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Consumers, Health, Agriculture and Food Executive Agency Sources, sampling and analytical methods for environmental contaminants Revision of both the environmental source and the main dietary contributors of the environmental contaminants and the fraction/molecule to be analysed. Revision of legislation on sampling and analysis in food and feed highlighting specificities for environmental contaminants. 2

Consumers, Health, Agriculture and Food Executive Agency 3

Consumers, Health, Agriculture and Food Executive Agency Content Sources of environmental contaminants Sampling & analysis legislation: - Sampling and sample preparation - Methods of analysis - Expression and interpretation of results* 4

Consumers, Health, Agriculture and Food Executive Agency Sources of environmental contaminants I 5 Environmental sourcesMain contributors to dietary exposure ContaminantAnalyte Leaded-gasoline, water pipes, industrial pollution, munitions, fertilizers, cans and kitchenware (dyes) Water, cereals, milk, fruits, vegetables LeadPb Metallurgy, paint, batteries, burning of fossil fuels, waste incineration, fertilizers Cereals, vegetables, potatoes, offal, fish, fruits CadmiumCd Geological sources, volcanoes, incineration, metallurgical processes, dental amalgams, thermometers Fish and fish productsMercuryMeHg Geological sources, metallurgical processes, industrial emissions, pesticides Cereals (rice)ArsenicAs i Forest fires, volcanoes, burning (wood, oil, gas, charcoal), industrial power generation, incineration, smoking Smoked meat, smoked fish, oils and fats, cereals, leafy vegetables, molluscs PAHs benzo(a)pyrene, benzo(a)anthracene benzo(b)fluoranthene and chrysene

Consumers, Health, Agriculture and Food Executive Agency Sources of environmental contaminants II 6 Environmental sources Main contributors to dietary exposure ContaminantAnalyte Thermal (fires, waste incineration, heaters) and chemical processes (pesticides’ production, chlorine bleaching of paper) Food of animal origin (fish, meat, eggs and milk products) Dioxins List of PCDDs + PCDFs* Chemical synthesis (transformer oils, dielectric fluids) PCBs List of DL-PCB* NDL-PCBs (6) Chemical synthesis (flame retardants) BFRs PBDEs, PBBs, TBBPA, HBCD Chemical synthesis (water- repellents, dirt repellent coatings) Fish and fish products Perfluoroalkylated substances PFOS, PFOA * Note 32-Annex to Regulation 1881/2006

Consumers, Health, Agriculture and Food Executive Agency 7 “X” mg/kg Hg in a fish

Consumers, Health, Agriculture and Food Executive Agency Sampling and analysis: Legislation 8 Heavy metals, As, PAHs REGULATION 333/2007 FOOD Dioxins and PCBs REGULATION 589/2014 FOOD REGULATION 152/2009 FEED

Consumers, Health, Agriculture and Food Executive Agency Sampling and sample preparation 9

Consumers, Health, Agriculture and Food Executive Agency Sampling criteria- similarities FOOD/FEED 10 DefinitionsMandatory No. final samples Scope

Consumers, Health, Agriculture and Food Executive Agency Sampling criteria- differences FOOD/FEED 11 Size of the aggregate sample Sublot vs sampled portion No. incremental samples

Consumers, Health, Agriculture and Food Executive Agency Environmental contaminants-FOOD Sampling and analytical methods REGULATION 333/ Specific issues for sample preparation

Consumers, Health, Agriculture and Food Executive Agency Sample preparation: specific issues 13 Specific procedures for heavy metals - Inert materials: polypropylene, PTFE - Stainless steel for cutting edges - Standard EN 13804:2013 Specific procedures for PAHs - Inert materials: aluminium, glass, polished stainless steel

Consumers, Health, Agriculture and Food Executive Agency 14 Specific criteria for sampling of fish Guidance document on sampling of whole fishes Dioxins and PCBs-FOOD Sampling and analytical methods REGULATION 589/2014

Consumers, Health, Agriculture and Food Executive Agency Sampling of fish (Dioxins) 15 Specific provisions for the sampling of lots containing whole fishes of comparable size and weight*  small fishes (< about 1 kg), the whole fish is taken as incremental sample -> aggregate sample > 3 kg -> the incremental samples = the middle part (100g)  larger fishes (> about 1 kg), the middle part of the fish is taken as incremental sample (100g)  fishes of intermediate size (about 1-6 kg) the incremental sample is taken as a slice of the fish from backbone to belly in the middle part of the fish.  For very large fishes (e.g. > about 6 kg), the incremental part is taken from the right side (frontal view) dorso-lateral muscle meat in the middle part of the fish (350 g) *For a lot containing fish of different size: predominant size or weight (>80%). Otherwise, refer to “GUIDANCE ON SAMPLING OF WHOLE FISHES OF DIFFERENT SIZE AND/OR WEIGHT“ (DGSANCO).GUIDANCE ON SAMPLING OF WHOLE FISHES OF DIFFERENT SIZE AND/OR WEIGHT

Consumers, Health, Agriculture and Food Executive Agency 16 Guidance document on sampling of feed Undesirable substances-FEED Sampling and analytical methods REGULATION 152/2009 R. 278/2012 NDL-PCBs R. 51/2013 Constituents of animal origin R.691/2013 GMOs, feed additives, undesirable substances R. 709/2014 Screening/ Confirmatory methods for dioxins and PCBs

Consumers, Health, Agriculture and Food Executive Agency Guidance on sampling of FEED 17  Specific aspects of the sampling procedure  Sampling of large batches/lots-silos  Examples of sampling of packaged feed  Sampling of roughage and succulent feed materials *Endorsed by the SCFCAH (June 2014): (DGSANCO).

Consumers, Health, Agriculture and Food Executive Agency Methods of analysis 18

Consumers, Health, Agriculture and Food Executive Agency Performance criteria for the methods of analysis Environmental contaminants-FOOD Sampling and analytical methods REGULATION 333/

Consumers, Health, Agriculture and Food Executive Agency Methods of analysis R. 333/ No specific methods are required Any method (fully validated is preferred)-accredited It shall comply with the performance criteria set out in the Annex - LOD- RSD r - LOQ- RSD R - Recovery- Specificity

Consumers, Health, Agriculture and Food Executive Agency 21 Methods of analysis: confirmatory and screening Dioxins and PCBs-FOOD Sampling and analytical methods REGULATION 589/2014

Consumers, Health, Agriculture and Food Executive Agency Methods of analysis R. 589/ GC-HRMS, GC-MS/MS −Costly −High expertise −Very sensitive GC-HRMS, GC-MS/MS −Costly −High expertise −Very sensitive Bioanalytical, GC-MS −Cost-effective high sample throughput −No congener level (sum) −No TEFs −Indicative results Bioanalytical, GC-MS −Cost-effective high sample throughput −No congener level (sum) −No TEFs −Indicative results “SCREENING METHODS” “CONFIRMATORY METHODS” GC-detectors −NDL-PCBs −ppb −Sum (6 congeners) −No TEFs GC-detectors −NDL-PCBs −ppb −Sum (6 congeners) −No TEFs

Consumers, Health, Agriculture and Food Executive Agency 23 Methods of analysis Undesirable substances-FEED Sampling and analytical methods REGULATION 152/2009

Consumers, Health, Agriculture and Food Executive Agency Methods of analysis R. 152/ No specific performance criteria are set for heavy metals - Performance criteria from Regulation 333/2007 (food) can be used Same approach for the analysis of dioxins and PCBs - screening methods/confirmatory methods for dioxins and DL-PCBs - GC detectors for NDL-PCBs

Consumers, Health, Agriculture and Food Executive Agency CONCLUSIONS: There are plenty of sources of environmental contaminants, both natural (fires, volcanoes) and anthropogenic (metallurgy, industrial emissions, incineration), that we shall bear in mind when performing the official control Common sampling and analysis criteria have been set in the EU legislation in order to unify criteria and make results comparable (legal repercussion) These criteria are mandatory when checking compliance with MLs (enforcement purposes) 25

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