HOW TO PROTECT YOUR INDUSTRY FROM FOOD FRAUD
EQCS – An example of Industry working together for
everyone’s benefit!
Dr David A Hammond
Fruit Juice and Authenticity Expert
Eurofins
E-mail: [email protected]
or [email protected]
Fixed line 44 (0)118 935 4028
Mobile No. 44 (0)798 965 0953
www.eurofins.com
Eurofins Background
Eurofins started in France (Nantes) over 28 years ago
The Group is a global leader in the bio-analytical testing market
The Group had a turnover of ca 1.4 billion Euros
Employs around 17K people world wide
Operation from 200 sites in 36 countries (Europe, N & S America & Asia)
Use of accredited quality systems
In depth industry expertise in technical & regulatory matters
Large investments in R&D and state-of-the-art equipment
Rapid reaction capabilities
www.eurofins.com
Please Note!!!
 Most suppliers are honest and will supply you with what
you ordered, however, not ALL are!
 If possible only use suppliers that you have visited and
audited or have been approved by a third party (such
SGF IRMA scheme)
http://www.sgf.org/en/home/fks/halbwarenkontrolle/
 This should not preclude you from testing these suppliers
raw materials also
 Everything has a price and if the price is TOO good there
maybe a very good reason why!
www.eurofins.com
What is the Legal Definition of Fruit Juice?
DEFINITIONS {EU regulation 2012 (12)}
1. (a) Fruit juice
“The fermentable but unfermented product obtained from the edible part of
fruit which is sound and ripe, fresh or preserved by chilling or freezing of
one or more kinds mixed together having the characteristic colour, flavour
and taste typical of the juice of the fruit from which it comes.
Flavour, pulp, and cells obtained by suitable physical means from the same
species of fruit may be restored to the juice.
In the case of citrus fruits, the fruit juice must come from the endocarp. Lime
juice, however, may be obtained from the whole fruit.
Where juices are processed from fruits with pips, seeds and peel, parts or
components of pips, seeds and peel shall not be incorporated in the juice.
This provision shall not apply to cases where parts or components of pips,
seeds and peel cannot be removed by good manufacturing practices.
The mixing of fruit juice with fruit purée is authorised in the production of
the fruit juice.”
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What Does This Mean Chemically?
Fruit Juice
Typically
Water
80 to 90%
Sugars
0.1 to 12 % (up to 20%)
Acids
0.3 to 1% (up to 7%)
Potassium
1000 to 3000 mg/l
Sodium
trace to 50 mg/l
Magnesium
40 to 150 mg/l
Calcium
40 to 150 mg/l
Phosphorous
40 to 300 mg/l
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The sugars concentrations seen in different juices
Different juices contain different levels of the three
simple sugars
Juice Type
Sucrose
(g/l)
Orange
Pineapple
Apricot
Apple
Blackcurrant
Pomegranate
Strawberry
40
45
30
10
Trace
Trace
6
Glucose Fructose Gluc to Fruc
(g/l)
(g/l)
ratio
20
23
50
20
27
60
25
20
23
20
60
36
65
28
0.9 - 1.0
0.9 - 1.1
1.0 - 3.0
0.3 - 0.5
0.6 - 0.9
0.8 - 1.0
0.8 - 0.95
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What Types of Adulteration Occurs?
1) Addition of Cheaper Sugar Materials
 Beet sucrose or medium invert to orange juice
 Cane sucrose or medium invert to pineapple juice
 Hydrolysed inulin syrups to apple or pear juice
2) Addition of undeclared acids to fruit juice
 Addition of citric acid to lemon juice
 Addition of L-malic acid low acid apple juice
3) Extension of an Expensive Juice with a Cheaper Material
 Addition of apple or grape juice to Red/Black juices
 Addition of Lime to Lemon
 Addition of Mandarin to Orange juice
4) Break down in GMP
 Blending errors with juices and/or aromas
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What are the Driving Forces? (prices June 2014)
5000
3800
4000
12.2K
4200
23K
3200
3000
2000
1000
2500
2200
2100
1350
3000
1250
650 600
460 370 490
0
www.eurofins.com
BAD NEWS?
1) Late 80’s firm selling apple “juice”, which unfortunately they had
forgotten to add apple juice too!!! Company fined and CEO sent
to jail for 2 yrs for his actions.
Detected by:


lack of chlorogenic acid,
Abnormally high glucose to fructose ratio (ca 1:1)
2) Early 90’s Californian company was selling adulterated orange
juice. Company settled out of court ($8 million)
Detected by:


very low oxygen isotope ratio (δ18O) added water and beet sugar
Presence of naringin in polyphenol profile (presence of grapefruit juice)
www.eurofins.com
Case from the Past
3) 1991 UK MAFF showed 16 out of 21 orange juices were
adulterated. Legal actions failed due to “legal loop holes”
MAFF study detected issues by:
 SNIF-NMR(R) , Carbon isotopic analysis, Oligosaccharide profiling (HPAECPAD), D-malic acid & pulpwash(?)
 Much of the orange juice was coming into the UK via blending
operations in Holland/Belgium and not from the original supplier!!!!
 UK based QA scheme based on spectral absorbance's of orange juice was
compromised!!!
4) Repeat study conducted by UK Government on orange in 1991
showed 7 failures out of 98 samples analysed
5) Whereas in 1997 & 1998 all 186 samples passed.
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And so it went on!!!
6) Early/mid 90’s company in Southern US, selling orange juice into
the schools program, had a fake electrical panel in the factory.
FDA’s analysis showed the product was adulterated but could not
detect problems in the factory. Finally authorities were “tipped
off”, by an employee, about a fake panel which hid a syrup room.
Owner jailed for 8 years!!!
7) 1995/96 apple juices adulterated with sugar syrups.
High fructose corn syrup (HFCS), Invert Syrup (IS) &
Inulin derived syrups (HFIS) were detected
 Oligosaccharide profiling (Cap-GC)
 High fumaric acid (added synthetic L-malic acid)
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Cap-GC test introduced!!
February 23, 1996
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Progress
1) All the bad publicity lead to reduced fruit juice sales around
Europe due to lack of “consumer confidence”
2) Led Industry across Europe to work together to reduce the risk of
adulteration happening
3) 1990 AIJN (European Juice Association) published the “Code of
Practice” for fruit juices
 Lays down compositional guidelines for fruit juices sold in the
EU (www.aijn.org)
4) 1994 draws up guidelines for pan-European Quality Control
Scheme (EQCS)
www.eurofins.com
AIJN code or Practice
Provides consistent criteria for quality and authenticity for fruit and
vegetable juices sold within the EU.
Prepared by experts in the field from industry, academia and
control laboratories
They meet twice a year for ongoing developments
 Reference guides (RG) for new fruits and/or vegetables
 Revisions to existing RG due to unusual regional or seasonal
data etc
RGs Split into two parts
 “A” criteria {Absolute :- legal limits & quality parameters}
 Brix, heavy metals (As, Cd, Hg & Pb), HMF, EtOH, lactic acid…
 “B” criteria {Authenticity parameters}
 Isotopic values, sugars, acids, minerals
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COP is available for a fee (300 Euros/yr) from the AIJN web site
(www.aijn.org)
Full access to the reference guides and other relevant items
 References to suitable methods
 Additional notes about specific methodologies and the
interpretation of the data
 Isotopic data
 Fingerprinting methods
 Anthocyanins
 Oligosaccahrides
 polyphenols
www.eurofins.com
EQCS
Aim is to provide interlocking QA schemes around Europe,
“Quality” assessments based on a uniform set of criteria (AIJN
COP)
Individual scheme audited on a biennial basis by other EQCS
members to ensure even assessments across Europe
Should provide for: Free and fair competition across Europe
 Protects the image of fruit juices and the industry from
adulteration issues that were experienced in the past
 Provides early warning of juice authenticity issues between
schemes
 Co-ordinates with SGF raw materials assurance scheme (IRMA)
www.eurofins.com
EQCS Members
AEAZN: Asociacion Espanola de Autocontrol de Zumos y Nectares (Spain)
AIJN: European Fruit Juice Association (Belgium)
BSDA: British Soft Drinks Association (UK)
DSK: Polish Association of Juice Producers (Poland)
DQCS: Dutch Quality control System (Netherlands)
Qualijus: L’institut Professionnal pour la Qualite des Jus de Fruit (France)
SGF: Sure Global Fair (Germany, regional and Global IRMA)
www.eurofins.com
EQCS schemes
Requires members to adopt AIJN COP as Quality criteria for Juices
Schemes have minimum sampling and analysis requirements
Scheme includes collection of finished products from retail market
 Analysis for quality and authenticity parameters
 Label check to ensure comply with legislation
Involves an annual audit of members factories
 Traceability audit of finished products
 Inspection of blending operations
 Inspection of finished product specifications
 Inspection of raw material specifications
 Collection of finished products and/or raw materials
 Analysis of products for authenticity and quality criteria
 Range of different parameters
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Types of “authenticity” analysis used
Isotopic methods are recommended for the detection of: Sugar addition (beet sucrose, cane sucrose)
 Water addition to NFC juice or “passing off” a FC off as NFC
 Acid addition to juice (lemon or other high acid product)
 Undeclared ascorbic acid addition to juice
Fingerprinting methods
 Analysis of red/black juices for addition of added colours
 Oligosaccharide analysis for sugar syrup addition (HFCS, IS HFIS)
 Polyphenol profiles for citrus and apple looking for mixtures
DNA method for detection of undeclared addition of mandarin to orange
Conventional analysis
1H-NMR as a screening method
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Types of quality analysis used
Assess for toxic heavy metals (As, Cd, Hg & Pb)
Assess levels of other heavy metals in COP (Cu, Fe, Sn & Zn)
Check for levels of pesticide residues in products (both organic
and conventional)
Nitrate levels in juice products
Patulin in apple juices
www.eurofins.com
Typical test screen taken from “old” BCI scheme
Citrus
Apple
x
x
x
Acidity
x
x
x
pH
x
x
x
Na, Ca, Mg & K
x
x
x
Phosphorous
x
x
x
Suc, Gluc & Fruc
x
x
x
L-malic acid
x
x
x
Citric acid
x
x
x
Lactic acid
x
x
Isocitric acid
x
x
A0
Density & Brix
A1
Compositional screen
Sorbitol
B
Pineapple
x
Isotopic screen
SNIF-NMR ® & 13C of ethanol
x
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Typical test screen taken from “old” BCI scheme
C
Citrus
Apple
Pineapple
Oligosaccharides by Cap-GC
x
x
x
Flavanoid glucosides
x
Vitamin C
x
Advanced chemical characterisation
Phenolic compounds (arbutin & phloridzin)
Pectins
D
x
x
Advanced isotopic analysis to detect dilution
18O
E3
x
of juice water and ethanol
x
Advanced isotopic analysis to detect vitamin C addition
13C
analysis of ascorbic acid
x
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Typical test screen taken from “old” BCI scheme
F
Apple
x
x
x
x
Contaminants
Nitrate
Patulin
H
Pineapple
GC-MS analysis to detect flavour addition
GC-MS screening + chiral analysis
G
Citrus
x
x
AIJN heavy metals (8)
x
x
x
Pesticide screen (160 molecules)
x
x
x
Mandarin analysis
Analysis for mandarin by DNA
OJ
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What should industry do?
Have clear specifications which define what you expect
 State compliance with EU regulations
 Mention compliance with AIJN COP
Know and audit your suppliers
If you don’t have the time or expertise sub-contract or use a producer who
is approved by a third party like SGF IRMA
 All IRMA approved suppliers are audited biennially
 Covers quality and authenticity issues
 Corporate and social responsibility issues also
Avoid buying on Spec if at all possible
Have a QA program in place to ensure your “raw” materials or “finished”
products are what is expected (depending where you are in the supply chain)
I will guarantee that if you do no testing you will NEVER detect any
problems. However the Press or the Regulator might coming asking difficult
questions one day in the future, and what will be you legal defence be?
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Authenticity testing
Some of the “bad guys” know exactly what they are doing and
tailor make what they do to make its detection as difficult as possible
You have to use sophisticated methods to catch them!!
This means that authenticity testing is a complex issue
This means it is not cheap either
Costs can be reduced by sharing analysis between competitors by
setting up a Quality Assurance Scheme
The advantage of this is that you can see what non-members are
doing and if they are using any unfair competition practices
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Adulteration Issues seen in the last few years
 Pomegranate {sugar addition, acid addition, juice blending}
 SNIF-NMR®, 13C-IMRS, Oligosaccharide and anthocyanin profiles
 Water addition to NFC orange juice {yield enhancement}

18O/16O
analysis in the sugars and the water of NFC juices
 Lemon juice {substitution of citric acid in the place of lemon juice}

13C-IRMS
and D-IRMS of citric acid
 Non-declared blending of juices {lemon/line, red/black}




Anthocyanin profile in Red/Black juices
Polymethoxyflavones in lemon juice (lime)
DNA method for mandarin in orange
Sorbitol (apple, pear, cherry & aronia)
 Addition of sugar to juice {sugar syrup addition}
 Oligosaccharide profile
 13C-SNIF-NMR
 1H-NMR for rapid cost effective screening of fruit juices
 1H-NMR
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Issues detected with:Sugar and sugar syrup addition
 SNIF-NMR®
 Oligosaccharide profiling
Water addition
 Assess 18O content of water and sugars
Addition of undeclared acid to lemon juice
 13C-IRMS & D-IRMS analysis
Undeclared juice blending
 Anthocyanin profile in red/black juices
 DNA methods in orange
 Polymethoxyflavones in lemon {lime}
Many of the above
 1H-NMR screening (cost effective screening tool)
www.eurofins.com
Detection of sugar addition by stable isotopic analysis
13C/12C
IRMS -5.0
C4
Cane
-10.0
-15.0
-20.0
C3
Unknown
-25.0
Beet
-30.0
-35.0
Fruit reference Zone
Low D content
85.0
90.0
95.0
100.0
SNIF-NMR®
High D content
105.0
110.0
115.0
120.0
125.0
130.0
2H/1H
32
Typical Cap-GC profile for apple
Sucrose
Apple Juice adulterated with HFSI
Inulin marker peaks
Sucrose
Oligosaccharide profiling HFCS
(high fructose corn syrup) added
Isomaltose
Marker peaks
Maltose
35
Issues detected with:Sugar and sugar syrup addition
 SNIF-NMR®
 Oligosaccharide profiling
Water addition
 Assess 18O content of water and sugars
Addition of undeclared acid to lemon juice
 13C-IRMS & D-IRMS analysis
Undeclared juice blending
 Anthocyanin profile in red/black juices
 DNA methods in orange
 Polymethoxyflavones in lemon {lime}
Many of the above
 1H-NMR screening (cost effective screening tool)
Internal isotopic approach for “water” addition
12
11
10
9
8
7
Lab-squeezed
samples
18
d O water (‰)
6
5
4
3
2
Water addition to NFC
Market NFC
juices
1
Market FC
juices
0
-1
-2
Max (95% c.i.)
-3
-4
-5
-6
-7
Authentic orange from a
specific origin
-8
-9
FJ from Conc
-10
d18O ethanol (‰)
Min (95% c.i.)
AIJN limit
Issues detected with:Sugar and sugar syrup addition
 SNIF-NMR®
 Oligosaccharide profiling
Water addition
 Assess 18O content of water and sugars
Addition of undeclared acid to lemon juice
 13C-IRMS & D-IRMS analysis
Undeclared juice blending
 Anthocyanin profile in red/black juices
 DNA methods in orange
 Polymethoxyflavones in lemon {lime}
Many of the above
 1H-NMR screening (cost effective screening tool)
Detection of added C3 and C4 derived citric
acid to lemon juice
Mixed C3 & C4
acids
C3 derived citric acids
C4 derived citric acids
Issues detected with:Sugar and sugar syrup addition
 SNIF-NMR®
 Oligosaccharide profiling
Water addition
 Assess 18O content of water and sugars
Addition of undeclared acid to lemon juice
 13C-IRMS & D-IRMS analysis
Undeclared juice blending
 Anthocyanin profile in red/black juices
 DNA methods in orange
 Polymethoxyflavones in lemon {lime}
Many of the above
 1H-NMR screening (cost effective screening tool)
Typical Pomegranate profile
Delpin-3,5-digluc
Cyan-3,5-digluc
Delpin-3-gluc
Cyn-3-gluc
Pel-3,5-digluc
Unknown
Pel-3-gluc
41
Pomegranate plus black carrot
Acylated “cyanidins”
Orange/mandarin separation (ADNid France)
Polymethoxyflavones (PMFs)
Lemon
Lime
7MeoC
Issues detected with:Sugar and sugar syrup addition
 SNIF-NMR®
 Oligosaccharide profiling
Water addition
 Assess 18O content of water and sugars
Addition of undeclared acid to lemon juice
 13C-IRMS & D-IRMS analysis
Undeclared juice blending
 Anthocyanin profile in red/black juices
 DNA methods in orange
 Polymethoxyflavones in lemon {lime}
Many of the above
 1H-NMR screening (cost effective screening tool)
Authentication Panacea!
For years juice chemists have been on a mission to find the ultimate
method that is :-
 Quick to apply
 Cheap to utilise
 Able to detect all adulterations
Tried :-




FT mid range Infra Red spectroscopy (FT-IR)
Near Infra Red Spectroscopy (NIR)
Pyrolysis mass spectrometry (Py-MS)
UV/Visible and fluorescence spectroscopy
However, all have failed in time to deliver early promise
NMR identifies adulterate OJ
Conclusions
The AIJN COP & EQCS has not stopped all issues
However, there have been far fewer issues & less bad coverage!
However, there are still adulterated juices out there on sale
So buyer “beware” adopt some/all of the options on slide 30
 Look at it as an “insurance policy”
Issues tend to occur when: Anything is in short supply
 More expensive products
 A product which is popular and a new addition to the “world” of
fruit or vegetable juices
Critical to remain vigilant and develop new methods
Thank you for your attention
If you would like more information please
feel free contact me
At
[email protected]
Telephone # 44 118 9354028
Mobile #
44 798 9650953
www.Eurofins.com
50
Useful reference data
AIJN code or Practice Published by AIJN, Rue de la Loi 221, Box 5, B- 1040 Brussels, www.aijn.org
Adulteration of Fruit Juice Beverages. Edited by Nagy, Attaway & Rhodes. Published by Marcel
Dekker Inc., New York. (ISBN 0-8247-7912-6)
Methods to Detect Adulteration of Fruit Juice Beverages Vols. 1 Edited by Nagy &Wade. Published
by AgScience, Auburndale, Florida, USA.(ISBN 0-9631397-3-8)
Handbook of indices of food quality and authenticity. Edited by Singhal, Kulkarni & Rege.
Published by Woodhead Publishing Ltd, Cambridge (ISBN 1 85573 299 8)
Food Authentication. Edited by Ashurst & Dennis. Published by Blackie Academic &
Professional, London, (ISBN 0 7514 0341 5)
Best collection of validated methods of analysis for fruit juices. International Fruit Juice Union
Methods of Analysis Handbook, Available from the IFU Website as a download for a fee; www.ifufruitjuice.com
AOAC analytical methods available to members as a download from the AOAC site (more limited
collection of procedures for fruit juices) www.AOAC.org
Fruit Processing & Flussiges Obst are very good magazines for juice related data and processing
issues published monthly by Flussiges Obst, Schonborn, Germany.
and of course Eurofins for all your analytical/consultancy needs
www.eurofins.com
[email protected]
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