Food Authenticity and Fraud

C H A P T E R

15 Food Authenticity and Fraud Romdhane Karoui Universite´ d’Artois, Faculte´ des Sciences Jean Perrin, Rue Jean Souvraz, Lens Cedex, France

O U T L I N E 15.1. Introduction

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15.2. Methods for Food Authentication and Adulteration 500 15.2.1. Chromatographic Techniques 500 15.2.2. Spectroscopic Techniques 502 15.2.3. Enzymes in Food Authentication 509

15.1. INTRODUCTION Product authenticity and adulteration are issues assuming increasing importance within the food industry (Downey and Beaucheˆne, 1997). They are a major concern not only to consumers, but also to producers and distributors (Fernandez et al., 2003). Indeed, regulatory authorities, food processors, retailers, and consumer groups have interests in ensuring that foods are correctly labeled. Many products may be deliberately mislabeled, especially those that are expensive and/or subject to natural fluctuations. With the harmonization of the European agricultural policy and the emergence of international markets, approaches to authenticating food

Chemical Analysis of Food: Techniques and Applications DOI: 10.1016/B978-0-12-384862-8.00015-7

15.2.4. DNA-Based Methods in Food Authentication 15.2.5. Differential Scanning Calorimetry 15.3. Conclusions

509 509 510

products have received much attention. This trend is the result of efforts by regional authorities and producers to protect and support local productions. Although grains, bread, milk, and spices have been adulterated since antiquity, fraudulent practices have been extended to other luxurious food commodities such as coffee, tea, and sugar. For example, coffee has been adulterated with chicory, roasted wheat, or burned sugar. The increasing globalization of the food industry in recent times and the consequent separation of producers and consumers have increased the risk of adulteration. Adulteration is defined as the process by which the quality of the product is reduced through the addition of a base substance or removal of a vital

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Copyright Ó 2012 Elsevier Inc. All rights reserved.

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element. Fraud occurs in several ways; thus, the methods applied in adulteration are at least as sophisticated as those needed to detect it. In general, food can be considered to be adulterated when the following occur: (i) admixture of inferior or cheaper substances; (ii) extraction of certain quality ingredients from the origin food; (iii) preparing or packing under unsanitary conditions; (iv) sale of insect infested food; (v) obtaining the food from a diseased animal; (vi) incorporation of a poisonous component; (vii) entry of injurious constituents from the container used; (viii) use of coloring matter other than or in greater quantities than those approved for the food; (ix) sale of substandard products which may or may not be injurious to health, etc. For example, water may be added to milk or to juice to increase their volumes; fat may be removed from milk and fructose may be added to honey, etc. Food characterization is a very important task, which has been classically undertaken by different physico-chemical, chromatographic, PCR, enzyme-linked immunosorbent assay and thermal methods, etc. Although heavy, they are considered to be among the most useful methods for the characterization of food products. Nowadays, the development of rapid methods for food authentication and adulteration is of great importance. Spectroscopic techniques are fast, of relatively low cost, and provide a great deal of information with only one test. They are considered sensitive, nondestructive, rapid, environmentally friendly, and noninvasive, which makes these methods suitable for on-line or at-line process control. In addition, spectroscopic techniques require limited sample preparation. In the last decade, rapid spectroscopic measurements have advanced in quality control in many areas of food production. Spectroscopic methods for measurements of food quality include ultraviolet and visible (UVeVis), fluorescence emission, infrared, nuclear magnetic resonance (NMR), electronic nose (EN), and isotopic analysis. These spectroscopic techniques

are based on different regions of the electromagnetic spectrum and different physical principles resulting in different sensing capabilities. The methods, however, share the ability to provide rapid multivariate information on the sample being monitored, which in turn makes it possible to determine several quality parameters simultaneously (Karoui et al., 2003).

15.2. METHODS FOR FOOD AUTHENTICATION AND ADULTERATION A summary survey of the most important analytical techniques utilized for the determination of the authenticity and adulteration of food products is given. For more details, the reader is referred to Part 1 of this book related to chemical analyses of food where each technique is discussed in much more detail. In the past decades, a large number of contributions dealing with food authenticity and adulteration of several food products (e.g., meat, cheese, juice, and rice) have been published (Ballin and Lametsch, 2008; Fajardo et al., 2010; Karoui et al., 2003; Kaskoniene and Venskutonis, 2010; Robards and Antolovich, 1995; Rodrı´guez-Ramı´rez et al., 2011; Vlachos and Arvanitoyannis, 2008; Zhang et al., 2011). In view of the structure of this book, each technique is studied concisely.

15.2.1. Chromatographic Techniques Although heavy, chromatographic techniques are among the most important methods used in food authentication and adulteration. Chromatographic techniques are usually classified according to the character of the stationary and the mobile phases, the form of the stationary phase, and the driving forces of separation as pointed out by Forga´cs and Cserha´ti (2003). Gas chromatography (GC) and high-performance liquid chromatography (HPLC) are the most used techniques.

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15.2.1.1. Gas Chromatography To be analyzed by GC, analytes that constitute the product should be easily vaporized without any decomposition. Generally, GC is coupled with mass spectrometry (MS) that is considered the most used detector as pointed out by Cordella et al. (2002). This detector gives structural information through the different m/z fragments obtained and analyte identification by library searching and/or comparison with the analytical standards. The use of GC needs the preparation of the sample including extraction and purification, which requests skilled operators and is time consuming, particularly for nonvolatile compounds. For them, derivatization (e.g., reduction and acylation of sugar; esterification and acylation of amino acids) must be applied to obtain volatile derivatives. The main advantages of GC are its high-level separation, sensitivity, and versatility for food authentication, as demonstrated for olive oil (Escuderos, 2011), meat products (Sivadier et al., 2008), coffee (Ristecevic et al., 2008), and various other food products (Lehotay and Hajslova, 2002). The main disadvantage is related to the derivatization procedure that is applied to nonvolatile compounds, which induces in certain cases a potential source of error as pointed out by Forga´cs and Cserha´ti (2003). GC is among the interesting methods for the separation and characterization of flavor components in foods such as cheese. For example, terpene profiles and content in milk and dairy products are influenced by feed and especially by grazed herbage. This relationship could be used to discriminate milk or cheese samples originating from grazing or not grazing system and to trace the geographical origin of these products and/or production site. However, due to the complexity of flavor components present in food products, highly sophisticated techniques such as enantio-capillary GC can be used to authenticate food flavor and essential oil compounds

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(Mosandl, 2004). Other chiral food constituents, such as hydroxy acids, amino acids, and catechins, determined using capillary GC, have demonstrated their potential as quality markers of cocoa beans (Caligiani et al., 2007). The practicability and potential of comprehensive two-dimensional GC coupled to both conventional flame ionization and time-of-flight mass spectrometric detection were compared with those of conventional onedimensional GC for the determination of flavor compounds in butter (Adahchour et al., 2005). The authors found that the two-dimensional GC could be considered as a promising and versatile technique for a wide-ranging screening of flavors and fragrances in butter. 15.2.1.2. High-Performance Liquid Chromatography HPLC can be used for food compounds that cannot be volatilized readily. As GC, (i) sample preparation is needed when HPLC is used and (ii) derivatization is usually utilized in order to increase retention of hydrophilic compounds in reverse phase (RP)-HPLC and to improve the sensitivity. In the context of food fraud and authentication, several and various types of detectors can be used. The most useful ones are single- or multiple-wavelength UVeVis detectors. Fluorescence detectors are particularly useful for the determination of very low analyte levels. As mentioned in the introduction, the aim of the present chapter is not to present an exhaustive application of HPLC in food authentication; thus, only some examples related to the use of HPLC coupled with chemometric tools are given below. For more details, the reader is referred to Chapter 10 related to HPLC. O’Shea et al. (1996) applied RP-HPLC to analyze retentate and permeate of the water-soluble fraction of 60 cheddar cheeses, varying in age (mild, mature, and extra-mature) and flavor quality (defective and nondefective). To determine the accuracy of the RP-HPLC, the authors applied factorial discriminant analysis (FDA) and poor

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classifications were obtained since only 33.3% and 48.3% of samples were correctly classified. In a similar approach, Ferreira and Cacote (2003) used the RP-HPLC for detecting and quantifying bovine, ovine, and caprine milk percentages in milks and Portuguese-protected denomination of origin (PDO) cheeses. A clear difference between the chromatographic profiles of b-lactoglobulin and a-lactalbumin extracted from the investigated milk samples was observed. The same authors have then made cheeses by using different proportions of bovine, caprine, and ovine milk. As expected, different chromatographic profiles were obtained for each type of milk binary mixtures, while similar chromatographic profiles were observed for each milk mixture and the respective fresh and ripened cheeses. In a similar approach, Pripp et al. (1999) compared three different Norwegian cheese varieties e Jarlsberg, Norvegia, and Sveitser e by applying principal-component analysis (PCA) to the proteolytic profile obtained by RP-HPLC and capillary electrophoresis (CE); better results for discriminating cheeses were obtained with CE than with RP-HPLC. To identify the indices of secondary proteolysis, BaraHerczegh et al. (2002) analyzed, by HPLC, 40 Hungarian Trappist cheeses throughout ripening as well as during storage. By applying PCA to the data sets, the authors pointed out the usefulness of amino acids for monitoring changes occurring during the ripening time and shelf life. The RP-HPLC and HPLC have been used for the determination of (i) carbohydrates, carboxylic acids, and metals in foods (Paredes et al., 2006, 2008); (ii) botanical origin of honeys (Cotte et al., 2004); and (iii) adulteration of vegetable oils (Benitez-Sa´nchez et al., 2003; Cserha´ti et al., 2005). In order to increase the accuracy and sensitivity of HPLC, this latter has been combined with mass spectrometry (MS) for the determination of myo-inositol in milk powder samples. The technique (HPLC-MS) was applied to six fortified commercial milk powder samples

containing myoinositol amounts ranging from 290 to 2200 mg kg
1 and the obtained results provide a sensitive and selective determination of myoinositol in the analyzed samples, with a run time of 4 min (Flores et al., 2011). The technique has also demonstrated its ability to simultaneously determine the existence of quinolones and fluoroquinolones in different infant and young children powdered milks (HerreraHerrera et al., 2011), aflatoxin M1 in milk samples since good accuracy and prediction were observed (Chen et al., 2011) as well as volatile nitrosamines in meat products (Campillo et al., 2011), and the replacement of goat’s cheese with sheep’s milk (Guarino et al., 2010).

15.2.2. Spectroscopic Techniques Spectroscopic techniques such as UVeVis spectrophotometry, fluorescence, infrared, EN, NMR, and stable isotope analysis are widely used for food authentication. The most successful approach for extracting quantitative, qualitative, or structural information from such spectra is to use multivariate mathematical analysis. These powerful methods and the computer technology necessary to use them have only become readily available in recent years, but their use has become a significant feature for the above-mentioned techniques. A broad range of techniques is now available including data reduction tools, regression techniques, and classification methods (Karoui and Blecker, 2011; Karoui et al., 2010). 15.2.2.1. UltravioleteVisible Spectroscopy The UVeVis spectrometry is a simple technique that has been applied for the determination of the quality of food products. It has been used with success for the determination of total carotenes in margarines (Luterotti et al., 2006) and total carotenoids in cereal grain products (Luterotti and Kljak, 2010) as well as for quality control of saffron spice (Maggi et al., 2011). Recently, Castro-Gira´ldez et al. (2010) have succeeded, following the use of Vis spectroscopy, to

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differentiate, after 24 h postmortem, pale, soft, and exudative meat from dark; firm, dry, and red; and firm and nonexudative meat samples. In another study, Le Moigne et al. (2008) pointed out the superiority of Vis spectrometry compared to front face fluorescence spectroscopy for predicting total soluble solids and total acidity of Cabernet Franc grapes during ripening. The obtained results confirmed previous findings by O’Farrell et al. (2004) who, following the use of PCA and pattern recognition, succeeded to differentiate between different food products (i.e., steamed skinless chicken fillets, roast whole chickens, sausages, pastry, bread crumb coating, and char-grilled chicken). Another interesting application of UV-spectroscopy concerns the characterization of anthocyanins from mulberry pigment (Qin et al., 2010) since, among several

analytical techniques (UVeVis, HPLC, and NMR), UVeVis gave the best results. 15.2.2.2. Fluorescence Spectroscopy Fluorescence spectroscopy is a rapid and nondestructive technique allowing the screening of a large number of samples (Karoui and Blecker, 2011). For this reason, fluorescence spectroscopy has been utilized not only for the authentication of different food products but also for the prediction of maturity of grapes (Le Moigne et al., 2008), some physico-parameters of cheeses (Karoui et al., 2006c), and heterocyclic aromatic amines in grilled meat (Sahar et al., 2010). Front face fluorescence spectroscopy has also been used for the (i) monitoring of rennet-induced milk coagulation (Herbert et al., 1999); (ii) determination of the geographic origin of milk (Fig. 15.1) and

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Mid mountains

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Mountains

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FIGURE 15.1 Discriminant analysis similarity maps determined by discriminant factors 1 and 2. FDA was performed on the first 5 concatenated PCs of PCA realized on the tryptophan, aromatic amino acids and nucleic acid, riboflavin, and vitamin Fluorescence spectra acquired on eight milk samples produced in lowland (430e480 m), 16 milk samples produced in mid-mountain (720e860 m), and 16 milk samples produced in mountain (1070e1150 m) regions.

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0.18

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Stabilized cheeses: M3

0.13 0.08 0.03 -0.22

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Q1 0.03

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-0.07 Traditional cheeses: M1 and M2

-0.12 -0.17 -0.22

FIGURE 15.2 Common components and specific weight analysis (CCSWA) similarity map defined by the common components 1 (q1) and 3 (q3) of external M1 zone (A), central M1 zone (A), external M2 zone (6), central M2 zone (:), external M3 zone (B), and central M3 zone ( ) cheeses.

•

different varieties of cheeses (Karoui et al., 2004a; 2004b; 2005a; 2005b; 2005c) (Fig. 15.2) and the botanical origin of honeys (Karoui et al., 2007a; Ruoff et al., 2005, 2006a) (Fig. 15.3); (iii) detection of hazelnut oil adulteration in virgin olive oil (Sayago et al., 2004); (iv) assessment of the mealiness of apples (Moshou et al., 2005); and (v) identification of bacteria of agro-alimentary interest (Leblanc and Dufour, 2002, 2004; Leriche et al., 2004). The technique has also demonstrated its ability to determine the freshness of (i) fish (Karoui et al., 2006d) (Fig. 15.4), (ii) rice (Hachiya et al., 2009), and (iii) eggs (2006a,b; 2007c, d) by (2006a; 2006b; 2007c; 2007d). The use of fluorescence spectroscopy combined with chemometric tools for quality and authenticity control of various food products has been extensively reviewed by Karoui and Blecker (2011). Recently (unpublished results), front face fluorescence spectroscopy was found to be accurate to (i) monitor network structure and molecular

interaction during the coagulation of different raw skim milk samples (raw, thermized, and pasteurized) and (ii) determine gelation time of rennet-induced coagulation of studied milk samples. 15.2.2.3. Infrared Spectroscopy The infrared region comprises that part of the electromagnetic spectrum in the wavelength range between 780 and 100,000 nm, and is divided into NIR, MIR, and far-infrared subregions (Osborne, 2000; Penner, 1994). The MIR operates between 4000 and 400 cm
1 (Reid et al., 2006), while NIR covers the wavelengths ranging from 780 to 2500 nm (Osborne, 2000). The NIR spectrum normally exhibits few welldefined sharp peaks compared to MIR. Comprehensive reviews on the use of NIR and MIR have been provided by Woodcock et al. (2008) and Karoui et al. (2010), respectively. These two techniques have been used for the authentication of

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0.12

Alpine rose

Chestnut

Fluorescence intensity (a.u.)

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Alpine polyfloral

0.08

0.06

0.04

0.02

350

400

450

500

Wavelength (nm)

FIGURE 15.3 Normalized fluorescence emission spectra (305e500 nm) recorded following excitation at 290 nm on alpine rose, alpine polyfloral, and chestnut honeys.

dairy products (Karoui et al., 2004a; 2004b; 2005a; 2005b; 2010) 2010; Mouazen et al., 2007, 2009; Pillonel et al., 2003b), cereal flours (Cocchi et al., 2004, 2006), meat products (Al Jowder et al., 1997; Downey and Beauchene, 1997; Rannou and Downey, 1997), olive oils (Caetano et al., 2007), botanical origins of honey (Ruoff et al., 2006b; Tewari and Irudayaraj, 2005), and maturity

of fruits and vegetables (Arana et al., 2005; Li et al., 2007). Figure 15.5 shows how MIR can discriminate among milk samples collected from ewes fed with three different systems. The technique has been utilized for the determination of (i) fish freshness (Karoui et al., 2007b) and (ii) adulteration of juice by sugar as pointed out by Reid et al. (2005; 2006).

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PC1 (84.9%)

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FIGURE 15.4 Principal-component analysis similarity map determined by principal component 1 (PC1) and principal component 2 (PC2) for the nicotinamide adenine dinucleotide (NADH) fluorescence spectra of fresh () and frozenethawed (C) fish fillets.

15.2.2.4. Electronic Nose Essentially the instrument consists of head space sampling, sensor array, and pattern recognition modules, to generate signal pattern that are used for characterizing odors. More than 10,000 odorous compounds are known to exist in nature, but only a few of these are likely to be important in solving any discrimination task by EN. The EN did not necessarily detect the most odorous compounds, but it may give a robust pattern based on a response to volatile compounds that is indicative of the quality changes occurring in food during ripening, maturation, etc. The application of this technique as a tool for monitoring freshness or detecting quality changes occurring during storage in several food products (e.g., meat,

pineapple, and sardines) has been demonstrated (El Barbbri et al., 2008, 2009; Torri et al., 2010). In addition, the EN has been used for detecting volatile compounds produced by the growth of fungi, molds, or microbes and monitoring oxidation phenomena in food (Boothe and Arnold, 2002; Jonsson et al., 1997; Keshri et al., 2002; McEntegart et al., 2000; Namdev et al., 1998; Olafsson et al. 1992; Olsson et al., 2002; Schnu¨rer et al., 1999). Other applications such as (i) safety and authenticity of pecorino cheeses (Cevoli et al., 2011); (ii) monitoring of the ripening stages of cheeses and predicting their volatiles compounds (Trihaas and Nielsen, 2005; Trihaas et al., 2005a,b); (iii) detection of lard adulteration in RBD palm olein (Che Man et al., 2005); (iv) identification of pork for halal

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F2 (24.1%)

4 Scotch bean

2 Control

F1 (75.9%) 0 -5

-3

-1

1

3

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Soybean -2

-4

FIGURE 15.5 Discriminant analysis similarity map with the leave one-out cross-validation data set determined by discriminant factors 1 (F1) and 2 (F2). Factorial discriminant analysis (FDA) was performed on the first principal-component (PC) scores of the principal-component analysis (PCA) performed on the 3000e2800, 1700e1500, and 1500e900 cm
1 spectral region of MIR spectra recorded on Sicilo-Sarde ewe’s milk belonging to three groups named scotch bean, soybean, and control.

authentication (Nurjuliana et al., 2011); (v) assessment of meat freshness (Yu Musatov et al., 2010); and (vi) determination of different types of damage to rice plants (Zhou and Wang, 2011) have been demonstrated. NIR spectrometry and EN have been jointly used for on-line monitoring of yogurt and filmjolk (Swedish yogurt-like sour milk) fermentation under industrial conditions (Navratil et al., 2004). The obtained results showed the potential of these two techniques for rapid online monitoring and assessment of process quality of yogurt fermentation. 15.2.2.5. Nuclear Magnetic Resonance Spectroscopy NMR is a versatile spectroscopic technique for studying opaque heterogeneous samples, which has already proved to have a number of

useful applications in food research. NMR has also become an indispensable analytical technique in medicine, chemistry, physics, biology, and food science. The NMR instrument communicates with the investigated object by electromagnetic waves in the radiofrequency range. This makes most NMR techniques noninvasive and nondestructive for the sample; rapid, not harmful for the operator; and nonpolluting for the environment. The applications of NMR methods in food research may be divided into three main groups according to the type of equipment used, as they can provide versatile information about the chemical composition and structure of biological systems at various levels. These are magnetic resonance imaging, low-field NMR, and high-resolution NMR. The NMR has been used for determining the effect of formulation on ice cream structure

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(Lucas et al., 2005a,b). The same research group determined the effect of the nature of fats, proteins, and emulsifiers on the behavior of fats (Lucas et al., 2005a) and the most significant factor was found to be the fat type. The NMR has also been used to (i) determine the geographic origin and characterize the water-holding capacity of milk and cheese samples as well as to monitor the ripening stage of cheeses (De Angelis Curtis et al., 2000; Hinrichs et al., 2007; Renou et al., 2004); (ii) trace European olive oils (Mannina et al., 2010); (iii) determine the glass transition temperature of food polymers (Ruan et al., 1998) and detect g-ray irradiated meat (Stefanova et al., 2010); and (iv) authenticate durum (Lamanna et al., 2011), olive oils (D’Imperio et al., 2007), green tea (Le Gall et al., 2004), juice (Cuny et al, 2008), and coffee (Charlton et al., 2002). The technique has been used to characterize lignin isolated from fruit and vegetable insoluble dietary fiber (Bunzel and Ralph, 2006). 15.2.2.6. Stable Isotope Analysis Techniques aimed at identifying the geographic origin of samples make use of the different distribution of isotopes in different geographic regions. The isotopes may be originating from the most common elements making up the organic materials such as H, C, O, N, S, or isotopes of trace elements that nonetheless are essential for normal functioning of organisms, such as zinc, selenium, magnesium, manganese, or contaminants picked up from the environment such as mercury, cadmium, lead, and so on. Stable isotopes of the above-mentioned organic materials carbon, nitrogen, sulfur, oxygen, and hydrogen are measured by gas isotope-ratio mass spectroscopy. These ratios are usually given as proportions (0/00) or as excess (delta (d) values, which are also given as 0/00). These delta values (for example, d15N, d13C) are the differences between the value of the sample and that of widely used natural standards, which are considered to

have a d value of zero. The transformation of absolute (percentage) values into relative (to a certain standard) delta values is used because the absolute differences between samples and standard are quite small at natural abundance levels and might appear only in the third or fourth decimal place if the percentage values were reported. The isotopic ratios of H and O, depending on the amount of drinking water consumed, cannot be easily falsified or masked by feeding diet ingredients from an origin outside of the region. Additionally, a method based on the properties of drinking water is not influenced by grazing versus feeding in a barn. In turn, the isotopic ratios of C and N give some indication of the type of diet fed, particularly when the diet differs in the proportions of C3 and C4 plants. The isotopic ratios of C and N are often also characteristic for production systems and feeding intensity (increasing maize proportions with intensive fattening of cattle) and the isotopic signature of previous feeding seems to persist (Renou et al., 2004). Stable isotope combined with chemometric tools has been used successfully for the authentication of dairy products (Fortunato et al., 2004; Manca et al., 2001; Pillonel et al., 2003a, 2005; Rossmann et al., 2000). On the basis of the O and H isotopic ratios, it was possible to differentiate between milks produced in plain (altitude 200 m) and those produced in mountain (altitude 1100 m) (Renou et al., 2004). The stable isotope analysis combined mostly with multivariate statistical analysis has demonstrated its ability to authenticate (i) meat samples (Nardoto et al., 2011; Osorio et al., 2011); (ii) lambs fed herbage or concentrate (Moreno-Rojas et al., 2008); (iii) olive oils (Royer et al., 1999); (iv) eggs laid by caged, barn, free range, and organic hens (Rogers, 2009); and (v) various foods with different PDO (Gonzalez et al., 2009). All the above-mentioned research studies pointed out the ability of the stable isotope to be used as a very potent tool solving problems related, particularly, to the origin assignment.

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However, the stable isotope approach also has some important constraints. Indeed, conclusions made from results using the stable isotope must be based on uniform environment features (e.g., climate, altitude, and distance from oceans) allowing few or no differences in isotopic ratios of the food products. Therefore, food products from animals originating from different, but climatically or geologically similar areas might have an identical isotopic signature.

15.2.3. Enzymes in Food Authentication Enzymes are essential constituents of living organisms and are responsible for postharvest and postmortem changes in foods. Enzyme reactions are frequently associated with a deterioration of food quality; it concerns, for example, the lipase, protease, polyphenol oxidase leading to undesirable color changes, and the formation of bitter peptides. In food products, enzymes have been used in several applications following the release of specific compounds that could characterize the quality of the product. It concerns (i) pancreatic lipase which is used for the determination of position partition of fatty acids in triglycerides (Damiani et al., 2006); (ii) determination of intensity of heat treatment such as alkaline phosphatase and peroxidase used in dairy products (Vamvakaki et al., 2006); (iii) assessment of fruit juices’ freshness (Hirsch and Carle, 2005); and (iv) determination of the amounts of several components in various food products (Sto´j and Targonski, 2006), etc. Enzymes are involved in the determination of various analytes using enzyme-linked immunosorbent assays (ELISAs). This latter has been used by the research group of Asensio for rapid identification of grouper and wrecker fish meals (Asensio and Samaniego, 2009; Asensio et al., 2008a,b) as well as for the authentication of foods (Asensio et al., 2008c). The technique has been successfully used for the detection of

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sunflower pollen in honey samples (Baroni et al., 2004) and the identification of meat products (Djurdjevic et al., 2005; Giovannacci et al., 2004) and gum arabic (Ireland et al., 2004).

15.2.4. DNA-Based Methods in Food Authentication DNA-based methods are of increasing importance for the determination of the quality of food products. The PCR has been used for the (i) authentication of Halal meat extracts (Farrokhi and Jafari Joozani, 2011), medicinal plant species (Moon et al., 2010), fruit juices (Scoot and Knight, 2009), milk species in cheeses (Mayer, 2005), Greek fish roe (Klossa-Kilia et al., 2002), and olive oil (Gime´nez et al., 2010); (ii) detection of ostrich mislabeling in meat products from the retail market (Rojas et al., 2011) and chicken in meat mixtures (Hopwood et al., 1999); and (iii) differentiation of salmon and other fish species (Nebola et al., 2010; Rasmussen et al., 2010). The use of PCR for quality and authenticity control of meat and meat products and fish and seafood products has been extensively reviewed by Rodrı´guez-Ramı´rez et al. (2011). For example, the authentication of scombroid products, from fresh fish to canned products, was determined by forensically informative nucleotide sequencing (FINS). This technique was used for the detection of mislabeling in the marketing of scombroid species as well as for the assessment of seafood traceability of these products such as salmon, trout, and bream or hake species (Espin˜eira et al., 2009).

15.2.5. Differential Scanning Calorimetry Differential scanning calorimetry (DSC) is a thermoanalytical technique in which the difference in the amount of heat required to increase the temperature of a sample and reference is measured as a function of temperature. It is a well-established measuring method that is

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utilized on a large scale in different areas of research, development, and quality inspection and testing. Thermal effects can be quickly identified and the relevant temperature and the characteristic caloric values determined using substance quantities in the milligram range. Measurement values obtained by DSC allow heat capacity, heat of transition kinetic data, purity, and glass transition to be determined. DSC curves serve to identify substances (Ho¨hne et al., 1996). When a material undergoes a change in physical state such as melting or transition from one crystalline form to another, or when a material reacts chemically, heat is either absorbed or liberated. According to Lund (1983), DSC offers a tremendous potential for studying physico-chemical changes that occur in foods. DSC is characterized by its usefulness for analyzing phase changes. Reactions that can lead to such phase changes are crystallization of water (melting and freezing), and evaporation of water and certain chemical reactions, for example, protein denaturation. DSC has been used to study the oxidative stability of edible oils (Tan et al., 2002), determine the traceability of virgin olive oil (Angiuli et al., 2006), characterize tropical oils (Dyszel and Baish, 1992), as well as authenticate olive oils (Ferrari et al., 2007). In dairy products, DSC has been used for detecting penicillin G, ampicillin, and tetracycline in ultra-high-temperature whole milk (Yildiz and Unluturk, 2009) and for differentiating between mozzarella cheeses made from cow’s milk and those made with water buffalo milk (Tunick and Malin, 1997). The technique has been used with success for dynamic thermal denaturation of fish myosins (Chan et al., 1992).

15.3. CONCLUSIONS Different analytical techniques, such as chromatography (GC, HPLC), UVeVis, fluorescence, infrared (NIR and MIR), EN, NMR,

stable isotope analysis, enzymes, DNA-based methods and differential scanning calorimetry, combined mostly with chemometric tools have been used for the authentication of various food products and the detection of adulteration. In this context, the combination of different analytical techniques (e.g., UVeVis, NIR, MIR, EN, NMR, fluorescence) with chromatography, stable isotope analysis, or DNA-based methods could provide valuable additional information related to the quality and/or authenticity of food products. An increased research effort in the field rapid spectroscopic methods could address some of the challenges of the measurements of food products and further explore the physicochemical changes that are (i) mostly not fully understood and (ii) responsible for the modification of the stability, organoleptic, and/or typicality of food products. It is hoped that reading this chapter constituting a brief introduction related to food authenticity and fraud will stimulate readers’ interest in the chemical analysis of food: techniques and application where each technique is described in detail in volume 1 and its application in volume 2.

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