Food Authentication1
Food Authentication1
Food Authentication1
A R T I C L E I N F O A B S T R A C T
Keywords:
Food authentication is a rapidly growing field due to increasing public awareness concerning
Food authentication
food quality and safety. This review presents critically the analytical techniques which are used
Analytical techniques
Geographical origin
for authenticity assessment, explaining how and why they give plausible solutions. Classification
Species of different methodologies is based on authenticity indicators providing insight into future develop-
Botanical origin ments. Analytical breakthroughs and novel techniques that emerged recently are discussed, along with
Scientometric evaluation their applications on food authentication. We have discussed current limits and gaps, related to infor-
Authenticity matics needs for data analysis of large quantities. Reporting standards and reference database are
Adulteration elaborated indicating urgent needs for the progress of this field. A scientometric evaluation highlighted
Fraud the research trends and emerging approaches of this evolving field. Popular analytical techniques are
commented, while the potential of the field is depicted in the temporal evolution of the research
output focusing on geographical distribution of research activity and preferred journals used for
dissemination.
© 2016 Elsevier B.V. All rights reserved.
Contents
1. Introduction ............................................................................................................................................................................................................................................................. 1
2. Analytical techniques ........................................................................................................................................................................................................................................... 2
2.1. Molecular techniques, genomics – proteomics .............................................................................................................................................................................. 2
2.2. Chromatographic techniques ............................................................................................................................................................................................................... 2
2.3. Isotopic techniques .................................................................................................................................................................................................................................. 3
2.4. Vibrational & fluorescence spectroscopy ......................................................................................................................................................................................... 3
2.5. Elemental techniques ............................................................................................................................................................................................................................. 4
2.6. NMR .............................................................................................................................................................................................................................................................. 4
2.7. Sensory analysis ....................................................................................................................................................................................................................................... 4
2.8. Non chromatographic mass spectrometry ...................................................................................................................................................................................... 4
2.9. Immunological techniques .................................................................................................................................................................................................................... 5
2.9.1. Chemometrics – bioinformatics ......................................................................................................................................................................................... 5
3. Research trends ...................................................................................................................................................................................................................................................... 6
3.1. Analytical techniques used for food authentication ..................................................................................................................................................................... 6
3.2. Research activity spreads to different countries ........................................................................................................................................................................... 6
3.3. Journals ........................................................................................................................................................................................................................................................ 7
4. Conclusions .............................................................................................................................................................................................................................................................. 8
References ................................................................................................................................................................................................................................................................ 9
1. Introduction
http://dx.doi.org/10.1016/j.trac.2016.02.026
0165-9936/© 2016 Elsevier B.V. All rights reserved.
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& emerging approaches, Trends in Analytical Chemistry (2016), doi: 10.1016/j.trac.2016.02.026
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or processing technologies (irradiation, freezing, microwave heating). This review presents latest techniques used in food authentica-
The declaration of specific quality attributes in high-value prod- tion and related research trends with the emphasis on recent
ucts is of particular interest since these products are often target analytical breakthroughs in this area.
of fraudulent labeling. Proof of provenance is an important topic
for food safety, food quality and consumer protection, as well as the 2. Analytical techniques
compliance with national legislation, international standards, and
guidelines [1]. Due to the globalization of food markets and the re- 2.1. Molecular techniques, genomics – proteomics
sulting increase in variability and availability of food products from
other countries, consumers are increasingly interested in knowing A variety of analytical techniques, for verification of foodstuff
the geographical origin along with the assumed quality of the prod- origin have been developed and tested. Molecular analysis for dis-
ucts they eat and drink. The quality assurance and the methods used crimination of original (authentic) food products from non-original
to authenticate foodstuffs are of great interest both from commer- is a major authentication methodology. Even though traditional
cial and legal points of view [2]. methods have being extensively used for food authentication,
Authenticity has been a major concern of consumers, produc- genomic and proteomic techniques are rapidly complementing or
ers, and regulators since ancient times [3]. Modern instrumentation, outright replacing earlier methods. Nucleotide- and protein-
advances in basic sciences and in information and communica- based methods for food authentication are mostly used for species
tion technologies provide means for precise measurement and detection and identification. Since DNA is identical in all somatic
elucidation of origin of foods [4]. Since the beginning of 20th century, cells of a given organism, it is invariant whether the DNA is ex-
organizations that set standards for and control the origin of in- tracted from blood, muscle, liver or any other tissue. High stability
gredients and the production process, have appeared all over the of DNA allows the analysis of highly processed food products, as
world e.g., the French ‘Institut National des Appellations d’Origine well as trace contaminants. DNA-based methods for food authen-
(INAO), Italy’s ‘Denominazione di Origine Controllata’, Spain’s tication depend on the highly specific amplification of DNA fragments
‘Denominación de Origen’, South Africa’s ‘Wine of Origin’ or the by the Polymerase Chain Reaction (PCR). This method belongs to
United States’ ‘American Viticultural Areas’. The production of con- “genomics”, because the whole genome of the sample is used [7].
sumer goods according to these standardized procedures normally On the other hand, proteins can act as markers for many proper-
results in better products and is rewarded with higher prices at the ties of the food products all along the food chain from farm to fork,
point of sale. Unfortunately, these financial benefits attract the pro- and therefore proteomics can be applied for a systematic search of
duction of counterfeit food and illegal food trades. new marker proteins or peptides. The advantage of genomics is that
In Europe, origin is one of the main authenticity issues concern- it can amplify minute traces of nucleotide material, while proteomics
ing food. European Union legislation reserving specific names for foods identifies specific products encoded by DNA. The sensitivity of these
and beverages of a particular quality or reputation has been abun- methods is very high since the amount of required material can be
dant since the dawn of the European integration process (Council as small as a few cells [8]. After the first discovery step using ref-
Regulation, EEC No 2081/92). These legislations introduced regula- erence samples, reliable analytical methodologies are needed for
tory framework for wines and spirits and quality schemes for food targeted detection and quantification of characterized markers in
products including PDO (Protected Designation of Origin) that links real unknown samples [9]. These proteogenomic techniques are con-
products to the defined geographical area where they are pro- stantly being improved, examples including PCR Single Strand
duced, PGI (Protected Geographical Indication) that links products Conformation Polymorphisms, (PCR-SSCP), random amplified poly-
to a geographical area where at minimum one production step oc- morphic DNA (RAPD), or the emerging field of Peptide Nucleic Acid
curred, and TSG (Traditional Specialities Guaranteed) that protects (PNA), and DNA fingerprinting that are used for food authentica-
traditional methods of production. Furthermore, recently defined op- tion [10]. Genomics and proteomics are usually applied to identify
tional quality terms such as OQT, “mountain product” and “product false description and mislabeling of foods. Interesting examples are:
of island farming” were defined (1151/2012 EU Regulation). The detection of GMOs, seafood authentication, authentication of kosher
purpose of these EU schemes is to protect the reputation of the re- and halal meat, detection of horse meat and pork in food labeled
gional foods and to promote good practices in rural and agricultural as beef, game meat authentication, botanical origin of foods (olive
activity. Such practices help producers obtain premium prices for au- oil, wine, tomato products, tea, and cocoa), species origin authen-
thentic products and minimize the unfair and misleading competition tication (meat, milk, fish).
from non-genuine products, usually of inferior quality or of differ- Another emerging sub-field of proteogenomic is microbial fin-
ent flavor (1151/2012 EU Regulation). The information includes a gerprinting for food authentication. PCR Denaturing Gradient Gel
characterization of the geographic region and reinforces the con- Electrophoresis technique (PCR-DGGE) is used for these type of
sumer perception of special quality attributed to mountain and island studies. Microbial flora fingerprints of specific food products such
products. In case of cultivated species, EU indicates that a reference as cheese [11]. This possibility arises from the production technol-
should be made to the country in which the food undergoes the final ogy of these foodstuffs, in which the use of starter cultures is
production stage. Vigorous research activities in EU are supported indispensable. Other examples where microbial fingerprinting can
by the coordination actions of the European Union, including “Food be used for identifying the authenticity of foods concern fruits, milk
Integrity”, “MoniQa” and “TRACE” within HORIZON 2020. and dairy products, wine, cocoa and organic foods.
Determination of food authenticity is an important issue in quality
control and food safety. Authenticity testing is a quality criterion 2.2. Chromatographic techniques
for food and food ingredients, increasingly a result of legislative pro-
tection of regional foods. Thus, there is a pressing need for accurate Chromatographic analysis provides rapid and reliable separa-
standardized food authentication techniques [3–6]. Food authen- tion of chemically similar compounds in complex food matrices [12].
ticity testing does not serve only consumers; the stakeholders include In food authentication, chromatographic techniques must over-
food industries who are seeking the opportunity to assure their food come several challenges inherent to food matrices. Food substrates
products labeling compliance and branding. Regulatory authori- consist of a great number of compounds, including peptides, lipids,
ties are asking for an extended and updated list of the analytical carbohydrates, amino acids, fatty acids, organic acids, nucleic acids,
methods for confirmation of authentic food products and to support phytochemicals and other small molecule (additives, such as colo-
law enforcement. rants, aromas, preservatives and other exogenous compounds) [13].
Please cite this article in press as: Georgios P. Danezis, Aristidis S. Tsagkaris, Federica Camin, Vladimir Brusic, Constantinos A. Georgiou, Food authentication: Techniques, trends
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These compounds are chemically diverse, ranging from the small The analysis of stable isotopes of bio-elements have been recog-
organic molecules (usually up to 1000 Da) to macromolecules (bio- nized by EU, OIV, CEN and AOAC as official methods since the 1990s
polymers), that can possess a wide range of polarities – some are to detect adulteration of wine, honey, fruit juice, or maple syrup with
apolar (like oils) while some others are strongly polar (like amino cheaper extenders, such as water or sugar syrup made from maize
acids). Chromatographic methods produce unique chemical finger- or sugar cane. Other examples of isotopic ratio applications include
prints that differentiate and authenticate foods. The authentication the discrimination of natural vs. synthetic vanillin and discrimina-
is based, on identification of minimal analytical differences between tion of champagne CO2 produced naturally by adding sugar to bottles
patterns or identification of unique marker compounds. from direct injection of industrial CO2. More recent applications of
Due to the chemical complexity of foodstuffs and high consum- multi-isotope ratio analysis (2H/1H or D/H, 13C/12C, 18O/16O, 15N/14N,
34 32
er demand for food quality and genuineness, high-resolution S/ S, 87Sr/86Sr) include geographical origin verification studies of
chromatographic techniques, such as gas (GC) or liquid chroma- wine, olive oil, orange fruit, honey, tomato, Chinese cabbage, meat,
tography (LC) coupled to mass spectrometry (MS), have emerged dairy products, eggs, seafood, and coffee. Remarkably, isotopic fin-
as useful food authentication tools. Double MS (triple quadru- gerprints are used as indicators for organically grown products [16].
pole) is replacing older instruments and most instruments principally Furthermore, the isotopic fingerprinting can be combined with
used are Gas Chromatography Mass Spectrometry (GC-MS/MS), other indicators (e.g., elemental analysis, NMR and GC) to improve
Liquid Chromatography Mass Spectrometry (LC-MS/MS) and Liquid the determination of the origin of a variety of food products.
Chromatography Time-of-Flight Mass Spectrometry (LC-TOF-MS).
LC separation is typically performed by targeting three primary 2.4. Vibrational & fluorescence spectroscopy
characteristics of the chemical compounds: polarity, electrical charge,
and molecular size. It is mostly used to detect proteins, amino acids, Spectroscopy, in particular vibrational spectroscopy, is a fast and
carbohydrates, vitamins, phenolic compounds, tryglycerides, chiral inexpensive method for both the assessment of food quality and food
compounds, and pigments, while Gas Chromatography is more suited authenticity. Novel instrumental techniques combined with
to the analysis of naturally volatile or semi-volatile molecules [14]. chemometric methods have enabled the development of rapid
Authentication by chromatography is based on the profile of spe- methods that apply multivariate (MVA) analysis, to near infrared (NIR)
cific compound profiles for each food product, such as fatty acids, and mid infrared (MIR) data to analyze food matrices. In Infrared ra-
triglycerides, waxes, sterols, hydrocarbons, alcohols, tocopherols, and diation (IR) region, solid, liquid or gaseous samples can absorb some
volatiles, which form profile characteristic for food identity origin. of the incoming infrared radiation at specific frequencies produc-
Examples where chromatographic techniques are used for iden- ing a spectral ‘fingerprint’ of the sample. The MIR fingerprints result
tifying the authenticity of foods include adulteration of high- from fundamental stretching, bending and rotating vibrations of the
quality products with inexpensive or sub-standard ingredients [14] molecules, whilst NIR spectra result from complex overtone and high
such as honey, wines, vegetable and olive oils, spirits, coffee, milk, frequency combinations at the shorter wavelengths. Raman spec-
cheeses, saffron, nuts and mushrooms. Such authentication is usually troscopy, another emerging methodology, is based on fundamental
done by matching measured compound profiles with the pre- vibration modes that can be assigned to specific chemical function-
determined target values. al groups within a sample molecule and therefore can provide useful
information for sample fingerprinting. Qualitative identification is
2.3. Isotopic techniques mostly done because of high detection limits featured by vibra-
tional techniques, mostly Raman. Analytical techniques deploy Fourier
Isotopes are atoms of the same element that differ by the mass Transform to – Infrared (FT-IR) and Raman (FT-Raman) fluores-
from each other. Different isotopes of the same element have equal cence. A major advantage of IR and Raman techniques is the rapid,
number of electrons (and protons) but different number of neu- non-destructive analysis of samples [17]. Surface Enhanced Raman
trons resulting in different mass. Stable isotopes are separated into Spectroscopy (SERS), in contrast to Raman spectroscopy, provides low
two groups by atomic mass, light (bio-elements) and heavy iso- detection limits for certain specific molecules, allowing applica-
topes. In the light isotope group, the ratios mostly investigated are tions to food adulterants determination.
2
H/1H, 13C/12C, 15N/14N, and 18O/16O, whereas 34S/32S is less common- Fluorescence spectroscopy is a simple, non-destructive, non-
ly used. In heavy isotopes group, most commonly used ratio in food invasive and relatively inexpensive analytical technique. It features
authentication is 87Sr/86Sr and more rarely 206Pb/204Pb, 207Pb/204Pb, low to very low detection limits as compared to other spectroscop-
208
Pb/204Pb, 143Nd/144Nd [15]. ic techniques. Molecules detected by fluorescence spectroscopy are
The analysis of isotopic ratios uses various methods such as polyaromatic hydrocarbons and heterocycles with rigid molecular
Isotope Ratio Mass Spectrometry (IRMS), Multi Collector – Induc- skeletons. Recently, simple accurate and low cost fluorometers com-
tively Coupled Plasma – Mass Spectrometry (MC-ICP-MS), and bined with advanced analytical software, gave the opportunity for
Thermal Ionization Mass Spectrometry (TIMS). IRMS interfaced with fast, reliable, repeatable measurements and elaboration of the
Elemental Analyser, Pyroliser, Equilibration devices, GC or HPLC is spectra. Hence, many fluorometric methods have been developed
used for the determination of light isotopes ratios, while heavy iso- to check the authenticity, adulteration, quality and composition of
topes are measured by MC-ICP-MS and TIMS. The ratio 2H/1H is foods [18]. A variant, Synchronous Fluorescence (SyF) utilizes
analysed also site-specifically in small molecules such as ethanol, excitation-emission plots increasing the discrimination power of flu-
using an NMR (Nuclear Magnetic Resonance) equipped with a deu- orescence. This allows applications to food authentication, for
terium probe. example to olive oil adulteration [18].
The isotopic ratios are applicable to food authentication because Characteristic examples of spectroscopic methodologies de-
stable isotope ratios change with the climatic conditions, geograph- ployed for food authentication include milk and soya bean meal
ical origin, soil pedology, and geology of the locations of food adulteration by melamine, honey adulteration by syrups (high fruc-
ingredients origin. As a primary indication, H and O isotopic data for tose corn, maltose, or jaggery syrup) and sugar solutions, adulteration
organic matter in food are linked to the H and O isotope data of water of olive oil by vegetable oils or lampante/pomace olive oils, ground
from the source region which have geographical variability, N and black pepper mixing with buckwheat and millet, culinary spices
C isotopes are related to the climate and the agricultural practices, adulteration by Sudan I dye, and meat adulteration. Authenticity
and S isotopes are affected by geology, volcanism, distance from the identification of milk, olive oils, honeys, wines, spirits, spices and
sea, and certain anthropogenic effects [2]. other food ingredients, saffron and lentil seeds have been reported.
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2.5. Elemental techniques sectors. Traditionally reliable results in sensory analysis require a
well-trained panel of human assessors. Organoleptic test panels com-
Elemental profiling is increasingly applied to assessment of food prise a set of techniques for accurate measurements of human
authenticity. Elemental profile refers to macro-elements (such as responses to foods [21]. Appearance, aroma, flavor and texture prop-
sodium, calcium and potassium), trace elements (such as copper, erties are important characteristics determining the quality-
zinc and selenium), rare earth elements (such as lanthanum, cerium authenticity of food products. These panels require extensive training
and samarium), or other elements occurring only at very low abun- of judges, adequate replication and detailed statistical analysis of
dance (such as iridium and gold). Plants derive their mineral content the observations. In all cases, the response obtained has to be prop-
from the soil. Fertilization, harvesting, botanical origin, soil type, erly evaluated because the sensory evaluation varies both among
pollution, and production year all cause variations of elemental con- panellists – they are individuals with different sensitivities, pref-
centrations. However, these variations are smaller than variation erences, and product knowledge. Assessment may change within
observed between production areas and geographic regions. Rare- a given panellist with time – depending on his fatigue, stress, health,
earth elements have great potential for geographical origin and other factors. Therefore, panellists are required to have a rea-
determination because their fingerprints are directly linked to the sonable level of sensory perception, commitment and motivation
geology of the area and could be minimally influenced by different but they should also be trained in the use of standardized and sys-
agricultural practices and harvest year. The elemental composi- tematic sensory methods to get reliable results.
tion of foods of animal origin reflects, to some extent, the mineral However, even if are perfectly trained, there is still need for the
content of the fodder and vegetation they eat. Beyond feed intake, panellists standardization of sensory analysis. That is possible with
elemental content depends on various factors such as drinking water, the development of instrumental techniques that could recognize
pollution and soil composition, all of which depend on geograph- objectively and quickly specific sensory perceptions in the same way
ic origin. Thus, vegetation is the compositional reflection of the bio- as an expert tasting panel does. Instrumental test of food quality
available and mobilized nutrients present in the underlying soils using perception sensors instead of human panel test is attracting
from which they were cultivated [2,6,19]. massive attention recently. Novel cross-perception multi-sensors data
The elemental fingerprint of foods is measured by a variety of fusion imitating multiple human perception has been proposed [22].
analytical techniques. Even though Atomic Absorption techniques Amongst the techniques, there is a clear need to refer to Gas Chro-
have been used in the past, nowadays Inductively Coupled Plasma- matography Olfactometry (GCO), biomimetic sensors: electronic
Mass Spectroscopy (ICP-MS) and Inductively Coupled Plasma- tongue (e-tongue), electronic nose, (e-nose), electronic eye, (e-
Atomic Emission Spectroscopy (ICP-AES) are almost exclusively used eye). The “e-nose” uses detection of the volatile compounds present
due to their ability for multi-element measurements [2,9,19]. Food in the headspace of a food sample by an array of semi-selective gas
authenticity applications of ICP-MS and ICP-AES include discrim- sensors [23]. First, the headspace (volatile compounds) of a sample
ination of geographical origin, organic vs conventional products, and is generated and the headspace is injected into the detection system
free range vs. cage egg production. Other examples of elemental fin- (sensors set). Each sensor is sensitive to all volatile molecules but
gerprinting analysis of food authenticity are the discrimination of each in their specific way. Most “e-noses” use sensor-arrays that react
origin of wine, honey, olive oil, coffee, cheese, fruits and veg- to volatile compounds on contact: the adsorption of volatile com-
etables, and also spices and food additives. pounds on the sensor surface causes a physical change of the sensor.
A specific response is recorded by the electronic interface trans-
2.6. NMR forming the signal into a digital value. Recorded results are then
computed based on statistical models. Further, e-nose data can be
Foodstuffs contain compounds such as amino acids, fatty acids correlated to those obtained with different methods for example
and sugars. NMR is one of the most suitable methods to obtain “high- sensory panel. The major benefits of sensory analysis are the simple
throughput” spectroscopic and structural information on a wide procedure, the quite minor sample preparation, rapidness and low
range of molecular compounds. It enables determination of complex cost.
compositional matrices of foodstuffs, with high analytical preci- The scientific community has just started to accept that we can
sion. The amount of any selected metabolite in a mixture can be define analytical instrumental specifications that characterize the
assessed with minimal sample preparation. In past, sensitivity of quality of the sample in the same way that the tasting panel does.
NMR was considered as a main limitation, but continuous devel- Detailed analysis of instrumental variables, with the help of sensory
opments in hardware resulted in high sensitivity of NMR. Therefore, information and, in some cases, of GCO will provide chemical in-
ΝΜR enables a collection of comprehensive metabolic profiles that formation about the markers, compounds responsible for the
can be used for food authentication. Site-Specific Natural Isotopic behavior of a given attribute. Examples, where sensory analysis can
Fractionation (SNIF-NMR), enables robust fingerprinting of natural be used for identifying the authenticity of foods are wines, olive oils,
molecules. A well-known application of SNIF-NMR is the determi- tea, beers and cheeses.
nation of geographical origin of wine, developed by the EU in 1990
(EU regulations 2670/90, 2347/91 and 2348/91). Profiling methods 2.8. Non chromatographic mass spectrometry
such as non-targeted 1H-NMR analysis have been applied for as-
sessing geographical provenance of food [20]. NMR analysis has been Another noticeable class of methodologies that should be men-
used for assessing adulteration, such as red wine adulteration with tioned is non chromatographic mass spectrometry techniques. Recent
anthocyanins, synthetic flavors sold as natural, addition of cane or MS applications include the use of stand-alone techniques for el-
corn sugar to maple syrup. Discrimination of origin/adulteration cases emental or molecular profiling and imaging. Among more efficient
by their metabolic profile using NMR includes wines, coffee, olive methods for food authentication are Proton transfer reaction mass
oils, honey, fish, spirits, vinegar, and saffron. spectrometry (PTR-MS), Matrix-assisted laser desorption/ionization
Time-of-Flight Mass Spectrometry/MALDI-TOF-MS and Ambient
2.7. Sensory analysis Mass Spectrometry techniques such as Direct Analysis in Real
Time/DART-MS.
Nowadays, consumers increasingly demand products that are not PTR-MS allows quantitative on-line monitoring of volatile organic
only safe and nourishing but also are desired to have high organo- compounds (VOC), by using soft chemical ionization method for ion-
leptic quality. Sensory analysis has become important in many food ization of organic molecules. VOC molecules react with charged ions,
Please cite this article in press as: Georgios P. Danezis, Aristidis S. Tsagkaris, Federica Camin, Vladimir Brusic, Constantinos A. Georgiou, Food authentication: Techniques, trends
& emerging approaches, Trends in Analytical Chemistry (2016), doi: 10.1016/j.trac.2016.02.026
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in most cases hydroxonium ions (H3O+). At that time, H3O+ ions trans- originally developed to facilitate the study of immunology but are
fer their proton exclusively to VOC molecules that have proton now finding widespread applications in many other fields as they
affinities higher than that of water, yielding protonated analyte VOCs. can be used to detect a host of molecules, ranging from proteins
Then, an electric field accelerates the ions through the reaction to small organic molecules in a complex sample matrix present in
chamber, leading to collision-induced dissociation of ions. After scan- foodstuffs [27]. Immunoassays became popular tools for verifying
ning a mass range, fingerprints of the volatile compounds are obtained. identity standards of various types of food and food ingredients
Therefore, PTR-MS gives instantaneously the absolute concentra- because they are fast, sensitive, highly specific, and cheap. In ad-
tions of VOCs. PTR-MS enables rapid detection of a variety of organic dition they are user-friendly, have a high throughput, and are
species, such as alkenes, alcohols, aldehydes, aromatics, ketones, ni- amenable to field-testing. In food industry antibodies are devel-
triles and sulphides, in complex matrices with very low detection oped against specific antigens (allergens, toxins, pathogens, etc.) [28]
limits. Nowadays, there is also a new hyphenation, PTR-TOF-MS, which and then used as capture molecules to trap their target antigens.
found considerable applications on food authentication [24]. The production of specific antibodies is thus the first crucial step
MALDI has demonstrated a great potential in fast screening in the development of an immunoassay. A major step forward that
analyses for food quality, safety and authentication, since chro- opened the door for the more general use of immunoassays was
matographic separation is usually not needed. Concerning sample the development of enzyme labels. Enzyme-linked immunosorbent
preparation, a matrix constituted by a weak organic acid, is mixed assay, ELISA, is the most used of immunological techniques [29].
with the sample and the resultant solution is deposited on a It has been used to verify the authenticity of several food com-
microtiter plate and allowed to crystallize. Then the plate is loaded modities such as meat, fish, and dairy products. It can also detect
in the mass spectrometer and a laser beam hits the spot where co- presence of genetically modified organisms (GMOs) and unde-
crystals of the matrix and the analyte are present. Due to the laser clared processes like food irradiation. Food authenticity assessment
energy, a part of the matrix, which has a strong absorption of the by immunological techniques includes determination of osteocalcin
laser wavelength, is vaporized together with the analyte in a “plume” in meat and bone meal, detection of glucomannan (use is banned
that expands at high velocity. The sample ions formed in the ion in Europe) in konjac plant products, detection of melamine and
source are extracted and accelerated in an electric field with high bovine IgG in milk, and detection of pork in ground beef and soybean
voltages. After passing the charged grid, the ions fly into the TOF proteins in meat products.
mass analyzer. Finally, the ions reach the detector where the con-
version and the amplification of ion current in an electrical signal
are accomplished. With MALDI-MS techniques require a low amount 2.9.1. Chemometrics – bioinformatics
of sample. They are very sensitive with sample preparation without All fingerprinting techniques produce a large volume of infor-
the need of analyte derivatization [25]. mation. Chemometrics [30] and bioinformatics [31] tools are
Ambient Mass Spectrometry is performed in an open atmo- fundamental for food authentication studies since huge amounts
sphere either directly on samples or matrices in their natural of data need to be handled. Data mining, data fusion and feature
environments or by using auxiliary surfaces. Ambient-MS has greatly selection are essential for the making sense out of the huge data
simplified and increased the speed of MS analysis. Nowadays there set generated through various analytical methods.
are a variety of different desorption and ionization mechanisms avail- Informatic infrastructure in the field of food authentication is
able. Most types of molecules with a large range of masses and in its infancy and its development is critical for systematic, com-
polarities can be ionized with great ease and simplicity with the prehensive, and broadly applicable assessment of food authenticity.
outstanding combination of the speed, selectivity, and sensitivity Food authentication must address multidimensional challenges. First,
of MS detection. Direct analysis in real time mass spectrometry there are no standard guidelines for description of the workflow,
(DART-MS) is one of the variants of ambient mass spectrometry. It so the design of experiments and reporting of results in the liter-
has become an established technique for rapid mass spectral anal- ature show large diversity. Thus, our ability to compare the results
ysis of a large variety of samples. The ionization process of DART- from similar studies is very limited. Most of the reports have limited
MS takes place at atmospheric pressure and takes only few seconds. description of study design limiting the value of the report. An
In DART, an electrical potential is applied to a gas with a high ion- example of a well-designed study with comprehensive descrip-
ization potential (typically nitrogen or helium) to form plasma of tion is [32], where conventional, organic, and courtyard eggs were
excited-state atoms and ions, and these desorb low–molecular weight compared. In this study, the data collection was matched between
molecules from the surface of a sample. It is suitable for fast anal- three production methods and the chicken species, their diet, and
ysis, with minimal sample preparation and high salt tolerance. DART- housing conditions were described. In contrast, many studies report
MS can be applied to compounds that have been deposited or that, for example, food sample was bought in supermarket with little,
adsorbed on to surfaces or that are being desorbed therefrom into if any, description of the samples. Although, the situation is im-
the atmosphere. DART could also be hyphenated with TOF-MS, giving proving in recent years, most reported studies do not have sufficient
solutions in authenticity studies [26]. number of samples for meaningful analysis. The databases of ref-
Non chromatographic MS techniques have been applied in food erence materials do not exist, so the reported results either
authentication to uncover incorrect description and mislabeling of demonstrate the separability between the classes in the data (such
foods with specific geographical label such as saffron, truffle, honey, as organic vs. non-organic), or simply report the data, such as mean
beer, olive oils, juices, and botanical origin of spices and species. value of observed trace elements. Food authentication involves
These techniques are also used to prevent food fraud such as dilu- technical, structural and legal concerns [5]. The methods and results
tion of olive oil by cheaper vegetable oils, and adulteration of donkey must be:
milk, of higher value types of milk (sheep’s and goat’s) with milk
of lower value (cow’s milk), of fresh cow’s milk with powdered milk, • Accurate to provide correct interpretation of data. This is mainly
of coffee, and of animal feed . achieved using standard certified reference materials to ensure
the accuracy of measurements.
2.9. Immunological techniques • Robust to take care of natural variability of sample content, mea-
surement error, and effects of processing, storage, and handling.
Immunoassays are analytical tools that rely on the specific in- Reference materials for this step do not exist and the number
teraction between antibodies and their cognate antigens. They were of studied samples is typically too low.
Please cite this article in press as: Georgios P. Danezis, Aristidis S. Tsagkaris, Federica Camin, Vladimir Brusic, Constantinos A. Georgiou, Food authentication: Techniques, trends
& emerging approaches, Trends in Analytical Chemistry (2016), doi: 10.1016/j.trac.2016.02.026
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6 G.P. Danezis et al./Trends in Analytical Chemistry ■■ (2016) ■■–■■
• Mutually comparable across different studies to ensure that they geographical origin determination, analytical methods rely largely
can be compared in a meaningful way to database references. on determination of chemical compositions, which may be quite
similar even when the matching materials come from different geo-
Food authentication will critically depend on establishment of graphical areas. Attempts have been made by determining some
databases that contain comprehensive and standardized informa- components as typical for certain areas or production methods. Other
tion about origin of foods including geographic origin, species/ methods that are applied include molecular methods when differ-
subspecies, production methods, and other critical information. Most ent strains/breeds of organisms are used in production.
studies done to date are of exploratory or sample classification nature Various analytical techniques have been assessed on their suit-
– they analyze preliminary data and show that the data are sepa- ability for food authentication studies throughout the years.
rable across classes [2]. Predictive models that can map unknown Chromatographic and molecular methods are the major approaches
sample to known class depend on existence of reference samples to food authentication solutions (Fig. 2). These two groups account
and appropriately defined databases. While effort has been made for almost half of published research. Isotopic, vibrational, UV & flu-
to record food ingredient fraud and adulteration [33] and the Eu- orescence spectroscopy, elemental techniques and NMR are also
ropean DOOR database (ec.europa.eu/agriculture/quality/door) lists prominent. Some other technologies such as non-chromatographic
more than 1500 foods of protected origin, an appropriate data- MS, microbial fingerprinting and sensory analysis, have not been
base needed for classification of unknown samples is lacking. exploited to the maximum, yet our opinion is that they will find
Chemometrics is definitely needed for solving the problem of extensive use in the near future. This warrants attention of the an-
authentication or identity confirmation. It must be combined with alytical community that has to benefit from cross scientific
database infrastructure and appropriate mathematical tools for food collaborations. A trend depicted by the increase in popularity during
authentication [34]. the last four years is that chromatographic, molecular, vibrational
and fluorescence spectroscopy techniques are emerging in food au-
3. Research trends thentication (Fig. 3).
More than 80% of food authentication publications are original 3.2. Research activity spreads to different countries
work published in research journals while review articles and con-
ference proceedings account for around 7–8 % each and book South European countries such as Italy, Spain, France, Portugal
chapters/books account for 5%. Determination of geographical origin, and Greece are involved in food authentication studies, as can be
adulteration, mislabeling and food safety are amongst the main seen in Fig. 4. This is expected as these countries produce a ma-
aspects in food control. Published research depicted in Fig. 1 shows jority of foodstuffs and wines registered as PDO, PGI, or TSG. Yet some
that growth in food authentication after 2000 is exponential. We countries with high scientific capabilities and large food produc-
identified 409 articles that were published during 2006–2008 and tion, for example USA, stay behind in food authentication. China is
907 during the period 2012–2014. an emerging country in the field, showing a rapid growth during
the last 5 years (Fig. 5). It is interesting to note that all countries
3.1. Analytical techniques used for food authentication in the top 10 list, except the USA and China, are European. This in-
dicates the interest of Europeans in food authenticity that is
Determining the food authenticity involves a range of verifica- supported by national and EU legislation in European countries. In-
tion approaches depending on the level of sophistication of the terest in Europe concerning food authentication is also shown by
suspected fraud. This section provides insight on analytical tech- continuous funding from FP 5 to the Horizon 2020 initiative.
niques to verify the origin of our food, in terms of regulatory and Fig. 5 depicts the temporal evolution of food authentication re-
more recently consumer and industry requirements. Concerning search per country. Italian scientists have been active in this field
Please cite this article in press as: Georgios P. Danezis, Aristidis S. Tsagkaris, Federica Camin, Vladimir Brusic, Constantinos A. Georgiou, Food authentication: Techniques, trends
& emerging approaches, Trends in Analytical Chemistry (2016), doi: 10.1016/j.trac.2016.02.026
ARTICLE IN PRESS
G.P. Danezis et al./Trends in Analytical Chemistry ■■ (2016) ■■–■■ 7
for many years, while Chinese are strongly involved nowadays. This – Europeans are most active, while USA and China come behind.
could be correlated to the high number of Italian authentic food South European countries, according this measure, are more active
products. Italy produces more PDO-PGI-PGI food products than any than Northern European countries – this is attributed to large
other country. A possible explanation for the intensively growing number of high quality food products produced there. Northern Eu-
activities in China could be attributed to the growth of the gross ropean countries have big biodiversity and unique climatic features
domestic product per capita and the interest associated with quality that contribute to the production of quality/authentic foods. No-
food products such as olive oil. Spain also has many authentic food ticeable is the leading position of Switzerland.
products.
Another measure that provides useful insight to research efforts 3.3. Journals
of individual countries in food authentication is the number of rel-
evant publications per million of population, shown in Fig. 6. Data Publications on food authentication are scattered across more
presented this way are normalized concerning country size. This than 150 journals! Food authentication papers are published by a
measure shows similar trends as other research activities on food variety of journals, although preferences for specific journals have
Please cite this article in press as: Georgios P. Danezis, Aristidis S. Tsagkaris, Federica Camin, Vladimir Brusic, Constantinos A. Georgiou, Food authentication: Techniques, trends
& emerging approaches, Trends in Analytical Chemistry (2016), doi: 10.1016/j.trac.2016.02.026
ARTICLE IN PRESS
8 G.P. Danezis et al./Trends in Analytical Chemistry ■■ (2016) ■■–■■
Please cite this article in press as: Georgios P. Danezis, Aristidis S. Tsagkaris, Federica Camin, Vladimir Brusic, Constantinos A. Georgiou, Food authentication: Techniques, trends
& emerging approaches, Trends in Analytical Chemistry (2016), doi: 10.1016/j.trac.2016.02.026
ARTICLE IN PRESS
G.P. Danezis et al./Trends in Analytical Chemistry ■■ (2016) ■■–■■ 9
Fig. 6. Food authentication publications per million capita of the top 10 Countries.
authentication. The most extensive use of molecular techniques is vast volumes of data are generated, but our ability to manage and
for determination of species and botanical origin, while all other analyze these date are falling behind the ability to generate these
techniques are mainly dealing with geographical origin and adul- data. To this end, various techniques described either under the term
teration. Mass spectrometry is a frontline technology rapidly chemometrics or data analytics are crucial for future successful de-
replacing other methods in many fields of food science. This trend velopment of prediction models.
extends to food authentication, due to unsurpassed advantages such
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Please cite this article in press as: Georgios P. Danezis, Aristidis S. Tsagkaris, Federica Camin, Vladimir Brusic, Constantinos A. Georgiou, Food authentication: Techniques, trends
& emerging approaches, Trends in Analytical Chemistry (2016), doi: 10.1016/j.trac.2016.02.026
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