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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
FT-NIR to Assess Geographic Origin of Olive Oils
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FT-NIR to Assess Geographic Origin of Olive Oils
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