Karine VANDERMEIREN est chercheuse au CODA-CERVA (Centre de recherche vétérinaire et agrochimique - sécurité chimique de la chaîne alimentaire) en Belgique. Le CODA-CERVA apporte un soutien scientifique à l'Etat et à l'Agence nationale pour la Sécurité de la Chaîne alimentaire (FAFSC), et agit au niveau international pour la sécurité alimentaire de la production, la santé animale et la santé publique.

1. Sûreté alimentaire
Quelles innovations pour
la maîtrise des contaminants
et l'authentification des produits
agricoles et alimentaires ?
> 13 & 14 novembre 2013
> Montpellier SupAgro INRA
www.rencontres-qualimediterranee.fr

2. Karine VANDERMEIREN
CODA‐CERVA
(Centre de recherche vétérinaire et
agrochimique ‐ sécurité chimique de la
chaîne alimentaire) ‐ Belgique.

3. Emerging contaminants in
the food chain:
health risks and new
challenges
Vandermeiren Karine (CODA-CERVA) & Van Loco Joris (WIV-ISP)

4. Emerging contaminants in the food chain:
health risks and new challenges
CODA – CERVA
(Veterinary and Agrochemical Research Centre)
www.coda‐cerva.be
Provides scientifique support to the federal government, the
Federal Agency for the Safety of the Food Chain (FAFSC) and at
the international level, in respect to food production safety,
animal health and public health
WIV – ISP
(Belgian Scientifique Institute of Public Health)
www.wiv‐isp.be
Provides scientifique support for public health policy and
formulates recommendations and priorities for a proactive policy
at the Belgian, European and international level
Vandermeiren Karine (CODA-CERVA) & Van Loco Joris (WIV-ISP)

5. Emerging contaminants in the food chain:
health risks and new challenges
Recent developments and issues
• Masked & emerging mycotoxins
• Detection and risk analysis of nanomaterials in the
food chain
• Migration from food packaging materials (EDCs)
• Toxins from bacteria (Cereulide, Staphylococcus
enterotoxins)
Vandermeiren Karine (CODA-CERVA) & Van Loco Joris (WIV-ISP)

6. Emerging contaminants in the food chain:
health risks and new challenges
Glossary
• Contaminants: chemical substances that have not been
intentionally added to food or feed
• Hazard: potential to cause an adverse health effect
• Risk: likelihood of the occurrence and severity of the negative
effect
• Emerging: resulting from a newly identified hazard or from an
unexpected new or increased significant exposure and/or
susceptibility to a known hazard.
Vandermeiren Karine (CODA-CERVA) & Van Loco Joris (WIV-ISP)

7. Emerging contaminants in the food chain:
health risks and new challenges
Main mycotoxins in food: structure
Ref: Murphy et al., 2006
LC‐MS/MS used at CODA‐CERVA
for the analysis of mycotoxins and
natural components
Vandermeiren Karine (CODA-CERVA)

8. Main mycotoxins in food: notifications
•
Mycotoxins = main hazard in border rejection notifications (RASFF, 2012)
•
Aflatoxins = primary mycotoxins (RASFF, 2012)
Vandermeiren Karine (CODA-CERVA))

9. Emerging mycotoxins
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Enniatins (ENNs) & beauvericin (BEA)
No (EU) legislation, although widespread in cereals (also in processed food incl
baby food)
Especially in Mediterranean countries
Additional risk: facilitation of carry-over of other mycotoxins due to ionophoric
properties
Climatic changes may induce a shift in mycotoxin profiles
Vandermeiren Karine (CODA-CERVA)

10. Masked mycotoxins
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Due to metabolization of native mycotoxins by plants
DON → DON3-G (deoxynivalenol-3-β-D-glucoside), 3ADON, 15ADON contribute
to the total dietary exposure to DON (JEFCA, 2010)
ZEN → ZEN14G (zearalenone-14-β-D-Glucopyranoside)
Ref: Berthiller et al, 2013
Vandermeiren Karine (CODA-CERVA)

11. Masked & emerging mycotoxins: risks
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•
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Different chemical behaviour, no commercial standards → escape routine
analyses → underestimation of total mycotoxine content
More or less risk for consumers?
• (incomplete) hydrolysis of masked mycotoxins into toxic parent forms
during mammalian digestion
• Bioavailability?
• No proper risk assessment due to lack of data on occurrence,
bioavailability and toxicology
Current legacy only for some main mycotoxins
Co-occurrence of masked & parent mycotoxins reported in cereal-based
foodstuff (breakfast cereals, bread, beer)
α-zearalenone (α-ZEL) is more estrogenic than zearalenone (ZEN)
Changes in mycotoxin profiles due to global warming
Vandermeiren Karine (CODA-CERVA)

12. Emerging contaminants in the food chain:
health risks and new challenges
Nanomaterials in food
•
•
Definition: a discrete entity that has three dimensions of the order of 100 nm or less
(SCENIHR,2007)
Application in food production chain → consumer exposure to NM is likely to occur
(Bouwmeester et al, 2009)
Vandermeiren Karine (CODA-CERVA)

13. Risk assessment of nanomaterials in food:
knowledge gaps
• risks upon oral (chronic) exposure and release into
the environment
• Small size
→ ≠ physico-chemical properties
→ ≠ biological interactions compared to
conventional chemicals (absorption,
metabolism, distribution, excretion)
• Several shapes, single particles or
agglomerated, encapsulation
• In situ detection and characterisation (combination
of techniques)
• Dose-metrics (particle size distribution, number of
particles, particle charge, total surface?) → toxicity
tests , dose-reponse relations, regulations
BF‐TEM (A) Ag‐NM spherical; (B) Au‐NM
spherical (C‐D) Au‐NM star shaped (E‐F) Au‐NM
bar shaped. Scale: 100 nm (A en B), 200 nm (C,
D, E en F).
Vandermeiren Karine (CODA-CERVA)

14. Nanomaterials in food:
detection and characterization
Transmission
Electronmicroscopy
ICP‐MS PQ ExCell (used for single particle analysis)
A
B
Vandermeiren Karine (CODA-CERVA)

15. Emerging contaminants in the food chain:
health risks and new challenges
Migration from Food Contact Materials
Recent food ‘crisis’ concerning the migration of photo-initiators into
food
• In 2005: 2-isopropylthioxanthenone (2-ITX) in Nidina products
(Nestlé)
• In 2009: Benzophenone (BP) in breakfast cereals
Photo-initiators used to cure inks can migrate into food via
• Set-off
• Migration from the prints
• Use of recycled cardboard and paper
Vandermeiren Karine (CODA-CERVA) & Van Loco Joris (WIV-ISP)

16. Evaluation Food Contact Material (FCM)
Yes
Analysis of the food
FCM in contact
with the food?
No
Analysis FCM
by simulating the ‘worst case’ scenario
migration with food simulant
Vandermeiren Karine (CODA-CERVA) & Van Loco Joris (WIV-ISP)

17. Evaluation of the migration of 15 photo-initiators
(PhI) from cardboard packaging with dry food
simulant Tenax® using UPLC-MS/MS
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Cardboard sample that has not
been in contact with food
In contact with tenax at 60°C
during 10 days
Extraction & quantification using
validated UPLC-MS/MS method
6 PhI were identified in this
sample
PhI were also detected in non
printed cardboards originating
from recycled cardboard or
paper
Vandermeiren
Vandermeiren Karine (CODA-CERVA) & Van Loco Joris (WIV-ISP)

18. Food Contact Materials: conclusions and
perspectives
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A large number of compounds might migrate from FCM into the Food
• > 9000 compounds are listed and could be used in FCM
• However for many compounds toxicity data are scarce of not existing
Formulations of printing inks, adhesives,…. are trade secret and not
known
Legislation is only partially harmonized within the EU
Strong need for
• New analytical methods to quantify the migrants in simulants and in
food
• insight to understand the kinetics of the migration of these
compounds
• Toxicity data of compounds used in FCM
• Data about the use of these compounds in FCM
• Risk evaluation of mixtures: additive, synergistic, antagonistic effects
(screening!) → genotoxicitiy & endocrine disrupting effects
Vandermeiren Karine (CODA-CERVA) & Van Loco Joris (WIV-ISP)

19. Emerging contaminants in the food chain:
health risks and new challenges
In vitro screening of EDC effects with CALUX®
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chemical-activated luciferase gene expression system
Screening of interference with estrogen, androgen, thryroid and fatty
acid (PPAR) nuclear receptors
Agonisitc & antagonistic effects
Pure compounds (bisphenols ,phtalates…)
mixtures (e.g. migration from FCM)
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PPARy2 antagonism
100
50
EC50
0
-12
-10
-8
-6
Rosiglitazone (log M)
1.123e-007
-4
RLU (% of max)
RLU (% of max)
PPARy2 activation
100
50
EC50
0
-14
1.089e-009
-12
-10
-8
-6
GW9662 (log M)
Vandermeiren Karine (CODA-CERVA) & Van Loco Joris (WIV-ISP)

20. Emerging contaminants in the food chain:
health risks and new challenges
Toxins of Bacteria
2004
Lethal food
intoxication in
Belgium
1 Family with 4
children intoxicated
after having eaten
leftovers of a pasta
dish. 1 young child of
6 years old died.
Van Loco Joris (WIV-ISP)

21. Toxins of bacteria
• Heat resistent toxins of bacteria may remain in food after
sterilisation of food
• Examples:
• Cereulide, emetic toxin of Bacillus cereus
• Staphylococcus enterotoxins
• Food intoxications
Van Loco Joris (WIV-ISP)

22. Toxins of bacteria: Cereulide
• Extreme resistance to
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Basic/acidic conditions
Proteolysis
Heat treatment (100,121,150°C)
• Potassium ionophore
• Intoxications – Foods & Conditions
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Pre-formed in food
Improper storage of (cooked) food
not destroyed when reheating leftovers
• Occasional lethal cases in Belgium
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2003
2009
Van Loco Joris (WIV-ISP)

23. Toxins of bacteria:
Staphylococcal Enterotoxins
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Produced in stationary phase (105 cells)
Thermo stable
Ph resistant
Food poisoning (FP)
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Gastro-enteritis
Emesis
Superantigen
Self-limiting (24h-48h)
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20-30 KDa proteins
Different variants found
(SEA-SET)
Van Loco Joris (WIV-ISP)

24. Toxins of bacteria: Analysis of an intoxication case
in Belgium with LC-MSMS (2011)
B. cereus counts and cereulide concentrations
B. cereus counts (cfu/g)
Cereulide concentration (ng eq/g)
spaghetti sauce
2,8E+05
151,6
white rice
2,4E+07
8692,5
soybean soup
1,3E+07
15,8
fried rice
1,5E+07
13183,9
white rice
3,6E+04
9,3
noodles
< 100
NP
chickpeas
3,0E+03
< LOD
sampling
leftovers
Sample
NP : Not Performed
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highest amounts of B. cereus in the leftovers
highest amounts of cereulide in the white and fried rice dishes
Cross contamination
Van Loco Joris (WIV-ISP)

25. Toxins of Bacteria:
conclusions & perspectives
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Bactria counts are not a reliable estimator of the toxin concentration
LC-MSMS is versatile and specific tool to analyse toxins of bacteria (i.e.
cereulide) in food samples, both for research and quality control
analyses
We have proven that cereulide is present in a large variety of foodstuffs,
at low concentrations (ppb), except for intoxication cases (>10 ppm)
Evidence of regular long term exposure to cereulide, however little is
known about other toxins of bacteria
Further research is needed to understand better the toxicity, the
exposure and health effects of these heat resistant toxins ( i.e.
staphylococcal toxins) and to develop new quantitative methods with
low detection limits
Van Loco Joris (WIV-ISP)

26. Emerging contaminants in the food chain:
health risks and new challenges
General conclusions
• Emerging risks demand new analytical technology
• Indicators for newly emerging hazards and risks?
• Changes in environment
• Changes in food production chain
• Changes in consumer behaviour
• Risk assessment of chemical mixtures requires new approaches
(focus on effects, bioassays, rapid screening techniques,…)
Vandermeiren Karine (CODA-CERVA) & Van Loco Joris (WIV-ISP)

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