PERFOOD PERfluorinated Organics in Our Diet Pim de Voogt - - PowerPoint PPT Presentation

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

Properties

• both hydrophobic and oleophobic

 Surface treatment:

Carpets, clothing, leather and paper products etc.

 Fluoropolymer production  Speciality chemicals

• non inflammable, surface active

 Wetting and leveling

Aqueous film forming foams, Coatings, Electronics, Herbicides, Metal Finishing, Oil wells, Polymerisation Carpet Protection Paper Textile Protection

Excerpt of 3M commercial www.swisspack.ch ATOFINA commercial

Perfluorinated organic compounds

www.wfrfire.com

PFOS PFOA

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

Rationale

• 2. COMMISSION RECOMMENDATION
• f 17 March 2010
• n the monitoring of PFAS in food

(2010/161/EU)

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

• ur diet.

PERFOOD

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

(NL) - Coordinator

• Stockholm University

(SE)

• Fraunhofer Institut (DE)
• NILU –Tromsoe (NO)
• Istituto Superiore di

Sanitá - Rome (IT)

• Vrije Universiteit -

Amsterdam (NL)

• Institute of Chemical

Technology – Prague (CZ)

• University of Antwerp

(BE)

• Bundesamt für

Risikoschätzung – Berlin (DE)

• KWR Watercycle

Research Institute – Nieuwegein (NL)

• 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

Work packages in PERFOOD

Integration in PERFOOD

WP7: Management and coordination WP3: Data on PFCs in the diet WP1: Analytical methods WP2: Quality assessment and quality control

WP6: Quantifying the dietary intakes in Europe WP 4: Tracking the sources Comparison WP 5: Impact on food contact materials and process technologies

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

S/N ratio in MS/MS and S/N ratio in MS/MS and exact MS exact MS

In LC LC-

• MS/MS

MS/MS record some noise can be typically seen, thus definition

• f LOD and LOQ could be based on S/N DEFINITION

S/N DEFINITION. 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 LOD/LOQ could NOT be based on S/N definition. In exact mass LC exact mass LC-

• MS

MS with narrow mass extraction window (TOF MS, 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. S/N = 66.3 S/N = 66.3

Time 3.20 3.40 3.60 3.80 4.00 4.20 4.40 4.60 4.80 5.00 % 100 2009-03-26 - 03 1: TOF MS ES- 511.961 40PPM 875 S/N:PtP=340282346638528860000000000000000000000.00

MeFOS MeFOSA, A, 0.5 ng/ml 0.5 ng/ml S/N=3.4e S/N=3.4e38

38

WP1+2 Analytical method development and analytical quality

food intakes

0,00 200,00 400,00 600,00 800,00 1000,00 1200,00 1400,00 1600,00 1800,00 2000,00 B CZ D I NL N S UK EU WHO Countries g p e rs o n d a y

• 01. Cereals & cereal products
• 02. Sweet products and

substitutes

• 03. Vegetables and pulses, fresh

and processed

• 04. Potatoes, starchy roots and

their products

• 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

WP 3 + 6 Surveys & RA SELECTION OF FOOD ITEMS

Available Food Consumption (FC) databases Samples list to cover the gap of knowledge on some food items Identification of LODs for the intake assessment to be used for the different food groups EFSA harmonised FC databases Use of PERFOOD data on single/composite foods with old and new FC DataBases Intake estimates via cauldrons Intake contribution to the aggregate exposure Intake estimates (food consumption x occurrence) ENV Indoor data Bio-monitoring data TKTD modelling

ISS, Rome (I) and BfR, Berlin (D)

WP 3 + 6

200 400 600 800 1000 1200 1400 1600

B CR D I NL N SW UK WHO EU Countries

Food intake ( g/ person/ day)

• 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

Consumption data EU

Consumption data EU

ISS, Rome (I) and BfR, Berlin (D) ISS, Rome (I) and BfR, Berlin (D)

WP 3 + 6

PFOS dietary intake in EU COUNTRI ES

5 10 15 20 25 30 35 40

BE CZ DE I T NL NO SE GB EU EU Countries I ntake (ng/ day kg-bw)

• 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

Dietary intake of PFOS in EU countries

ISS, Rome (I) and BfR, Berlin (D)

WP 3 + 6

Survey– Sampling Manual

Sampling Protocol for food items for the PERFOOD project

• Univ. of Antwerp (B), NILU – Tromsoe (N) , ICT-Prague (CZ)

WP 3 + 6

PERFOOD first step sampling list Were are the samples measured

EAST EU WEST EU NORTH EU SOUTH EU total per food category total samples peal ed N B CR CzR BE NO I T Lab 1 Lab2 Lab 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

pulses

• 03. Vegetables and

pulses Leafy vegetables Leafy vegetables x lettuce and other salads x X x X 4 spinaches x X 2 chicory x X 8 2 x Stem vegetables Stem vegetables

Survey– Sampling + Distribution

NILU Tromsoe (N) Univ of Antwerp– Antwerp (B)

WP 3 + 6

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 (silage, minerals, corn etc.) Tap water Urine Animals to slaughter (muscle, liver and blood) feces

WP4 Tracking Sources

Oberboden Unterboden

Drainageschicht

Drainageablauf

75 cm

Schematic graph of lysimeter Fraunhofer Institut - IME – Schmallenberg (D)

WP4 Tracking Sources Field + Lab experiments: plants

FI -IME – Schmallenberg (D), Univ of Amsterdam (NL)

Greenhouse experiments, 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.

A

100°, 15 min

B

100°, 15 min 40°

Fraunhofer Institut - IVV – Freising (D)

Objectives and Approaches WP5

Objectives Approaches

• 3. To measure and model migration

kinetics in order to check if existing migration models can explain the

• bserved behaviour

Apply developed methods and existing migration models

• 4. To calculate FCM-related dietary

exposure from migration data using statistical data on FCM usage and consumption rates Crosslink to WP 6 and European FACET project

Verpackung Lebensmittel

Diffusion Verteilung Diffusion

Migration

C

LM,t

? ? ? ? ? ? C

t=0

Verpackung Lebensmittel

Diffusion Verteilung Diffusion Diffusion Verteilung Verteilung Diffusion

Migration

C

LM,t

? ? ? ? ? ? C

t=0

Migration

C

LM,t

? ? ? ? ? ? C

t=0

Fraunhofer Institut - IVV – Freising (D)

Objectives and Approaches WP5

Objectives Approaches

• 5. To identify food process technologies,

having an impact on distribution and levels

• f FC and PFCs, and to balance

“suspicious” technologies Home cooking Technical processes (milk/potatoes) Mass balanced experiments (degradation/volatilization)

• 6. To investigate the impact of drinking

water/beverage processing on PFC levels Charcoal treatment advanced oxidation (UV-peroxide,

• zonisation) dune infiltration

Fraunhofer Institut - IVV – Freising (D)

Age distribution and water flow of recharged Rhine water transported from river Rhine to Leiduin by pipeline and wells sampled (circled #) in the cross section. Water flow follows the arrows, from left to right KWR – Nieuwegein (NL), Univ of Amsterdam (NL)

Study area cross section of dune transect sampled in this study (full scale = ~1500m x ~50 m)

WP5 Impact of Processing: DW

• Inf. river water (n = 12)

PFHxA PFHpA PFOA PFBS PFHxS PFOS 25 50 75 100

%

Dutch freshwater (n = 12)

PFHxA PFHpA PFOA PFBS PFHxS PFOS 25 50 75

• Inf. rainwater (n = 12)

PFHxA PFHpA PFOA PFBS PFHxS PFOS 25 50 75

%

North Sea water (n = 8)

PFHxA PFHpA PFOA PFBS PFHxS PFOS 25 50 75

WP4+5 Tracking Sources/ Processing

Patterns of PFAS in infiltrated ground water

KWR – Nieuwegein (NL), Univ of Amsterdam (NL)

250 500 750 1000 1250 5 10 15

PFOA Linear Branched

• Conc. (ng/L)

250 500 750 1000 1250 5 10 15

PFOS Distance (m)

• Conc. (ng/L)

Concentrations of non-branched and branched isomers of PFOA and PFOS along the transect sampled in infiltrated water body

Outlook

• Improvement of analytical data quality through

publicly available method protocols

• Website: www.perfood.eu
• Results of PERFOOD project important (and

available) for stakeholders: Dissemination workshops 2011/2012 (PFCs-III/IV)

The presentation is part of the EU project PERFOOD (KBBE-227525), and the financial support of the European Union is gratefully acknowledged.

Acknowledgement

Reviews of Environmental Contamination and Toxicology Vol.208 Perfluorinated alkylated substances Series: Reviews of Environmental Contamination and Toxicology, Vol. 208 De Voogt, Pim (Ed.) 1st Edition., 2010, 132 p. 34 illus., 17 in color., Hardcover ISBN: 978-1-4419-6879-1 Available in hard cover and as electronic book ABOUT THIS BOOK

• Atmospheric Perfluorinated Acid Precursors: Chemistry, Occurrence and Impacts by Cora J. Young and Scott A.

Mabury.

• Isomer Profiling of Perfluorinated Substances as a Tool for Source Tracking: A Review of Early Findings and Future

Applications by Jonathan P. Benskin, Amila O. De Silva, and Jonathan W. Martin.

• Biodegradation of Fluorinated Alkyl Substances

by Tobias Frömel and Thomas P. Knepper.

• Perfluorinated Substances in Human Food and Other Sources of Human Exposure

by Wendy D’Hollander, Pim de Voogt, Wim De Coen, and Lieven Bervoets.

• Index.