Food Authentication

Constantinos A. Georgiou, Agricultural University of Athens, Greece Georgios P. Danezis, Agricultural University of Athens, Greece

List of Contributors xv

Preface xix

Part A Introduction and Status 1

1 Introduction, Definitions and Legislation 3
Demetrios G. Sotirchos, Georgios P. Danezis and Constantinos A. Georgiou

1.1 Introduction 3

1.2 Definitions 4

1.2.1 Food Origin 4

1.2.2 Label 4

1.2.3 Adulteration and Fraud 4

1.3 Geographical Indications 5

1.3.1 PDO, PGI, and TSG 6

1.3.2 Wines 8

1.4 Organics 11

1.5 Conclusion 14

References 14

Legislation Acts 16

2 Food Authentication by Numbers 19
Georgios P. Danezis and Constantinos A. Georgiou

2.1 Introduction 19

2.2 Research Trends 19

2.3 Analytical Techniques 20

2.4 Countries 22

2.5 Journals 24

References 24

Part B Consumer Attitudes Towards Authentic Food and Market Analysis 25

3 The Concept of Authenticity and its Relevance to Consumers: Country and Place Branding in the Context of Food Authenticity 27
Athanasios Krystallis

3.1 Introduction: The Challenge of Authenticity 27

3.1.1 The Origin of Authenticity and its Marketing Relevance 27

3.1.2 The Philosophy of Authenticity 29

3.2 Countries as Brands: The Country-of-Origin (COO) Effect on Product Choices 30

3.2.1 Do Places get the Reputation they Deserve? 30

3.2.2 Countries as Brands 31

3.2.3 Impact of Country Names on Attitudes Towards Products 33

3.3 Place Branding: Geographic Indication Labels and their Effect on Food Choice 42

3.3.1 Mediterranean Diet: A Typical Place Marketing Paradigm 42

3.3.2 Regulatory Initiatives of Place Branding: Designation of Origin Labelled (DOL) Food and the PDO/PGI/TSG Schemes 50

3.3.3 The Industry’s Response: Is Place Branding a Panacea? 62

3.4 Conclusion: Towards a Definiton of Authenticity in a Business Context 75

Acknowledgements 77

References 78

Part C Geographical, Botanical, and Species Origin, Method of Production and Food Frauds Detection 83

4 Elemental Fingerprinting 85
Georgios P. Danezis, Constantinos A. Papachristidis and Constantinos A. Georgiou

4.1 Introduction 85

4.2 Elemental Techniques 86

4.2.1 ICP‐MS 86

4.2.1.1 Operation Principle: Main Features 86

4.2.1.2 Mass Analyzers 87

4.2.1.3 Interferences 90

4.2.1.4 ICP‐MS versus Other Techniques 92

4.2.2 ICP‐AES and Other Techniques 94

4.3 Sample Preparation: Pretreatment 95

4.3.1 Digestion 95

4.3.2 Direct Solid Sampling Analysis 97

4.3.3 Sampling Problems and Remedies 97

4.3.3.1 Wines and Beverages 97

4.3.3.2 Food Waste Water 98

4.3.3.3 Vegetables and Mushrooms 98

4.3.3.4 Fruits 98

4.3.3.5 Cereals 98

4.3.3.6 Fats and Oils 98

4.3.3.7 Meat 99

4.3.3.8 Seafood 99

4.3.3.9 Dairy Products 99

4.3.3.10 Honey 99

4.4 Applications 99

4.4.1 Elemental Fingerprinting Rational and Trends 99

4.4.2 Elemental Fingerprinting Authenticates Various Food Products 101

4.4.2.1 Wines 103

4.4.2.2 Beverages 103

4.4.2.3 Fruits and Vegetables 103

4.4.2.4 Oils 104

4.4.2.5 Cereals – Pulses 105

4.4.2.6 Dairy Products 105

4.4.2.7 Meat 106

4.4.2.8 Fish and Fish Products 106

4.4.2.9 Honey 107

4.4.2.10 Coffee and Tea 107

4.4.2.11 Spices – Food Ingredients 108

4.4.2.12 Organic Foods 108

4.4.3 Chemometrics 109

4.5 Conclusions and Outlook 111

References 111

5 Isotopic Fingerprinting 117

5.1 Light Isotopes 118
Dana Alina Magdas and Gabriela Cristea

5.1.1 Introduction 118

5.1.2 Application of Stable Isotope Ratios in Food Control 119

5.1.2.1 Fruit Juices 119

5.1.2.2 Wines and Sparkling Wines 121

5.1.2.3 Mineral Waters 122

5.1.2.4 Vanilla 124

5.1.2.5 Spices 125

5.1.2.6 Fish 125

5.1.2.7 Beef 126

References 127

5.2 Heavy Isotopes 131
Andrea Marchetti, Caterina Durante and Lucia Bertacchini

5.2.1 Introduction 131

5.2.2 Quality vs. Geographical Traceability 132

5.2.3 The Isotopic Approach to Food Traceability 134

5.2.3.1 Traceability Models Based on the Use of 87Sr/86Sr 136

5.2.3.2 Mass Bias 137

5.2.3.3 Correction of the Mass‐Dependent Bias 138

5.2.4 Bioavailability 141

5.2.4.1 Applications 142

5.2.4.2 Case Study: Extra Virgin Olive Oils 147

5.2.4.2.1 Sampling and Sample Treatment 148

5.2.4.2.2 Soil Sampling and Treatment 149

5.2.4.2.3 Branch and Olive Treatment 150

5.2.4.2.4 Analytical Determination: Strontium Isotope Ratio 150

5.2.4.2.5 Instrumentation 151

5.2.4.2.6 Accuracy and Precision Evaluation 152

5.2.4.2.7 87Sr/86 Sr for Soil, Branch and Olive Samples 152

5.2.4.3 Case Study: Lambruschi PDO 155

5.2.4.3.1 Sampling and Sample Treatment 156

5.2.4.3.2 Lambrusco Winemaking Sampling 157

5.2.4.3.3 Soil, Branch and Juice Sampling 159

5.2.4.3.4 Soil, Branch and Juice Pretreatments 160

5.2.4.3.5 87Sr/86 Sr in Lambrusco Winemaking 160

5.2.4.3.6 87Sr/86 Sr from Soils to Lambrusco Wines 161

References 165

Legislation 176

6 Nuclear Magnetic Resonance – Metabolomics 177
Donatella Capitani, Anatoly P. Sobolev and Luisa Mannina

6.1 Introduction 177

6.2 Olive Oils 179

6.3 NMR for Investigating Fruit Metabolomics 182

6.3.1 NMR Metabolomics Applied to Kiwifruits 183

6.3.2 NMR Metabolomics Applied to Blueberries 188

6.4 NMR Metabolomics of Transgenic Vegetable Food 190

References 193

7 Chromatography 199

7.1 Introduction to Chromatography – Techniques 200
Joana Santos and M. Beatriz P.P. Oliveira

7.1.1 Introduction 200

7.1.2 Chromatography 202

7.1.2.1 HPLC and Hyphenated Techniques 203

7.1.2.1.1 Liquid Chromatography–Mass Spectrometry 210

7.1.2.2 GC and Hyphenated Techniques 215

7.1.2.2.1 Gas Chromatography–Mass Spectrometry 223

Acknowledgements 224

References 225

7.2 Chromatography – Applications 233
Ana I. Ruiz‐Matute, M. Luz Sanz, F. Javier Moreno and Marta Corzo‐Martínez

7.2.1 Introduction 233

7.2.2 Carbohydrates 233

7.2.3 Food Proteins and Peptides 240

7.2.4 Fatty Acids and Triacylglicerols 246

7.2.5 Volatile Compounds 249

7.2.6 Phenolic Compounds 256

7.2.7 Organic Acids 258

7.2.8 Conclusions 258

Acknowledgements 259

References 259

8 Vibrational and Fluorescence Spectroscopy 277

8.1 Vibrational Spectroscopy 278
Daniel Cozzolino

8.1.1 Introduction 278

8.1.2 Instrumentation and Software 280

8.1.3 Applications of Vibrational Spectroscopy in Food Authenticity 284

8.1.3.1 Fish and Seafood 284

8.1.3.2 Fish and Meat By‐Products 284

8.1.3.3 Wine 285

8.1.3.4 Cereal grains 287

8.1.3.5 Honey 288

8.1.3.6 Meat and Meat Products 291

8.1.4 Concluding Remarks and Future Perspectives 291

References 292

8.2 Fluorescence Spectroscopy 298
Georgios Mousdis and Fotini Mellou

8.2.1 Fluorescence 298

8.2.1.1 Basic Principles 298

8.2.1.2 Instrumentation 299

8.2.1.3 Types of Fluorescence Spectra 301

8.2.1.4 Factors Affecting Fluorescence Intensity 302

8.2.1.4.1 Concentration and Inner Filter Effect 302

8.2.1.4.2 Quenching 303

8.2.1.4.3 Scatter 303

8.2.1.4.4 Molecular Environment 303

8.2.2 Chemometrics 303

8.2.3 Applications in Foods and Drinks 305

8.2.3.1 Edible Oils 305

8.2.3.2 Meat and Meat Products 307

8.2.3.3 Fish and Fish Products 308

8.2.3.4 Eggs 309

8.2.3.5 Caviar 309

8.2.3.6 Milk and Cheese Products 309

8.2.3.7 Cereals 311

8.2.3.8 Honey, Sugar, and Syrups 312

8.2.3.9 Fruits 313

8.2.3.10 Alcoholic Beverages 313

8.2.4 Conclusions and Perspectives 315

References 315

9 Molecular Techniques – Genomics and Proteomics 325
Ignacio Ortea, Karola Böhme, Pilar Calo‐Mata and Jorge Barros‐Velázquez

9.1 Introduction 325

9.2 DNA‐Based Methods 326

9.2.1 Randomly Amplified Polymorphic DNA (RAPD) 328

9.2.2 Simple Sequence Repeats (SSR) 328

9.2.3 DNA Sequencing 330

9.2.4 Multiplex PCR with Species‐Specific Primers 331

9.2.5 Real‐Time PCR 331

9.2.6 PCR‐SSCP 333

9.2.7 PCR‐RFLP 333

9.2.8 DNA Hybridization and Microarrays 335

9.2.9 Peptide Nucleic Acid (PNA) ‐Based Approaches 335

9.3 Proteomics for Species and Geographical Origin Authentication 336

9.3.1 Gel‐Based Methods 337

9.3.2 MS‐Based Methods 341

9.3.3 MS/MS‐Based Methods 342

9.3.4 Directed Approaches 342

9.4 Future Trends 343

References 344

10 Immunological Techniques 355
Yun‐Hwa Peggy Hsieh and Jack Appiah Ofori

10.1 Introduction 355

10.2 Immunoassays 356

10.3 Meat Speciation 357

10.4 Fish and Shellfish Authentication 362

10.5 Fruit Juices 364

10.6 Botanical Origin of Honey 365

10.7 Irradiated and Genetically Modified Foods 366

10.7.1 Detection of Irradiated Foods 367

10.7.2 Detection of GM Foods 368

10.8 Conclusions 369

References 369

11 Sensory Analysis 377
Laura Aceña, Montserrat Mestres, Olga Busto and Ricard Boqué

11.1 Introduction 377

11.2 Organoleptic Evaluation and Food Quality 377

11.3 Human Sensory Panels: Response and Subjectivity 378

11.4 Instrumental Sensory Analysis 378

11.4.1 Looking for Objectivity 378

11.4.2 Gas Chromatography‐Olfactometry (GCO) 379

11.4.2.1 GCO Device: How it Works 379

11.4.2.2 Olfactometric Techniques 380

11.4.2.3 Applications 380

11.4.3 Electronic Nose 381

11.4.3.1 Emulating the sense of smell 381

11.4.3.2 Types of Electronic Noses: Instrumental Aspects 381

11.4.3.3 Applications of E‐Noses in Food Analysis 382

11.4.4 Electronic Tongue 382

11.4.4.1 Emulating the Sense of Taste 382

11.4.4.2 Types of Electronic Tongues 382

11.4.5 Multivariate Data Analysis 384

11.5 Future Trends 386

References 387

12 MALDI Mass Spectrometry: A Promising Non-Chromatographic Technique 393
Cosima D. Calvano, Antonio Monopoli and Carlo G. Zambonin

12.1 Introduction 393

12.2 MALDI MS Principles 394

12.3 MALDI-TOF-MS for Food Proteins and Peptides Analysis 396

12.4 MALDI-TOF-MS for Lipids Analysis 397

12.5 MALDI-TOF-MS for Illegal Mixture Detection 397

12.5.1 Hazelnut Oil in Olive Oil: Lipid Analysis 397

12.5.2 Hazelnut Oil in Olive Oil: Protein Analysis 399

12.5.3 Cow Milk in Goat and Sheep Milk: Protein Analysis 399

12.5.4 Powder Milk in Liquid Milk: Protein and Lipid Analysis 401

12.6 MALDI-TOF-MS for Microbial Contamination Detection 402

Acknowledgements 404

References 404

13 Detection of Food Processing Techniques 413
Aristidis S. Tsagkaris, Georgios P. Danezis and Constantinos A. Georgiou

13.1 Introduction 413

13.2 Freezing–Thawing 414

13.2.1 Methods of Detection 414

13.3 Irradiation 415

13.3.1 Physical Methods for Irradiation Detection 417

13.3.2 Chemical Methods for Irradiation Detection 418

13.3.3 Biological Methods for Irradiation Detection 418

13.4 Heating Techniques 418

13.4.1 Methods of Detection 419

13.5 Conclusion 420

References 420

14 Adulteration Stories 423
Aristidis S. Tsagkaris, Constantinos A. Papachristidis, Georgios P. Danezis and Constantinos A. Georgiou

14.1 Introduction 423

14.2 A Flashback 424

14.3 Food Fraud Incidents 425

14.3.1 Bootleg Liquor, India, 2015 425

14.3.2 Horse Meat Scandal, EU, 2013 425

14.3.3 Adulteration with Melamine, China, 2008 and 2007 427

14.3.4 Food Extension in the ConAgra Incident, USA, 1997 427

14.3.5 Low‐Cost Mixture Marketed as 100% Pure Apple Juice in the Beech‐nut Incident, USA, 1987 427

14.3.6 Arsenic in Beer, UK, 1880 and 1900 428

14.3.7 Bright Poisonous Inorganic Colors for Sweets, UK, 1858 428

14.3.8 Adulteration of Bread with Alum in London, UK, 1839 429

14.4 Conclusions 429

References 429

15 Organic Foods 431
Yolanda Picó

15.1 Introduction 431

15.2 Biochemical Markers and Analytical Platforms 432

15.3 Sampling 433

15.4 Sample Preparation and Extraction 440

15.5 Instrumental Analysis 441

15.5.1 Multi‐Elemental Composition 441

15.5.2 Stable Isotope Analysis 441

15.5.3 Biocrystallisation 443

15.5.4 Infrared Spectroscopy 443

15.5.5 Proton Transfer Reaction Mass Spectrometry (PTR‐MS) 444

15.5.6 Gas Chromatography–Mass Spectrometry (GC‐MS) 444

15.5.7 Liquid Chromatography–Mass Spectrometry (LC-MS) 445

15.5.8 Direct Analysis in Real‐Time High‐Resolution Mass Spectrometry (DART‐HRMS) 446

15.5.9 Biological Methods 447

15.6 Data Analysis 447

15.7 Conclusions and Future Trends 448

References 449

16 Screening and High-Throughput Multi-Contaminants Methods 453
Natasa P. Kalogiouri and Nikolaos S. Thomaidis

16.1 Introduction 453

16.2 Sample Preparation 454

16.2.1 Sample Extraction 454

16.2.1.1 Solid‐Phase Micro‐Extraction 454

16.2.1.2 Matrix Solid‐Phase Dispersion Extraction 460

16.2.1.3 Supercritical Fluid Extraction 460

16.2.1.4 Accelerated Solvent Extraction 461

16.2.1.5 Liquid–Liquid Extraction 461

16.2.1.6 QuEChERS 461

16.2.1.7 Microwave‐Assisted Extraction 462

16.2.2 Sample Clean‐Up 462

16.2.2.1 Gel Permeation Chromatography 463

16.2.2.2 Solid‐Phase Extraction 463

16.2.2.3 Dispersive Solid‐Phase Extraction 463

16.3 Separation and Detection 464

16.3.1 Gas Chromatography Coupled to Conventional Detectors and Mass Spectrometry 464

16.3.2 Liquid Chromatography–Mass Spectrometry 465

16.3.3 Ambient Mass Spectrometry 468

16.3.4 Immunoassays 468

16.3.5 Biosensors 469

16.4 Conclusions 469

References 470

17 Chemometrics – Bioinformatics 481
Marina Cocchi, Mario Li Vigni and Caterina Durante

17.1 The Role of Chemometrics in Food Authentication 481

17.1.1 Authenticity Issues 482

17.1.2 Nature and Challenge of Datasets Arising from Fingerprinting Techniques 482

17.2 Methodology 483

17.2.1 Exploratory Data Analysis 484

17.2.1.1 PCA in Practice 488

17.2.2 Classification and Discrimination 489

17.2.2.1 PLS‐DA 492

17.2.2.2 SIMCA 493

17.2.2.3 Assessing Classification Performance 494

17.2.2.4 Assessing Model Dimensionality 495

17.2.2.5 Case Study 496

17.2.3 Multiway Techniques 497

17.2.3.1 An Illustrative Example 500

17.2.4 Assessing Feature Relevance 500

17.2.4.1 PCA Models 500

17.2.4.2 PLS, PLS‐DA Models 503

17.2.4.3 SIMCA Model 506

17.2.5 Data Fusion 506

17.2.5.1 DF Application Example 507

17.2.6 ANN‐Based Methodology 508

17.2.6.1 A Few Hints About ANN Methodology 509

17.2.6.2 A Working Example 511

References 513

18 Conclusions and Prospects 519
Georgios P. Danezis and Constantinos A. Georgiou

References 521

Index 527