contaminants émergents dans la chaîne alimentaire : risques pour la santé et nouveaux enjeux

Sûreté alimentaireQuelles 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

Karine VANDERMEIRENCODA‐CERVA

(Centre de recherche vétérinaire et agrochimique ‐ sécurité chimique de la

chaîne alimentaire) ‐ Belgique.

Emerging contaminants in the food chain:

health risks and new challenges

Vandermeiren Karine (CODA-CERVA) & Van Loco Joris (WIV-ISP)

Emerging contaminants in the food chain: health risks and new challenges


CODA – CERVA (Veterinary and Agrochemical Research Centre)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)Provides scientifique support for public health policy and formulates recommendations and priorities for a proactive policyat the Belgian, European and international level

www.coda‐cerva.be

www.wiv‐isp.be



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)



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.

Emerging contaminants in the food chain:health risks and new challenges

Vandermeiren Karine (CODA-CERVA)

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))

Main mycotoxins in food: notifications

• Mycotoxins = main hazard in border rejection notifications (RASFF, 2012)

• Aflatoxins = primary mycotoxins (RASFF, 2012)


Emerging mycotoxins

• 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


Masked mycotoxins

• 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


Masked & emerging mycotoxins: risks

• 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



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)


• risks upon oral (chronic) exposure and release intothe environment

• Small size → ≠ physico-chemical properties→ ≠ biological interactions compared to conventional chemicals (absorption, metabolism, distribution, excretion)

• Several shapes, single particles or agglomerated, encapsulation

Risk assessment of nanomaterials in food: knowledge gaps

• In situ detection and characterisation (combinationof techniques)

• Dose-metrics (particle size distribution, number of particles, particle charge, total surface?) → toxicitytests , 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).

Transmission Electronmicroscopy

Nanomaterials in food: detection and characterization

Vandermeiren Karine (CODA-CERVA)A B

ICP‐MS PQ ExCell (used for single particle analysis)



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

Evaluation Food Contact Material (FCM)

FCM in contactwith the food?

Yes

No

Analysis of the food

Analysis FCM by simulating the ‘worst case’ scenario migration with food simulant


Evaluation of the migration of 15 photo-initiators (PhI) from cardboard packaging with dry food simulant Tenax® using UPLC-MS/MS

• 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


Food Contact Materials: conclusions and perspectives

• 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



• 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)

In vitro screening of EDC effects with CALUX®


PPARy2 activation

-12 -10 -8 -6 -40

50

100

EC50 1.123e-007

Rosiglitazone (log M)

RLU

(% o

f max

)

PPARy2 antagonism

-14 -12 -10 -8 -60

50

100

EC50 1.089e-009

GW9662 (log M)

RLU

(% o

f max

)


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.

Toxins of Bacteria

Van Loco Joris (WIV-ISP)


• Heat resistent toxins of bacteria may remain in food aftersterilisation of food

• Examples:• Cereulide, emetic toxin of Bacillus cereus• Staphylococcus enterotoxins

• Food intoxications

Toxins of bacteria

• Extreme resistance to • Basic/acidic conditions• Proteolysis• Heat treatment (100,121,150°C)

• Potassium ionophore• Intoxications – Foods & Conditions

• Pre-formed in food• Improper storage of (cooked) food• not destroyed when reheating leftovers

• Occasional lethal cases in Belgium• 2003• 2009

Toxins of bacteria: Cereulide


• Produced in stationary phase (105 cells)• Thermo stable• Ph resistant• Food poisoning (FP)

• Gastro-enteritis• Emesis• Superantigen• Self-limiting (24h-48h)

• 20-30 KDa proteins• Different variants found

(SEA-SET)

Toxins of bacteria: Staphylococcal Enterotoxins


Sample 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

• highest amounts of B. cereus in the leftovers• highest amounts of cereulide in the white and fried rice dishes• Cross contamination

NP : Not Performed

Toxins of bacteria: Analysis of an intoxication case in Belgium with LC-MSMS (2011)

lefto

vers

sam

plin

g

B. cereus counts and cereulide concentrations


• 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

Toxins of Bacteria: conclusions & perspectives



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,…)


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contaminants émergents dans la chaîne alimentaire : risques pour la santé et nouveaux enjeux

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