2010 Global Perspective 6 Part

8/3/2019 2010 Global Perspective 6 Part

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Food Authenticity

Profiling Foods

Michal Godula


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What is Food Authenticity?

Food authenticity is about misrepresentation by either

mislabeling or by adulterating usually with lower cost

material

Typical examples:

Wine authenticity illegal sugar addition to grape juiceAddition of sugar to honey

Addition of hazelnut oil to olive oils

Mislabeling geographical origin (wine, olive oil)

Mislabeling organic food products

Adulteration of meat with cheaper species


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Major Food Authentication Schemes and Systems

Protected Designation of Origin (PDO)

covers agricultural products and foodstuffs which are

produced, processed and prepared in a given

geographical area using recognized know-how.

Protected Geographical Indication (PGI)

covers agricultural products and foodstuffs closely linked

to the geographical area. At least one of the stages ofproduction, processing or preparation takes place in the

area.

Traditional Speciality Guaranteed (TSG)

highlights traditional character

http://ec.europa.eu/agriculture/quality/

Council Regulation (EC)

No 510/2006 of 20 March 2006

Council Regulation (EC)No 509/2006 of 20 March

2006


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DOOR Database

More than 1200 entries

Different countries participate

Number of different foods listed

Typically:olive oils, wines, cheeses, honey, beer etc


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Food Authentication Challenges

Chemically identical foods or identical chemical entities

Unique marker compounds rarely found - more often smallanalytical differences (isotopic patterns)

Large natural variability based on climatic conditions,fertilizers used, variety, processing

Techniques must be able to distinguish small differences

Databases of authentic foods must be available to

understand natural variability


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Which Techniques Can be Applied?

Technique Parameters measured

Infrared spectroscopy (NIR, MIR) Spectral profile, characteristic frequencies

Raman spectroscopy Spectral profile, characteristic frequencies

Nuclear Magnetic Resonance Spectral profile, characteristic frequencies

Atomic absorption and emissionspectroscopy, ICP/MS

Elemental composition

Mass spectrometry (GC/MS, LC/MS) Volatile components, phenoliccompounds

Chromatography (HPLC/RID) Amino acids, carbohydrates, phenoliccompounds

IRMS Stable Isotope Ratios


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Other Approaches

DNA based methods like PCR

used mainly for adulteration of meat and meat based products

- addition of chicken and pork meat into minced beef

- differentiation of cattle breed

- adulteration of foie gras with chicken*

Immunology based approach

most of the techniques based on ELISA detection of specific proteins- presence of vegetable proteins in milk or meat

- adulteration of sheep/goat milk with cow milk

* L.M. Reid et al. / Trends in Food Science & Technology 17 (2006) 344353


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Data Analysis: Chemometric Approach

Typically large number of variables involved, ie delta value, elemental

composition, mass spectra, compound concentration etc

Multivariate analysis must be applied

Supervised or unsupervised methodsUnsupervised: classification of sample without any knowledge about the

origin

Supervised: similarity of unknown to authentic material

Choosing appropriate approach is the key to successful analysis

Gonzalves, A, Trends in Analytical Chemistry, Vol. 28, No. 11, 2009


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Chemometric Methods Used

Unsupervised methods ANOVA

MANOVA

Principal Component Analysis (PCA) - reduces dimensionality Cluster Analysis (CA) - grouping of samples based on their similarity

Supervised methods (discriminant techniques)

Linear discriminant analysis (LDA) - characterize or separate two or more

classes

Partial Least Squares (PLS) - fundamental relations between two matrices

Artificial Neural Networks (ANN) - complex relationships modelling


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Isotopes - Sources of Variation


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H2O

HDO

HDO

H2O

Evaporation & Reprecipitation

Climatic Factors Affecting D/H Ratio


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Interpolated 2H of Precipitation

Produced by James Elhringer (University of Utah)


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IRMS Information Delivered

Precise Isotope Ratios

Element minor Isotope natural abundance [%]

Hydrogen 2H (D) 0.01557Carbon 13C 1.11140

Nitrogen 15N 0.36630Oxygen 18O 0.20004Sulfur 34S 4.21500

others

Thats where the information is


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Multiple Element

Isotope Ratio

Mass Spectrometry

H2

N2

CO

CO2

HH22

NN22

COCO

COCO22

13C1313CC18O1818OO

18

O1818

OO

15N1515NN

DDD

CSIACSIACompound Specific

Isotope Analysis

BSIABSIA

Bulk StableIsotope Analysis

GasBenchGasBenchGas Specific

Isotope Analysis

Authenticity Control of Food and Beverages


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Capillary Reactor

DELTAplusXP

GC SeparationElemental AnalyzerConversion

Ref. gases

Open

Split

Reactor

On-line

ConversionGC Separation

of complex mixtures

2H and 18O

or13C and 15N and 34S

2H or18O or13C or15N

of all Compounds

BSIABSIABulkBulk

StableStable

IsotopeIsotope

AnalysisAnalysis

CSIACSIACompoundCompound

SpecificSpecific

IsotopeIsotope

AnalysisAnalysis

DELTAplusXP

Ref. gases

Open

Split

Different Approaches to IRMS


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Sample Introduction Conversion to Simple Gases

BSIA: Elemental Analyzer (EA) for C, N, S CO2, SO2, N2

BSIA: High temperature conversion (TC/EA) for C, H CO2, H2

CSIA: High temperature conversion (GC/TC) for C,H CO2, H2

CnTC/EA

Hx Oy H2x/2

COy

Cn-y

>1400 C

irm GC/MS0.015 %

2H

99.985 %H2

HD

18O


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ion source

magnet

m/z 2 (H2)m/z 3 (HD)

universal triple collector

for N2, CO, O2,CO2, SO2

m/z 4

under continuous flow conditions

4He is about 107 times more

abundant than HD

with

energy filter

Multi Collectors for Simultaneous Detection

H2N2CO

O2

CO2SO2

HH22NN22COCO

OO22

COCO22SOSO22

Principles of Multicollector IRMS

C d S ifi I t A l i GC I li k


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Compound Specific Isotope Analysis - GC Isolink

Advantages of irm-GC/MS with GC-ISoLinkAllows simultaneous determination of C, N and H within one sequence

Combustion (C, N) x high temperature conversion (H)

Provides chromatographic profile of the sample AND isotopic ratio information

CSIA E l T il Fi i ti b GC/C IRMS


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CSIA Examples Tequila Fingerprinting by GC/C-IRMS

H Ad lt ti


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Honey Adulteration

Problem: addition of cheap sugarsto honey

Current analytical approach:

EA-IRMS to assess 13C value of

honey and its protein fraction (limitcca 7% of C4 sugar addition)

Solution: irm-LC/MS using IsoLink interface allows:

- comparison of13C value of different sugars

- determination of the sugar pattern

TMO application note 30024 or Testing honey adulteration by13 C-EA/LC-IRMS, Elflein L., Apidologie (2008),

H Ad lt ti E l


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Honey Adulteration Examples

Honey 1 Honey 2

Honey 5

TMO appnot e30024

Assessing the Origin of Cheeses in Europe


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Assessing the Origin of Cheeses in Europe

Measurands taken: Stable isotope ratios, major, trace and radioactive

elements

Techniques used: IRMS, AAS, ICP-MS

Cheese

Lyophilization

Extraction H2O

IRMS

Fat extraction

Hydrolysis to

glycerol

Lyophilization

Extraction,

H2O pH 4.3

Dry insoluble

fraction

Wet Digestion

Dilution

ICP/MS, AAS

Pillonel L et al, Lebensm.-Wiss. u.-Technol. 36 (2003) 615623

Assessing the Cheese Origin in Europe


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Assessing the Cheese Origin in Europe

Pillonel L et al, Lebensm.-Wiss. u.-Technol. 36 (2003) 615623

Infrared Spectroscopy


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Infrared Spectroscopy

Benefits:Ease of use

Fast response

No or limited sample preparation

Low price Limitations:

Lower sensitivity

Small spectral differences

Typical examples:

Near Infrared Spectroscopy (NIR, FT-NIR)

Different Sampling accessories: Sample cup spinner heterogeneousmaterials, SabIR Fiber Optic Probe material identification, Viscous

Liquid Sampler syrups, suspensions, Softgel detector (Gum), Fiber

Optic probes in-process testing of solids and liquids

FT NIR to Assess Geographic Origin of Olive Oils


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FT-NIR to Assess Geographic Origin of Olive Oils

Antaris FT-NIR with sample cup spinner

Direct measurement in 2mm path length cell

4 cm-1 resolution

Spectral range - 10000 and 4500 cm-1

O. Galtier et al.; Analytica Chimica Acta 595 (2007) 136144



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Quantification of fatty acids and triglycerols

Classification in registered designation origin

O. Galtier et al.; Analytica Chimica Acta 595 (2007) 136144

Pros/Cons of Different Analytical Approaches


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Pros/Cons of Different Analytical Approaches

MethodsSample preparation

costsSpeed

Investment andoperating costs

Probability of success

NMR

IRMS

ChromatographyGC/MS, LC/MS

Infrared Spectroscopy(NIR. IR, Raman)

Elemental analysis(ICP/MS, AAS, ICP)

Which Technique is the Most Appropriate?


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Which Technique is the Most Appropriate?

Isotope Ratio Mass Spectrometry considered as standard

approach

Organic mass spectrometry gaining popularity

Elemental analysis can provide additional information to

IRMS

Non-destructive techniques offer high speed and almost no

sample preparation (FTNIR, FTIR, Raman)

Sophisticated data analysis - chemometric approaches

Thermo Scientific offers solution for all authenticity analysis

approaches

2010 Global Perspective 6 Part

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