The title is in blue Arial 32 bold

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• Recent Applications of Stable Isotopes Techniques
  
• to check the authenticity of food products

Eric Jamin Authenticity Analytical Unit
Manager Eurofins Scientific, Nantes
(France) ericjamin_at_eurofins.com Phone (33)
2 51 83 21 00
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Eurofins laboratories the origin...

• 1981 Invention of the SNIF-NMR method allowing
  the determination of the botanical origin of
  alcohol (Pr. G and M Martin, Nantes University)
• Creation of Eurofins Laboratory, specializing in
  the application of isotopic methods
• 1997 Introduction in Paris stock exchange
• 2010 Network of 150 laboratories present in 30
  countries, gt8000 staff, 40,000 methods

• Nantes (France) Competence Center for
  authenticity
• and isotopic measurements

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Authenticity
Why Is it necessary to check ?

• Verify raw materials
• Check new suppliers
• Protect brand image

and avoid headlines like .
THE INDEPENDENT, February 1991
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ORANGE cases
A wide range of adulteration issues
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How to check? The analytical tools available

• Compositional analysis
• Identification and quantification of major and
  minor components
• Stable isotope analysis
• Origin of the components
• Molecular biology and immunology
• plant and animal species identification
• Profiling methods
• Spectroscopic patterns of global matrices applied
  for screening

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Stable isotopes at natural abundance
Food products are composed of 4 main elements C,
H, O and N.
These elements are naturally present in several
isotopic forms (same atomic number, different
weights), following a distribution influenced by
natural phenomena and human processes.
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Stable Isotope Analyses
IRMS Isotopic Ratio Mass Spectrometry

• Access to overall isotope ratios of a product or
  constituent
• Combustion or Pyrolysis of the organic product
• Can be coupled to Gas Chromatography unit

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Stable Isotope Analyses
SNIF-NMR ?

• measures non-statistical deuterium distribution
  within a given molecule
• method pioneered by Eurofins Scientific

Site-specific Natural Isotopic Fractionation
studied by deuterium Nuclear Magnetic Resonance
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Isotopic methods recognition
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Stable Isotope Analyses
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Influence of geographical origin on stable
isotope ratios
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Carbon metabolism
Where does the sugar in a plant come from
Carbon dioxide
CO2 (-8 )
C3
C4
most plants values around -25
Gramineae family e.g. sugarcane, maize, values
around -10
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What are the latest improvement of isotopic
methods for fruit juices?

• Use of multi-component profiles to increase the
  sensitivity (narrower ranges of variation)

• Use of multi-element profiles and site-specific
  methods
• to discriminate more sources

• Use of GC-IRMS to analyse flavour compounds
• at low concentrations

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Isotopic analyses in direct fruit juice Improved
detection of sugar addition
J. Agric. Food Chem. (2003) 51, 18, 5202-5206
J. Agric. Food Chem. (2006), Vol. 54, No. 2,
279-284
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Detection of sugar addition in fruit juices
d
d
13
C
13
C
Cane, corn
()
()
Ethanol From sugars
Orange
Beet
Beet
Beet
105.0
115.0
105.0
115.0
85.0
90.0
95.0
100.0
110.0
120.0
125.0
130.0
100.0
110.0
120.0
125.0
130.0
85.0
90.0
95.0
Ethanol from sugars
(D/H)
(D/H)
I (
ppm
)
I (
ppm
)
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NEW application of 13C SNIF-NMR to
pineappleimproved detection of sugar addition
Added C4 sugar
J. Agric. Food Chem. 2010, 58, 1158011585
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Isotopic analyses in direct fruit juice Improved
detection of water addition
J. Agric. Food Chem. (2003) 51, 18, 5202-5206
J. Agric. Food Chem. (2006), Vol. 54, No. 2,
279-284
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Practical application NFC juice authentication
J. Agric. Food Chem. (2003) 51, 18, 5202-5206
J. Agric. Food Chem. (2006), Vol. 54, No. 2,
279-284
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Detection of added ascorbic acid

• Industrial ascorbic acid is derived from sugar
  sources
• Global 13C only detects C4 sources

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Detection of added ascorbic acid(acerola juice
and dietary supplements, etc.)
Fruit processing, July-August 2009, pp 170-175
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Commercial sources of vanillin
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Principal Component Analysis of (D/H)i and
13C/12C ratios of vanillin from various sources
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Geographical origin of plant productWorldwide
origins of RICE
Combines 13C 15N 18O Measurements
Also available for cereals, fruits, wine, coffee,
olive oil, meat, honey, etc
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Salmon / Sea bass / sea bream / Cod etc. Wild
or farmed?
Differentiation of wild and farmed fish by
isotopic methods
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Animal or vegetal source?example Squalane and
squalene
squalene
squalane
mixture
d13C (/VPDB)
-29
-27
-19
-22

• Determination of origin can be performed
• using EA-IRMS on pure compounds or GC-C-IRMS on
  cosmetics

Rapid Commun. Mass Spectrom 2010, 24, 1810-1814
SOFW-Journal 136 1/2-2010
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Conclusion the analytical challenge

• Adulteration is a moving issue due to changes in
  prices, regulation etc. and remains a constant
  challenge for the analyst
• A number of routine applications recognized as
  official methods exist (wines, spirits, fruit
  juices, honey, flavours,)
• Further analytical developments are needed to
  establish always more efficient methods
• Customised projects can be set up to solve
  problems of product origin, suspected
  counterfeits, brand protection, etc.

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Thank you for your attention!
And feel free to contact us, should you need
more information Nantes (France) laboratories
eurofinsfr_at_eurofins.com Tel. [phone]
www.eurofins.com