PERFOOD PERfluorinated Organics in Our Diet Pim de Voogt University of Amsterdam - UvA-IBED, Amsterdam / KWR-CWG, Nieuwegein w.p.devoogt@uva.nl / pim.de.voogt@kwrwater.nl
Presentation overview • Introduction – key figures • Objectives • Work packages: coherence • Work packages: examples of ongoing work • Results & Outlook
Perfluorinated organic compounds Properties - both hydrophobic and oleophobic Surface treatment: Carpets, clothing, leather and paper Carpet Protection products etc. Excerpt of 3M commercial Fluoropolymer production ATOFINA commercial Speciality chemicals - non inflammable, surface active Wetting and leveling Aqueous film forming foams, Coatings, Textile Protection Electronics, Herbicides, Metal Finishing, Oil wells, Polymerisation PFOA PFOS Paper www.wfrfire.com www.swisspack.ch
Rationale What is significance of findings of PFAS in environment for human exposure? EFSA (2009): insufficient data for human exposure through diet incl. d.w.+beverages In this scientific opinion the EFSA considered it unlikely that adverse effects of PFOS and PFOA are occurring in the general population, but noted uncertainties with regards to developmental effects in living organisms . The EFSA recommended that further data on PFAS levels in food and in humans would be desirable, particularly with respect to monitoring trends in exposure. EFSA Journal (2008) 653, pp. 1-131. 1.Call for tender FP7 2. COMMISSION RECOMMENDATION of 17 March 2010 on the monitoring of PFAS in food (2010/161/EU)
PERFOOD Project Objectives • qualify and quantify PFCs in our diet • understand how PFCs are transferred from the environment into dietary items • quantify the possible contribution from food/beverage contact materials and food and water processing to the overall PFC levels in our diet.
Key Figures PERFOOD • THEME 2, FOOD, AGRICULTURE AND FISHERIES, AND BIOTECHNOLOGY [FP7-KBBE-2008-2B] • EC project number: 227525 • Total funding: 2,999,432 € • Total cost of the project: 4,011,385 € • 10 partners • Total Person Months: 362.5 = 30 person years... Period: 2009-2012 (3y)
PERFOOD Consortium • University of Amsterdam • Institute of Chemical (NL) - Coordinator Technology – Prague (CZ) • Stockholm University • University of Antwerp (SE) (BE) • Fraunhofer Institut (DE) • Bundesamt für • NILU –Tromsoe (NO) Risikoschätzung – Berlin • Istituto Superiore di (DE) Sanitá - Rome (IT) • KWR Watercycle • Vrije Universiteit - Research Institute – Amsterdam (NL) Nieuwegein (NL)
Work packages in PERFOOD • Development of tools for reliable analysis of PFCs in diet – WP1: Analytical methods – WP2: Quality assessment quality control • WP3 providing data on the PFCs in the diet • WP4 Tracking the sources of PFCs to food, beverages, and drinking water • WP 5 Impact of food contact materials and process technologies • WP 6 Quantifying the dietary intakes in Europe • WP 8 Dissemination
Integration in PERFOOD WP7: Management and coordination WP 5: Impact on food WP6: Quantifying contact materials and the dietary intakes process technologies in Europe WP3: Data on Comparison PFCs in the diet WP 4: Tracking the sources WP2: Quality WP1: Analytical assessment and methods quality control
WP1+2 Analytical method development and analytical quality • Compound selection PFCA/PFSA/PFPA • Highly sensitive methods and QA protocols for these PFAS • Matrix effects • Evaluation of performance of food control laboratories by means of an interlaboratory study (open to food laboratories) • Production and certification in two food matrix CRMs through Interlab Comparison: y 2+3 • Specific applications (e.g. DART/DESI /EPED for Food Contact Materials) ItM-Stockholm Univ (S), Free Univ –Amsterdam (NL), ICT – Prague (CZ) N
WP1+2 Analytical method development and analytical quality S/N ratio in MS/MS and exact MS exact MS S/N ratio in MS/MS and In LC LC- -MS/MS MS/MS record some noise can be typically seen, thus definition of LOD and LOQ could be based on S/N DEFINITION S/N DEFINITION. In exact mass LC exact mass LC- -MS MS with narrow mass extraction window (TOF MS, In exact mass LC-MS with narrow mass extraction window (TOF MS, QTOF MS, Orbitrap…) no or very low noise is in record, thus definition of QTOF MS, Orbitrap…) no or very low noise is in record, thus definition of LOD/LOQ could NOT be based on S/N definition. LOD/LOQ could NOT be based on S/N definition LOD/LOQ could NOT be based on S/N definition. 2009-03-26 - 03 1: TOF MS ES- S/N:PtP=340282346638528860000000000000000000000.00 511.961 40PPM 100 875 S/N = 66.3 S/N = 66.3 38 S/N=3.4e 38 S/N=3.4e % MeFOSA, A, 0.5 ng/ml 0.5 ng/ml MeFOS 0 Time 3.20 3.40 3.60 3.80 4.00 4.20 4.40 4.60 4.80 5.00
WP 3 + 6 Surveys & RA SELECTION OF FOOD ITEMS food intakes 01. Cereals & cereal products 02. Sweet products and 2000,00 substitutes 03. Vegetables and pulses, fresh 1800,00 and processed 1600,00 04. Potatoes, starchy roots and their products 1400,00 06. Meat, meat products and g p e rs o n d a y substitutes 1200,00 07. Fish, seafood and their products 1000,00 08. Eggs 800,00 09. Milk and dairy products 600,00 10. Fats (vegetable and animal) 400,00 11. Miscellaneous 200,00 12. Water and other non-alcoholic beverages 0,00 13. Coffee, tea, infusions B CZ D I NL N S UK EU WHO 14. Alcoholic beverages Countries
Samples list to cover the gap of Available knowledge on some food items Food Consumption (FC) databases ISS, Rome (I) and BfR, Berlin (D) WP 3 + 6 Use of PERFOOD data on single/composite foods with old and Identification of LODs for new FC DataBases the intake assessment to be used for the different food groups EFSA harmonised FC databases Intake estimates Intake estimates via cauldrons (food consumption x occurrence) ENV Indoor data Bio-monitoring data TKTD modelling Intake contribution to the aggregate exposure
Consumption data EU Consumption data EU 1600 ISS, Rome (I) and BfR, Berlin (D) WP 3 + 6 1400 ( g/ person/ day) 1200 1000 800 Food intake 600 400 200 0 B CR D I NL N SW UK WHO EU Countries ISS, Rome (I) and BfR, Berlin (D) 01. Cereals & products 02. Sweets 03. Vegetables and pulses 04. Potatoes, starchy roots 05. Fruit 06. Meat & products 07. Fish, seafood 08. Eggs 09. Milk and dairy products 10. Fats 11. Miscellaneous 12. Water and non-alcoholic beverages 13. Coffee, tea, infusions 14. Alcoholic beverages
Dietary intake of PFOS in EU countries PFOS dietary intake in EU COUNTRI ES 40 35 ISS, Rome (I) and BfR, Berlin (D) WP 3 + 6 30 I ntake (ng/ day kg-bw) 25 20 15 10 5 0 BE CZ DE I T NL NO SE GB EU EU Countries 01. Cereals & cereal products 02. Sweet products and substitutes 03. Vegetables and pulses, fresh and processed 04. Potatoes, starchy roots and their products 05. Fruit, fresh and processed 06. Meat, meat products and substitutes 07. Fish, seafood and their products 08. Eggs 09. Milk and dairy products 10. Fats (vegetable and animal) 11. Miscellaneous 12. Water and other non-alcoholic beverages 13. Coffee, tea, infusions 14. Alcoholic beverages
Survey– Sampling Manual WP 3 + 6 Sampling Protocol for food items for the PERFOOD project Univ. of Antwerp (B), NILU – Tromsoe (N) , ICT-Prague (CZ)
Survey– Sampling + Distribution WP 3 + 6 Were are the PERFOOD first step sampling list samples measured total per WEST NORTH SOUTH peal EAST EU food EU EU EU ed total category N B CR samples NILU Tromsoe (N) Univ of Antwerp– Antwerp (B) Lab CzR BE NO I T Lab 1 Lab2 3 01. Cereals 01. Cereals x Rice X X 2 Wheat X X X X 4 Oats X x 2 X x 2 Barley X X 2 Maize X 13 1 02. Sweets 02. Sweets Sugar x X X 3 x Sugar (cane) X 1 Honey x X X X 4 Cocoa powder X 9 1 03. Vegetables and 03. Vegetables and pulses pulses Leafy vegetables Leafy vegetables x lettuce and other x X x X salads 4 spinaches x X 2 chicory x X 2 x 8 Stem vegetables Stem vegetables
WP4 Tracking Sources Transfer of PFCAs and PFSAs from feed to beef cattle Study approach • A mass balance over a beef cattle herd in an enclosed barn will be established • Feed, water, urine and feces samples will be collected over several months • Blood and tissue samples will be collected as the animals are slaughtered • Information on feeding rates will be collected in collaboration with the farmer Homogenized feed Urine (silage, minerals, corn etc.) feces Tap water Animals to slaughter (muscle, liver and blood)
WP4 Tracking Sources Field + Lab experiments: plants Oberboden 75 cm Unterboden Drainageschicht Drainageablauf Schematic graph of lysimeter Fraunhofer Institut - IME – Schmallenberg (D) Greenhouse experiments, FI -IME – Schmallenberg (D), Univ of Amsterdam (NL) see poster S Felizeter
WP 5 Impact FCM & Processing Background – Migration • Migration behaviour of PFAS is puzzling. For instance, PAPs are clearly mobile in packaging, while the much smaller PFOA molecules are not (Begley 2007). • Migration into emulsions (e.g. butter) of surfactant containing food simulants (Begley 2007) is much higher compared to normal food simulants (95% Ethanol, Isooctane) or oil. 100°, 15 min A B 100°, 15 min 40° Fraunhofer Institut - IVV – Freising (D)
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