HOW TO PROTECT YOUR INDUSTRY FROM FOOD … · HOW TO PROTECT YOUR INDUSTRY FROM FOOD FRAUD ... Hydrolysed inulin syrups to apple or pear juice 2) ... 1994 draws up guidelines for

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HOW TO PROTECT YOUR INDUSTRY FROM FOOD FRAUD

EQCS – An example of Industry working together foreveryone’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

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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 whatyou ordered, however, not ALL are!

If possible only use suppliers that you have visited andaudited or have been approved by a third party (suchSGF IRMA scheme)

http://www.sgf.org/en/home/fks/halbwarenkontrolle/

This should not preclude you from testing these suppliersraw materials also

Everything has a price and if the price is TOO good theremaybe 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 offruit which is sound and ripe, fresh or preserved by chilling or freezing ofone or more kinds mixed together having the characteristic colour, flavourand taste typical of the juice of the fruit from which it comes.

Flavour, pulp, and cells obtained by suitable physical means from the samespecies of fruit may be restored to the juice.

In the case of citrus fruits, the fruit juice must come from the endocarp. Limejuice, however, may be obtained from the whole fruit.

Where juices are processed from fruits with pips, seeds and peel, parts orcomponents 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 ofthe 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)

Glucose(g/l)

Fructose(g/l)

Gluc to Frucratio

Orange 40 20 20 0.9 - 1.0Pineapple 45 23 23 0.9 - 1.1Apricot 30 50 20 1.0 - 3.0Apple 10 20 60 0.3 - 0.5

Blackcurrant Trace 27 36 0.6 - 0.9Pomegranate Trace 60 65 0.8 - 1.0Strawberry 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)

3800

2100

4200

1350

2200

1250

3200

2500

3000

460 370 490 650 600

0

1000

2000

3000

4000

500023K12.2K

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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)

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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 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)

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AIJN code or Practice

Provides consistent criteria for quality and authenticity for fruit andvegetable juices sold within the EU.

Prepared by experts in the field from industry, academia andcontrol 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 seasonaldata 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: L’institut 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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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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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 don’t have the time or expertise sub-contract or use a producer whois 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 anyproblems. However the Press or the Regulator might coming asking difficultquestions 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)

32

13C/12C

Detection of sugar addition by stable isotopic analysis

SNIF-NMR®

Fruit reference ZoneBeet

Cane

Unknown

-35.0

-30.0

-25.0

-20.0

-15.0

-10.0

-5.0

85.0 90.0 95.0 100.0 105.0 110.0 115.0 120.0 125.0 130.02H/1H

IRMS

C3

C4

Low D content High D content

Typical Cap-GC profile for apple

Sucrose

Apple Juice adulterated with HFSI

Inulin marker peaks

Sucrose

Oligosaccharide profiling HFCS(high fructose corn syrup) added

35

Marker peaks

Isomaltose

Maltose



SNIF-NMR®


Water addition








Many of the above


Internal isotopic approach for “water” addition

-10

-9

-8

-7

-6

-5

-4

-3

-2

-1

0

1

2

3

4

5

6

7

8

9

10

11

12

d18O ethanol (‰)

d18 O

wa

ter

(‰)

Lab-squeezedsamples

Market NFCjuices

Market FCjuices

Max (95% c.i.)

Min (95% c.i.)

AIJN limit

Authentic orange from aspecific origin

FJ from Conc

Water addition to NFC



SNIF-NMR®


Water addition








Many of the above


Detection of added C3 and C4 derived citricacid to lemon juice

Mixed C3 & C4

acids

C3 derived citric acids C4 derived citric acids



SNIF-NMR®


Water addition








Many of the above


41

Typical Pomegranate profile

Delpin-3,5-digluc

Cyan-3,5-digluc

Delpin-3-gluc

Cyn-3-gluc

Unknown

Pel-3-gluc

Pel-3,5-digluc

Pomegranate plus black carrot

Acylated “cyanidins”

Orange/mandarin separation (ADNid France)

Polymethoxyflavones (PMFs)

Lemon

Lime

7MeoC



SNIF-NMR®


Water addition








Many of the above


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

50

Thank you for your attentionIf you would like more information please

feel free contact me

[email protected]

Telephone # 44 118 9354028Mobile # 44 798 9650953

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51

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 MarcelDekker Inc., New York. (ISBN 0-8247-7912-6)

Methods to Detect Adulteration of Fruit Juice Beverages Vols. 1 Edited by Nagy &Wade. Publishedby 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 UnionMethods 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 limitedcollection of procedures for fruit juices) www.AOAC.org

Fruit Processing & Flussiges Obst are very good magazines for juice related data and processingissues 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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HOW TO PROTECT YOUR INDUSTRY FROM FOOD … · HOW TO PROTECT YOUR INDUSTRY FROM FOOD FRAUD ... Hydrolysed inulin syrups to apple or pear juice 2) ... 1994 draws up guidelines for