MS/FID detection and cryogenic
modulation for analysis of the unsaponifiable fraction of EVOO,
sunflower oil and peanut oil after derivatisation, noting good sep-
aration, and different compound types located in the specific zones
of the 2D plane.
A similar column set was applied in combination with high
resolution TOFMS (HRTOFMS) [86], for analysis of higher molar
mass compounds in vegetable oil. Use of HRTOFMS allows in-depth
profiling of accurate mass ions for compound attribution. Higher
molar mass compounds were identified with a good mass accuracy
of <10 ppm (mostly <5 ppm). The same approach was applied for
analysis of the unsaponifiable fraction of Quinoa (Chenopodium
quinoa) seed oil after derivatisation, achieving a good separation
and identification of the unsaponifiable fraction compounds. The
identification of a-, b-, g- and d-tocopherol isomers was achieved
using both quadrupole mass spectrometry (qMS) and TOFMS.
Identification of sterols was achieved using injection of standards
and MS database searching with literature comparison [87].
In a comparable analysis of less volatile compounds in coffee oil
with sample derivatisation, a mid-polar 1D/non-polar 2D column
set with cryogenic modulation was employed [44]. Separations of
sterols, hydrocarbons, FAs, diterpene alcohols and esters, and di-
and triacylglycerols, were achieved, some of which would other-
wise coelute in a single column separation.
4. Authenticity and adulteration of vegetable oils
Vegetable oils comprise an important and high value global
market commodity in great demand. Attributed to their high de-
mand and price, some vegetable oils are prone to adulteration.
Addition of less expensive, refined or waste cooking oil to expen-
sive or unrefined oil, and mixing of refined oil with cold pressed oil
have been significant problems. Prevention of adulteration is
required for the safety of the consumer, and assessment of adul-
teration to ensure the quality of the edible oils [88,89]. Due to
8
Trends in Analytical Chemistry 138 (2021) 116238
economic reasons, some vegetable oils, such as sesame oil and
virgin olive oil are more prone to adulteration than others [90,91].
Conventional physical and chemical techniques can be applied to
verify oil quality, such as saponification value, iodine value, acid
value, specific gravity, refractive index, viscosity, melting point and
peroxide value, and are used to support overall characterisation;
however, these techniques are not sufficiently advanced or selec-
tive enough to detect some oil adulterations [89,92,93]. Authen-
ticity can be verified through analysis of various targeted chemical
compositions, which are useful to pinpoint adulteration, of the
particular oil under investigation [89,93].
The technique of GC plays an important role in vegetable oil
authenticity. Table 3 highlights several compound classes that have
been analysed using GC‒MS to detect vegetable oil adulteration,
with the adulterating oil listed. Most often, FAs, sterols and VOCs
are used to provide evidence of adulteration. The combination of
GC data with chemometric analysis to build methods able to clas-
sify samples according to their characteristics and, therefore, detect
vegetable oil adulteration based on one or more target compound
analysis, has also been widely investigated and shown to be a great
resource to highlight vegetable oil adulteration [90,94].
4.1. FAs as target compounds
Fatty acids have been investigated as a target compound class to
detect adulteration since the FA profile usually differs from one oil
source to another. An increase in linolenic acid content in avocado,
sesame and virgin olive oils was used to detect adulteration by
addition of soybean oil [95,96,101,102]. The higher level of erucic
acid in olive oil, sesame oil and peanut oil can be taken as an in-
dicator for adulteration with rapeseed oil [94,102,103]. The adul-
teration of olive oil with peanut oil can lead to higher content of
eicosanoic, docosanoic and tetracosanoic acids, and saturated FAs
[94]. High levels of palmitic acid in sesame oil can be regarded as
adulteration with corn oil [101].
Heidari et al. [100] analysed FAs after derivatisation to FAMEs to
detect olive oil adulteration with lard using GCeMS. A non-polar
column was applied due to its higher thermal stability. The addi-
tion of lard to olive oil increases the content of saturated FAs such as
palmitic, stearic and myristic acids; myristic acid is mainly present
in lard, while it decreases the proportion of unsaturated FAs such as
oleic acid.
The presence of trans-FAs in unrefined vegetable oils also may
indicate adulteration with refined oils. trans-FAs are not present in
high concentration in crude vegetable oils. These FAs are usually
formed during the refining process, arising from exposure to the
high temperature applied in the deodorisation step. An increase of
trans-FAs isomers in EVOO was used to detect adulteration with
cheaper refined oils [97].
Combining FA profiles of a target vegetable oil with chemo-
metric analysis has been used to build methods to detect adulter-
ation. Zhang et al. [90] used GCeMS with SIM mode profiles of five
vegetable oils (soybean, rapeseed, sunflower, peanut and sesame
oils) to detect adulteration. Applying multivariate statistical
methods, identified FAs classified the five types of edible oils into
five groups, to develop a model to simultaneously detect adulter-
ation. The model was able to detect adulteration of edible oil with
other vegetable oils at an adulteration level of 10% (Fig. 4). Low
abundant FAs were suggested to be more important for classifica-
tion of the five types of edible oils, and additional parameters such
as phytosterols may be required to assess the authenticity of soy-
bean oils.
Xing et al. [102] studied adulteration of sesame oil with other
vegetable oils such as rapeseed, soybean, sunflower and maize oils,
based on FA composition, applying discriminate analysis (DA) and
M.F.S. Mota, H.D. Waktola, Y. Nolvachai et al. Trends in Analytical Chemistry 138 (2021) 116238

Table 3
Selected examples of target compounds that can be analysed using GCeMS techniques to detect vegetable oil adulteration.

Adulterated oil Oil used to adulterate Target compound: effect of adulteration Ref

Avocado Soybean FA: Higher content of linolenic, linoleic and stearic acids; lower [95]
content of oleic and palmitic acids
Sterols: Lower value of b-sitosterol; higher values of
campesterol and stigmasterol
EVOO Peanut FA: Higher content of eicosanoic acid, docosanoic acid, [94]
tetracosanoic acid, and saturated FAs
EVOO Rapeseed FA: Higher level of linolenic, g-linolenic, 11-eicosenoic, erucic [94]
and nervonic acids
EVOO Soybean FA: Higher level of linolenic acid [91,96]
Sterols: Higher level of campesterol and D7-stigmastenol;
lower level of the apparent b-sitosterol
EVOO Sunflower Sterols: Higher level of D7-stigmastenol, campesterol, [91,96]
stigmasterol, D7-campesterol and D7-avenasterol
EVOO Safflower Sterols: Higher level of D7-stigmastenol and campesterol [91]
EVOO Canola Sterols: Higher level of total sterol content and campesterol [91]
concentration; decrease in apparent b-sitosterol concentration.
EVOO Corn Sterols: Higher level of campesterol; lower level of apparent b- [96]
sitosterol
EVOO Refined FA: Higher level of trans-FAs [97]
EVOO Refined, solvent extracted olive Sterols: Higher level of stigmasta-3,5-diene [91,97e99]
Olive Lard FA: Higher level of palmitic, stearic and myristic acids; lower [100]
level of oleic acid
Sesame Soybean FA: Higher content of linoleic and linolenic acids [101,102]
VOC: Higher content of 2-propenal
Sesame Corn FA: Higher content of palmitic acid [101]
VOC: Higher content of 2-propenal
Sesame Rapeseed FA: Higher content of erucic acid [102]
Peanut Rapeseed FA: Higher content of erucic and linolenic acids [103]
EVOO, sunflower, sesame, soybean, Palm oil Tocotrienol: Higher amount of g-tocotrienol [20]
corn, peanut, rapeseed, grapeseed
Vegetable Refined waste cooking (used for Sterols: Increase in cholesterol level [104]
frying animal foods)
Virgin coconut Animal fats (lard, chicken, mutton tallow, Sterols: Increase in cholesterol level [105]
beef tallow & mixtures)

PCA, as an effective qualitative adulteration tool. Partial least-

squares regression (PLSR) was successfully applied to quantita-
tively identify the type and the level of vegetable oil added to the
sesame oil.
Although it is a relatively easy and somewhat satisfactory
method for detecting vegetable oil adulteration, in many cases FA
profiles do not generate reliable information about the authenticity
of some vegetable oils that have similar FA composition. In these
instances, detection of adulteration should target other classes of
compounds [96,101].

4.2. Tocopherols and tocotrienols as target compounds

Zhang et al. [20] proposed tocopherols and tocotrienols as being

Fig. 4. Scores plot between the first 2 principal components (PCs) for five types of
edible oils and their blended/adulterated oils based on their FA profiles. 300 blended
oils were simulated by mixing five oils with random proportions, while, 60 adulterated
oils were simulated by blending 10% content of four other oils with random pro-
portions to 90% soybean, peanut, sunflower, rapeseed, and sesame oils, respectively.
Adapted with permission from Ref. [90]. Copyright (2014) ACS publications.
of great importance for indication of oil adulteration. Their study
used GCeMS for simultaneous analysis of tocopherols and toco-
trienols and found that most vegetable oils such as EVOO, sun-
flower, sesame, soybean, corn, peanut, rapeseed, palm and
grapeseed oils have either no or low amounts of g-tocotrienol
whereas a high amount of g-tocotrienol was detected only in palm
oil. Thus, high amount of g-tocotrienol may indicate adulteration of
these oils with palm oil. Sesame oil contains an amount of a-
tocopherol 20e60 times lower when compared to the other oils,
which may be used as a parameter to distinguish sesame oil
adulteration.
4.3. Sterols as target compounds
Sterols comprise the major part of the unsaponifiable matter of
vegetable oils, and are recognised as being plant-specific. Sterol

9
M.F.S. Mota, H.D. Waktola, Y. Nolvachai et al.
profiling plays a decisive role in classifying contamination of some
vegetable oils, e.g., EVOO, with other cheaper ones. Jabeur et al. [96]
reported an increase in campesterol and D7-stigmastenol and
decrease of the apparent b-sitosterol in EVOO adulterated with
soybean oil; a higher level of campesterol and lower level of
apparent b-sitosterol in EVOO adulterated with corn oil; and a
higher level of D7-stigmastenol in EVOO adulterated with sun-
flower oil. The addition of as little as 1% of sunflower oil to EVOO
was reported to significantly increase the D7-stigmastenol per-
centage. Research conducted on assessment of EVOO authenticity
also reported similar results; an increase in campesterol level
indicated adulteration with soybean and corn oils; an increase in
D7-stigmastenol suggested adulteration with soybean, canola and
safflower oils [91]. Increases in campesterol and stigmasterol levels
with decrease in b-sitosterol content were detected when avocado
oil was adulterated with soybean oil [95].
Cholesterol has been investigated as a target compound to prove
adulteration of plant oil with animal fat and/or waste cooking oil.
This sterol is present in high concentration in animal fat, but it is
usually low in vegetable oils [104,105]. Zhao et al. [104] used
GCeMS to detect vegetable oil adulteration with waste cooking oil.
Samples were analysed without derivatisation and with a non-
polar column to provide good separation of target compounds.
The content and ratio of cholesterol, b-sitosterol, and campesterol
were used as a criterion for detection of vegetable oils adulterated
with waste cooking oil. A large amount of cholesterol (>20 mg/kg)
indicates adulteration, as do relative ratios of b-sitosterol, cam-
pesterol, and cholesterol in vegetable oils. The method proved to be
accurate for detection of vegetable oils adulterated with 5% of
refined waste cooking oil with 75 correct detections of adulteration
out of 81 oil samples in multi-laboratory analysis. However, this
method is only suitable to detect adulteration with waste cooking
oil used for frying animal foods, not for frying non-animal foods.
Xu et al. [105] used sterols to detect virgin coconut oil adulter-
ation with animal fats, comparing 1DGC with GC
GC separation.
Derivatisation to trimethylsilyl (TMS) ethers indicated incomplete
separation of cholesterol from cholestenol for GCeFID and GCeMS
analysis on a non-polar column. GC
GC analysis with the same
non-polar column for 1D and a mid-polar 2D column improved
resolution of the two compounds. Analysis by GC
GCeTOFMS was
reported as a precise, reliable, and easy method to detect adulter-
ation of virgin coconut oil with animal fats simply by assessing their
cholesterol level. Virgin coconut oil adulteration with lard, chicken
fat, mutton tallow, beef tallow, or their mixtures at a level as low as
0.25% could be determined.
4.4. Stigmastadiene as target compounds
A high content of stigmastadiene is one of the most used target
compounds to detect low level EVOO adulteration with refined oils.
Stigmastadiene is formed during the refining process of edible oils
by dehydration of b-sitosterol, and is quantified using GC‒MS after
derivatisation [97,106]. Tfouni et al. [98] showed the importance of
stigmastadiene analysis for the detection of adulteration; therefore,
FA, sterol and stigmastadiene composition were analysed in 70
EVOO samples. Nineteen samples were reported as adulterated and,
among these, 14 samples showed all three parameters to be altered
(FA, sterol and stigmastadiene composition), indicating the addition
of an oil of a different vegetable origin. However, five samples did
not present alteration in FA composition, so stigmastadiene analysis
was necessary to detect the addition of refined oil. An unaltered FA
composition indicated absence of vegetable oil from another source.
Srigley et al. [91] noted the presence of D5,23-stigmastadienol in
refined olive oil, and blended EVOO with sunflower oil, and the
absence of this compound in pure EVOO analysis. Previous study
10
Trends in Analytical Chemistry 138 (2021) 116238
detected presence of this compound in solvent-extracted olive oils
[99].
4.5. VOCs as target compounds
Among the FA, TAG and VOC content, VOC proved to be the best
marker compound class to detect adulteration in sesame oil with
corn or soybean oils. The detection of 2-propenal can discriminate
between pure and adulterated sesame oils with 5% of corn or
soybean oils [101]. Hu et al. [72] suggested VOC analysis to detect
adulteration through application of HS GC
GCeTOFMS to identify
VOCs in soybean, peanut, rapeseed and sunflower seed oils.
Multivariate statistical methods were used to classify the four
edible oils into four different groups. According to this study, 15
VOCs were selected as the most important compounds to classify
edible oils and, therefore, used for identifying possible adulteration.
The VOCs include 2-methyl-propanal, 3-methyl-butanal, 2-methyl-
butanal, camphene, 2,5-dimethyl-pyrazine, 3-nonen-2-one, 3-
methyl-2-butenal, cyclohexane, 2-pentanone, 2-hexenal, (E,E)-
2,4-nonadienal, 3-ethyl-2,5-dimethyl-pyrazine, 2-n-butylfuran, 2-
furanmethanol and N-methylene-ethenamine.
Target VOCs for adulteration of sesame oil with soybean oil were
analysed through HS SPME GC
GCeTOFMS. For this purpose, ses-
ame oil, soybean oil and sesame oil adulterated with 5% of soybean
oil were subjected to analysis. The SPME conditions were optimised
and validated via central composite design and the chosen fibre
DVB/CAR/PDMS was evaluated based on the number of retained
compounds. The GC
GCeTOFMS analysis applied a non-
polar
mid-polar column set. Twenty-five VOCs were selected to
distinguish sesame oils and adulterated oils, with their concen-
trations found to be different in the two groups of oils, i.e., 25 VOCs
can be used as markers to detect adulteration [107]. Zhao et al. [71]
applied HS GC
GCeTOFMS (non-polar
mid-polar column set) to
identify marker compounds in the pure oils, then to detect adul-
teration of sesame and peanut oils with soybean oil. Thirty common
volatiles were identified in the pure oils and 31 compounds that are
crucial for flavour formation were selected from volatiles in
different pure and adulterated oils as potential markers for PCA and
CA. Adulteration of peanut oil and sesame oil with soybean oil at
levels of 5 and 10% respectively were detectable.
5. Contaminants
Throughout the food supply chain, from farm-to-table, food can
be exposed to various chemical contaminants. Example may
include pesticides from raw material, hydrocarbons as a residual
solvent or contaminant during processing and logistics, mineral oil
saturated (MOSH) and mineral oil aromatic (MOAH) hydrocarbon
residues from fuel contamination, and alkylphenols or other
migration contaminants from plastic packaging. GC‒MS is
commonly used for such contaminant analysis, so brief comment
will be made here.
Pesticides and related chemical treatments during food pro-
duction, applied to crops to control various insect and biological
stresses, are concerning issues worldwide, requiring residue mea-
surement. GC is a highly sensitive technique for pesticide detection
[108]. GCeMS can be deployed as a generalist tool, where a whole
range of compounds across many chemical classes can be detected
with the availability of SIM mode or multiple reaction monitoring
mode (MRM) in GCeMS/MS, for increased sensitivity and selec-
tivity. Meanwhile GC hyphenated with nitrogen-phosphorous
detection (NPD), flame photometric detection (FPD), or electron
capture detection (ECD) is a specialist tool, and they are commonly
used for organophosphorus pesticide or trace chlorinated com-
pound detection in a wide range of food samples.
M.F.S. Mota, H.D. Waktola, Y. Nolvachai et al.
Apart from the detection method, an appropriate extraction
technique is another important aspect to minimise interference
from the sample matrix. Different extraction methods have been
developed over the years for pesticide detection in an oil matrix.
Examples include low-temperature lipid precipitation [109],
dissociation extraction [110], and QuEChERS [111] techniques. A
study reported the application of QuEChERS with GCetriple
quadrupole MS (QQQMS, MRM mode) for the analysis of 255 pes-
ticides in olive oil, peanut oil and soybean oil, with the LOQ range of
5e50 mg/kg [112].
Hydrocarbons (MOSH, MOAH) can be in a form of a residual
solvent or intrinsically formed during production [113] or as a result
of the exposure to a contaminated source. Hydrocarbon contami-
nants may be analysed by HS GCeMS techniques [114]. HS SPME
with GCeMS (SIM mode) was reported for the analysis of benzene,
toluene, ethylbenzene and xylene isomers (BTEX), alkylated mon-
oaromatic hydrocarbon (C1- to C4-benzenes) and light poly-
aromatic hydrocarbons (PAHs, up to four aromatic rings) in EVOO
[115]. The LOD and LOQ values were in the range of 0.05e1.6 mg/kg
and 0.2e5.26 mg/kg, respectively. Interestingly, the reported values
incorporated distribution constant calculation, taking into account
specific affinities of the SPME fibre for different compounds. An
alternative method was reported for analysis of BTEX by using a
thermal desorption unit (TDU) in combination with GCeMS (SIM
mode) [116]. With this method, oil samples (corn, olive and sun-
flower oils) were placed inside a microvial insert, which were then
introduced into a glass desorption tube. The whole tube was placed
in the TDU unit. With the above set up, the study was shown to
have a good detection limit of 0.7e1.2 mg/L, and linearity range of
10e200 mg/L.
Alkylphenols and bisphenol A are endocrine disrupting chem-
icals. Isotope dilution GCeMS was reported for the detection of
bisphenol A, 4-octylphenol, and 4-nonylphenol in vegetable oils
[117]. The samples were extracted by solid phase extraction and
then derivatised with heptafluorobutyric anhydride prior to
GCeMS (SIM mode) analysis with a non-polar column. LOD and
LOQ were approximated to be 0.83 mg/kg and 2.5 mg/kg, respec-
tively, with a recovery value of 64e110%.
For a more comprehensive analysis of the contaminant, a
method was developed for multiresidue analysis of PAHs, phthalate
esters, and alkylphenols in edible vegetable oils [118]. Samples
were extracted with hexane saturated acetonitrile, allowing the
sample to be directly analysed (without derivatisation) by
GCeQQQMS (MRM mode). The LOD and recovery values were
0.1e4.0 mg/kg and 70.0e110.8%, respectively.
6. Concluding remarks
Seed and vegetable oils are important nutrients for human
health. The composition of compounds in these oils ranges from
major or bulk compounds, to trace components, and for various
purposes, both the major and minor constituents are important
analytically. In general, the analytical separation challenge can range
from relatively straightforward, to very complex if the compounds
are at trace level, constitute multiple chemical classes, and suffer
matrix interference. While, single column GCeMS remains a pop-
ular choice for many components of the edible oil analysis due to its
simplicity, and with the instrument being readily available in most
laboratories and provides some measure of identification (e.g.,
retention index and MS library), multidimensional separations
continue to be developed. The expectation of providing a compre-
hensive profiling of the oil sample, and the increased separation
space provided allowing more compounds to be separated, is that
improved identification will result, sometimes with improved LOD.
Enhanced reliability of identification, and improved quantification
11
Trends in Analytical Chemistry 138 (2021) 116238
increase the value of the fingerprint that results, and can be usefully
applied to identify the plant oil origin, total composition, and assist
in authenticity analysis with various compound classes employed as
markers. Increasing applications of GC
GC hyphenated with high
resolution mass analysis in both MS and MS/MS mode are to be
expected as a natural evolution of the field, to address oil quality and
improved compound identification in future.
CRediT roles
Maria Fernanda S. Mota: Contribution to original draft sections;
Writing e original draft; Writing e review & editing.
Habtewold D. Waktola: Contribution to original draft sections;
Writing e original draft; Writing e review & editing.
Yada Nolvachai: Contribution to original draft sections; Writing
e original draft; Writing e review & editing.
Philip J. Marriott: Conceptualization; Funding acquisition;
Project administration; Resources; Supervision; Writing e review
& editing.
Declaration of competing interest
The authors declare they have no Conflict of Interest in sub-
mission of this manuscript.
Acknowledgements
We acknowledge funding from the ARC Linkage program grant
LP150100465. MFSM acknowledges Coordenaç~ ao de Aperfeiçoa-
mento de Pessoal de Nível Superior - Brasil (CAPES) - Finance Code
001 funding.
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