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Review

Received: 24 December 2016 Revised: 23 March 2017 Accepted article published: 10 April 2017 Published online in Wiley Online Library:

(wileyonlinelibrary.com) DOI 10.1002/jsfa.8364

Modern analytical methods for the detection of


food fraud and adulteration by food category
Eunyoung Hong,a Sang Yoo Lee,a Jae Yun Jeong,b,c Jung Min Park,b,c
Byung Hee Kim,d Kisung Kwone and Hyang Sook Chuna*

Abstract
This review provides current information on the analytical methods used to identify food adulteration in the six most adulterated
food categories: animal origin and seafood, oils and fats, beverages, spices and sweet foods (e.g. honey), grain-based food, and
others (organic food and dietary supplements). The analytical techniques (both conventional and emerging) used to identify
adulteration in these six food categories involve sensory, physicochemical, DNA-based, chromatographic and spectroscopic
methods, and have been combined with chemometrics, making these techniques more convenient and effective for the analysis
of a broad variety of food products. Despite recent advances, the need remains for suitably sensitive and widely applicable
methodologies that encompass all the various aspects of food adulteration.
© 2017 Society of Chemical Industry

Keywords: food authentication; adulteration; fraud; food categories; analytical methods; geographical origin

INTRODUCTION protection and food safety, food researchers have engaged in


Food adulteration and fraud are by no means contemporary phe- the research and development of rapid and accurate analytical
nomena and are likely to be as old as the manufacturing of techniques for food adulteration and fraud.
food. Public awareness of these issues is growing, including the Recently, focus of food fraud prevention has changed from
more specific subcategory of economically motivated adulter- assessing the exposure to danger (risk) itself toward assessing
ation, which can involve serious public health risks. The key char- the possibility of the risk (vulnerability). Many traditional food risk
acteristics of food fraud are non-compliance with food laws and/or assessment tools are not holistically applicable for trying to quan-
misleading the consumer, intentional fraud, and the purpose of tify or predict food fraud incidents. Analysis of historical incidents
financial gain. Food authentication is an important means for and changes in the underlying fraud opportunity factors is impor-
ensuring food safety, food quality and consumer protection, as tant to reduce vulnerability of food fraud. Risk analysis, vulnerabil-
well as for compliance with national legislation, international stan- ity assessments and prioritization will facilitate a strategy that is
dards, and other guidelines.1 proactive and can prevent food fraud before it occurs.
With an increasing number of food product recalls per year and This comprehensive review documents food adulteration and
a recent string of adulteration incidents that resulted in serious fraud events in several categories of food products, describes
economic and health costs,2 the issue of food fraud has become the common characteristics of incidents that have allowed the
more sinister with increased destructive potential in a globalized adulteration and its detection, and encourages the strengthening
food supply chain. Many product ingredients are derived from of our capabilities for the detection of adulteration in a globalized
other countries, both as individually sourced products and ingredi- food environment.
ents made by individual food companies and as internally sourced
products within a multinational company. It can be difficult to
detect and trace the source of unintentional contamination and ∗ Correspondence to: HS Chun, Department of Food Science and Technology,
related food safety concerns and even more difficult to detect Chung-Ang University, Ansung-si, Gyeonggi-do, Republic of Korea.
and trace back instances of intentional product fraud, especially E-mail: hschun@cau.ac.kr
in highly processed foods with inputs from multiple suppliers. a Advanced Food Safety Research Group, BK21 Plus, School of Food Science and
Authenticity has consequently become a major concern for all Technology, Chung-Ang University, Gyeonggi-do, Republic of Korea
parties involved in the food industry, such as farmers, producers,
b Science and Technology Management Policy, University of Science & Technol-
suppliers, retailers, consumers and regulators, at all levels of the
ogy, Gyeonggi-do, Republic of Korea
production and distribution process, from raw materials to finished
products. From the legislative point of view, quality standards have c R&D Strategy, Korea Food Research Institute, Gyeonggi-do, Republic of Korea
been established, including quality labels that specify the major
d Department of Food Science and Nutrition, Sookmyung Women’s University,
components of each product. From the economic point of view,
Seoul, Republic of Korea
product authentication is essential to avoid unfair competition
that can destabilize the market and disrupt not only regional, e New Hazardous Substances Team, National Institute of Food and Drug Safety
but even national economies. With this imperative for consumer Evaluation, Chungcheongbuk-do, Republic of Korea

J Sci Food Agric (2017) www.soci.org © 2017 Society of Chemical Industry


www.soci.org E Hong et al.

1200
PCR MS NMR
HPLC LC GC
1000 IR IR-MS Raman
ELISA Biosensor
Number of cases reported

800

600

400

200

0
Milk and dairy Meat and Fish and Oils and fats Fruit juice Coffee and Alcoholic Spices Sweetners Grain-based Organic foods Dietary
products meat products sea food tea beverages foods supplements

Animal origin food and seafood Beverages Spices and sweetness Others

Food category

Figure 1. Major technologies for the detection of food fraud, as reported in the literature from 2005 to 2015.

ADULTERATED FOOD CATEGORIES AND polymorphism (AFLP), simple sequence repeats (SSR)], spectro-
scopic methods [infrared (IR), near infrared (NIR), mid-infrared
ANALYTICAL METHODS IN THE LITERATURE
(MIR), Fourier transform infrared (FTIR), Raman, nuclear magnetic
In general, foods and food ingredients commonly associated with
resonance (NMR), site-specific natural isotope fractionation
food fraud include oil, fish, honey, milk and dairy products, meat
(SNIF)-NMR, inductively coupled plasma-atomic emission
products, grain-based foods, fruit juices, wine and alcoholic bev-
spectrometer (ICP-AES)] and immunoassays [enzyme-linked
erages, organic foods, spices, coffee, tea, and some highly pro-
immunosorbent assay (ELISA)] (Fig. 1).
cessed foods. It is not known conclusively how extensive food
The food categories with a high incidence of adulteration in
fraud is worldwide. Previous reviews focused mainly on the ana- the literature search were milk and milk products, meat and meat
lytical methods that were based on techniques for detecting adul- products, fish and seafood, oils and fats, fruit juice, coffee and
teration in specific foods and food products. However, there are tea, alcoholic beverages, spices and extracts, sweeteners (includ-
few systematic reviews on the analytical methods utilized for each ing honey), cereals and pulses, and organic foods. These food
category of adulterated food. categories were regrouped into six categories: ‘animal origin and
Trends in analytical methods used in the detection of food seafood’ for milk and dairy products, meat and meat products, and
fraud were investigated by a keyword search of the literature. This fish and seafood; ‘oils and fats’; ‘beverages’ for fruit juice, coffee and
study used the Thomson Innovation literature search tool (Web of tea, and alcoholic beverages; ‘spices and sweeteners’ for spices and
Science; WoS) to analyze quantitatively research trends related to extracts, and sweeteners; ‘grain-based food’ for cereals and pulses;
technologies for detecting food fraud. The literature for the period and ‘others’ for organic food and dietary supplements. A broad
1995–2015 was searched using the formula: [(food*) AND (fraud* range of analytical methods to detect food adulteration has been
or adultera* or misbrand* or authentic* or nonauthentic* or ‘non reported.
authentic*’ or ‘food crime’ or forensic* or ‘geographical*origin*’)]. Detection methods were ranked according to their number of
In total, 2614 publications relating to food fraud were collected as uses in the literature. MS accounted for the largest proportion
valid results and were analyzed in terms of food categories and at 20.6%; PCR for 18.5% and LC for 11.6%. MS also accounted
types of detection technology. for the greatest proportion in Asian countries and South Korea
Many techniques have been used to detect adulteration and (20.7% and 38.1%, respectively). A notable observation is that
fraud in food: chromatographic analysis [thin layer chromatog- MS is used extensively in most food categories, and is also the
raphy (TLC), high-performance liquid chromatography (HPLC), most frequently used method in the analysis of spices, extracts,
gas chromatography (GC)], mass spectrometry (MS)-based cereals, grains and pulses. However, LC and GC are also used to
methods [liquid chromatography(LC)-MS/MS, GC/MSD], elec- a significant degree for spices, oils and organic foods. NMR is
trophoretic methods [sodium dodecyl sulfate-polyacrylamide used frequently to discriminate the authenticity of oils, cereals,
gel electrophoresis (SDS-PAGE), polymerase chain reaction (PCR), grains, alcoholic beverages and fruit juices. PCR is the predominant
PCR-restriction fragment length polymorphism (RFLP), random detection technology used for the food categories of meat and
amplified polymorphic DNA (RAPD), amplified fragment length meat products, fish and seafood, and milk and milk products. In

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Adulterated food categories and their analytical methods www.soci.org

addition to MS, HPLC and LC are often used for fruits, fruit juices Table 1 details the different detection methods applied to a range
and sweeteners. IR spectroscopy, Raman, immunosorbent assays of milk and dairy products. The authenticity of butter depends on
(e.g. ELISA), and biosensors are used less compared to the other confirmation that the lipid content is cow’s milk fat. The adulter-
detection methods. ation of butterfat can be detected through the characterization
of the fatty acids by GC analysis. Also, the rapidity and low sam-
ple preparation needs of spectroscopic techniques such as NIR,
AUTHENTICATION AND ADULTERATION BY FTIR, attenuated total reflectance (ATR)-MIR and Raman made
FOOD CATEGORY themselves suitable for in-factory quality control, which could be
Animal origin of food and seafood carried out by non-technical personnel.21 Melamine can be used
Milk and dairy products to spuriously raise estimated protein levels in diluted milk and
Milk is a fairly expensive raw material, and therefore, from an it caused serious health risks for consumers in 2008.22 Recently,
economic point of view it has been attractive to replace part of it a simple, precise, accurate, and validated reverse-phase HPLC
with other dairy or non-dairy ingredients.3 Species identification of method was developed for the determination of melamine in
milk (buffalo’s, cow’s, goat’s and sheep’s milk) and dairy products 300 samples of milk (pasteurized and ultra-high temperature
(cheese, butter and milk powder) is important in determining processed milk) and dairy products (infant formula milk powder,
food composition, traceability, allergic pathologies and accurate yogurt and cheese).23
consumer information.
A common adulteration of dairy products is the substitution Meat and meat products
of expensive high-quality milk with cheaper and lower quality Recently, interest in meat authenticity has increased. Many con-
milk from other species.4 Many different analytical methods are sumers are aware of the importance of origin, accurate labeling
available for the identification of the species of origin for milk and ingredients to avoid the adulteration of meat and meat prod-
and dairy products, which include immunological, electrophoretic ucts. This review provides an overview of the possible analytical
and chromatographic techniques. However, immunological and methods used for the authentication of meat and meat products
electrophoretic methods are not always capable of distinguishing (Table 1). Authentication problems with respect to meat and meat
milk from closely-related species in food products with complex products are grouped into four major categories: meat species,
matrices and are also significantly less sensitive with heat-treated meat processing treatment (cooked meat and fresh versus thawed
material. Additionally, chromatographic methods are difficult to meat), meat geographic origin and non-meat ingredient addition
apply to everyday use when sample numbers are large.5 More (additives and water).
recently, DNA-based methods such as real-time PCR, multiplex The most common methodologies used to determine the
PCR, PCR-RFLP and species-specific PCR have been successfully authenticity of meat and meat products are unquestionably
applied to identifying the origin of milk species in dairy products, DNA-based techniques: real-time PCR, multiplex PCR and
DNA is sufficiently stable to withstand different chemical treat- species-specific PCR. A frequent adulteration of meat prod-
ments and high temperatures, and small quantities of DNA can be ucts is the addition of pork to beef products, which is carried
detected using species-specific primers.4,6 – 8 Recently, high reso- out for economic gain. Particularly for minced and homogenized
lution melting (HRM) analysis has proved to be a powerful, fast meat products, the development of a method to identify species
and accurate technique that is cheaper and simpler than alterna- is an important authenticity issue.24 On 15 January 2013, the Food
tive approaches requiring post-PCR processing, enzyme restriction Safety Authority of Ireland published a press release identifying
and electrophoresis, labeled probes for single nucleotide polymor- horse and donkey DNA in (minced) beef products including
phism detection sequencing, or TaqMan-probe based real-time burgers, beef sausage and meat balls using real-time PCR.25,26
PCR.9 HRM was shown to be capable of identifying the presence The majority of results with horse meat reported to date appear
of cow’s milk down to 1.0 g kg−1 in putative Feta and could quan- to have been represented as percentage DNA in extracted DNA
tify the range of a mixture with sheep’s and goat’s milk in different rather than as percentage horsed meat in the sample. The PCR
Feta cheese commercial products.7 amplification of pork mitochondrial genes (12S and 18Sribosomal
The discrimination of geographical origin to guard the pro- RNA subunits and cytochrome b) and the displacement loop
tected designation of origin (PDO) and avoid fraudulent label- region (D-loop) was successfully applied for the identification
ing of milk and dairy products has been mostly studied using of pork derivatives and was found to be a suitable technique
multi-element and multi-isotope-ratio analysis with isotope-ratio for routine food analysis and halal certification.27,28 In addition,
mass spectrometry (IRMS), inductively coupled plasma mass spec- multiplex PCR can be used to differentiate turkey, ostrich, chicken
trometry (ICP-MS) and ICP-AES.10,11 The results have demonstrated and duck in poultry meat mixtures.29
that stable isotope ratios of C, N, O, S and Sr of milk and cheese were Game meat is often a target for fraudulent labeling as a result
linked to their territories of origin, as a result of variations in the of the high commercial value associated with its products. The
type of vegetation and the environment.12 Additionally, the prod- PCR-RFLP technique has been successfully used to discriminate
uct origin of dairy products has been studied using metabolite game species such as red deer, fallow deer, roe deer, cattle,
fingerprinting techniques involving NMR and FTIR.10,13 – 15 Accu- sheep and goat.30 – 32 Identification of chicken and turkey in
rate determination of geographical origin for dairy products seems goose and mule duck foie gras by species-specific PCR has been
feasible when multi-analytical approaches, such as metabolomics reported.33 Analytical methods including chromatography and
combined with chemometrics, are studied. spectroscopy can reveal other animal meat (chicken, lamb, goat
Milk and dairy products can also be adulterated by adding other and deer) in beef.34,35
products such as whey, starch, non-milk fat, water, vegetable The integrity of DNA-based methods may be severely affected
proteins, vegetable oil, lard, margarine, hydrogen peroxide, by meat handling such as cooking and processing. It was
melamine, artificial flavor and synthetic triacylglycerols. For their reported that meat cooked at high temperatures resulted in
detection, several analytical techniques can be applied.16 – 20 an overall low yield of DNA.36 Accordingly, a species-specific

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www.soci.org E Hong et al.

Table 1. Methods to assess the authenticity of animal origin in food and seafood

Food category Adulterant Target marker Detection technology Reference

Milk and dairy products


Milk and milk powder Different milk species SSR, cytochrome b Species-specific PCR, 5

(cow’s, sheep’s and buffalo’s PCR-RFLP


milk)
12S rRNA Real-time TaqMan PCR 7

Different geographical origins 1 H NMR spectra, 1 H NMR, ICP-AES, IRMS with 11

(Italy) Multi-element composition, PCA


13 C/12 C, 15 N/14 N

Water, starch, sodium citrate, MIR spectra ATR-MIR with PLS-DA 17


hydrogen peroxide, sucrose
Soy, brown rice, pea and Chromatographic profiles UHPLC-UV with PCA, SIMCA 18

hydrolyzed wheat protein


Cheese Different milk species D-loop, tRNALys Real-time PCR, HRM analysis 8

(cow’s, sheep’s and goat’s milk)


Different geographical origins 𝛿 13 Ccasein, 𝛿 15 Ncasein , IRMS, ICP-OES, ICP-MS with 12

(alpine versus pre-alpine Italy) 𝛿 18 glycerol , 𝛿 34 Scasein , CDA


Multi-element composition
Ripening time (hard, semi-hard), ATR-FTIR spectra ATR-FTIR with LDA 16
manufacturing technique
(fossa, non-fossa)
Vegetable oils (palm oil, palm Fatty acid profiles, GC-FID, GC-MS with PCA 19
olein oil), refined sugar, starch, Phytosterol
flour, emulsifier, refined salt,
citric acid
Butter (animal fat) Different geographical origins FTIR spectra FTIR with PCA, PLS 15
(Morocco)
Vegetable oils (palm kernel, bean, C4:0 fatty acid, GC-FID, NIR 20
sunflower, and linseed oil), fish 21
NIR spectra
oil
Synthetic triacylglycerols 13 C NMR spectra, 13 C NMR, MALDI-TOF-MS 22

MALDI-TOF mass spectra


Milk, milk powder, infant Different milk species Species-specific mtDNA Multiplex PCR 9
formula powder, cheese, (cow’s, sheep’s, goat’s and
butter, yoghurt buffalo’s milk)
Melamine Melamine RP-HPLC-PAD 23

Meat and meat products


Raw minced meat (beef, Horse, donkey Cytochrome b Real-time PCR 25 26
pork, chicken, turkey,
duck, goose, pheasant, Pork D-loop, 18S rRNA TaqMan real-time PCR, 27
ostrich, lamb, horse, goat, direct real-time LAMP 28
dog, deer, rabbit, cat, red Duck Cytochrome b, 18S rRNA Multiplex PCR 29
kangaroo, Korean water 30
Different meat species 12S rRNA T-RFLP
deer) and processed meat
(pig, dog, cattle, goat, sheep,
(jerky, pressed ham,
horse, chicken, deer, buffalo,
sausage, hamburger petty
turkey)
and steak, minced rib,
nuggets, cutlet, meat ball)

Game meat Domestic species Cytochrome b, Multiplex PCR 31


(red deer, fallow deer, roe (buffalo, sheep, goat, cattle,
deer, chamois, steinbock, swine)
mouflon, pyrenean ibex)
12S rRNA PCR-RFLP, Lab-on-a-chip 32

Fois gras Goose, mule duck, chicken, 12S rRNA Species-specific PCR 33
turkey, swine
Beef Different geographical origins 1 H NMR spectra NMR 40

(Korea, Australia, New Zealand,


United states)
(Ireland, Brazil, USA, other 13 C/12 C, 15 N/14 N IRMS 41
European)

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Table 1. continued

Food category Adulterant Target marker Detection technology Reference

Chicken (broilers) Different geographical Multi-element composition ICP-MS 42


origins (Brazil, France,
Germany, Hungary,
Switzerland)
Pork Thawed pork NMR parameter, Structure of LF-NMR with PCA, 44
muscle cells light microscopy
Thawed chicken Vis/NIR spectra, Vis/NIR 45

Beef, pork, chicken or complex Soybean proteins UV-spectra RP-HPLC-UV 46


mixture meat products

Fish and seafood products


Thunnus (bigeye tuna, yellowfin Skipjack, eastern little tuna, Cytochrome b, D-loop, 16S PCR-RFLP, real-time PCR 58
tuna, albacore, bluefin tuna) frigate mackerel, oriental rRNA
bonito
Caviar (Sturgeon species) Paddlefish species Cytochrome b, 1 H NMR PCR-RFLP, 1 H NMR 59 61
spectra
Gadoids (Atlantic cod) Alaska pollock, poor cod, Cytochrome b, 12S and 16S PCR-RFLP, FINS 60
blue whiting, blue ling, rRNA
greater forkbeard
Flatfishes (Sole, flounder, megrim, Greenland halibut 12S rRNA PCR-RFLP 62
turbot)
Eels (European eel) American eel, Japanese eel, Cytochrome b PCR-RFLP, PCR-SSCP 63
shortfin eel
Clams (grooved carpet shell) Pullet carpet shell 𝛼-actin PCR-SSCP 64

Salmonids Trout, pink salmon Cytochrome b, parvalbumin, PCR-SSCP 65


growth hormone
Cytochrome b, COI DNA Multiplex PCR, real-time PCR 66

Grouper Neil perch, wreck fish 5S rRNA Multiplex PCR 68

Cephalopods (Loliginidaespecies) Ommastrephidae species Cytochrome b PCR-RFLP, FINS 67

Mussels (Mytilusspecies) Perna, Aulacomya, 18S rDNA, ITS1, adhesive PCR-RFLP, FINS, multiplex 70
Semimytilus, Perumytilus, protein PCR
Choromytilus and
Brachidontes species

PCR assay was developed for the authentication of goat meat, assessed using low-field NMR, light microscopy and visible/NIR
with a sensitivity of 1.0 g kg−1 for detection of adulteration.37 spectroscopy.44,45 Furthermore, vegetable protein such as soy
It has also been demonstrated that good quality DNA could protein used in the fraudulent substitution of animal protein can
be extracted from cooked meat prepared by boiling, roasting, be frequently detected by RP-HPLC methods.46
pressure cooking or pan frying,38,39 indicating the applicability
of the PCR approach for surveillance where prepared food is Fish and seafood
sold.
Forms of fish and seafood fraud include intentionally increasing
Moreover, proper labeling of meat products is important for
the product weight and using illegal additives in production.
ensuring fair-trading and enabling consumers to make informed Methods to increase weight include adding excess water to
choices. Meat products, particularly protected geographical frozen product (overglazing), soaking products such as scal-
indication (PGI) products of selected breeds produced in a par- lops in sodium tripolyphosphate so that they retain water and
ticular area, have higher value in the market. Determination of overbreading.47 For example, frozen breaded shrimp must be at
geographic origin has been performed with varying degrees least 500 g kg−1 shrimp by Food and Drug Administration (FDA)
of success, and the accuracy might be improved by combining standards. Overbreading may cause consumers to pay shrimp
different approaches.40 – 42 However, when PDO and PGI state- prices for excess bread crumbs. The differentiation between
ments are to be verified, an accurate link to a specific origin only fresh and frozen-thawed shrimp has been successfully evaluated
appears to be feasible when a combination of parameters and by visible/NIR spectroscopy with chemometricmethods.48 The
multivariate statistics are applied. Among the methods that are fundamental advantage of NIR applications is that damage to the
employed is NMR coupled with pattern recognition techniques, commercial product can be avoided.
which has been used to investigate the geographical origin of A frequent form of seafood fraud perpetrated for the purpose of
meat.40 Different investigations indicate that incorrect labeling, economic gain is species substitution.49 Market surveys in Europe
where thawed meat was labeled as fresh meat, is present in and North America have reported mislabeling of seafood species
8–15% of analyzed samples.43 The effects of freezing, thawing at levels of 15–43% with an exceptionally high level of 75% for red
and cooking on the water distribution in pork of two qualities snapper products.50 – 55 Therefore, the development of analytical
(normal and high ultimate pH) and in chicken were successfully methods for species identification is necessary to detect and

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www.soci.org E Hong et al.

Table 2. Methods to assess the authenticity of oils and fats

Food category Adulterant Target marker Detection technology Reference

Virgin olive oil Pomace oil NIR, FTIR, FT-Raman spectra NIR, FTIR, FT-Raman with PLS 79

Refined olive oil,Lampante 31 P NMR spectra 31 P NMR with one-way 80


olive oil ANOVA, HCA, DA
Vegetable oil (canola, Raman spectra Raman with PLS, 81
corn, flaxseed, grape Bay-LS-SVM,
seed, peanut, rapeseed, Fatty acid, FTIR spectra GC-FID, FTIR with PLS, PCR, 82
safflower, sesame, LDA
soybean, sunflower, rice 83
ATR-FTIR spectra ATR-FTIR with PCA, PLS,
bran and walnut oil)
PLS-DA
Hazelnut oil 1 H NMR spectra 1 H NMR MIR spectra with 84
PLS
Vegetable oils (canola, 1 H NMR spectra, GC-MS 1 H NMR, GC-MS with PCA, 85
palm, corn, soybean, chromatograms PLS-DA, OPLS-DA, PLS
sunflower, rice brain,
peanut and coconut oil)
and fats (chicken fat,
lard, mutton tallow,
beef tallow)
Geographical origin (Italy) NMR spectra NIR, MIR NMR with PCA NIR, MIR with 86 87
Sabina versus other spectra PLS-DA, SIMCA
areas of Italy or
Mediterranean
countries
Geographical origin 1 H and 31 P NMR spectra 1 H and 31 P NMR with CDA, 88
(Greek) Koroneiki versus CBTs
Crete, Peloponnesus
Geographical origin GC-MS spectra, Six volatile HS-SPME/GC, GC-MS with 89
(Spain) Discrimination compounds PCA, LDA, SLDA
of Andalusia, La Rioja,
and Catalonia
Sesame oil Corn, soybean, sunflower, 𝛿 13 C, 𝛿 2 H, 𝛿 18 O, 1 H NMR IRMS, 1 H NMR, GC-FID with 91
perilla, cottonseed, spectra, Fatty acid OPLS-DA
canola oil
Other geographical origin Lignan HPLC-UV 92
(Korea versus China, 𝛿 13 C, 𝛿 2 H, 𝛿 18 O values IRMS with CDA 93
India)
Coconut oil Corn, sunflower, olive, FTIR spectra FTIR with PLS 94
palm oil
Lard Radial plots of GC-SAW, FTIR Fast GC-SAW, FTIR with 95
spectra PLS-DA
Mustard oil Argemone oil Sanguinarine HPTLC 96

Cod-liver oil Lard FTIR spectra FTIR with PLS 97

deter willful, as well as unintentional, substitution and to enforce metabolic characterization of caviar specimens (n = 91) by 1 H NMR
labeling regulations.56 spectroscopy with multivariate statistical models [Soft Indepen-
Species identification of fish and seafood products is difficult dent Modeling by Class Analogy; SIMCA and orthogonal partial
because the morphological features that can usually be identi- least square discriminant analysis (PLS-DA)] has been performed.61
fied have been removed during processing steps such as cook- The NMR metabolic profile could be used to provide the estima-
ing, smoking, salting and canning.54 Additionally, most of them tion of the freshness and origination of caviar sample. PCR-RFLP
are heat labile. For the identification of fish and seafood species can also be used to identify the gadoids such as Atlantic cod
in heat-processed products, a DNA method rather than protein and flatfish species (sole, flounder, megrim, turbot, etc.) present
analysis is preferable.57 Protein-based methods are generally reli- in an extensive range of commercial products.62,63 More recently,
able for testing fresh or lightly processed seafood, although they PCR-single stranded conformational polymorphism (SSCP) assays
become impractical in heavily processed foods where proteins are have been developed that allow the identification of various fish
degraded. This part of the review will be limited to discussing the and seafood such as salmonids, eels and clams.64 – 66 SSCP anal-
PCR-based methods for the authentication of numerous species ysis has also been used for species identification of fishery prod-
of fish and seafood (Table 1). The identification of fish species in ucts as a rapid and low-cost alternative to RFLP. Species-specific
tinned tuna and sardine cans has been successfully carried out multiplex PCR allows for the simultaneous and rapid identification
using PCR analysis.58,59 In particular, there is a need to detect fraud of multiple species in a single PCR tube, including mixed species
related to sturgeon caviar, one of the most exclusive and expensive and heavily processed samples, and can be applied to both con-
fishery products, and PCR-RFLP analysis provided a powerful and ventional and real-time PCR. The development of such a method
easy method for the identification of mislabeled caviar.60 Recently, for salmon and grouper species identification would have several

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advantages.67,68 Forensically informative nucleotide sequencing high quality extra virgin olive oils that show particular quality
(FINS) is a PCR-related technique that is useful for the identifica- properties attributed to their geographical area of production, the
tion of cephalopod (Loligospecies versus Family Ommastrephidae) European Union (EU) legislates and regulates the creation of a PDO.
and mussel species.69,70 NMR has been extensively used to develop accurate analytical fin-
Although genetic techniques have been extensively researched gerprinting methods for the authentication or certification of the
for certain fish and seafood groups, many challenges remain. In geographical origin of olive oils, aided by suitable chemometric
the near future, emerging techniques, such as microarray and analysis. The main advantage of NMR is that it does not require
next-generation sequencing, may provide high-throughput and complicated sample preparation and the determination of very
automated platforms for DNA analysis that can be applied to the different chemical species can be performed in a single experi-
regulatory screening of fish or seafood products.71 Furthermore, ment. Multivariate analysis such as principal component analysis
DNA barcoding was confirmed to be particularly effective in the (PCA) allowed a good discrimination and gave some affinity indi-
traceability of fish and seafood products.72 To date, more than cations for the US market olive oils in comparison with other single
70 000 barcode sequences from 8300 species (26% of the total) cultivars of extra virgin olive oils, such as Coratina (Italy), Picual
have been stored in the framework of an international collabora- (Spain), Kalamata (Greece) and Sfx (Tunisia).86 Also, a less expen-
tive research: the Fish Barcode of Life Initiative (FISH-BOL; www sive variety from Greece or Turkey can be substituted in place of
.fishbol.org). However, more extensive studies are required to con- olive oil from Italy as claimed on the label. The geographical ori-
firm the potential use of this technique for all kinds of seafood as a gin of European extra virgin olive oils (Ligurian versus non-Ligurian
reliable ‘traceability tool’.73 and harvesting years) was evaluated by NIR, 1 H NMR and head
space-solid phase microextraction (HS-SPME)-GC/MS.87 – 89 Analyt-
ical parameters, such as DNA-based markers, that are independent
Oils and fats from environmental fluctuations, have proved to be useful tools for
Edible oils and fats, including salad and cooking oils, margarine, the identification of cultivars used in olive oil production.90
shortening and butter, are classified as the foods most frequently Many adulterated sesame oils distributed in Korea are known to
counterfeited and with the most sophisticated fraud.74 There are contain more than one kind of foreign edible oil, such as corn, soy-
two major adulterations in edible oils and fats: admixing a cold bean, sunflower, perilla, cottonseed and canola oil. Recently, the
press oil with a refined one and replacing more expensive oils and combined analysis of stable isotope ratio, 1 H NMR spectroscopy
fats with cheaper ones.75 and fatty acid profiles of the oils was successfully used to con-
Several analytical techniques have been applied to detect adul- firm sesame oil authenticity in Korea.91 Chinese and Indian sesame
teration or confirm authentication for the botanical origin of a veg- oils that are deliberately labeled as being of domestic origin often
etable oil admixture. The suggested approach to the issue can be appear in Korean local markets because Korean sesame oils are
summarized as the combination of a two-step analytical methods. three to four times more expensive than Chinese or Indian sesame
Screening methods employ fingerprinting spectroscopic methods products.92 This situation has created the need for analytical meth-
such as FTIR and Raman spectroscopy where the composition of ods that aim to distinguish Korean sesame oil from the oil obtained
the majority of the oil mixtures is expected to be correctly identi- from imported sesame seeds. Carbon, hydrogen and oxygen sta-
fied. Confirmation methods such as fatty acid profile using GC-MS ble isotope ratios (𝛿 13 C values of −29.8%, 𝛿D values of −181.9%
can be followed based on reliable validated routine analytical and 𝛿 18 O values of 16.8%) were useful parameters with respect to
methods.76 differentiating Korean sesame oil from Chinese and Indian sesame
Olive oil, especially, is an attractive target for economically moti- oils distributed in Korea.93
vated adulteration because of its high demand and potential profit Virgin coconut oil may be adulterated with cheaper oils and
margin. Virgin olive oil has been adulterated with lower grades fats such as palm oil and lard. Apart from the nutritional aspect
of olive oil (refined or pomace olive oil) and other cheaper veg- (virgin coconut oil is healthier), the blending of lard has major
etable oils (e.g. hazelnut, sunflower, soybean, cotton, corn, walnut implications in certain religious societies such as among Islamic
and canola oil).77 The chemical composition of the olive oils varies and Jewish individuals. The detection and quantification of
widely depending on fruit variety, degree of fruit ripeness, environ- virgin coconut oil adulteration with palm oil (5.0–500 g kg−1 )
mental conditions, growing region, and techniques of processing or lard (10–500 mL L−1 ) were monitored using FTIR combined
and storage. These properties are related not only to the fatty acid with PLS analysis and fast gas chromatography with surface
composition of its lipid matrix, but also especially to the presence acoustic wave (GC-SAW) detector systems.94,95 High-performance
of several minor compounds such as polyphenols, tocopherols and thin layer chromatography (HPTLC) methods are used rou-
carotenoids.78 In recent years, many studies have been performed tinely to assess the adulteration of edible oils by argemone oil
aiming to characterize and classify olive oils using diverse tech- because of its toxicity.96 The ability to analyze the adulteration
niques such as chromatography (GC, HPLC) and spectroscopy (NIR, of cod-liver oil with much cheaper oil-like animal fats such as
FTIR, FR-Raman, NMR and MS).79 – 82 In particular, FTIR coupled with beef, chicken, mutton and lard has become necessary in recent
chemometrics was able to distinguish 100% of olive oil blends with years. FTIR spectroscopy, which is a nondestructive and fast tech-
an olive oil content higher or lower than 500 g kg−1 . ATR-FTIR spec- nique, has been used to distinguish cod-liver oil samples from
tra of vegetable oils can be used to distinguish olive oils of different animal fats.97
categories and varieties from other edible oils such as sunflower,
corn, soybean and canola oils.83 Other spectroscopic techniques, Beverages
such as 1 H NMR, can be used to detect olive oil adulteration with Fruit juices
hazelnut oil at a level of approximately 1.3 g kg−1 but with some The production of fruit juices represents an important and rapidly
limitations.84,85 growing sector of the beverage industry. Similar to other highly
In addition, an important consumer choice factor is the geo- priced food commodities, orange juice, other valuable fruit juices
graphical origin of olive oil production. To guarantee and promote and purees are likely targets for food adulteration and fraud.98

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Table 3. Methods to assess the authenticity of beverages (fruit juices, coffee, tea and alcoholic beverages)

Food category Adulterant Targetmarker Detection technology Reference

Fruit juices
Apple juice Beet medium invert syrup, 13 C/12 C, 2 H/1 H ratios GC-IRMS 100
high fructose corn syrup FTMIR-ATR spectra FTMIR-ATR with PLS 101
sugars
Different varieties and Volatile compounds HS-SPME-GC-MS with 102
geographical origin PCA, LDA, SLDA
Orange juice Apple or grapefruit juice TIC chromatograms HPLC-MS with PCA, LDA 103

Water 18 O/16 O isotope ratio SNIF-NMR, IRMS 105

C4 sugar 13 C/12 C isotope ratio IRMS 106

Pomegranate Apple, pear, grape, cherry, Anthocyanins, sugar, HPLC-UV, HPLC-RI, flame 107
juice plum, blueberry, organic acid, amino photometer
blackberry or aronia juice acid, potassium
Grape juice FTIR spectra FTIR with PCA, PLS 108

Kiwi, peach, Different geographical origin 1 H NMR spectra 1 H NMR with PCA, 104
blueberry juice PLS-DA

Coffee
Arabica coffee Robusta coffee ESI-MS spectra of polar FT-ICR-MS with PLS 111
compounds
(caffeoylphenylalanine
or
p-coumaroyltyrosine)
Kahweol, UV–vis spectrometer 112
16-O-methylcafestol
1 H NMR spectra (sugars, 1 H-NMR HR-MAS NMR 113 114
amino acids,
chlorogenic acids,
caffeine,
16-O-methylcafestol,
etc.)
Chloroplast trnL-trnF PCR-RFLP 115

Roasted coffee Defective beans Volatile compounds SPME-GC-MS 116

Corn, coffee husks DR spectra DRIFTS with PCA, LDA 117

Barley Volatile compounds SPME-GC-MS with PCA 118

Barley, corn, soybean, coffee 1 H NMR spectra 1 H NMR 119


husks
Different geographical LC-MS, GC-FID LC-MS, GC-FID with PCA 120
origin (Asia, South chromatograms,
America, Africa) carbohydrate, protein,
monosaccharide,
amine
Different manufacturing 1 H NMR spectra, 1 H NMR with PCA, LDA 121
sources 5-(hydroxymethyl)
-2-furaldehyde
Caffeinated/decaffeinated UV-visible spectra UV-visible 122
coffee, shelf-life condition spectrophotometer
(expired/non-expired) with SIMCA, PCA,
SPA-LDA
Tea
Green tea Different geographical origin FT-NIR spectra FT-NIR with LDA, KNN, 124
(Abhui, Henan, Jiangsu or ANN, SVM, PCA
Zhejiang province)
Different geographical Color change profiles Colorimetric artificial 125
origin and grade levels tongue and nose
Pu-erh green tea Regular green tea GC-MS chromatogram, HS-SPME/GC-MS with 126
volatile compounds CA, PCA

Oolong tea Similar varieties GC-MS chromatogram, HS-SPME/GC–MS with 127


volatile compounds PCA, HCA, S-LDA
Green, green Different tea types UPLC-DAD UPLC-DAD-MS with PCA 128
pu-erh, white chromatograms
tea

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Table 3. continued

Food category Adulterant Target marker Detection technology Reference

Green, white, Different geographical origin 1 H NMR spectra 1 H NMR with PCA, PLS-DA, 129
oolong tea (China, Japan, South Korea) OPLS-DA
Green, black, Different geographical origin 𝛿 13 C, 𝛿 15 N, 𝛿D values, ICP-MS, IRMS 130
oolong tea (Asian, Indian tea) multi-element
composition
Alcoholic beverage
Wine Different grape varieties FTMIR spectrum, volatile FT-MIR, GC-FID with PCA, 132
composition LDA, ANOVA
Volatile compounds HS-SPME-GC-MS with PCA, 133
(monoterpenoids, PLS-DA, OPLS-DA
esters,
C13 -norisoprenoids)
Non-volatile compounds ESI-LC-QTOF with PCA 134

Different geographical origin Multi-elemental ICP-MS with ANOVA, CA, 137


(Italy) composition LDA,PCL
Different geographical origin Polyphenolic compounds HPLC-UV, HPLC-FLD, LC-MS 138
(Spain) with PCA, PLS1-DA,
PLS2-DA
Sugars, water, synthetic 13 C/12 C, 18 O/16 O stable IRMS, HPLC-UV with ANOVA, 140
sweeteners, synthetic red isotopes, chromatogram LDA
dyes, coloring agents of synthetic sweeteners,
synthetic red dyes, HMF
and antochyanins
Tequila Different tequilas categories UV-visible absorption UV-visible spectroscopy 141
(100% blue agave and spectra
mixed), types (white, rested,
aging), adulterants (ethanol,
water, rum, other tequilas)
Whisky Different brands, ageing and Electropherograms, CE-UV, LC-MS/MS 143
blending parameter
(syringaldehyde,
coniferaldehyde,
sinapaldehyde, vanillin)
ESI FT-ICR MS spectra, ESI FT-ICR MS with PCA 144
elemental composition
(carboxylic acids,
phenols, fat acids, sulfur
of nitrogen)
Beer Different labelled Rochefort Volatile compounds HS-SPME-GC-TOF-MS with 145
and Trappist beer PLS-DA, LDA, ANN-MLP

The most frequent profit-driven fraudulent procedures are simple for the authenticity testing of fruit juice. In this regard, linear
dilution with water, the addition of sugars, acids, colorant agents discrimination analysis (LDA) classification models constructed
and/or cheaper alternatives (typically juices obtained from apples, and validated by employing a highly variable sample set were
pears, grapefruits and so on).99 able to reliably detect the addition of relatively low-priced juice
Apple juice is one of the most popular juices worldwide. An (apple or grapefruit) as low as 150 mL L−1 of total volume into
improved procedure for determining 13 C and 2 H isotope ratios more expensive juice (orange) with 100% prediction.103 Also, the
using gas chromatography-isotope ratio mass spectrometry usefulness of the NMR-based metabolic profiling was highlighted
(GC-IRMS) has been developed for identifying the addition of using some of the results regarding quality, adulteration, varieties
low-cost commercial sugar syrups (beet and cane syrup) to pure and the geographical origin of fruits and fruit juices, such as kiwi,
apple juices and related products.100 Moreover, inspection of peach and blueberry.104 Improved detection of water addition in
the attenuated total reflectance Fourier-transform mid-infrared fruit juices is performed by the analysis of the isotopic ratios of
(FTMIR-ART) spectral profile allows the detection of added sugars oxygen (18 O/16 O) of ethanol derived from the sugars in orange
such as glucose, fructose and inverted cane sugar to commercial juice using the preparation steps of the SNIF-NMR method fol-
apple beverages. The discrimination analysis has high precision lowed by IRMS.105 Additionally, stable carbon isotope ratio analysis
and is useful for detecting changes in sugar content.101 The (SCIRA) can be used to identify adulterated juices because the
implementation of a successful traceability system in the apple ratio of 13 C to 12 C is different for the C4 sugars in orange juice.106
juice industry will require the ability to distinguish variety and Pomegranate juice is typically adulterated in two ways. Other
geographical origin of raw materials; this can be achieved using highly concentrated juices (aronia, blueberry or blackberry) or nat-
HS-SPME-GC/MS with multivariate analysis.102 ural grape pigments are added to imitate the color of pomegranate
Non-targeted HPLC-MS metabolomic fingerprinting coupled juice and poor quality juice or peel extract with non-pomegranate
with chemometric analysis was shown to be a powerful tool sugars is added for a stringent taste. Authentic commercial

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www.soci.org E Hong et al.

Table 4. Methods to assess the authenticity of spices and sweeteners

Food category Adulterant Targetmarker Detection technology Reference

Spices
Turmeric, curry, Sudan I, II, III, IV dye UV-visible spectra UV-visible spectrophotometer, 147 149
paprika powder chromatograms HPLC-DAD with KNN, SIMCA,
PLS-DA
Chili powder Sudan I dye NIR and Raman spectra NIR and Raman with PCA, 148
PLS-DA
Dried red beet pulp, almond RAPD primers (OPA-02, 08, PCR-RAPD 150
shell dust, 10, 12, 13, 15, OPC-07, 08,
Ziziphusnummularia fruits OPD-05, 11, OPJ-18)
Black pepper Papaya seeds RAPD primers (OPC-01, 04, PCR-RAPD 151
06, 07, 08)
Saffron (Crocus Turmeric,safflower, Crocus 1 H NMR spectra 1 H NMR with PCA, OPLS-DA, 152
sativus L.) sativus stamens, Gardenia O2PLS-DA
jasminoides fruit extract
Turmeric powder Curcuma zedoaria, Curcuma RAPD primers (OPA01, PCR-RAPD 153
(Curcuma longa) malabarica OPE18)
Pepper, cumin, Mesocarp, endocarp, starch, Micrograph Microscopic 154
mustard powder monosodium glutamate,
endosperm, seed coat
Sweeteners
Honey Feeding honeybee with 𝛿 13 C values C4 % sugar ratio EA-IRMS 155
industrial sugar syrups (high 1 H NMR spectra, 1 H-13 C FT-NMR, GC-FID with GDA 156
fructose corn syrup, bee HMBC spectra, syrup
feeding syrup, sucrose sugar composition
glucose monohydrate sugar)

C4 and C3 artificial sugars (high Raman spectra Raman with PLS-LDA 157
fructose corn syrup, maltose 158
Separate plot of e-nose, e-nose, e-tongue with PCA-LDA
syrup, cane sugar, beet sugar
e-tongue
syrups)
Different botanical origins FTIR spectra FTIR with PCA 160
(acacia, rape, lime, heather, 1 H-NMR spectra Botanical NMR with PCA, O2PLS-DA 161
honeydew, cornflower, makers
sunflower, clover, chestnut,
linden, orange, eucalyptus,
polyfloral)

Different geographical origin 1 H NMR spectra, Kynurenic NMR, LC-TOF-MS with GP 162 164
(Corsica versus non-Corsica) acid
Volatile compounds HS-SPME-GC, GC-TOF-MS with 159
LDA, DPLS, SIMCA, SVM
Royal jelly Yogurt, water, egg white, sweet 10-hydroxy- 2-decenoic acid HPLC-UV 165
condensed milk mixed with (10-HDA)
propolis, unripe banana and
corn starch slurry
Vanillin non-Wanillaplanifolia Chromatograms HPLC-UV 166

Maple syrup Corn syrup 𝛿 18 O, 𝛿 2 H, 𝛿 13 C values, molar IRMS, ICP-OES, ICR-MS 167
ratios of Na/(Na + K) and
Na/(Na + Ca)

pomegranate juice is characterized by a consistent composition well as the addition of other substances (coffee husks and stems,
of components such as pomegranate polyphenols, sugar profiles, maize, barley, chicory, wheat middlings, brown sugar, soybean, rye
organic acids, amino acids and potassium using HPLC and flame and triticale) to coffee blends with the aim of making them less
photometry.107 FTIR is an especially good method for providing a expensive.109,110
rapid classification of pomegranate juice concentrate and grape The world’s commercial coffee comes from only two species:
juice concentrate.108 Coffea arabica (arabica coffee) and Coffea canephora (robusta cof-
fee). Arabica coffee is the most appreciated by consumers because
Coffee of its intense aroma, low bitterness and low caffeine content. This
In the past two decades, there has been continual growth in is reflected in the selling price, which is usually 20–25% higher
the global consumption of coffee. The adulteration of roasted than that of robusta. Therefore, proof of authenticity and the
coffee is both frequent and diversified. It can involve the quality detection of frauds involving the illegal admixture of cheaper
of the beans (species, geographical origin and defective beans), as robusta coffee beans into high-quality arabica coffee are crucial

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Table 5. Methods to assess the authenticity of grain-based foods

Food category Adulterant Targetmarker Detection technology Reference

Basmati rice Non-Basmati long-grain 1 H NMR spectra 1 H NMR with PCA, ICA, 170
rice, round-grain rice LDA, SIMCA, FDA,
PLS-DA
RM241, BAD2 (betaine Real-time PCR with HRM 171
aldehyde (high resolution
dehydrogenase 2) melting)
Different geographical 13 C/12 C, 18 O/16 O, IRMS, ICP-MS with CDA 172
origin (USA, Europe, Multi-element
Basmati regions; India composition
and Pakistan)
Durum wheat (flour, pasta) Soft wheat C17:0/C21:0 HPLC-UV, LC-MS/MS 173
alkylresorcinols ratio
Microsatellite DNA Real-time PCR 174

Different species 𝜔-Secalin, chloroplast trnL Real-time PCR 175


(Triticum durum,
Triticum aestivum,
Triticum dicoccum,
Triticum turgidum,
Triticum dicoccoides,
Triticum spelta,
Hordeum vulgare,
Avena sativa, Zea mays,
Oryza sativa, Secale
cereal, Sorghum
bicolor, Triticosecale)
Different geographical 13 C/12 C, 18 O/16 O, 15 N/14 N, IRMS 176
origin (Canada,
Australia, Turkey, Italy)
Gluten-free product Wheat, barley, rye 𝜔-Gliadin (wheat), Real-time PCR 177
𝜔-Secalin (rye), Hordey
(barley), Avenin (oat)
Chloroplast trnL, Gliadin QC-PCR, ELISA 178

Cereals Different component rpoC2 Multiplex PCR 179


ratio (adlay, barley,
maize, rice, wheat)

in coffee analysis. Fourier transform ion cyclotron resonance mass at levels as low as 10 g kg−1 in roasted coffee samples.118 Recently,
spectrometer (FT-ICR-MS) has proved to be suitable for the identi- the proposed 1 H NMR method was found to be highly effective
fication of major polar compounds in aqueous coffee extracts and for the identification and quantification of the main adulterants in
for quantifying blends of the two most common coffee varieties.111 roasted and ground coffees, including barley, corn, soybean and
Also, the identification of arabica and robusta varieties is possible coffee husks.119 It should be noted that this methodology could
via the marker compounds, kahweol and 16-O-methylcafestol be applied for rapid evaluation of the presence of a larger number
predominant in robusta coffee by ultraviolet (UV)-visible spec- of adulterants.
trometry, HPLC and 1 H NMR.112,113 Especially, the determination of The flavor and taste of coffee are the most important criteria for
the 16-O-methylcafestol by NMR has advantages in terms of speed evaluating its quality and they are influenced by environmental
and relative simplicity. In addition, a high-resolution-magic-angle factors including soil, climate and species. Fraudulent retailers
spinning (HR-MAS) NMR approach has been used for assessing the can sell inferior quality products marked as those from reputable
evolution of chemical composition during the roasting process manufacturers. Therefore, it is necessary to identify the origin of
in arabica and robusta varieties.114 Furthermore, DNA extracted a coffee sample; 1 H NMR, LC-MS, GC-FID and multivariate statis-
from both green and roasted beans can be used in a PCR-RFLP tics have been successfully utilized in classifying geographical
based analysis to differentiate between arabica and robusta types and botanical origin.120,121 Many consumers prefer to consume
of coffee.115 decaffeinated coffee aiming to avoid undesirable health effects.
GC-MS combined with chemometric techniques has been Therefore, assessing compliance with decaffeination standards is
mainly used for the study of volatile profiles, especially pyrazines, an important issue. UV-visible spectrometry and successive pro-
pyrroles and phenols of green and roasted defective coffee jections algorithm (SPA)-LDA modeling could provide a promising
seeds.116 In addition, coffee-related fraud has included admix- technique for assessing the conservation state and decaffeination
tures with cheaper materials, including coffee husks and other of coffee samples.122
roasted grains. Diffuse reflectance infrared Fourier transform
spectroscopy (DRIFTS) enables satisfactory simultaneous dis- Tea
crimination between roasted coffee and commonly employed Tea (Camellia sinensis L.) has been an important drink for over
adulterants such as coffee husks and corn.117 SPME-GC-MS was 1000 years because of its health benefits. In general, green and
successfully employed to detect adulteration with roasted barley oolong tea are consumed mainly in Asia and Northern Africa,

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Table 6. Methods to assess the authenticity of others (organic foods and medicinal plants)

Food category Adulterant Target marker Detection technology Reference

Organic foods
Vegetables Conventional vegetables 15 N/14 N 1 H NMR spectra IRMS 1 H NMR 181 183
(rocket, endive, parsley,
chicory, leek, garlic, onion,
cauliflower, carrot, potato,
tomato, sweet pepper,
kohlrabi)
Grains Conventional wheat, barley, Multi-elemental composition ICP-OES, ICP-MS with PCA 182
faba bean and potato
Conventional maize GC-MS chromatograms, malic GC/MS with PCA, ANOVA 184
acid, myo-inositol and
phosphate
Fruits Conventional oranges, 15 N/14 N, ascorbic acid, total IRMS, HPLC, digital 185
peaches, strawberries, and soluble solids refractometer
clementines
Milk Conventional milk 13 C/12 C, 𝛼-linolenic acid IRMS 186
(C18:3𝜔3)
Beef Conventional beef 13 C/12 C, 15 N/14 N, 34 S/32 S EA-CF-IRMS 187

Salmon Conventional salmon 13 C/12 C, 15 N/14 N, 18 O/16 O, fatty IRMS, GC-FID with ANN 188
acids
Eggs Conventional eggs Carotenoids HPLC-UV 189

Wine Non-organic wine Infrared spectra MIR 190

Medicinal plants
Food supplement Sildenafil, sibutramine, MS spectra, NMR spectra HPLC-MS, NMR 192
1,3-dimethylamylamin,
yohimbine, and tadalafil
Bearberry Arctostaphylos pungens HPTLC fingerprint and HPTLC, HPLC-DAD, NMR 193
(Arctostaphylos densitograms, arbutin,
uva-ursi) hydroquinone, 1 H NMR
spectra
Echinacea species Parthenium integrifolium L. OPC-2, OPH-13 PCR-RAPD with ANOVA 194
(Echinacea
angustifolia, Echinacea
pallida, Echinacea
purpurea)
Black cohosh (Actaea Different species (Actaea Polyphenols, triterpene HPLC-PDA, LC-MS 195
racemosa L., syn. cimicifuga L. etc.) glycosides, LC-MS TIC spectra
Cimicifuga racemosa
L.)
Garcinia cambogia Garcinia indica Anthocyanins HPLC-UV, LC/MS 196
(cyanidin-3-O-sambubioside,
cyanidin-3-O-glucoside)
Panax ginseng Different geographical 1 H-NMR spectra, DOSY spectra, NMR with PCA 197
origin (Korea, China) and HMBC spectra
age (4, 5 and 6 years old)
Different Korean ginseng 45S nrDNAs Multiplex-PCR 198
cultivars
Red ginseng Different geographical LC-MS-MS spectra, Ra1, Rb1 or LC-MS/MS, electronic nose 199
origin (Korea, China) Rg2 ginsenosides
Cynanchum wilfordii Cynanchum auriculatum UPLC/QTOF-MS-BPI UPLC-QTOF-MS with PCA, 200
chromatograms PLS-DA, OPLS-DA
Conduritol F HPLC-UV with PCA, HCA 201

trnL-trnF Real-time PCR 202

white tea in Asia and Europe, pu-erh tea in Asia, and black successfully applied to discriminate the geographical origin of
tea worldwide.123 Economic adulteration includes the use of tea green tea.124 The flavor of green tea is the most important ele-
from other geographical origins, lower quality grades, reduced or ment for tea evaluation. In recent years, discrimination of green
extended aging and substitution with similar but less valued vari- teas according to varieties and grade levels has been recognized; it
eties. Thus, methodologies that aim to confirm the provenance of is based upon artificial nose and tongue techniques that use colori-
tea and deter incorrect labeling are becoming important tools for metric sensor arrays.125 HS-SPME-GC/MS fingerprint-based analy-
monitoring fraudulent practices. Fourier transform near-infrared sis of volatile compounds with multivariate statistical method scan
(FT-NIR) spectroscopy with supervised pattern recognition can be be a useful tool in discriminating Pu-erh green teas126 from regular

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green teas and in classifying oolong tea varieties.127 Moreover, be detected by measuring stable isotope content (𝛿 13 C and 𝛿 18 O).
a newly developed ultra-performance liquid chromatographic Furthermore, a large number of chemical parameters can be inves-
(UPLC)-DAD-MS method has been used for the tentative identi- tigated such as isotopic parameters, anthocyanins, sweeteners and
fication and quantification of the major constituents in different red dyes that are used to correct deficiencies of taste and color.140
type of teas (green pu-erh, green, and white teas).128 The repu- The identification of adulterated and fake tequilas and correct
tation of particular countries for the production of high-quality discrimination between categories (100% blue agave and mixed)
unique products allows the market to demand higher prices. This and types (white, rested and aged) can be accomplished using
tempts unscrupulous producers to fraudulently label their prod- UV-visible spectroscopy and chemometrics.141 Whiskey brand
ucts as originating from one of these areas to take advantage authenticity is usually established by determining the profile of
of the higher price. Accordingly, there is a need to protect both volatile organic compounds by GC analysis.142 However, whiskey
buyer and seller by developing analytical protocols that can be adulteration is becoming more sophisticated and sometimes
used to identify the provenance of foodstuffs. Metabolite profiles counterfeit samples display similar volatile organic compound
for diverse teas (green, oolong and white teas) collected from the profiles. A rapid analytical methodology using capillary elec-
most famous tea-producing areas (China, Japan and South Korea) trophoresis (CE) has been developed to determine the amounts
might be useful for assessing tea quality or discriminating distinct of aromatic aldehydes vanillin, syringaldehyde, coniferaldehyde,
tea products from different locations. The simultaneous identifi- and sinapaldehydein whiskey.143 More recently, ESI FT-ICR MS
cation of diverse tea metabolites could be achieved through a was shown to be a powerful technique for the direct molecu-
1
H-NMR-based metabolomics approach.129 Additionally, trace ele- lar analysis of Scotch whisky, and for being able to provide a
ment analysis in combination with stable isotope data, specifically characteristic profile of its polar constituents.144 Specialty beers
𝛿N and 𝛿D, can be used to determine the growing region of an such as Rochefort and Trappist have unique characteristics,
unknown tea sample with a high degree of confidence.130 including flavor. HS-SPME-based sampling procedures coupled
to GC-time-of-flight mass spectrometry (TOF-MS) was developed
Alcoholic beverages for obtaining fingerprints (GC profiles) of beer volatiles and these
The verification of wine identity and authenticity has an urgent data have been used to authenticate beer products.145
importance in the current context of growing market globaliza-
tion. As a result, wine authentication is indispensable and essential Spices and sweeteners
for today’s consumer protection. Variety, provenance, production Spices
year and quality ratings, which are the most important attributes Spices are especially susceptible to adulteration because they are
used for the characterization, description and pricing of wines, can typically sold in powdered form. They have long and complicated
be reflected in their total composition of small molecules. Tradi- supply chains, and so reliable and cost-effective testing method-
tionally, the only way to discriminate between wines was using ologies for ground spices are challenging to develop, and perfor-
sensory evaluation by a panel of experts. However, the wine indus- mance losses in final food products can be difficult to detect.146
try needs analytical tools that allow rapid and inexpensive analy- The synthetic dyes, compared to most natural dyes, have higher
sis to verify the authenticity of high-value products. Higher alco- stability and lower production costs. Sudan dyes are classified as
hols, esters and volatile fatty acids are especially useful for inves- Class 3 carcinogens (IARC, 1975, pp. 224–231)147 and are banned
tigating differences and similarities between wines cultivars.131 worldwide as coloring agents for human consumption. The use
Analytical data from several instrumental techniques, such as FT- of UV-visible spectroscopy with multivariate classification tech-
MIR, GC-FID and HS-SPME-GC/MS, have been used to investi- niques is a simple and inexpensive methodology for determin-
gate the chemical composition of wine aiming to distinguish ing the possible contamination of culinary spices with Sudan I–IV
between different grape varieties, with each providing a unique dyes.147 The methods employed are rapid, easy to use, and require
set of information.132,133 More recently, the non-targeted elec- minimal or no sample preparation. Chili powder is a globally
trospray ionization liquid chromatography-hybrid quadrupole/ traded commodity and, since 2003, has been found to be adul-
time-of-flight mass spectrometry (ESI-LC-QTOF-MS) metabolomics terated with Sudan dyes. Both NIR and Raman spectroscopies are
method was demonstrated to be a powerful tool for wine charac- capable of detecting the presence of Sudan I dye in chili powder.148
terization and authenticity testing.134 Also, 1 H-NMR spectroscopy In addition, of the 23 dyes investigated with the new multi-dye
is currently employed to characterize wine in terms of targeted general screening method using LC-UV/visible detection in chilli
as well as non-targeted analysis in only a few minutes, therefore powder, canned chicken in a curry sauce, fennel, palm oil, paprika
allowing the simultaneous investigation of diverse parameters.135 and turmeric, 19 are adequately dealt with by the new method.149
The identification of the geographical origin of wines is espe- The advantages of the new multi-dye general screening method
cially of great interest for wine consumers and producers as a guar- are that no clean-up is required, other than filtration, and there is
antee of quality.136 Trace element patterns observed using ICP-MS no concentration stage.
can be used to fingerprint wines and reflect the provenance or Chili powder is also adulterated by adding dried red beet pulp,
region of origin.137 Polyphenolic compounds that may play a almond shell dust and powdered Ziziphus nummularia fruits.
significant role in the classification of wines from different geo- RAPD-PCR is a good method for the identification of plant-based
graphical origins have been identified by high-performance liquid adulterants in chili powder.150 RAPD-PCR techniques have also
chromatography coupled with diode array detection (HPLC-DAD) been used to differentiate black pepper from its adulterant Carica
and fluorescence and by LC-MS with chemometric analysis by PCA papaya.151 Among the major candidates for adulteration con-
and PLS-DA.138 In winemaking, typical adulteration practices are ducted for economic gain, saffron is one of the most targeted
the non-authorized addition of natural or synthetic sweeteners, spices.74 Common fraudulent practices include the addition
the addition of ethanol, dilution with water and the addition of of inferior plant material with a similar appearance to extend
synthetic substances to hide various defects of the product.139 the more expensive saffron. Authentic saffron and four typical
Exogenous addition of sugar and water in counterfeited wines can plant-derived materials utilized as bulking agents, Crocus sativus

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www.soci.org E Hong et al.

stamens, safflower, turmeric and gardenia, have been investi- differentiated using 1D 1 H NMR and 2D heteronuclear single
gated. A two-step approach, which relied on the application of quantum correlation spectroscopy coupled with multivariate
both orthogonal PLS-DA and bidirectional orthogonal PLS-DA data analysis.162 ICP-MS has been used in combination with data
(O2PLS-DA) models to the 1 H NMR data, was used to identify mining approaches for the estimation of the geographical origin
authentic and adulterated saffron.152 Turmeric powder has been of Brazilian honeys.163 NMR spectroscopic fingerprints have been
adulterated with rhizomes of cheaply available Curcuma species, used for the confirmation of claims made on honeys of Corsican
especially those containing the coloring pigment curcumin, such (France) and non-Corsican (Australia, Germany, Ireland and Italy)
as Curcuma zedoaria and Curcuma malabarica, which leads to provenance.164 Additionally, GC × GC-TOF-MS combined with
toxicity and a poor quality product. RAPD-derived sequence methods such as LDA, discriminant partial least squares (DPLS)
characterized amplified region (SCAR) markers could successfully and support vector machines (SVM) can be successfully applied to
detect C. zedoaria and C. malabarica adulteration. The efficiency of detect mislabeling of Corsican honeys.159
the SCAR markers for detecting adulteration even at low concen- Royal jelly is popularly known to have many nutrients and is
trations (10 g adulterant kg−1 of turmeric powder) substantiates sold as a food supplement. Because of the product’s high price,
their applicability as a qualitative diagnostic tool for detecting royal jelly can be adulterated by adding less expensive products
plant-based adulterants in turmeric powder.153 In recent years, that cannot be detected organoleptically, such as starch corn
microscopic powder identification techniques have been able to slurry, yogurt, egg white, condensed milk mixed with propolis,
clearly distinguish between the characteristic constituents and unripe banana and water. The physicochemical composition of
the adulterating substances, and they are much more intuitive, pure royal jelly, as well as some adulterated samples, can be
rapid, accurate and available than organoleptic inspection and analyzed by determining moisture, ash, lipids, nitrogen/proteins,
physical or chemical identification.154 carbohydrates, starch and 10-hydroxy-2-decenoic acid.165
Vanillin is used worldwide as a flavor and aroma. Because of
Sweeteners the high cost to cultivate Vanilla planifolia most of the marketed
Increasing environmental pollution and the spread of disease have vanillin is produced by chemical methods. Vanillin fingerprint
been blamed for a decrease in the global honeybee population. chromatograms are used to discriminate vanillin from different
This fact, coupled with a higher demand, means that honey is origins. Three alignment algorithms have been tested: correlation
becoming an increasingly scarce commodity and, consequently, optimized warping, target peak alignment and semi-parametric
honey adulteration is on the rise. Honey adulteration can be direct time warping.166 The addition of as little as 100 g kg−1 corn syrup to
(dilution with water or directly added sugar and syrups) or indi- pure maple syrup can be detected using elemental concentrations
rect (feeding of bees with industrial sugars and syrups). Adulter- and the stable isotopic composition of maple syrups.167
ated honey produced by honeybee colonies fed with different lev-
els of sugar and sugar derived from C4 plants such as corn and Grain-based foods
sugar cane can be evaluated by using the difference between the In most countries, cereals including wheat, rice and corn are the
𝛿 13 C value of protein and honey (Δ𝛿 13 C) and the C4 % ratio.155 main agricultural products. The price of cereal is chiefly deter-
Adulteration of honey by sugar syrups can also be detected mined by its protein content, starch content and/or hardness,
using one-dimensional (1D) and two-dimensional (2D) NMR cou- often with substantial price increments between grades.
pled with multivariate statistical analyses.156 The best discrimina- Rice (Oryza sativa L.) is the most important cereal crop in terms
tion model involved 1D-spectra and a cross-verification analysis of world production.168 Basmati, an aromatic variety of rice of
showed a prediction capacity for this model of 95.2%. The 2D NMR high quality, is found in the foothills of the Himalayan mountains
analyses also gave satisfactory results (cross-verification showed and especially all over Pakistan and India. Basmati is sold at a very
90.5% accuracy). In addition, honey can easily be adulterated high market price at a ratio of 4:1 to common rice. Because of the
directly with various cheaper sweeteners, such as high fructose potential gain, traders tend to heavily adulterate the crop with
corn syrup, maltose syrup, cane sugar and beet sugar syrups, non-fragrant varieties.169 1 H NMR spectra of rice type (Basmati,
resulting in higher commercial profits. Honey adulteration can also non-Basmati long-grain rice and round-grain rice) can be used
be detected using several modern methods such as Raman spec- as a feasible and accurate screening tool for the identification
troscopy, an electronic nose or an electronic tongue.157,158 of geographical origin (or rice cultivars).170 DNA-based meth-
Consumer choice is linked to unique organoleptic and aro- ods coupled with HRM analysis are available to detect Basmati
matic properties of honey that depend principally on the botan- adulteration. Compared with other techniques, HRM analysis is
ical and geographical origins of the product. The geographi- a high resolution, cost-effective method that could be extended
cal categorization of honeys can raise its commercial value and to quantifying adulterations in rice varieties and commercial rice
contribute to the micro economy of the region. Among phyto- food products.171 The geographical origin of premium long-grain
chemicals, volatile organic compounds have been proposed as the rice can be analyzed using IRMS and ICP-MS.172 European rice
key markers for differentiating honeys from different geographi- samples generally contain relatively high levels of magnesium
cal origins.159 Most of the honey samples from rape, false acacia, whereas Indian/Pakistani samples are characterized by relatively
heather and honeydew, which possess different physical-chemical low 18 O abundance.
and sensorial properties, can be classified correctly by FTIR.160 NMR Because durum wheat (Triticum durum Desf.) is approximately
approaches have proven successful for the development of classifi- 20% more expensive than common wheat (Triticum aestivum L.)
cation models specific for different types of polyfloral and unifloral and considered to be of superior quality for the manufacture of
honey samples.161 The high accuracy obtained by the classification pasta products, efficient methods for the detection of accidental
models (>91%) suggests that metabolomic tools can be used to or intentional admixture of common wheat to durum wheat
discriminate the origin of honey samples. product are required. To detect and estimate adulteration, the
A total 57 samples with geographical origin from Italy, Hungary, C17/C21 alkylresorcinols ratios of common wheat adulteration in
South America and China (geographical origin) were successfully durum wheat can be analyzed using HPLC and LC-MS/MS173 and

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numerous methods use the detection of specific proteins sepa- Irish beef have been analyzed for the authentication of organic
rated by electrophoresis or HPLC. NIR spectroscopy in conjunction beef using elemental analyzer (EA)-pyrolysis interfaced in contin-
with chemometric techniques such as PLS and wavelet interface to uous flow (CF)-IRMS.187 Additionally, identification of organically
linear modeling analysis (WILMA) also provide satisfactory results, farmed Atlantic salmon has been analyzed by 𝛿 15 N value and the
yielding a lower uncertainty value than those associated with content of linoleic acid.188 Carotenoid HPLC-DAD profiling com-
traditional analytical methods for the percentage of adulterant bined with k-nearest neighbor classification has been used to iden-
present in quantified samples. Moreover, DNA-based methods can tify the organic or non-organic status of chicken eggs.189 Com-
be applied to detect the adulterants in parental lines of the hybrid bined discriminant techniques could be suitable and easily imple-
wheat seed and also in processed foods. In particular, analysis mented by the wine industry to classify wines produced with
of DNA microsatellites has proven effective in detecting wheat organic systems.190
adulteration.174,175 However, they are unsuitable for characterizing
the geographical origin of durum wheat semolina samples cul- Dietary supplements
tivated in different countries. This challenge has been effectively The amount of herbal medicine and dietary supplements on the
tackled by a multi-isotopic approach considering 13 C, 18 O and 15 N market is constantly increasing. The adulteration of plants used
isotopes.176 to make herbal medicines and dietary supplements is a peren-
The only treatment for celiac disease is a life-long avoidance of nial problem that has caused many disputes.191 Common issues
wheat, barley and rye. Accordingly, the detection and discrimina- include the substitution of one ingredient for another, use of a
tion of cereal contamination in gluten-free foods is essential for species other than that stated on the label, and the inclusion of
celiac disease patients. Real-time PCR, quantitative competitive undeclared prescription and non-prescription drugs. Therefore,
(QC)-PCR and ELISA methods have been established for the spe- the development of new and improved analytical methodolo-
cific discrimination of wheat, rye, barley and oats in gluten-free gies for the detection and structural identification of adulterants,
food.177,178 Recently, food fraud in cereal food products derived including new/unknown analogues, is crucial when aiming to pro-
from a ready-to-eat powder (e.g. Sunsik) is a great concern to reg- tect public health and ensure the quality of dietary supplements.
ulatory authorities and consumers, especially the mislabeling or A search for undeclared and unauthorized substances frequently
incorrect labeling of allergenic constituents in Korea. Thus, specific reported in food supplements by European Union rapid alert sys-
primers for each species have been developed based on sequence tem for food and feed (RASFF) was carried out each year from 2009
polymorphisms in chloroplast rpoC2m and multiplex PCR can to 2016. The most frequently found illegal ingredients in food sup-
detect components of commercial flow-mixed products.179 plements in these years were sildenafil and its analogues, sibu-
tramine and its derivative, 1,3-dimethylamylamin, yohimbine and
Others tadalafil.192 In the review, HPLC-MS and high field NMR has been
Organic foods suggested for the simultaneous detection and determination of
Most consumers consider that organic foods are healthier, safer, the above most illegal ingredients.
environmentally friendlier and of higher product quality com- Bearberry [Arctostaphylos uva-ursi (L.)] is a well-known medicinal
pared to conventional foods. Organic products generally have plant, widely used to treat a variety of urinary disorders. Recently,
a premium price over conventional products, which explains Arctostaphylos pungens has been fraudulently sold as bearberry
the appearance of fraud cases.180 Accordingly, suitable authen- raw material. It has morphological characters that are similar to
tication tools to rapidly distinguish organic and conventional A. uva-ursi and is marketed at a lower cost. Two typologies of
crops are needed. The nitrogen isotopic signature (15 N/14 N ratio HPTLC fingerprints, confirmed by NMR and HPLC-DAD, can be used
or 𝛿 15 N signature) of a product is reported to be a promising to quickly detect the substitution of A. uva-ursiwith A. pungens in
method for differentiating between organic and conventional bearberry products.193 Another interesting case study of dietary
products grown with or without the use of synthetic fertilizers.181 supplement adulteration is related to Echinacea species mar-
The multi-elemental composition of organic and conventional keted for an immune modulating activity. RAPD markers are
wheat, spring barley, faba beans and potato has been analyzed capable of distinguishing the presence of Parthenium integri-
with inductively coupled plasma optical emission spectroscopy folium L., an adulterant of Echinacea angustifolia, at levels down
(ICP-OES) and ICP-MS.182 Recently, 1 H NMR profiling techniques to 10 g kg−1 .194 Chemical investigation can be important for the
with linear discriminant analysis demonstrated good discrimina- authentication of Actaea racemosa L., syn. Cimicifuga racemosa
tion between conventionally and organically grown tomatoes.183 L., better known as black cohosh and Garcinia cambogia. Black
Maize (Zea mays) kernels, grown conventionally and organically, cohosh and G. cambogia products are in growing demand as alter-
have been investigated using a GC-MS based metabolite profiling natives to estrogen therapy and as anti-obesity agents, although
methodology.184 The stable isotope ratio of nitrogen (expressed as they can be adulterated with similar but lower-priced species
𝛿 15 N), ascorbic acid and total soluble solids were found to be the (mainly Actaea cimicifuga L. and Garcinia indica). The identifica-
most significant isotopic and chemical markers for distinguishing tion and quantification of adulteration in these dietary supple-
between organic and conventional fruits.185 These results suggest ments has been established by chromatographic and spectromet-
that good discrimination between organic and conventional fruit ric methods.195,196
of different species can be achieved by combining use of isotopic Panax ginseng C.A. Meyer has been used as a traditional medic-
and chemical markers. inal herb in Asia. Because the composition of ginseng roots
The higher price of organic milk and the limitation of natural and commercial red ginseng concentrates can vary significantly
resources has led to an increased risk of conventional milk being according to origin and age, it is important to discriminate
fraudulently labeled as organic milk. Analysis of the stable isotope between ginseng roots from different sources. Several types of
ratio of carbon (𝛿 13 C) and 𝛼-linoleic acid (C18:3𝜔3) content in milk technology have been introduced for the differentiation of the
fat is a useful indicator of organic milk.186 The stable isotope ratios geographical origin and cultivars of ginseng; the main methods
of light elements (𝛿 13 C, 𝛿 15 N and 𝛿 34 S) of organic and conventional used are NMR, LC-MS/MS, electronic nose analysis and multiplex

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www.soci.org E Hong et al.

PCR.197 – 199 Recently, recognition has grown for the need to dis- 11 Bontempo L, Larcher R, Camin F, Hölzl S, Rossmann A, Horn P et al.,
tinguish the dried roots of Cynanchum wilfordii (called Becksuo, in Elemental and isotopic characterisation of typical Italian alpine
cheeses. Int Dairy J 21:441–446 (2011).
Korea) from those of Cynanchum auriculatum in the Korean herbal 12 Drivelos SA and Georgiou CA, Multi-element and multi-isotope-ratio
medicine market. Although C. wilfordii and C. auriculatum have analysis to determine the geographical origin of foods in the
similar morphology, the types and quantities of their metabolites European Union. Trends Anal Chem 40:38–51 (2012).
differ. HPLC and UPLC-QTOF-MS-based metabolomics can discrim- 13 Consonni R and Cagliani L, Ripening and geographical characteri-
inate the roots of C. wilfordii and C. auriculatum.200,201 Moreover, zation of Parmigiano Reggiano cheese by 1 H NMR spectroscopy.
Talanta 76:200–205 (2008).
genotype analysis involving real-time PCR amplification can easily, 14 Bassbasi M, De Luca M, Ioele G, Oussama A and Ragno G, Prediction of
quickly and accurately distinguish the two species.202 the geographical origin of butters by partial least square discrimi-
nant analysis (PLS-DA) applied to infrared spectroscopy (FTIR) data.
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CONCLUSIONS 15 Lerma-García M, Gori A, Cerretani L, Simó-Alfonso E and Caboni M,
Classification of Pecorino cheeses produced in Italy according to
Our review of the analytical methods used to examine these six their ripening time and manufacturing technique using Fourier
food categories supports the conclusion that challenges remain transform infrared spectroscopy. J Dairy Sci 93:4490–4496 (2010).
with respect to the use of these techniques for industrial and reg- 16 Botelho BG, Reis N, Oliveira LS and Sena MM, Development and ana-
ulatory purposes. In addition, food authentication is a multidisci- lytical validation of a screening method for simultaneous detec-
tion of five adulterants in raw milk using mid-infrared spectroscopy
plinary field that has input from the diverse areas of instrumenta- and PLS-DA. Food Chem 181:31–37 (2015).
tion, biology, informatics, mathematics and statistics, agriculture, 17 Jablonski JE, Moore JC and Harnly JM, Nontargeted detection of
and food technology. Because the many embodiments of fraud adulteration of skim milk powder with foreign proteins using
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High resolution 13 C NMR detection of short-and medium-chain
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