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HOW TO PROTECT YOUR INDUSTRY FROM FOOD FRAUD

EQCS An example of Industry working together for


everyones benefit!

Dr David A Hammond
Fruit Juice and Authenticity Expert

Eurofins
E-mail: davidhammond@eurofins.com
or davidfruitjuice@aol.com
Fixed line 44 (0)118 935 4028
Mobile No. 44 (0)798 965 0953

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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

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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!

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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 pure 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 Glucose Fructose Gluc to Fruc
(g/l) (g/l) (g/l) ratio

Orange 40 20 20 0.9 - 1.0


Pineapple 45 23 23 0.9 - 1.1
Apricot 30 50 20 1.0 - 3.0
Apple 10 20 60 0.3 - 0.5
Blackcurrant Trace 27 36 0.6 - 0.9
Pomegranate Trace 60 65 0.8 - 1.0
Strawberry 6 25 28 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
12.2K 23K
4200
4000 3800
3200
3000
3000
2500
2100 2200
2000
1350 1250
1000 650 600
460 370 490

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BAD NEWS?

1) Late 80s 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 90s Californian company was selling adulterated orange


juice. Company settled out of court ($8 million)
Detected by:
very low oxygen isotope ratio (18O) added water and beet sugar
Presence of naringin in polyphenol profile (presence of grapefruit juice)

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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 (HPAEC-
PAD), 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 90s company in Southern US, selling orange juice into


the schools program, had a fake electrical panel in the factory.
FDAs 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)

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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

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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)

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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: Linstitut Professionnal pour la Qualite des Jus de Fruit (France)

SGF: Sure Global Fair (Germany, regional and Global IRMA)

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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

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Typical test screen taken from old BCI scheme

Citrus Apple Pineapple


A0 Density & Brix x x x
A1 Compositional screen
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
Sorbitol x
B Isotopic screen
SNIF-NMR & 13C of ethanol x

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Typical test screen taken from old BCI scheme

Citrus Apple Pineapple

C Advanced chemical characterisation

Oligosaccharides by Cap-GC x x x

Flavanoid glucosides x

Vitamin C x

Phenolic compounds (arbutin & phloridzin) x

Pectins x x

D Advanced isotopic analysis to detect dilution

18O of juice water and ethanol x

E3 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

Citrus Apple Pineapple

F GC-MS analysis to detect flavour addition

GC-MS screening + chiral analysis x x

G Contaminants

Nitrate x x x

Patulin x

AIJN heavy metals (8) x x x

Pesticide screen (160 molecules) x x x

H 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 dont 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)

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Detection of sugar addition by stable isotopic analysis

13C/12C
IRMS -5.0
C4
-10.0 Cane

-15.0

-20.0

Unknown
C3
-25.0

Fruit reference Zone


-30.0 Beet

Low D content High D content SNIF-NMR


-35.0
2H/1H
85.0 90.0 95.0 100.0 105.0 110.0 115.0 120.0 125.0 130.0

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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

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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)
Internal isotopic approach for water addition

12
11
10
9
8
7
6 Lab-squeezed
5 samples
d O water ()

4
3 Market NFC
2
Water addition to NFC juices
1
0 Market FC
juices
18

-1
-2
-3 Max (95% c.i.)
-4
-5
-6 Authentic orange from a Min (95% c.i.)
-7 specific origin
-8
-9 FJ from Conc AIJN limit
-10

d18O ethanol ()
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

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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
davidfruitjuice@aol.com
Telephone # 44 118 9354028
Mobile # 44 798 9650953
www.Eurofins.com

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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.ifu-
fruitjuice.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
davidfruitjuice@aol.com

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