Microchemical Journal 152 (2020) 104295

Contents lists available at ScienceDirect

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

Review Article

Recent development in the application of analytical techniques for the T

traceability and authenticity of food of plant origin
Syed Abdul Wadooda, Guo Bolia, Zhang Xiaowena, Imtiaz Hussainb, Wei Yimina,
⁎

a
Institute of Food Science and Technology, Key Laboratory of Agro-Products Processing, CAAS/, Ministry of Agriculture, Beijing 100193, PR China
b
Department of food science and technology, The University of Poonch Rawalakot, AJK, Pakistan

ARTICLE INFO ABSTRACT

Keywords: The traceability of agro-products are very crucial as the food with know and guaranteed origin charged a high
Food traceability premium; meanwhile, the authenticity of the food product is also very necessary, since the adulteration of agro-
Plant origin products with cheap ingredients or chemicals pose a serious health threat to the consumer. Therefore there is
Chromatography clearly need to demonstrate these authenticity problems by modern analytical techniques. This review attempted
Spectrometry and spectroscopy
to highlight the current overview in the application of analytical techniques such as liquid and gas chromato-
Sensor technology
graphy, isotope ratio and elemental analysis, spectroscopic, DNA based and sensor technologies for the au-
thentication of food of plant origin, with a special focus on geographical origin traceability and authenticity
during the last five years. Papers cited here mainly include fruits, cereals, pulses, tea, coffee, spices, edible oil,
fruit juices, and alcoholic beverages. The effectiveness of these techniques in laboratory and industrial level and
also their advantages and drawbacks are discussed.

1. Introduction
In the last few years, agro-products safety and quality have gained
an increase attention, and the determination of food authenticity and
geographical origin are now major concerns for consumers, retailers,
farmers, and for food authorities, since several major food adulterations
and mislabeling events were happened [1]. A survey conducted by the
UK Food Standard Agency revealed that consumers pay more focus to
high-quality food products, and one of the basic parameters was iden-
tified geographical origin [2]. In another study, it is pointed out that
about 82% of the customers considered geographical origin as a quality
indicator before purchasing the agricultural-products [3]. The certain
and guaranteed geographical origin usually charged a high premium
and false labeling regarding geographical origin by unauthorized tra-
ders is detrimental to honest producers and consumers [4]. In addition,
many incidences regarding food adulteration have been reported in
recent years. Some of these incidences include: the addition of mela-
mine to wheat gluten to increase the protein content [5], contamination
of paprika powder with lead oxide [6], contamination of cayenne
pepper with red lead (Pb3O4) in order to achieve a vibrant color [7],
etc. These adulteration practices with chemical materials or cheap in-
gredients for financial gain pose serious health risk to the consumers
and resulted in several thousand hospitalizations in different incidences
around the globe [8], so product authenticity and authentication are
emerging topics and it demands to the researchers to work more in-
tensively in this area.
In the past few years, analytical techniques have made significant
progress and several analytical methods have been employed to de-
termine the food authenticity and adulteration detection. Most com-
monly used techniques for food authenticity and traceability includes
liquid and gas chromatography, isotope ratio and elemental analysis,
spectroscopic techniques, DNA based techniques, and sensor techni-
ques. Each technique has its own pros and cons. As for physic-chemical
analysis liquid and gas chromatographic techniques are widely used, for
identifying detrimental substances which is time taking, expensive,
labor intensive, and involve many purification steps [9]. Furthermore,
isotope ratio, elemental analysis, and DNA based methods even proved
very sensitive but also presented the same drawbacks. Therefore, in
recent past, great attention has been paid to establish non-destructive
and non-invasive techniques for instance, vibrational, hyperspectral,
fluorescence, nuclear magnetic resonance (NMR) spectroscopy, and
sensor techniques such as electronic tongues and electronic noses etc.
These techniques are rapid, cost-effective, involve less or no sample
preparation, environmental friendly, easy to operate and can be
adopted for online or at-line process control. However, sometimes it is
hard to determine the authenticity of agro-product with high accuracy
due to their less sensitivity and high signal to noise ratio.
Over the last few decades, with the development in the advanced

⁎
Corresponding author.
E-mail address: weiyimin36@hotmail.com (W. Yimin).

https://doi.org/10.1016/j.microc.2019.104295
Received 25 July 2019; Received in revised form 27 September 2019; Accepted 27 September 2019
Available online 13 October 2019
0026-265X/ © 2019 Elsevier B.V. All rights reserved.
S.A. Wadood, et al.
statistical analysis, the application of analytical techniques has gained
increasing attention in food authentication issues. Recently, some stu-
dies reviewed the application of analytical methods for the authenticity
of food of animal origin, and few studies focused on the traceability of
agro-products using a specific analytical technique [9–13]. In this ar-
ticle, we will provide a comprehensive overview of the application of
different analytical techniques to determine the authenticity and geo-
graphical traceability of food of plant origin during the last five years.
The effectiveness of these techniques in laboratory and industrial level,
as well as their advantages and drawbacks, will be discussed.
2. Analytical techniques used for the determination of
authenticity and traceability of plant origin food
2.1. Liquid chromatographic techniques
The analytical technique high performance liquid chromatography
(HPLC) is widely employed to analyze, separate, and quantify compo-
nents that are dissolved in a sample mixture. The HPLC instrument is
equipped with mobile phase reservoir, high pressure pump, injector,
analytical column, and detector. Different components can be separated
by subjecting the sample mixture in to the analytical column which
traveled through the mobile phase. The different compounds pass
through the column and the speed of each component varies due to the
difference in their partitioning behavior among the mobile phase and
the sorbent (stationary phase). Based on the nature of sorbent, a com-
ponent can be separated depend on their charge, molecular mass, hy-
drophobicity and so on. Various detectors such as ultraviolet–visible
(UV–vis), fluorescence, electrochemical, and diffractometer are most
commonly used in HPLC [3]. The recent report by Esteki et al. [14]
brings new details about the use of liquid chromatography in food
identification, proposing therefore novel and more beneficial prospects
of this technique.
In food analysis, HPLC is used for quantitative analyses of chemical
components present in food but also to verify authenticity and geo-
graphical traceability of agro products through chromatographic pro-
file. For agro products, HPLC method could be an effective tool to
perform several measurements such as chemical profile, detect adul-
terant, level of additive used, and environmental pollutant [15–19]. In
addition, HPLC method can also apply to check the authenticity and
geographical traceability of agro products through flavonoids profile,
primary and secondary metabolites, metal binding protein and peptides
[20–22]. Liquid chromatography combined with mass spectrometry
proved even more valuable and powerful analytical tool for regional
traceability of agro products. This technique has been used in several
studies to analyze different chemical constituents for the geographical
identification of agro products. Recent literature regarding the use of
this technique for geographical traceability is summarized in Table 1
and described in this section. In this perspective, Bat et al. [21] used
ultra-performance liquid chromatography/triple quadrupole tandem
mass spectrometry UPLC/QqQ-MS technique to detect primary and
secondary metabolites for the geographical traceability of apple juice.
Their results showed that phenolic compound profiling coupled with
chemometrics successfully differentiate geographical origin; especially
the minor phenolic compounds flavanols and flavonols were established
as a potential marker of authentic apple juice for the differentiation of
different apple cultivars and geographical origin. These results were
consistent with the findings of Guo et al. [23] who also reported that
polyphenol could serve as characteristic indices to confirm the geo-
graphical origin of apple juices. In another study, Guo et al. [24]. de-
veloped UHPLC-TOFMS method for the detection of polyphenol con-
tents in kiwifruit juices for geographical traceability. The authors stated
that polyphenol composition of kiwi fruits provides valuable insights
into the determination of their geographical and botanical origin. A
study was conducted to trace the geographical origin of red wine
through phenolic contents procured from different regions of Italy.
2
Microchemical Journal 152 (2020) 104295
HPLC-MS technique was employed to quantified phenolic compounds
including gallic acid, caffeic acid, p coumaric, trans-ferulic acid, trans-
resveratrol, (−)-epicatechin, and (+)-catechin by direct injecting
sample mixture into HPLC-MS. Results revealed significant differences
in polyphenol contents between wine made with the same monovarietal
grapes procured from different geographical origins. The authors con-
cluded that different environmental factors play an important role in
wine quality and significantly influence the chemical composition of
wine [25].
The saffron is a high cost product and its quality is largely associated
with geographical origin. Many unfair traders mislabeled saffron for
financial gain which causes serious damage to honest traders. That is
why in a recent study, D'Archivio et al. [26] analyzed saffron samples
by HPLC coupled with diode array detection procured from different
regions of Italy. HPLC fingerprints of crocins, picrocrocin, flavonoids,
and number of minor metabolites was different in different regions
samples and hence easily categorized on the basis of HPLC fingerprints.
In a similar approach, Liu et al. [22] discriminate Chinese and Iranian
saffron samples. Different non-volatile components were analyzed by
HPLC method. The authors stated that flavonoids, picrocrocin and
different types of crocins served as potential variables in discriminating
the saffron origin. Recently, Papapetros et al. [27] have employed
HPLC-RID to detect major sugars contents (glucose and fructose) of
different cherry cultivars collected from different areas of Greece. One
of the main findings was that sugar content along with volatile and
conventional quality parameters varied among different regions sam-
ples and achieved good classification percentages for cultivar and
geographical differentiation. In an additional study, Mahne Opatić et al.
[28] analyzed different chemical markers (total phenolics, carotenoids,
ascorbic acid) of commercial tomato samples by HPLC system coupled
with a diode array detector. By applying chemometric such as linear
discriminant analysis, satisfactory classification percentages (80%)
were obtained. The authors reported that cultivar, microclimatic con-
dition, and agricultural practices are the main factors which affect the
ascorbic acid and carotenoid contents of tomato. The obtained results
were in agreement with the previous findings [29,30]. A study was
conducted to discriminate the origin of ginger. The authors developed
HPLC-DAD method to detect a pungent bioactive component of ginger,
gingerol, and related compounds. By employing series of multivariate
analysis namely hierarchical cluster analysis (HCA), principal compo-
nent analysis (PCA), and linear discriminant analysis (LDA) the char-
acteristics pattern of each origin was created through the variation of a
chromatographic profile. Consequently, the ginger profile tended to be
grouped and separated on the basis of the geographical origin [31]. In
addition, many studies investigate the authenticity of food products
using chromatographic profile. Recently, the authenticity of organic
and conventional orange juices was successfully achieved using
HPLCeHR-MS. The authors identified some flavonoid and fatty acids as
potential marker involved in the discrimination of organic juices [32].
HPLC-MS is a helpful technique for geographical traceability of
agro-products as it allows identification and quantification of several
compounds in one measurement. HPLC is highly sensitive, robust, cost-
effective, and reproducible technique. This technique is a reliable and
powerful tool for geographical traceability of agro-products. However,
liquid chromatography techniques applied to determine geographical
traceability of agro-products usually include many extraction and
purification steps, which are deemed as bottlenecks in analytical
methods.
2.2. Gas chromatography
Gas chromatography (GC) is one of the most widely used separation
technique applied in food research, mainly to analyze volatile and semi-
volatile substances, aromatic compounds and contaminant like pesti-
cides [9]. A sample mixture of different components can be investigated
by injecting in to the GC, where the mixture is changed into vapors
S.A. Wadood, et al. Microchemical Journal 152 (2020) 104295

Table 1
A summary overview of chromatographic techniques used for determining the authenticity and traceability of plant origin food.
Food Purpose of analysis Detection technique Number of samples Data processing technique References

Apple juice Cultivar & geographical origin UPLC/QqQ-MS NA LDA [18]

Apple juice Cultivar & geographical origin HPLC-PDA 58 PCA, SLDA [20]
Kiwi juice Geographical origin UHPLC-TOFMS 51 PCA, SLDA [21]
Wine Geographical origin HPLC-MS, HS-SPME-GCMS 28 PCA, CA [22]
Saffron Geographical origin HPLC-DAD 144 LDA [23]
Saffron Geographical origin HPLC, GC/MS 98 OPLSDA [19]
Cherry Botanical & geographical origin HPLC-RID, SPME-GCMS 78 LDA, MANOVA [24]
Tomato Geographical origin HPLC-DAD 30 ANOVA, LDA [25]
Ginger Geographical origin HPLC-DAD 80 HCA, LDA, PCA [28]
Orange juices Organic v conventional HPLCeHR-MS, SPME-GCMS NA HCA, PLSDA, PCA [29]
Rice Geographical origin HS-SPME/GC–MS 24 PLS-DA, HCA [30]
Wheat Botanical origin DHE-GC–MS 209 PLS-DA, PCA [31]
Extra virgin olive oil Geographical origin SPME/GC–MS, FGC E- nose 278 PCA, PLS-DA [32]
Extra virgin olive oil Botanical & geographical origin HS-SPME/GC–MS NA Linear regression, correlation [33]
Apple Botanical & geographical origin HS-SPME/GC–MS 42 PLS-DA [34]
Caper berries geographical origin GC-FID NA PCA, CDA, ANOVA [35]
Walnut oil geographical origin GC-FID 180 SIMCA, PCA [36]
Tea Botanical origin HS-SPME/GC–MS 75 HCA, PCA, SLDA [37]
Tea Botanical & geographical origin HS-SPME/Es-GC–MS NA PCA, PLS-DA, HCA [38]

without decomposition in a heated chamber. The gas mixture passes
through the GC column where they interact with the coating of the
column consequently, the components become separated. The GC
column consists of a liquid stationary phase which is adsorbed onto the
surface of thin fused-silica capillary tube. An inert carrier gas (helium)
transports the sample through the column. Various detectors can be
employed in GC such as, electron capture detector (ECD), flame ioni-
zation detector (FID), mass spectrometry (MS), photo-ionization de-
tector (PID), flame photometric detector (FPD), thermionic detector
(TD), and atomic emission detector (AED). The choice of one depends
on the nature of the compound to be analyzed for instance, in the case
of organic compounds FID show better performance with high sensi-
tivity, low noise, and large linear response range. In general, MS is
regarded very powerful detector and mostly used in the food research
[3]. GC coupled with MS qualitatively and quantitatively analyzes the
complex mixtures containing different components. The quantitative
and qualitative analysis of chromatographic profiles of different agro
products provides valuable insights for the determination of authenti-
city and geographical origin of agro products [9].
Mislabeling of agro-products for financial gain is a matter of con-
cern for honest traders, producers, and consumers. To address the au-
thenticity problems regarding agro products, systematic and high
through-put traceability methods using modern analytical chemistry,
which show high accuracy and sensitivity, are very crucial. In this
context, Lim et al. [33] developed a volatile organic compound based
method to differentiate white rice samples from China and Korea using
headspace solid-phase microextraction combined with gas chromato-
graphy mass spectrometry (HS-SPME/GC–MS). By applying partial least
square discriminant analysis (PLS-DA), a very good classification of
white rice for both China and Korea was achieved. These authors found
12 discriminatory biomarkers including hexanal, 1-hexaanol, and hy-
drocarbons which have been known to be associated with geographical
conditions. In a different study, Starr and colleagues performed volatile
compound analysis on 81 wheat cultivars and landraces, grown under
controlled conditions, in order to explore the possibility of dis-
criminating wheat varieties on the basis of their volatile compound
profiles [34]. Volatile compounds were extracted by dynamic head-
space extraction and analyzed by GC–MS. Multivariate analysis was
applied to the volatile compounds data which showed a great diversity
in the volatile profile between samples. Results revealed that esters,
alcohols, and some furans are the main discriminatory markers between
landraces and modern varieties, whereas differences in modern vari-
eties were characterized by terpenes, pyrazines, and straight chain al-
dehydes.
The high prices of extra virgin olive oil (EVOO) make them the ideal
candidate for fraudulent activities. Therefore, a lot of research has been
conducted to develop reliable analytical methods coupled with che-
mometrics to ensure olive oil authenticity. A recent review by
Gonzalez-Fernandez et al. [35] summarizes the recent research of
analytical techniques coupled with chemometric procedures such as
artificial neuron network for the authenticity of extra virgin olive oil.
Recently, Melucci et al. [36] have employed flash gas chromatography
electronic nose (FGC E-nose) and SPME coupled to GC–MS to analyze
volatile compounds of extra virgin olive oil for geographical trace-
ability. FGC E-nose chromatograms served as fingerprints and the
chemometrics was applied to the non-target chromatographic signals of
the volatile fractions. A PLS-DA model discriminate 100% olive oil
samples. The geographical discrimination performance was compared
with SPME/GC–MS, and the results attained for both techniques on the
same data set were not significantly different. The authors concluded
that both techniques are able to discriminate the geographical origin of
extra virgin olive oil through volatile compounds profile; however,
SPME/GC–MS delivered more consistent analytical information on the
identity of volatile compounds. In another study, Cecchi and Alfei [37]
explored some newly identified volatile compounds of extra virgin olive
oil (EVOO) using HS-SPME/GC–MS for geographical traceability. The
author identified C6 compounds as main volatile compounds in EVOO
derived from polyunsaturated fatty acids through the lipoxygenase
pathways. The proportion of C6 compounds was different in specific
cultivars. The authors stated that genetic factors strongly affect volatile
formation and concluded that terpene hydrocarbons are a potential
marker for the geographical and genetic discrimination of EVOO. In a
similar approach, Giannetti et al. [38] identify apple cultivars and their
geographical origin through the analysis of volatile compounds by
using HS-SPME/GC–MS. Overall 118 volatile compounds were identi-
fied and these variables were subjected to partial least square dis-
criminant analysis (PLS-DA) model. The generated model executed very
good classification percentages both in the original count (91%) and
cross-validation (87%), enabling to obtain good separation among dif-
ferent regions. The model highlighted most relevant variables for the
discrimination of apple cultivar and origin which includes: ethanol,
ethyl acetate, propyl propanoate, 1-hexanol, isobutyl acetate, Z-2
hexen-1-ol acetate, and D-limonene, as these variables showed best
discriminatory power. In an additional study, Papapetros et al. [27]
differentiate geographical and botanical origin of sweet cheery cultivars
on the basis of volatile compounds profile. Identification and semi-
quantification of volatile compounds were done using SPME/GC–MS.
Multivariate statistical analysis was applied to the volatile compound

3
S.A. Wadood, et al.
and the results showed that geographical origin has a significant effect
on the volatile compounds of cherries. The most prominent volatile
compounds which were found to be significant (p < 0.05) include:
hexanal, acetaldehyde, (E)-2 hexenal, 2-buten-1-ol, (E)−2-hexen-1-ol,
3-methyl, hexane, heptane, acetone, 1, 3-butadiene, 1-methyl, 1, 3-
pentadiene, and dL-limonene. These compounds were then subjected to
linear discriminant analysis (LDA) and the clear separation between
different geographical origins was obtained. In a different approach,
Mottese et al. [39] discriminate Sicilian capers and caper berries (cap-
paris spinosa L) through fatty acids profile. Gas chromatography coupled
with a split injector and a flame ionization detector (GC-FID) was used
to analyzed fatty acid composition. A stepwise canonical discriminant
analysis (CDA) was applied to fatty acid composition and the model
generated very high correct classification percentages (99%). The
model was cross-validated using leave one out cross validation proce-
dure and the obtained percentages were more than 82% which suggest
the reliability of fatty acid composition for geographical traceability of
caper berries. In another study, Mahnaz Esteki et al. [40] succeeded by
using GC-FID to determine the fatty acid profile of the walnut oil.
Multivariate statistical methods (PCA-LDA) were employed to the
chromatographic fingerprints to discriminate the walnut origin. Results
revealed that different geographical origin can be identified on the basis
of fatty acid fingerprints. The authors stated that the high classification
percentages for the training set indicate the strong relationship between
the fatty acid profile and geographical origin. In a similar approach,
Mahnaz Esteki et al. [41] investigated fatty acid fingerprints using GC-
FID for the detection of apricot adulteration in almond powder. Clas-
sification methods (PCA and PCA-DA) were used to classify almond,
apricot kernel and mixture. Additionally, PLS and LS-SVM were used
for the quantification of adulteration ratios of almond. The developed
model showed high values of root mean square error of prediction
(RMSEP) and coefficient of determination (R2) in validation set for both
PLS and LS-SVM suggesting the reliability of developed method for
testing almond adulteration. In another study, fatty acids composition
was used to differentiate pistachio cultivars. The authors identifies
palmitic (C16:0), palmitoleic (C16:1), stearic (C18:0), oleic (C18:1),
linoleic (C18:2), linolenic (C18:3), arachidic (C20:0), and gondoic
(C20:1) acid as a potential marker to discriminate the pistachio culti-
vars [42].
Tea is an easy target for fraudulent activities and its quality largely
depends on climatic conditions and processing methods. Regarding
studies on tea, Lin et al. [43] successfully discriminate tea cultivars on
the basis of volatile compounds. The significant difference was ob-
served for major volatile contents in different tea cultivars, combined
with the results of chemometrics HCA, PCA, and LDA, it is noted that
the cultivar differences of aromatic profile remain prominent for tea
varieties and the variety feature dominated the other factors like
quality and origin. In a recent study, Mu et al. [44] establish novel
technique based on headspace solid-phase microextraction combined
with enantioselective gas chromatography mass spectrometry (HS-
SPME/Es-GC–MS) to discriminate different tea cultivar and geo-
graphical origin. Fifteen vital chiral volatile compounds present in tea
were analyzed with this approach. Results revealed that enantiomeric
ratios of different volatile compounds were significantly affected by the
geographical origin and the leaf types of tea cultivar. By applying a
series of multivariate analysis PCA, PLS-DA, and HCA the character-
istics pattern of each origin and cultivar was created through the var-
iation of volatile compounds. The concentrations of S-E- nerolidol, S-
citronellol, R-linalool, (1R, 2R)-methyl jasmonate, S-α-ionone, and the
2 enantiomers of linalool oxide A significantly varied between the
different groups and categorized as a most influential marker in dis-
criminating the geographical origin and tea cultivars. In the case of
wine, Sagratini et al. [25] investigate the geographical origin of Italian
red wine through volatile compounds profile. HS-SPME/GC–MS was
used to determine the volatile composition of wine. The authors found
ethyl hexanoate, ethyl decanoate, and ethyl octanoate as most
4
Microchemical Journal 152 (2020) 104295
dominating esters, while phenyl ethanol and 3- methyl- 1- butanol were
dominating alcohols in regional traceability of wine. The authors con-
cluded that environmental factors like climatic condition and soil
composition strongly associated with wine quality and greatly affect the
chemical composition of wine such as volatile compounds.
Gas chromatography has become most widely used analytical
technique for the quantification of volatile compounds in agro products
due to its versatility, reproducibility, and most importantly high sen-
sitivity. However, the drawback of GC is its high cost (both in term of
buying and maintenance of the system) and it involves highly specia-
lized operator to perform and interpret data.
2.3. Isotope ratio mass spectrometry (IRMS)
Isotope ratio mass spectrometry (IRMS) is particularized mass
spectrometer that detects precise and exact deviations in the natural
isotopic abundance of light stable isotopes. The conventional organic
mass spectrometers scan a mass range for characteristics fragment ions
in order to give structural information on the sample being examined.
Unlike conventional organic spectrometers, IRMS do not scan the mass
range to provide structural information. IRMS comprises of an inlet
system, an electron ionization source, a magnetic sector analyzer for
separating the ion, a Faraday-collector detector array for registering the
ion and a computer controlled data gaining system [45]. IRMS tech-
nique can distinguish the samples containing chemically identical
compounds on the basis of their isotope content. The most commonly
used isotope ratios of elements for the determination of geographical
origin and authenticity of agro products included 13C/12C, 2H/1H,
15
N/14N, 18O/16O and 34S/32S [3]. Generally, elemental analyzer cou-
pled with isotope ratio mass spectrometer (EA-IRMS) is used to measure
bulk stable isotope analysis of the sample. EA is an automated sample
preparation instrument which converts the analyzed sample into simple
gas for IRMS analysis. The isotopic values generated as a result of these
analyses demonstrate the isotopic composition of all the constituent in
the sample mixture as a whole [45]. IRMS technique is widely used in
food traceability studies as isotopic composition of different elements
provides sufficient information regarding geographical and botanical
origin of agro products.
IRMS technique coupled with chemometrics has been applied in
numerous studies to evaluate the authenticity and geographical origin
of agro products Table 2. In this perspective, Longobardi et al. [46]
discriminate the geographical origin of Italian sweet cherries on the
basis of stable carbon, hydrogen and oxygen isotopes. Different statis-
tical analysis was applied to the isotopic data. Firstly, a univariate t-test
was applied to highlight the statistical significant difference. δ18O and
δ2H exhibit significant differences among different regions sample. In
general, δ18O and δ2H showed an increasing trend from north to south
regions. Hydrogen and oxygen stable isotopes of agro products are
strongly associated with environmental factors (humidity, temperature,
rainfall) and geographical characteristics (altitude, latitude, and dis-
tance from the ocean) of the production area. These findings confirm
that δ18O and δ2H are potential markers to identify the geographical
origin of sweet cherries. Finally, to assess the discrimination efficiency
for cherry origin, linear discriminant analysis was applied to isotopic
data and very good correct classification (94%) and cross-validation
percentages (91%) were attained. These results are confirmed by de
Rijke et al. [47] who reported that δ18O and δ2H are very good in-
dicator to trace the geographical origin of bell pepper. In another study,
Longobardi et al. [48] discriminate Canadian and Italian lentils (Lens
culinaris Medik.) using isotope ratio mass spectrometry technique. The
δ13C, δ2H, δ15N, δ18O and δ34S were analyzed. The authors succeeded
to distinguish lentils samples from different countries using δ2H, δ18O
and δ 34S as these isotopes showed highly significant difference among
different regions samples. The authors found decrease in δ2H and δ18O
values with an increase in altitude, suggesting the isotopic fractionation
pattern on the basis of latitude and environmental factors. Recently,
S.A. Wadood, et al. Microchemical Journal 152 (2020) 104295

Table 2
A summary overview of mass spectrometry techniques used for determining the authenticity and traceability of plant origin food.
Food Purpose of analysis Detection technique Number of samples Data processing technique References

Sweet cherries Geographical origin IRMS 112 PCA, LDA [40]

Bell pepper Geographical origin GC-IRMS, GC–MS 60 LDA, KDA, Box plot [41]
Lentil Geographical origin IRMS 93 PCA, PL-DA, k-NN [42]
wine Geographical origin IRMS, ICP-MS 188 ANOVA, PLS-DA, SVM [43]
wine Geographical origin IRMS, ICP-MS 100 ANOVA, DA [44]
Wheat Geographical origin IRMS 270 ANOVA, MANOVA [45]
wheat Geographical origin IRMS 105 ANOVA, Boxplot [46]
Wheat Geographical origin IRMS 60 ANOVA [47]
Wheat Geographical origin IRMS 675 ANOVA, MANOVA, LDA [48]
Rice Geographical origin IRMS NA Blocked split plot, ANOVA [49]
Rice Geographical origin IRMS 37 ANOVA, LDA [50]
Rice Geographical origin ICP-MS, IRMS 59 ANOVA, PCA, OPLSDA [52]
Rice Geographical origin Q-ICP-MS, MC-ICP-MS 84 Correlation, paired t-test [53]
Tea Geographical origin ICP-MS NA ANOVA, MANOVA, SLDA [54]
Wine Geographical origin ICP-MS 134 ANOVA, CDA [57]
Wine Geographical origin & winery process ICP-MS 65 MANOVA, CVA [58]
Wine Geographical origin ICP-MS 57 PCA, LDA [59]
Chili pepper Geographical origin ICP-MS 29 SIMCA, UNEQ, PF, MRM [61]

Fan et al. [49] studied multielement fingerprints including the com- developed with nine minerals element and three stable isotopes (δ13C,
position of δ18O isotopic ratio to classify Chinese wine samples. The δ15N, δ18O) showed good accuracy with 100% correct classification and
results suggest that isotopic analysis of δ18O of wine water and ele- 75.5% cross-validation. The authors concluded that rice samples from
mental profile combine with the multivariate analysis is a promising the different origins can be differentiated on the basis of elemental and
approach to differentiate the geographical origin of wine. In another isotopic composition.
study, geographical identification of wine from different regions of IRMS is a helpful analytical technique for tracing the geographical
Romania was accomplished using δ13C of wine ethanol and δ18O of origin and determining the authenticity of numerous agricultural pro-
wine water [50]. The authors found that δ18O has strongly associated ducts. However, this technique has some limitations. The possible in-
with climatic condition and location, whereas δ13C alone has less sig- fluence of environmental factors like altitude, latitude, climate, and
nificance for the geographical discrimination at a regional level. The distance from the ocean should take into account while using the stable
carbon and oxygen stable isotopes and trace elements were subjected to isotope analysis. Samples may be categorized as an identical isotopic
discriminant analysis which allowed above 90% of the correct classi- signature if it's come from similar climate and geological site.
fication of the wine samples. The trace elements and δ18O were iden- Moreover, this technique is quite expensive both in term of buying and
tified as a suitable indicator to discriminate wine provenance. maintenance of a system. Furthermore, it is extremely important to
Regarding studies on cereals, Liu et al. [51] pointed out that δ13C, analyze large sample data to correctly classify the geographical origin
δD, δ15N of different wheat not only associated with geographical origin of agricultural products.
but also strongly influenced by wheat cultivars and production years.
The use of these isotopic parameters allowed to differentiate the bota-
2.4. Inductively coupled plasma mass spectrometry (ICP-MS)
nical and geographical origin of wheat across different years. In a si-
milar approach, Luo et al. [52] categorized the geographical origin of
ICP-MS is very powerful analytical technique used for the quanti-
wheat using δ13C and δ15N values of wheat originated from different
tative determination of metals and non-metals in a wide range of
countries. The results indicated that wheat from different countries
sample at low concentration, typically parts per billion (ppb) or trillion
could be potentially distinguished by using light stable carbon and ni-
(ppt) [57]. Through ICP-MS, samples are decomposed to neutral com-
trogen isotopes. These results were further confirmed by Rashmi et al.
ponents in high temperature argon plasma and examined on the basis of
[53] who reported similar results for δ13C in differentiating the wheat
mass to charge ratios. ICP-MS comprises on four main steps such as
from adjoining states of India. The authors stated that variation in the
sample introduction, aerosol generation, ionization by an argon plasma
δ13C can be attributed to geological and environmental factors like
source, mass discrimination, and the detection system [3]. ICP-MS is a
temperature, altitude, and latitude etc. In another study, Wadood et al.
sophisticated and highly reliable technique due to its high sensitivity,
[54] discriminated the geographical origin of wheat by analyzing δ13C,
multi-element characteristics, rapid speed, and isotopic capabilities.
δ15N values of different fractions of wheat. The authors stated that
Furthermore, unlike atomic emission spectrometer, ICP-MS can detect
wheat kernel along with different wheat fractions improved the geo-
solid as well as liquid samples.
graphical classification results to the considerable extent and concluded
ICP-MS can provide the geographical origin information of agro-
that fractional fingerprints could be effective to investigate the geo-
products by the analysis of several inorganic elements which serves as
graphical origin of wheat. Chen et al. [55] employed IRMS technique to
the fingerprint for geographical traceability. Major applications of ICP-
discriminate the geographical origin of rice collected from two regions
MS in food traceability studies are summarized in Table 2 and described
of China. Light stable isotopes (δ13C, δD, δ15N, δ18O) were analyzed
here. In this context, Chung et al. [58] analyzed the multi-element
from superior and inferior grains of rice cultivar. The authors reported
profile of rice samples procured from six different Asian countries using
that δ18O and δD showed great potential in identifying the geographical
ICP-MS to investigate geographical origin. Rice samples were clearly
origin of rice whereas, δ13C and δ15N failed to discriminate the culti-
discriminated through principal component analysis (PCA) and ortho-
vating site of rice. Recently, Kukusamude and Kongsri [56] discriminate
gonal projection to latent-structure discriminant analysis (OPLS-DA) as
Thai jasmine rice using isotopic and elemental profile. ANOVA showed
different countries exhibited a different proportion of micro and macro
significant differences for δ13C and δ18O among different regions while
elements. The authors reported that K, Mg, Na, Ca, Mn, Fe, and Zn was
δ15N values did not exhibit any significant differences. Linear dis-
the most abundant element groups in the rice and their concentration
criminant analysis was further applied to the elemental and isotopic
significantly varied among different countries samples. In another
data and the cultivation area was clearly differentiated. LDA model
study, Lagad et al. [59] used rare earth element along with strontium

5
S.A. Wadood, et al.
isotope to investigate the geographical origin of Indian basmati rice.
The authors found that rare earth elements (La, Ce, Pr, Nd, Sm, Eu, Gd,
Dy, Er, Yb) of rice and those of soil strongly correlate with each other.
The authors further highlighted that the observed rare earth element
pattern of Indian basmati rice can be used to distinguish the rice ori-
ginated from other countries. With regard to the wheat, Zhao et al. [60]
analyzed different elements in wheat grain and corresponding soil. The
relationships among different elements between wheat grain and soil
were studied and the elements associated with parent soil were sub-
jected to principal component analysis (PCA), and linear discriminant
analysis (LDA) to discriminate geographical origin. The authors found
that Cr, Mn, Ga, Rb, Sr, Zr, and Cd in wheat grain and its provenance
soil was strongly correlated and showed great potential to discriminate
geographical origin. These results were further confirmed by Liu et al.
[61] where they applied Multiway ANOVA and LDA to the elemental
data to discriminate geographical origin of Chinese winter wheat.
Multiway ANOVA showed that elements such as Mn, Sr, Mo, and Cd
were closely associated with the region explaining 34.2%, 39.6%,
35.0%, and 78.8% of the total variation. These elements were used to
develop a discriminant model which correctly classified 98.5% of wheat
samples among different regions. Recently, Zhao et al. [62] analyzed
minerals profile in tea samples for geographical, cultivar, and seasonal
discrimination. Multiway ANOVA showed that grown origin, cultivar,
and harvest season, and their interaction significantly influence the
mineral profile in tea leaves. The authors reported that the content of
Mg, Rb, Ni, Cd, Sr, Ba, Cs, and Pb in tea leaves is mainly associated with
origin; those of Al, Cu, and U mainly related to cultivar; whereas V, Na,
As, Sn, and Se were mostly influenced by season. In their study, Cabrita
et al. [63] showed the capability of ICP-MS in combination with linear
discriminant analysis (LDA) to identify the geographical origin of red,
white, and palhete amphora wines. Multielement composition showed a
significant difference among red, white, and palhete wine, and LDA
allowed a classification according to wine origin and wine type. In
another study, Hopfer et al. [64] employed ICP-MS technique to de-
termine the elemental profile of red wine. Wines were categorized ac-
cording to vineyard origin, winery processing, and the combination of
both factors. Results showed that vineyard origin and wine making
process both significantly influence the elemental composition of wine.
Authors concluded that studying the combined effects of grape growing
and winery processing provides valuable insights into the geographical
traceability of red wine. Another study reported the potential use of
ICP-MS in discriminating the geographical origin of Argentinean wine.
Multielement composition of main varieties from four winegrowing
region of Argentina was determined by ICP-MS. Pattern recognition
techniques PCA and LDA achieved successful discrimination results.
The results of PCA explained 95.95% of the total variance. LDA allowed
correct classification of 96% using ultra-trace elements (Ba, As, Pb, Mo,
and Co) among four geographical regions [65]. In a similar approach,
Šelih et al. [66] analyzed the multielement composition of Slovenian
bottled wines using ICP-MS. Chemometrics like PCA and counter-pro-
pagation artificial neural networks (CPANN) were applied to the ele-
mental data to achieve the geographical classification of wine. The best
classification percentages (82%) were achieved by CPANN. Considering
the small size of Slovenian wine growing regions, the authors consider
the classification results were satisfactory.
A study was conducted to discriminate the geographical origin of
chili pepper. Different class modeling techniques, namely unequal dis-
persed classes (UNEQ), potential functions (PF), soft independent
modeling of class analogy (SIMCA), and multivariate range modeling
(MRM) were applied to the elemental data. Firstly, the model was built
by subjecting all variables and the best and comparable percentages in
terms of CV efficiency were achieved with the use of MRM (83.2%) and
SIMCA (82.3). On the other hand, MRM generates very high percen-
tages (96.5%) as compared to SIMCA (85.1%) in terms of force model
efficiency. In the second approach, the variables were reduced by
stepwise linear discriminant analysis (S-LDA) and the selected variables
6
Microchemical Journal 152 (2020) 104295
were used for class-modeling. MRM again provided the best results both
in term of CV efficiency (87.7%) and forced model efficiency (96.5%).
The significant performance of MRM suggests the potential of this ap-
proach to effectively extract the valuable information from complex
data [67].
Due to high sensitivity, rapidity, and versatility, ICP-MS has become
a widely used technique for the analysis of mineral elements in agro-
products. The only drawback is the requirement of a costly and complex
system. Besides, highly trained operators are required to handle and run
the instrument.
2.5. Spectroscopic techniques
Over the last few years, the spectroscopic techniques have made a
significant progress, as it provides complex chemical information re-
garding the sample being scanned. These techniques work over diverse
and limited frequency ranges which is mostly associated with the pro-
cess being studied and the degree of change in the associated energy
[8]. A wide array of vibrational spectroscopic techniques namely near-
infrared (NIR), mid infrared (MIR), Raman spectroscopy, hyperspectral
imaging, etc. have been employed in food sector for detecting the
adulteration and determining the authenticity of food products. The
main advantages of these techniques include non-destructiveness, low-
cost, rapid, and can be considered for both qualitative and quantitative
analysis of agro products.
2.5.1. Near infrared spectroscopy
NIR spectra of food samples encompass broad bands rising from
overlapping absorption mostly associated with overtones and combi-
nations of vibrational bands including chemical bonds such as NeH,
CeH, OeH [68]. In general, an infrared spectrum is usually acquired by
passing infrared radiation at a wavelength in a range of 780–2500 nm
through the sample and defining what fraction of the incident radiation
is absorbed at a particular energy [69]. In the last decade, instrumental
evolution, the analytical techniques, and the software based on math-
ematical and chemometric approaches have made a significant pro-
gress, which make data interpretation more precise and rapid. Conse-
quently, the NIR spectroscopy has become a most effective, reliable,
and standard analytical tool for quality control measurements in a
broad range of analytical fields including food industries [70]. NIR
offers different spectral modes such as reflectance, transmission, in-
teractance, and transflectance to predict the internal and external
properties of a given sample. The choice of each mode depends on the
nature of the product to be analyzed. Generally, reflectance mode is
used to analyze the powdered or solid samples, transflectance for a thin
or vibrant, and transmission mode is used to collect the spectra of liquid
samples. Reflectance mode is very useful for analyzing the physical and
chemical characteristics of the target sample, and has gained a special
interest in the food sector for quality control analysis due to its com-
patibility with physical and chemical properties of food products [8].
Many studies have been done on the detection of adulterations in
various food products using NIR reflectance mode Table 3. Recently,
Shafiee and Minaei [71] analyzed pure and synthetic lime juice through
NIR spectroscopy. Reflectance spectra of synthetic and pure lime juice
were recorded and subjected to different chemometric models. The best
results were achieved using a support vector machine (SVM) with the
highest accuracy of 97%. The authors concluded that NIR in combi-
nation with chemometrics is a potential tool to detect the lime juice
quality in term of natural or synthetic nature. The transmission mode
has also adopted in many studies to measure the internal and external
properties of the target object, as light passing over the object conveys
useful information about its spectral properties. Using this method oil
and juices have been tested for adulteration and authenticity [72,73].
NIR spectroscopy has also applied for geographical and varietal
differentiation of several agro-products. In this context, Zhao et al. [74]
discriminated wheat procured from different areas of China.
S.A. Wadood, et al. Microchemical Journal 152 (2020) 104295

Table 3
A summary overview of spectroscopic techniques used for determining the authenticity and traceability of plant origin food.
Food Purpose of analysis Detection technique Number of samples Data processing technique References

Lime juice Adulteration NIRS 72 SVM, RF [65]

Extra virgin olive oil Varietal discrimination NIRS, ATR-FTIR 82 PCA, LDA, SIMCA [66]
Wheat Geographical origin NIRS 240 LDA, PCA, DPLS [68]
wheat Geographical origin NIRS 249 DPLS [69]
Herba Epimedii Geographical origin NIRS 114 BPNN, DA, SVM, k-NN [70]
Almond Varietal discrimination NIRS, AT-FTIR 120 PCA, PLS-DA, QDA [71]
Apple juice Quality determination FT-IR NA PCA, SIMCA [76]
Vinegar Quality discrimination ATR-FTIR 67 PCA [77]
Black seed oil Adulteration detection FTIR NA PCA, PLS [80]
Extra virgin olive oil Adulteration detection FTIR PCR, PLS, DA [81]
Sesame oil Adulteration detection ATR-FT-IR 36 ANOVA, PCA, CA [78]
Rapeseed oil Adulteration detection FT-IR 24 PCR, PLS, DA [79]
Rice Cultivar discrimination NIR-HSI NA PLS-DA, SIMCA, k-NN, SVM, RF [86]
Coffee Varietal identification HSI NA EMD, WT, SVM [88]
1
Rice Geographical origin H-NMR 106 ANOVA, PCA, LDA [94]
1
Wheat Geographical & botanical H-NMR 100 ANOVA, LDA [95]
1
Lentil Geographical origin H-NMR 85 PCA, PLS-DA, LDA [96]
1
Citrus Geographical origin H-NMR 56 PCA. PLS-DA [97]
1
Wine Grape variety, origin, vintage H-NMR 265 PCA, LDA, MANOVA [98]

List of abbreviations: UPLC/QqQ-MS (ultra-performance liquid chromatography/triple quadrupole tandem mass spectrometry); HPLC-PDA (high performance
liquid chromatography coupled to photodiode array detection); UHPLC-TOFMS (ultra- high performance liquid chromatography –time-of-flight mass spectrometry);
HPLC-MS (high performance liquid chromatography coupled to mass spectrometry); HS-SPME-GCMS (head space solid-phase microextraction coupled to gas
chromatography mass spectrometry); HPLC-DAD (high performance liquid chromatography coupled to diode array detection); GC/MS (gas chromatography coupled
to mass spectrometry); HPLC-RID (High Performance Liquid Chromatography-Refractive Index Detector); DHE- GC–MS (Dynamic headspace extraction- coupled to
gas chromatography mass spectrometry); FGC E- nose (flash gas chromatography electronic nose); GC-FID (gas chromatography-flame ionization detector); HS-
SPME/Es-GC–MS (headspace solid-phase microextraction combined with enantioselective gas chromatography mass spectrometry); IRMS (isotope ratio mass
spectrometry); GC-IRMS (gas chromatography coupled with isotope ratio mass spectrometry); ICP-MS (Inductively coupled plasma mass spectrometry); Q-ICP-MS
(Quadrupole-Inductively coupled Plasma-mass spectrometry); MC-ICP-MS (multi-collector–inductively coupled plasma mass spectrometry); NIRS (near infrared
spectroscopy); ATR-FTIR (attenuated total reflection-Fourier transform infrared); NIR-HIS (near infrared hyperspectral imaging); NMR (nuclear magnetic resonance);
LDA (Liner discriminant analysis); SLDA (stepwise linear discriminant analysis); PCA (principal component analysis); PLS-DA (partial least square discriminant
analysis); ANOVA (analysis of variance); MANOVA (multivariate analysis of variance); DA (discriminant analysis); CA (cluster analysis); CDA (canonical discriminant
analysis); SVM (support vector machine); DPLS (discriminant partial least square); PLS (partial least square); PCR (principal component regression); SIMCA (soft
independent modeling of class analogy); k-NN (k-nearest neighbors); RF (random forest); BPNN (back propagation neural network); EMD (Empirical mode de-
composition; WT (Wavelet transform).

Reflectance spectra of wheat kernel and whole meal were recorded and
after spectral pretreatment, linear discriminant analysis (LDA) based on
PCA and discriminant partial least square (DPLS) were applied. The
results showed a significant difference among NIR spectrum of wheat
from different regions. The best classification percentages were
achieved with DPLS suggesting that NIRS combined with chemometrics
is a promising technique for geographical classification of wheat. In a
similar approach, González-Martín et al. [75] discriminate the geo-
graphical origin of wheat and flour sample using NIR spectroscopy. The
Infrared spectrum was acquired at a wavelength in a range of
1100–2000 nm. Spectral data was pretreated and then supervised pat-
tern recognition method (DPLS) was applied which correctly classified
76% and 96% of wheat and flour sample among different geographical
origin. Recently, Yang et al. [76] explored the NIR spectroscopy com-
bined with chemometrics for the geographical traceability of Herba
Epimedii. Different classification models namely back propagation
neural network (BPNN), discriminant analysis (DA), k-nearest neighbor
(k-NN), and support vector machine (SVM) was applied to the spectral
data, and their performances in terms of recognition precision were
compared. The result revealed that the SVM model was superior over
the other models in the discrimination of geographical origin with
100% recognition rates for the calibration set and 94.4% for the pre-
diction set, respectively. In another approach, this technique (NIR) has
shown its potential to differentiate the Spanish intact almonds varieties.
Different almond varieties were analyzed using the reflectance mode
for spectral acquisition and subsequently pre-processed and employed
to build classification model quadratic discriminant analysis (QDA) to
classify almond according to variety. The established model achieved
highest overall accuracies (94.5%) which suggested that spectroscopic
technique (NIR) in combination with chemometrics is a powerful tool to
reliably differentiate almond according to their varieties [77].
NIR spectroscopy has many advantages such as rapid, non-de-
structive, cost-effective, and simple, since it does not require any
sample processing. In addition, this technique made possible to detect
numerous components together; however, the main disadvantage is the
low sensitivity associated with high signal-to-noise ratio. Moreover,
superposition of various overtones and combination bands in the NIR
region leads to low structural selectivity of NIR spectra.
2.5.2. Fourier transform infrared (FT-IR) spectroscopy
FT-IR spectroscopy is widely used analytical tool for the quality
determination of food products both in chemical industries and re-
search laboratories [78]. This technique relies on the mid-infrared
(MIR) region of the electromagnetic spectrum (4000 to 400 cm−1), and
generates the chemical profile of the sample by screening the funda-
mental vibrational and associated rotational stretching of molecules
[79]. Unlike NIR, FTIR provides much more chemical information re-
garding the analyzed sample, as it monitors the fundamental vibrations
rather than overtones and combination modes. Generally, mid infrared
region can be split into two broad categories: the region of the func-
tional group (4000–1500 cm−1), and the fingerprint region
(1500–400 cm−1). The functional group region can further be split into
different regions: single bonds region (4000–2500 cm−1) which mainly
corresponds to X-H stretching (X indicates carbon, nitrogen, oxygen, or
sulfur), the region of triple bonds (2500–2000 cm−1), and the double
bonds region (2000–1500 cm−1) [80]. Usually, the functional group
region provides a large amount of information which is used to inter-
pret the mid infrared (MIR) spectra, while the fingerprint region is
generally complex due to various overlapped bands generated by dif-
ferent compounds in this region [81]. Despite the complex spectra and

7
S.A. Wadood, et al.
overlapped bands, the fingerprint region has been used for the identi-
fication and discrimination of contaminant and quality screening of
food products (beverages), including the detection of Alicyclobacillus,
and Bacillus strains in apple juice [82].
Alike NIR spectroscopy, FTIR spectroscopy allows the measurement
of solid, liquid, and gases samples through various measurement
modes, namely attenuated total reflectance (ATR), high-throughput
transmission (HTT), diffuse reflectance (DF), and transmission cell [8].
However, ATR method is broadly applied in food sector for quality and
authenticity analysis because of the advantage of no or minimum
sample preparation.
Recently, ATR-FT-IR spectroscopy coupled with multivariate ana-
lysis has been introduced to ensure the authenticity of high quality food
products. In this context, Ríos-Reina et al. [83] explored the potential of
ATR-FTR combined with multivariate analysis as a rapid tool for
characterizing different categories of high quality PDO vinegar. Dis-
tinctive bands associated with categories were observed in the region
1800–900 cm−1 which were associated with certain compounds (acetic
acids, alcohols, esters) that increase during the aging process. Principal
component analysis revealed that aging process significantly affects the
ATR-FTIR spectra obtained in each PDO. Similar approach has been
used to investigate the authenticity of high-value edible oils, especially,
extra virgin olive oil, rapeseed oil, virgin coconut oil, black seed oil, and
sesame oil [84–88]. ATR- FT-IR was also applied as a simple and eco-
nomical tool for quality evaluation of beer [81].
The transmission mode of FT-IR has also adopted in the food sector
for investigating the authenticity of high quality food products. For
example, FT-IR coupled with transmission cell was applied to determine
the authenticity of extra virgin olive oil. The spectra of EVOO was
obtained by introducing a small amount of oil sample between two KBr
disk, and subsequently spectra data was subjected to the linear dis-
criminant analysis (LDA), and the botanical origin of oil was success-
fully discriminated [89].
FT-IR spectroscopy combined with chemometrics is a useful tech-
nique that has a wide array of applications in the agro sector, since FT-
IR sampling methods have made a significant development over the last
few years. Usually, both spectroscopic techniques (NIR and FT-IR)
achieve the same task and, in some situations, one of these methods
offer some merits over the other. FT-IR spectroscopy has a lot of ad-
vantages; however, it also has some drawbacks that should be con-
sidered prior to the sample analysis such as the strong absorption of
water in the MIR region particularly in the case of aqueous samples that
could induce some trouble in the analysis of the spectra.
2.5.3. Hyperspectral imaging
Recently, hyperspectral imaging (HSI) has recognized as a potential
non-destructive analytical technique that relies on vibrational spectro-
scopy for food authenticity and quality analysis. Unlike NIR and FT-IR,
it attains both spatial and spectral information from the target object.
The spatial features allow the characterization of complex samples
having different characteristics, whereas, the spectral features made it
possible to identify the wide range of multi-constituent surface and
subsurface features [8]. This technique is more convenient for sample
analysis as it is fast and many samples can be examined at the same
time, which is not possible in case of other spectroscopic techniques.
HSI instrument is designed in a way that it can be applied to gather the
hyperspectral data for samples having different shapes and sizes. Fur-
thermore, spectral collecting region, spatial region, field of view can be
adapted on the basis of the application. Due to these merits and
equipment flexibility, HIS has recently become the most widely used
analytical tool in agro-sector for agro-products quality and safety as-
sessment [90].
HIS attains the spectral and spatial information about the target
object over the visible, ultraviolet, and NIR region at a spectral range of
300–2600 nm [90]. Numerous HSI methods have been established for
optical sensing of wide range of samples in different regions, for
8
Microchemical Journal 152 (2020) 104295
instance, visible (380–800 nm), ultraviolet (200–400 nm), VIS/NIR
(400–1000 nm), NIR (900–1700 nm), and short wave infrared
(970–2500 nm). Each technique offers certain advantages for a specific
application. In the past few years, several studies intensively explored
the potential of HIS for food authenticity and quality analysis; detection
of waxed rice Li et al. [91], rice cultivar discrimination Kong et al. [92],
fungal contamination in maize William et al. [93], authenticity of
coffee bean varieties Zhang et al. [94], detection of adulterants in
grounded spice September [95], and detection of insect-damaged ve-
getable soybean Huang et al. [96].
HIS equipped with reflectance, fluorescence, and transmission
techniques has been widely used for many years to investigate the
quality and safety of food products. In recent past, Timlin et al. [97]
introduced the Raman HIS which emerged as a novel technique that
offers the benefits of Raman spectroscopy with digital imaging to en-
visage the morphology and composition of the target object. Most re-
cently, this technique was successfully applied to detect the variation in
the lycopene content of tomatoes during ripening stages [98]. Although
Raman HIS has not yet been explored for the examination of a wide
variety of agricultural commodities; however, the combination of
Raman scattering and HIS could be a potential analytical technique for
experts in the field of food quality and authenticity.
2.5.4. Nuclear magnetic resonance
NMR based metabolomics is recognized as one of the main analy-
tical technique. The basic working principle of NMR is the estimation of
radiofrequency radiation that is absorbed by the nuclei of the atoms
present in a strong atomic field. The absorption of atomic nuclei can be
altered by the surrounding environment around atoms, which are re-
sponsible for even minute variations to the peripheral magnetic field;
consequently, the entire molecular structure of food sample can be
acquired [3,9]. Several isotopes (1H, 13C 15N, 17O, 19F, 31P) are used in
NMR, among them 1H, and 13C are usually employed. NMR based
metabolomics are widely applied in the food industry to curtail the
fraudulent labeling and quality control of food materials, and can be
categorized into three classes: high-resolution NMR, low-field NMR,
and magnetic resonance imaging (MRI) [11,99].
In recent years, NMR spectroscopy has been successfully applied to
various food products for authenticity and geographical traceability
Table 3. Thus, Huo et al. [100] discriminate the geographical origin of
rice through 1H-NMR based metabolomics. Multivariate analysis such
as PCA and LDA was applied to the metabolomics. PCA showed clear
separation among the different regions samples. LDA was applied to
extract the variables mainly responsible for separation, for instance,
sucrose, glucose, fructose succinate, polyphenols, trigonelline, and as-
paragine showed differences due to the variation in latitude, tempera-
ture, and precipitation in these regions. In another study, Lamanna
et al. [101] discriminate geographical and botanical origin of wheat
through 1H-NMR profiling. Chemometrics were applied to the NMR
profile in order to discriminate the origin of samples. A linear-model
discriminate three geographical regions by achieving about 80% clas-
sification accuracy. The amino acids and aromatic compounds were the
prominent compounds which executed significant variation among
different regions. However, the NMR profile showed poor performance
while discriminating the botanical origin of wheat and failed to achieve
satisfactory results. In a similar approach, Longobardi et al. [102] dis-
criminate the geographical origin of lentils (Lens Culinaris Medik). A
series of chemometrics were applied to 1H-NMR profile such as (SIMCA,
K-NN, PCA-LDA, and PLS-DA) and results were compared. The best
classification percentages with 100% recognition and 96% prediction
abilities were attained for the PCA-LDA. Finally, metabolomics that
significantly contributed to the lentil classification were identified.
Another study proposed a 1H-NMR based analytical method for geo-
graphical classification of Argentinian citrus. Classification model such
as PCA and PLS-DA achieved discrimination between orange juices on
the basis of regions and varieties. PCA loadings revealed that citric acid
S.A. Wadood, et al.
and ethanol were the main discriminatory markers for geographical and
varietal classification [103]. With regard to wine, Godelmann et al.
[104] employed 1H-NMR in combination with chemometrics (PCA,
MANOVA, LDA) to identify grape variety, year of vintage, and geo-
graphic origin of German wines. Each NMR spectrum could be regarded
as an individual fingerprint of wine sample and they succeeded in
discriminating wine according to grape variety, vintage year, and
geographical region with an average prediction accuracy of 95%, 96%,
and 89%, respectively.
Recently, 1H-NMR spectroscopy coupled with chemometrics has
been developed to determine the authenticity of coffee samples. In this
context, Consonni et al. [105] explored the potential of 1H-NMR to
differentiate organic and conventional roasted coffee samples. Che-
mometrics were applied to the NMR profile for possible metabolite
separation. Classification model (OPLS-DA) successfully discriminated
organic and conventional coffee samples by confirming β-(1–3)-D-ga-
lactopyranose, β-(1–4)-D-mannopyranose, fatty acids, quinic acids and
its cyclic aster as the distinctive metabolite for organic coffee, while
those for conventional ones include: CGA isomers, trigonelline, caf-
feine, and acetate, respectively. In another study, de Moura Ribeiro
et al. [106] succeed to detect different adulterants (corn, coffee husk,
barley, and soybean) in roasted coffee using 1H-NMR based metabo-
lomics. In an additional study, Consonni et al. [107] reported the
capability of 1H-NMR based metabolite in roasted coffee for geo-
graphical origin identification. Metabolomics such as fatty acids,
chlorogenic acids, acetate, lactate, and trigonelline was identified as
main discriminatory compounds characterizing the samples from three
main coffee producing regions America, Africa, and Asia, respectively.
In a similar approach, 1H-NMR technique was used to investigate the
geographical origin of Brazillian coffee samples. The authors reported
that the compound such as catechol, caffeine, trigonelline, and n-me-
thylpyridine was most important for geographical differentiation of
coffee [108].
NMR spectroscopy has numerous advantages, as it is non-destruc-
tive, environmental friendly, does not require complex sample pre-
paration, and the determination of various chemical compounds can be
achieved in a single run. However, the major challenges are to acquire
good spectrum both in term of resolution and quality and its low sen-
sitivity. Indeed, pulse sequence assignment procedure in the experiment
is very critical as the use of wrong one may induce negative con-
sequences. Another main drawback of this technique is the complex
optimization of the instrument and also NMR is more expensive as
compared to other spectroscopic techniques and it needs highly spe-
cialized operator.
3. Other techniques
3.1. DNA-based techniques
DNA is a self-replicating material which serves as a carrier of ge-
netic information of an organism. DNA based techniques focused on the
detection and determination of nucleic acid probes and their sequences,
which serve as a characteristic fingerprint to detect the adulterants and
determine the authenticity of food products [9]. DNA is a macro-
molecule made of coding sequences that resemble to the gene scattered
with extended non-coding stretches where, DNA shows tandem repeats,
which are repetitive elements typically known as short tandem repeats
(STRs) or microsatellites. They are also known as DNA markers because
the number of repetitions may vary from one sample to others which
allow to determine the authenticity of the analyzed sample, exactly in
the same manner as human identification in forensic science [109]. The
accessibility of thousands of DNA markers and cost-effective sequencing
methods offer remarkable applications of DNA based approaches to
address the authenticity issues in the food industry. A wide variety of
DNA-based markers are available for determining the agro-products
authenticity for instance, random amplified polymorphic DNA (RAPD),
9
Microchemical Journal 152 (2020) 104295
single nucleotide polymorphism (SNP), restriction fragment length
polymorphism (RELP), amplified fragment length polymorphism
(AFLP), simple sequence repeat (SSR), etc. [110]. In recent past, a DNA-
based multiplex detection tool, PPLMD (padlock probe ligation and
microarray detection tool) has been established which is expanded to a
15-plex traceability tool with a special focus on agro-products like
aromatic rice (basamti) and wheat [111]. For food authenticity, a
combination of microsatellite markers and either real-time PCR or ca-
pillary electrophoresis have been widely adopted as molecular techni-
ques.
The authenticity of high-value food products is very challenging.
Therefore, sound molecular techniques are necessary to distinguish
adulterated food with inferior ingredients. PCR is a promising tool to
address the authenticity problems, and this technique has been adopted
in many recent food authenticity studies. In this regard, Pegels et al.
[112] developed TaqMan real time RT- PCR method to detect wheat,
barley, oat, and rye in processed products for human and pet con-
sumption. The results revealed that this technique was able to achieve
high specificity and sensitivity with detection limit ranging from
0.00001 to 0.1% in an experimental flour binary mixture model. The
established method was then employed at the field level to investigate
the labeling of different human and pet food products regarding the
traces of these crops in different food matrices. The assays successfully
distinguished the food with different labeling scheme, in which the
presence of the targeted cereals was either confirmed, not confirmed, or
confirmed as possible traces. In a similar approach, López-Calleja et al.
[113] detect the traces of sunflower and poppy in different commercial
food products using TaqMan real time RT- PCR. Results revealed that
this technique is highly sensitive and selective, which made it possible
to detect traces of sunflower and poppy in food samples. Adulteration of
coffee with cereals is a common practice. In order to detect the adul-
teration of commercial coffee with cereals, Ferreira et al. [114] devel-
oped a method based on RT-PCR. By comparing the standard curves
attained by serial dilution of DNA extracted from rice, barley, and corn,
the method was found sensitive and specific to quantify up to 16 pg, 0.6
pg, and 14 pg of rice, barley, and corn DNA, respectively. The applic-
ability of the developed method was verified by evaluating different
commercial coffee samples procured from different countries, and those
classified as superior did not match the tested cereals DNA; however,
barley DNA was traced in various traditional samples. In a different
approach, Bucher and Köppel [115] developed duplex digital droplet
ddPCR to detect the adulteration of basmati with non-basmati rice. The
newly developed assay showed the ability to screen non-basmati rice
content in the range of 1% or higher. The authors compared the results
with those obtained with RT-PCR and microsatellite analysis (MA) and
the best correlation was found between ddPCR and MA. In another
study, Barrias et al. [116] developed DNA based biosensor to check the
authenticity of wine. Genomic data was extracted from must, leaf, and
wine of three V. Vinifera varieties and was tested on a newly developed
DNA based biosensor LPG (long-period grating), which successfully
distinguished varieties, suggesting its potential to be applied in wine
authenticity.
DNA based methods have advantages of being rapid, robust, sensi-
tive, and relatively simple to amplify DNA. However, it is necessary to
recognize the exact sequences, which flank both sides of the target DNA
region. In addition, similar species within a sample can cause cross
reaction during DNA fragmentation, and more fragmented DNA offers
lower amplification [3]. Therefore, special care should be taken during
the sample fragmentation before DNA amplification, since it can alter
the final results to a considerable extent.
3.2. Sensor technology
Sensor techniques usually referred to electronic nose or electronic
tongue technology. Electronic noses are utilized to distinguish and de-
tect complex aromas from food matrices, which are based on the
S.A. Wadood, et al.
detection by a sensor array that is composed of broadly tuned sensors,
treated with various odor-sensitive chemical constituents. An odor sti-
muli then served as a characteristic fingerprint from the group of sen-
sors [117]. Generally, electronic noses comprise of three elements
which include: sample transfer system, detection system, and data
calculating systems. The electrochemical gas sensor procedure includes
interaction among gaseous molecules and sensor coating constituents
which control the electric current traveling through the sensor, de-
tectable by a transducer, which transforms the modulation into a re-
cordable electric signal, which is subsequently conditioned and ampli-
fied. Afterward, a digital converter transforms the electronic signal into
a digital value, and a computer system further process the digital signal
and shows the output, which is later, used to perform statistical analysis
[118].
Electronic tongues are considered as the equivalents of electronic
noses. The output of non-particular series of sensors exhibit different
characteristic patterns for different taste producing chemical compo-
nents, and the resultant data are statistically computed. Nowadays,
huge numbers of chemical sensors are involved in the development of
electronic tongues and the choice of the sensor group depends on the
chemical composition of the object being analyzed. Irrespective to the
kind of sensors used, an electronic tongue technology includes an au-
tomatic sampler, an array of chemical sensors with different selectivity,
and the computer system equipped with a software with a proper al-
gorithm to read the signal and generate the corresponding results
[117]. These techniques are recently used in many authenticity studies.
Dong et al. [119] explored the potential of e-nose and tongue to dif-
ferentiate different Robusta coffee cultivars. Chemometrics like k-NN
and PLS-DA were used for this purpose, which achieved 92.8% and
91.7% correct classification with k-NN and PLS-DA, respectively. The
obtained results showed that the selected analytical techniques coupled
with chemometrics are useful to distinguish different coffee cultivars. In
a similar approach, Ma et al. [120] assessed the potential of electronic
noses combine with multivariate analysis to distinguish the geo-
graphical area of kiwi fruit. Different regions samples were successfully
categorized by stepwise linear discriminant analysis and SIMCA. In
another study, Heidarbeigi et al. [121] detect the adulteration of saf-
fron with yellow styles, safflower, etc. using e-nose. The extracted e-
nose signal features were analyzed by PCA and the results were further
confirmed by BP-ANN. The results demonstrate the potential of e-nose
to detect the saffron adulteration with remarkable classification accu-
racy. Alcoholic beverages are also an important target for fraudulent
activities. In recent years, a lot of research have been done on the au-
thenticity of alcoholic beverages, especially for wine using e-tongue
technology [117]. In a study, Gutiérrez et al. [122] explored the po-
tential of hybrid electronic tongue for the classification of wine ac-
cording to grape cultivar, vintage and also for the prediction of che-
mical parameters in wine quality control. E-tongue data obtained for
different grape varieties and vintages were processed through PCA and
PLS-DA and the clear separation among different varieties and vintages
were achieved. Some studies also demonstrated the capability of elec-
tronic tongues for the authenticity of edible oils. In a recent study,
Apetrei and Apetrei [123] demonstrate the effectiveness of electronic
tongues to detect adulterants in extra virgin olive oils. A series of
chemometrics were applied to the electronic tongue data which showed
the potential of this technique (a) to differentiate pure oil according to
their botanical origin; (b) to categorize the adulterated EVOO when the
adulteration was exceeding 5% (c) to predict the composition of EVOO
and seed oils mixture within the range of 2–25% (r > 0.99 in both PLS
training and validation set). In another study, Dias et al. [124] em-
ployed potentiometric e-tongue to successfully discriminate 18 Portu-
guese and Spanish monovarietal extra virgin olive oil according to
cultivar.
Advantages of these sensor technologies include simple procedure
with a relatively smaller amount of sample preparation, fast, and low-
cost analysis. However, there are several drawbacks associated with
10
Microchemical Journal 152 (2020) 104295
these techniques which discourage their applicability in several cases
such as identification of detected chemical compound is not possible
like in case of GC–MS and the detection limit is also high [3]. Moreover,
these techniques are sensitive to water vapors drifts of the recorded
response happen during the day.
4. Future perspectives and conclusion
Due to globalization and complex food system, food is vulnerable to
adulteration. A great attention has been paid to agro-product quality
and authenticity due to recent food borne outbreaks and scandals in the
food industry, which have seriously damaged the consumer confidence.
In the past few years, a wide range of analytical applications have been
introduced for food authentication purpose such as chromatographic
techniques, elemental and isotope analysis, sensor technology, DNA
based methods but these techniques have mostly focused on research
work and rarely been implemented in official food control laboratories
or for routine analysis in food industry, because many of these tech-
niques are expensive, labor intensive, or time consuming. Recently,
some industries and governmental agencies developed database for
IRMS technique and adopted as an official standard for food traceability
as it is very stable and highly sensitive. On the other hand, spectro-
scopic techniques have been emerged as a potential analytical tool and
considered as a best alternative to chromatographic or spectrometry
techniques for food authenticity studies. These techniques are non-de-
structive, non-invasive, very fast, easy to operate and can be applied
both in the industry for routine analysis and in official food control
laboratories. Literature suggests that spectroscopic techniques coupled
with appropriate chemometrics are a promising tool to retain the
maximum information contained in the spectral data. However, there
are still some barriers and limitations in the implementation of these
non-destructive techniques in the food sector. By considering the sui-
table spectroscopic technique for the physical and chemical nature of
the target sample, some of these constraints can be evaded. On the
other hand, the continued progress is expected in future to address the
instrumental and software limitations of these techniques and result in
the establishment of cost effective analytical method with high accu-
racy and processing speed for food industry applications.
Declaration of Competing Interest
None.
Acknowledgment
This work was funded by National Natural Science Foundation of
China (No. 31371774) and Innovation Project of Chinese Academy of
Agricultural Sciences(CAAS).
References
[1] G. Vinci, R. Preti, A. Tieri, S. Vieri, Authenticity and quality of animal origin food
investigated by stable-isotope ratio analysis, J. Sci. Food Agric. 93 (2013)
439–448, https://doi.org/10.1002/jsfa.5970.
[2] Food Standard Agency, Food labelling country oforigin, 2001. doi:10.2875/
415662.
[3] D.M.A.M. Luykx, S.M. van Ruth, An overview of analytical methods for de-
termining the geographical origin of food products, Food Chem. 107 (2008)
897–911, https://doi.org/10.1016/j.foodchem.2007.09.038.
[4] S.A. Wadood, G. Boli, W. Yimin, Geographical traceability of wheat and its pro-
ducts using multielement light stable isotopes coupled with chemometrics, J. Mass
Spectrom. 54 (2019) 178–188, https://doi.org/10.1002/jms.4312.
[5] V. Lakshmi, Food adulteration, Int. J. Sci. Invent. Today 1 (2012) 101–113.
[6] K. Everstine, Economically motivated adulteration: implications for food protec-
tion and alternate approaches to detection, Doctorate thesis UNIVERSITY OF
MINNESOTA, 2013.
[7] D.I. Ellis, V.L. Brewster, W.B. Dunn, J.W. Allwood, A.P. Golovanov, R. Goodacre,
Fingerprinting food: current technologies for the detection of food adulteration
and contamination, Chem. Soc. Rev. 41 (2012) 5706, https://doi.org/10.1039/
c2cs35138b.
S.A. Wadood, et al.
[8] S. Lohumi, S. Lee, H. Lee, B.-.K. Cho, A review of vibrational spectroscopic tech-
niques for the detection of food authenticity and adulteration, Trends Food Sci.
Technol. 46 (2015) 85–98, https://doi.org/10.1016/j.tifs.2015.08.003.
[9] M. Kamal, R. Karoui, Analytical methods coupled with chemometric tools for
determining the authenticity and detecting the adulteration of dairy products: a
review, Trends Food Sci. Technol. 46 (2015) 27–48, https://doi.org/10.1016/j.
tifs.2015.07.007.
[10] O. Abbas, M. Zadravec, V. Baeten, T. Mikuš, T. Lešić, A. Vulić, J. Prpić, L. Jemeršić,
J. Pleadin, Analytical methods used for the authentication of food of animal origin,
Food Chem. 246 (2018) 6–17, https://doi.org/10.1016/j.foodchem.2017.11.007.
[11] M. Esteki, Z. Shahsavari, J. Simal-Gandara, Use of spectroscopic methods in
combination with linear discriminant analysis for authentication of food products,
Food Control 91 (2018) 100–112, https://doi.org/10.1016/j.foodcont.2018.03.
031.
[12] M. Esteki, Z. Shahsavari, J. Simal-Gandara, Gas chromatographic fingerprinting
coupled to chemometrics for food authentication, Food Rev. Int. 0 (2019) 1–44,
https://doi.org/10.1080/87559129.2019.1649691.
[13] M. Esteki, J. Simal-Gandara, Z. Shahsavari, S. Zandbaaf, E. Dashtaki, Y. Vander
Heyden, A review on the application of chromatographic methods, coupled to
chemometrics, for food authentication, Food Control 93 (2018) 165–182, https://
doi.org/10.1016/j.foodcont.2018.06.015.
[14] M. Esteki, Z. Shahsavari, J. Simal-Gandara, Food identification by high perfor-
mance liquid chromatography fingerprinting and mathematical processing, Food
Res. Int. 122 (2019) 303–317, https://doi.org/10.1016/j.foodres.2019.04.025.
[15] K. Weikle, Determination of citric acid in fruit juice, Concordia Coll. J. Anal.
Chem. 3 (2012) 57–62.
[16] M. Farré, Y. Picó, D. Barceló, Application of ultra-high pressure liquid chroma-
tography linear ion-trap orbitrap to qualitative and quantitative assessment of
pesticide residues, J. Chromatogr. A. 1328 (2014) 66–79, https://doi.org/10.
1016/j.chroma.2013.12.082.
[17] J. Li, X. He, M. Li, W. Zhao, L. Liu, X. Kong, Chemical fingerprint and quantitative
analysis for quality control of polyphenols extracted from pomegranate peel by
HPLC, Food Chem. 176 (2015) 7–11, https://doi.org/10.1016/j.foodchem.2014.
12.040.
[18] T. Rejczak, T. Tuzimski, Recent trends in sample preparation and liquid chroma-
tography/mass spectrometry for pesticide residue analysis in food and related
matrixes, J. AOAC Int 98 (2015) 1143–1162, https://doi.org/10.5740/jaoacint.
SGE1_Rejczak.
[19] Z. Jandrić, M. Islam, D.K. Singh, A. Cannavan, Authentication of Indian citrus
fruit/fruit juices by untargeted and targeted metabolomics, Food Control 72
(2017) 181–188, https://doi.org/10.1016/j.foodcont.2015.10.044.
[20] J.L. Gómez-Ariza, A. Arias-Borrego, T. García-Barrera, Multielemental fractiona-
tion in pine nuts (Pinus pinea) from different geographic origins by size-exclusion
chromatography with UV and inductively coupled plasma mass spectrometry de-
tection, J. Chromatogr. A. 1121 (2006) 191–199, https://doi.org/10.1016/j.
chroma.2006.04.025.
[21] K.B. Bat, B.M. Vodopivec, K. Eler, N. Ogrinc, I. Mulič, D. Masuero, U. Vrhovšek,
Primary and secondary metabolites as a tool for differentiation of apple juice
according to cultivar and geographical origin, LWT 90 (2018) 238–245, https://
doi.org/10.1016/j.lwt.2017.12.026.
[22] J. Liu, N. Chen, J. Yang, B. Yang, Z. Ouyang, C. Wu, Y. Yuan, W. Wang, M. Chen,
An integrated approach combining HPLC, GC/MS, NIRS, and chemometrics for the
geographical discrimination and commercial categorization of saffron, Food Chem
253 (2018) 284–292, https://doi.org/10.1016/j.foodchem.2018.01.140.
[23] J. Guo, T. Yue, Y. Yuan, Y. Wang, Chemometric classification of apple juices ac-
cording to variety and geographical origin based on polyphenolic profiles, J. Agric.
Food Chem. 61 (2013) 6949–6963, https://doi.org/10.1021/jf4011774.
[24] J. Guo, Y. Yuan, P. Dou, T. Yue, Multivariate statistical analysis of the poly-
phenolic constituents in kiwifruit juices to trace fruit varieties and geographical
origins, Food Chem 232 (2017) 552–559, https://doi.org/10.1016/j.foodchem.
2017.04.037.
[25] G. Sagratini, F. Maggi, G. Caprioli, G. Cristalli, M. Ricciutelli, E. Torregiani,
S. Vittori, Comparative study of aroma profile and phenolic content of mon-
tepulciano monovarietal red wines from the marches and abruzzo regions of Italy
using HS-SPME–GC–MS and HPLC–MS, Food Chem 132 (2012) 1592–1599,
https://doi.org/10.1016/j.foodchem.2011.11.108.
[26] A.A. D'Archivio, A. Giannitto, M.A. Maggi, F. Ruggieri, Geographical classification
of Italian saffron (Crocus sativus L.) based on chemical constituents determined by
high-performance liquid-chromatography and by using linear discriminant ana-
lysis, Food Chem 212 (2016) 110–116, https://doi.org/10.1016/j.foodchem.2016.
05.149.
[27] S. Papapetros, A. Louppis, I. Kosma, S. Kontakos, A. Badeka, M.G. Kontominas,
Characterization and differentiation of botanical and geographical origin of se-
lected popular sweet cherry cultivars grown in Greece, J. Food Compos. Anal. 72
(2018) 48–56, https://doi.org/10.1016/j.jfca.2018.06.006.
[28] A. Mahne Opatić, M. Nečemer, S. Lojen, J. Masten, E. Zlatić, H. Šircelj, D. Stopar,
R. Vidrih, Determination of geographical origin of commercial tomato through
analysis of stable isotopes, elemental composition and chemical markers, Food
Control 89 (2018) 133–141, https://doi.org/10.1016/j.foodcont.2017.11.013.
[29] D. Erba, M.C. Casiraghi, A. Ribas-Agustí, R. Cáceres, O. Marfà, M. Castellari,
Nutritional value of tomatoes (Solanum lycopersicum L.) grown in greenhouse by
different agronomic techniques, J. Food Compos. Anal. 31 (2013) 245–251,
https://doi.org/10.1016/j.jfca.2013.05.014.
[30] M. Leiva-Brondo, M. Valcárcel, C. Cortés-Olmos, S. Roselló, J. Cebolla-Cornejo,
F. Nuez, Exploring alternative germplasm for the development of stable high vi-
tamin C content in tomato varieties, Sci. Hortic. (Amsterdam) 133 (2012) 84–88,
11
Microchemical Journal 152 (2020) 104295
https://doi.org/10.1016/j.scienta.2011.10.013.
[31] S. Yudthavorasit, K. Wongravee, N. Leepipatpiboon, Characteristic fingerprint
based on gingerol derivative analysis for discrimination of ginger (Zingiber offi-
cinale) according to geographical origin using HPLC-DAD combined with che-
mometrics, Food Chem 158 (2014) 101–111, https://doi.org/10.1016/j.
foodchem.2014.02.086.
[32] F.J. Cuevas, G. Pereira-Caro, J.M. Moreno-Rojas, J.M. Muñoz-Redondo, M.J. Ruiz-
Moreno, Assessment of premium organic orange juices authenticity using HPLC-
HR-MS and HS-SPME-GC-MS combining data fusion and chemometrics, Food
Control 82 (2017) 203–211, https://doi.org/10.1016/j.foodcont.2017.06.031.
[33] D.K. Lim, C. Mo, D.-.K. Lee, N.P. Long, J. Lim, S.W. Kwon, Non-destructive pro-
filing of volatile organic compounds using HS-SPME/GC–MS and its application
for the geographical discrimination of white rice, J. Food Drug Anal 26 (2018)
260–267, https://doi.org/10.1016/j.jfda.2017.04.005.
[34] G. Starr, M.A. Petersen, B.M. Jespersen, A.S. Hansen, Variation of volatile com-
pounds among wheat varieties and landraces, Food Chem 174 (2015) 527–537,
https://doi.org/10.1016/j.foodchem.2014.11.077.
[35] I. Gonzalez-Fernandez, M.A. Iglesias-Otero, M. Esteki, O.A. Moldes, J.C. Mejuto,
J. Simal-Gandara, A critical review on the use of artificial neural networks in olive
oil production, characterization and authentication, Crit. Rev. Food Sci. Nutr. 59
(2019) 1913–1926, https://doi.org/10.1080/10408398.2018.1433628.
[36] D. Melucci, A. Bendini, F. Tesini, S. Barbieri, A. Zappi, S. Vichi, L. Conte, T. Gallina
Toschi, Rapid direct analysis to discriminate geographic origin of extra virgin olive
oils by flash gas chromatography electronic nose and chemometrics, Food Chem
204 (2016) 263–273, https://doi.org/10.1016/j.foodchem.2016.02.131.
[37] T. Cecchi, B. Alfei, Volatile profiles of Italian monovarietal extra virgin olive oils
via HS-SPME–GC–MS: newly identified compounds, flavors molecular markers,
and terpenic profile, Food Chem. 141 (2013) 2025–2035, https://doi.org/10.
1016/j.foodchem.2013.05.090.
[38] V. Giannetti, M. Boccacci Mariani, P. Mannino, F. Marini, Volatile fraction analysis
by HS-SPME/GC-MS and chemometric modeling for traceability of apples culti-
vated in the Northeast Italy, Food Control 78 (2017) 215–221, https://doi.org/10.
1016/j.foodcont.2017.02.036.
[39] A.F. Mottese, A. Albergamo, G. Bartolomeo, G.D. Bua, R. Rando, P. De Pasquale,
E. Saija, D. Donato, G. Dugo, Evaluation of fatty acids and inorganic elements by
multivariate statistics for the traceability of the Sicilian Capparis spinosa L. J. Food
Compos. Anal. 72 (2018) 66–74, https://doi.org/10.1016/j.jfca.2018.05.009.
[40] M. Esteki, B. Farajmand, S. Amanifar, R. Barkhordari, Z. Ahadiyan, E. Dashtaki,
M. Mohammadlou, Y. Vander Heyden, Classification and authentication of Iranian
walnuts according to their geographical origin based on gas chromatographic fatty
acid fingerprint analysis using pattern recognition methods, Chemom. Intell. Lab.
Syst. 171 (2017) 251–258, https://doi.org/10.1016/j.chemolab.2017.10.014.
[41] M. Esteki, B. Farajmand, Y. Kolahderazi, J. Simal-Gandara, Chromatographic
fingerprinting with multivariate data analysis for detection and quantification of
apricot kernel in almond powder, Food Anal. Methods. 10 (2017) 3312–3320,
https://doi.org/10.1007/s12161-017-0903-5.
[42] M. Esteki, P. Ahmadi, Y. Vander Heyden, J. Simal-Gandara, Fatty acids-based
quality index to differentiate worldwide commercial pistachio cultivars, Molecules
24 (2018) 58, https://doi.org/10.3390/molecules24010058.
[43] J. Lin, P. Zhang, Z. Pan, H. Xu, Y. Luo, X. Wang, Discrimination of oolong tea
(Camellia sinensis) varieties based on feature extraction and selection from aro-
matic profiles analysed by HS-SPME/GC–MS, Food Chem. 141 (2013) 259–265,
https://doi.org/10.1016/j.foodchem.2013.02.128.
[44] B. Mu, Y. Zhu, H.-.P. Lv, H. Yan, Q.-.H. Peng, Z. Lin, The enantiomeric distribu-
tions of volatile constituents in different tea cultivars, Food Chem. 265 (2018)
329–336, https://doi.org/10.1016/j.foodchem.2018.05.094.
[45] C.A. Georgiou, G.P. Danezis, Elemental and isotopic mass spectrometry,
Comprehensive Analytical Chemistry, Elsevier, 2015, pp. 131–243, https://doi.
org/10.1016/B978-0-444-63340-8.00003-0.
[46] F. Longobardi, G. Casiello, A. Ventrella, V. Mazzilli, A. Nardelli, D. Sacco,
L. Catucci, A. Agostiano, Electronic nose and isotope ratio mass spectrometry in
combination with chemometrics for the characterization of the geographical
origin of Italian sweet cherries, Food Chem. 170 (2015) 90–96, https://doi.org/
10.1016/j.foodchem.2014.08.057.
[47] E. de Rijke, J.C. Schoorl, C. Cerli, H.B. Vonhof, S.J.A. Verdegaal, G. Vivó-Truyols,
M. Lopatka, R. Dekter, D. Bakker, M.J. Sjerps, M. Ebskamp, C.G. de Koster, The use
of δ2H and δ18O isotopic analyses combined with chemometrics as a traceability
tool for the geographical origin of bell peppers, Food Chem. 204 (2016) 122–128,
https://doi.org/10.1016/j.foodchem.2016.01.134.
[48] F. Longobardi, G. Casiello, M. Cortese, M. Perini, F. Camin, L. Catucci,
A. Agostiano, Discrimination of geographical origin of lentils (Lens culinaris
Medik.) using isotope ratio mass spectrometry combined with chemometrics, Food
Chem. 188 (2015) 343–349, https://doi.org/10.1016/j.foodchem.2015.05.020.
[49] S. Fan, Q. Zhong, H. Gao, D. Wang, G. Li, Z. Huang, Elemental profile and oxygen
isotope ratio (δ 18 O) for verifying the geographical origin of Chinese wines, J.
Food Drug Anal. 26 (2018) 1033–1044, https://doi.org/10.1016/j.jfda.2017.12.
009.
[50] O.R. Dinca, R.E. Ionete, D. Costinel, I.E. Geana, R. Popescu, I. Stefanescu,
G.L. Radu, Regional and vintage discrimination of romanian wines based on ele-
mental and isotopic fingerprinting, Food Anal. Methods. 9 (2016) 2406–2417,
https://doi.org/10.1007/s12161-016-0404-y.
[51] H. Liu, B. Guo, Y. Wei, S. Wei, Y. Ma, W. Zhang, Effects of region, genotype,
harvest year and their interactions on δ13C, δ15N and δd in wheat kernels, Food
Chem. 171 (2015) 56–61, https://doi.org/10.1016/j.foodchem.2014.08.111.
[52] D. Luo, H. Dong, H. Luo, Y. Xian, J. Wan, X. Guo, Y. Wu, The application of stable
isotope ratio analysis to determine the geographical origin of wheat, Food Chem.
S.A. Wadood, et al.
174 (2015) 197–201, https://doi.org/10.1016/j.foodchem.2014.11.006.
[53] D. Rashmi, P. Shree, D.K. Singh, Stable isotope ratio analysis in determining the
geographical traceability of Indian wheat, Food Control 79 (2017) 169–176,
https://doi.org/10.1016/j.foodcont.2017.03.025.
[54] S.A. Wadood, B. Guo, H. Liu, S. Wei, X. Bao, Y. Wei, Study on the variation of
stable isotopic fingerprints of wheat kernel along with milling processing, Food
Control 91 (2018) 427–433, https://doi.org/10.1016/j.foodcont.2018.03.045.
[55] T. Chen, Y. Zhao, W. Zhang, S. Yang, Z. Ye, G. Zhang, Variation of the light stable
isotopes in the superior and inferior grains of rice (Oryza sativa L.) with different
geographical origins, Food Chem. 209 (2016) 95–98, https://doi.org/10.1016/j.
foodchem.2016.04.029.
[56] C. Kukusamude, S. Kongsri, Elemental and isotopic profiling of Thai jasmine rice
(Khao Dawk Mali 105) for discrimination of geographical origins in Thung Kula
Rong Hai area, Thailand, Food Control 91 (2018) 357–364, https://doi.org/10.
1016/j.foodcont.2018.04.018.
[57] S.A. Drivelos, C.A. Georgiou, Multi-element and multi-isotope-ratio analysis to
determine the geographical origin of foods in the European Union, TrAC - Trends
Anal. Chem. 40 (2012) 38–51, https://doi.org/10.1016/j.trac.2012.08.003.
[58] I.M. Chung, J.K. Kim, K.J. Lee, S.K. Park, J.H. Lee, N.Y. Son, Y.I. Jin, S.H. Kim,
Geographic authentication of Asian rice (Oryza sativa L.) using multi-elemental
and stable isotopic data combined with multivariate analysis, Food Chem. 240
(2018) 840–849, https://doi.org/10.1016/j.foodchem.2017.08.023.
[59] R.A. Lagad, S.K. Singh, V.K. Rai, Rare earth elements and 87 Sr/ 86 Sr isotopic
characterization of Indian Basmati rice as potential tool for its geographical au-
thenticity, Food Chem. 217 (2017) 254–265, https://doi.org/10.1016/j.
foodchem.2016.08.094.
[60] H. Zhao, B. Guo, Y. Wei, B. Zhang, Multi-element composition of wheat grain and
provenance soil and their potentialities as fingerprints of geographical origin, J.
Cereal Sci 57 (2013) 391–397, https://doi.org/10.1016/j.jcs.2013.01.008.
[61] H. Liu, Y. Wei, Y. Zhang, S. Wei, S. Zhang, B. Guo, The effectiveness of multi-
element fingerprints for identifying the geographical origin of wheat, Int. J. Food
Sci. Technol. 52 (2017) 1018–1025, https://doi.org/10.1111/ijfs.13366.
[62] H. Zhao, C. Yu, M. Li, Effects of geographical origin, variety, season and their
interactions on minerals in tea for traceability, J. Food Compos. Anal. 63 (2017)
15–20, https://doi.org/10.1016/j.jfca.2017.07.030.
[63] M.J. Cabrita, N. Martins, P. Barrulas, R. Garcia, C.B. Dias, E.P. Pérez-Álvarez,
A.M. Costa Freitas, T. Garde-Cerdán, Multi-element composition of red, white and
palhete amphora wines from Alentejo by Icpms, Food Control 92 (2018) 80–85,
https://doi.org/10.1016/j.foodcont.2018.04.041.
[64] H. Hopfer, J. Nelson, T.S. Collins, H. Heymann, S.E. Ebeler, The combined impact
of vineyard origin and processing winery on the elemental profile of red wines,
Food Chem. 172 (2015) 486–496, https://doi.org/10.1016/j.foodchem.2014.09.
113.
[65] S.M. Azcarate, L.D. Martinez, M. Savio, J.M. Camiña, R.A. Gil, Classification of
monovarietal Argentinean white wines by their elemental profile, Food Control 57
(2015) 268–274, https://doi.org/10.1016/j.foodcont.2015.04.025.
[66] V.S. Šelih, M. Šala, V. Drgan, Multi-element analysis of wines by ICP-MS and ICP-
OES and their classification according to geographical origin in Slovenia, Food
Chem. 153 (2014) 414–423, https://doi.org/10.1016/j.foodchem.2013.12.081.
[67] A. Naccarato, E. Furia, G. Sindona, A. Tagarelli, Multivariate class modeling
techniques applied to multielement analysis for the verification of the geo-
graphical origin of chili pepper, Food Chem. 206 (2016) 217–222, https://doi.
org/10.1016/j.foodchem.2016.03.072.
[68] B.G. Osborne, Near-Infrared spectroscopy in food analysis, Encycl. Anal. Chem. 90
(2000) 78–84, https://doi.org/10.1002/9780470027318.a1018.
[69] B.H. Stuart, Infrared Spectroscopy: Fundamentals and Applications, John Wiley &
Sons, Ltd, Chichester, UK, 2005, https://doi.org/10.1002/0470011149.
[70] V. Baeten, P. Dardenne, Spectroscopy: developments in instrumentation and
analysis, Grasas Y. Aceites 53 (2002) 45–63, https://doi.org/10.3989/gya.2002.
v53.i1.289.
[71] S. Shafiee, S. Minaei, Combined data mining/NIR spectroscopy for purity assess-
ment of lime juice, Infrared Phys. Technol. 91 (2018) 193–199, https://doi.org/
10.1016/j.infrared.2018.04.012.
[72] N. Sinelli, M. Casale, V. Di Egidio, P. Oliveri, D. Bassi, D. Tura, E. Casiraghi,
Varietal discrimination of extra virgin olive oils by near and mid infrared spec-
troscopy, Food Res. Int. 43 (2010) 2126–2131, https://doi.org/10.1016/j.foodres.
2010.07.019.
[73] L. Xie, X. Ye, D. Liu, Y. Ying, Application of principal component-radial basis
function neural networks (PC-RBFNN) for the detection of water-adulterated
bayberry juice by near-infrared spectroscopy, J. Zhejiang Univ. Sci. B. 9 (2008)
982–989, https://doi.org/10.1631/jzus.B0820057.
[74] H. Zhao, B. Guo, Y. Wei, B. Zhang, Near infrared reflectance spectroscopy for
determination of the geographical origin of wheat, Food Chem. 138 (2013)
1902–1907, https://doi.org/10.1016/j.foodchem.2012.11.037.
[75] M.I. González-Martín, G. Wells Moncada, C. González-Pérez, N. Zapata San
Martín, F. López-González, I. Lobos Ortega, J.M. Hernández-Hierro, Chilean flour,
wheat grain, Tracing their origin using near infrared spectroscopy and chemo-
metrics, Food Chem. 145 (2014) 802–806, https://doi.org/10.1016/j.foodchem.
2013.08.103.
[76] Y. Yang, Y. Wu, W. Li, X. Liu, J. Zheng, W. Zhang, Y. Chen, Determination of
geographical origin and icariin content of Herba Epimedii using near infrared
spectroscopy and chemometrics, Spectrochim. Acta - Part A Mol. Biomol.
Spectrosc. 191 (2018) 233–240, https://doi.org/10.1016/j.saa.2017.10.019.
[77] V. Cortés, J.M. Barat, P. Talens, J. Blasco, M.J. Lerma-García, A comparison be-
tween NIR and ATR-FTIR spectroscopy for varietal differentiation of Spanish intact
almonds, Food Control 94 (2018) 241–248, https://doi.org/10.1016/j.foodcont.
12
Microchemical Journal 152 (2020) 104295
2018.07.020.
[78] G. Downey, Food and food ingredient authentication by mid-infrared spectroscopy
and chemometrics, TrAC Trends Anal. Chem. 17 (1998) 418–424, https://doi.org/
10.1016/S0165-9936(98)00042-9.
[79] D.W. Sun, Infrared Spectroscopy for Food Quality Analysis and Control, 1st ed.,
Elsevier Inc., 2009.
[80] R. Karoui, G. Downey, C. Blecker, Mid-Infrared spectroscopy coupled with che-
mometrics: a tool for the analysis of intact food systems and the exploration of
their molecular structure−quality relationships − a review, Chem. Rev. 110
(2010) 6144–6168, https://doi.org/10.1021/cr100090k.
[81] E. Polshin, B. Aernouts, W. Saeys, F. Delvaux, F.R. Delvaux, D. Saison, M. Hertog,
B.M. Nicolaï, J. Lammertyn, Beer quality screening by FT-IR spectrometry: impact
of measurement strategies, data pre-processings and variable selection algorithms,
J. Food Eng 106 (2011) 188–198, https://doi.org/10.1016/j.jfoodeng.2011.05.
003.
[82] M.A. Al-Holy, M. Lin, O.A. Alhaj, M.H. Abu-Goush, Discrimination between
Bacillus and Alicyclobacillus isolates in apple juice by fourier transform infrared
spectroscopy and multivariate analysis, J. Food Sci 80 (2015) M399–M404,
https://doi.org/10.1111/1750-3841.12768.
[83] R. Ríos-Reina, R.M. Callejón, C. Oliver-Pozo, J.M. Amigo, D.L. García-González,
ATR-FTIR as a potential tool for controlling high quality vinegar categories, Food
Control 78 (2017) 230–237, https://doi.org/10.1016/j.foodcont.2017.02.065.
[84] G. Ozulku, R.M. Yildirim, O.S. Toker, S. Karasu, M.Z. Durak, Rapid detection of
adulteration of cold pressed sesame oil adultered with hazelnut, canola, and
sunflower oils using ATR-FTIR spectroscopy combined with chemometric, Food
Control 82 (2017) 212–216, https://doi.org/10.1016/j.foodcont.2017.06.034.
[85] Z. Wu, H. Li, D. Tu, Application of fourier transform infrared (FT-IR) spectroscopy
combined with chemometrics for analysis of rapeseed oil adulterated with refining
and purificating waste cooking oil, Food Anal. Methods. 8 (2015) 2581–2587,
https://doi.org/10.1007/s12161-015-0149-z.
[86] A. Rohman, D. Wibowo, Sudjadi, E. Lukitaningsih, A.S. Rosman, Use of fourier
transform infrared spectroscopy in combination with partial least square for au-
thentication of black seed oil, Int. J. Food Prop. 18 (2015) 775–784, https://doi.
org/10.1080/10942912.2014.908207.
[87] A. Rohman, Y.B. Che Man, F.M. Yusof, The use of FTIR spectroscopy and che-
mometrics for rapid authentication of extra virgin olive oil, J. Am. Oil Chem. Soc.
91 (2014) 207–213, https://doi.org/10.1007/s11746-013-2370-5.
[88] Y. B., C. Man, A. Rohman, Analysis of canola oil in virgin coconut oil using FTIR
spectroscopy and chemometrics, J. Food Pharm. Sci. 1 (2013) 5–9 https://journal.
ugm.ac.id/jfps/article/view/1835/1643.
[89] M.J. Lerma-García, G. Ramis-Ramos, J.M. Herrero-Martínez, E.F. Simó-Alfonso,
Authentication of extra virgin olive oils by Fourier-Transform infrared spectro-
scopy, Food Chem. 118 (2010) 78–83, https://doi.org/10.1016/j.foodchem.2009.
04.092.
[90] H. Huang, L. Liu, M. Ngadi, Recent developments in hyperspectral imaging for
assessment of food quality and safety, Sensors 14 (2014) 7248–7276, https://doi.
org/10.3390/s140407248.
[91] B. Li, M. Zhao, Y. Zhou, B. Hou, D. Zhang, Detection of waxed rice using visible-
near infrared hyperspectral imaging, J. Food Nutr. Res. 4 (2016) 267–275, https://
doi.org/10.12691/jfnr-4-5-1.
[92] W. Kong, C. Zhang, F. Liu, P. Nie, Y. He, Rice seed cultivar identification using
near-infrared hyperspectral imaging and multivariate data analysis, Sensors 13
(2013) 8916–8927, https://doi.org/10.3390/s130708916.
[93] P.J. Williams, P. Geladi, T.J. Britz, M. Manley, Investigation of fungal development
in maize kernels using NIR hyperspectral imaging and multivariate data analysis,
J. Cereal Sci. 55 (2012) 272–278, https://doi.org/10.1016/j.jcs.2011.12.003.
[94] C. Zhang, F. Liu, Y. He, Identification of coffee bean varieties using hyperspectral
imaging: influence of preprocessing methods and pixel-wise spectra analysis, Sci.
Rep. 8 (2018) 1–11, https://doi.org/10.1038/s41598-018-20270-y.
[95] D.J.F. September, Detection and Quantification of Spice Adulteration by Near
Infrared Hyperspectral Imaging, Graduate thesis Stellenbosch University, 2011.
[96] M. Huang, X. Wan, M. Zhang, Q. Zhu, Detection of insect-damaged vegetable
soybeans using hyperspectral transmittance image, J. Food Eng. 116 (2013)
45–49, https://doi.org/10.1016/j.jfoodeng.2012.11.014.
[97] J.A. Timlin, A. Carden, M.D. Morris, J.F. Bonadio, C.E. Hoffler, K.M. Kozloff,
S.A. Goldstein, Spatial distribution of phosphate species in mature and newly
generated mammalian bone by hyperspectral raman imaging, J. Biomed. Opt. 4
(1999) 28, https://doi.org/10.1117/1.429918.
[98] J. Qin, K. Chao, M.S. Kim, Investigation of Raman chemical imaging for detection
of lycopene changes in tomatoes during postharvest ripening, J. Food Eng. 107
(2011) 277–288, https://doi.org/10.1016/j.jfoodeng.2011.07.021.
[99] U. Erikson, I.B. Standal, I.G. Aursand, E. Veliyulin, M. Aursand, Use of NMR in fish
processing optimization: a review of recent progress, Magn. Reson. Chem. 50
(2012) 471–480, https://doi.org/10.1002/mrc.3825.
[100] Y. Huo, G.M. Kamal, J. Wang, H. Liu, G. Zhang, Z. Hu, F. Anwar, H. Du, 1H-NMR-
based metabolomics for discrimination of rice from different geographical origins
of China, J. Cereal Sci. 76 (2017) 243–252, https://doi.org/10.1016/j.jcs.2017.
07.002.
[101] R. Lamanna, L. Cattivelli, M.L. Miglietta, A. Troccoli, Geographical origin of
durum wheat studied by 1H-NMR profiling, Magn. Reson. Chem. 49 (2011) 1–5,
https://doi.org/10.1002/mrc.2695.
[102] F. Longobardi, V. Innamorato, A. Di Gioia, A. Ventrella, V. Lippolis, A.F. Logrieco,
L. Catucci, A. Agostiano, Geographical origin discrimination of lentils (Lens culi-
naris Medik.) using 1H-NMR fingerprinting and multivariate statistical analyses,
Food Chem. 237 (2017) 743–748, https://doi.org/10.1016/j.foodchem.2017.05.
159.
S.A. Wadood, et al.
[103] M.O. Salazar, P.L. Pisano, M. González Sierra, R.L.E. Furlan, NMR and multivariate
data analysis to assess traceability of argentine citrus, Microchem. J. 141 (2018)
264–270, https://doi.org/10.1016/j.microc.2018.05.037.
[104] R. Godelmann, F. Fang, E. Humpfer, B. Schütz, M. Bansbach, H. Schäfer, M. Spraul,
Targeted and nontargeted wine analysis by 1H-NMR spectroscopy combined with
multivariate statistical analysis. differentiation of important parameters: grape
variety, geographical origin, year of vintage, J. Agric. Food Chem. 61 (2013)
5610–5619, https://doi.org/10.1021/jf400800d.
[105] R. Consonni, D. Polla, L.R. Cagliani, Organic and conventional coffee differ-
entiation by NMR spectroscopy, Food Control 94 (2018) 284–288, https://doi.
org/10.1016/j.foodcont.2018.07.013.
[106] M.V. de Moura Ribeiro, N. Boralle, H. Redigolo Pezza, L. Pezza, A.T. Toci,
Authenticity of roasted coffee using 1H-NMR spectroscopy, J. Food Compos. Anal.
57 (2017) 24–30, https://doi.org/10.1016/j.jfca.2016.12.004.
[107] R. Consonni, L.R. Cagliani, C. Cogliati, NMR based geographical characterization
of roasted coffee, Talanta 88 (2012) 420–426, https://doi.org/10.1016/j.talanta.
2011.11.010.
[108] A.T. Toci, M.V. de Moura Ribeiro, P.R.A.B. de Toledo, N. Boralle, H.R. Pezza,
L. Pezza, Fingerprint and authenticity roasted coffees by 1H-NMR: the Brazilian
coffee case, Food Sci. Biotechnol. 27 (2018) 19–26, https://doi.org/10.1007/
s10068-017-0243-7.
[109] F. Fridez, Basmati rice fraud under the magnifying glass of DNA analysis, Chim.
Int. J. Chem. 70 (2016) 354–356, https://doi.org/10.2533/chimia.2016.354.
[110] L.R. Vemireddy, V.V. Satyavathi, E.A. Siddiq, J. Nagaraju, Review of methods for
the detection and quantification of adulteration of rice: basmati as a case study, J.
Food Sci. Technol. 52 (2014) 3187–3202, https://doi.org/10.1007/s13197-014-
1579-0.
[111] M.M. Voorhuijzen, J.P. van Dijk, T.W. Prins, A.M.A. Van Hoef, R. Seyfarth,
E.J. Kok, Development of a multiplex DNA-based traceability tool for crop plant
materials, Anal. Bioanal. Chem. 402 (2012) 693–701, https://doi.org/10.1007/
s00216-011-5534-x.
[112] N. Pegels, I. González, T. García, R. Martín, Authenticity testing of wheat, barley,
rye and oats in food and feed market samples by real-time PCR assays, LWT - Food
Sci. Technol. 60 (2015) 867–875, https://doi.org/10.1016/j.lwt.2014.10.049.
[113] I.M. López-Calleja, S. de la Cruz, I. González, T. García, R. Martín, Duplex real-
time PCR using TaqMan® for the detection of sunflower (Helianthus annuus) and
poppy (Papaver rhoeas) in commercial food products, LWT - Food Sci. Technol. 65
(2016) 999–1007, https://doi.org/10.1016/j.lwt.2015.09.026.
[114] T. Ferreira, A. Farah, T.C. Oliveira, I.S. Lima, F. Vitório, E.M.M. Oliveira, Using
13
Microchemical Journal 152 (2020) 104295
real-time PCR as a tool for monitoring the authenticity of commercial coffees,
Food Chem 199 (2016) 433–438, https://doi.org/10.1016/j.foodchem.2015.12.
045.
[115] T.B. Bucher, R. Köppel, Duplex digital droplet PCR for the determination of non-
Basmati rice in basmati rice (Oryza sativa) on the base of a deletion in the fragrant
gene, Eur. Food Res. Technol. 242 (2016) 927–934, https://doi.org/10.1007/
s00217-015-2599-3.
[116] S. Barrias, J.R. Fernandes, J.E. Eiras-Dias, J. Brazão, P. Martins-Lopes, Label free
DNA-based optical biosensor as a potential system for wine authenticity, Food
Chem. 270 (2019) 299–304, https://doi.org/10.1016/j.foodchem.2018.07.058.
[117] M. Peris, L. Escuder-Gilabert, Electronic noses and tongues to assess food au-
thenticity and adulteration, Trends Food Sci. Technol. 58 (2016) 40–54, https://
doi.org/10.1016/j.tifs.2016.10.014.
[118] S.D. Rodríguez, D.A. Barletta, T.F. Wilderjans, D.L. Bernik, Fast and efficient food
quality control using electronic noses: adulteration detection achieved by unfolded
cluster analysis coupled with time-window selection, Food Anal. Methods. 7
(2014) 2042–2050, https://doi.org/10.1007/s12161-014-9841-7.
[119] W. Dong, J. Zhao, R. Hu, Y. Dong, L. Tan, Differentiation of Chinese robusta
coffees according to species, using a combined electronic nose and tongue, with
the aid of chemometrics, Food Chem. 229 (2017) 743–751, https://doi.org/10.
1016/j.foodchem.2017.02.149.
[120] Y. Ma, B. Guo, Y. Wei, S. Wei, H. Zhao, The feasibility and stability of distin-
guishing the kiwi fruit geographical origin based on electronic nose analysis, Food
Sci. Technol. Res. 20 (2014) 1173–1181, https://doi.org/10.3136/fstr.20.1173.
[121] K. Heidarbeigi, S.S. Mohtasebi, A. Foroughirad, M. Ghasemi-Varnamkhasti,
S. Rafiee, K. Rezaei, Detection of adulteration in saffron samples using electronic
nose, Int. J. Food Prop. 18 (2015) 1391–1401, https://doi.org/10.1080/
10942912.2014.915850.
[122] M. Gutiérrez, A. Llobera, J. Vila-Planas, F. Capdevila, S. Demming, S. Büttgenbach,
S. Mínguez, C. Jiménez-Jorquera, Hybrid electronic tongue based on optical and
electrochemical microsensors for quality control of wine, Analyst 135 (2010)
1718, https://doi.org/10.1039/c0an00004c.
[123] I.M. Apetrei, C. Apetrei, Detection of virgin olive oil adulteration using a vol-
tammetric e-tongue, Comput. Electron. Agric. 108 (2014) 148–154, https://doi.
org/10.1016/j.compag.2014.08.002.
[124] L.G. Dias, A. Fernandes, A.C.A. Veloso, A.A.S.C. Machado, J.A. Pereira, A.M. Peres,
Single-cultivar extra virgin olive oil classification using a potentiometric electronic
tongue, Food Chem. 160 (2014) 321–329, https://doi.org/10.1016/j.foodchem.
2014.03.072.