PERFOOD PERfluorinated Organics in Our Diet

Pim de VoogtUniversity of Amsterdam - UvA-IBED, Amsterdam /

KWR-CWG, Nieuwegeinw.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

PFOSPFOA

What is significance of findings of PFAS in environment for human exposure?

EFSA (2009): insufficient data for human exposure through diet incl. d.w.+beveragesIn 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 of 17 March 2010

on 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 our 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 andS/N ratio in MS/MS and exact MSexact MSIn LCLC--MS/MSMS/MS record some noise can be typically seen, thus definition

of LOD and LOQ could be based on S/N DEFINITIONS/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 LCexact 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 definitionLOD/LOQ could NOT be based on S/N definition.

S/N = 66.3S/N = 66.3

Time3.20 3.40 3.60 3.80 4.00 4.20 4.40 4.60 4.80 5.00

%

0

100

2009-03-26 - 03 1: TOF MS ES-511.961 40PPM

875S/N:PtP=340282346638528860000000000000000000000.00

MeFOSMeFOSA,A, 0.5 ng/ml0.5 ng/ml

S/N=3.4eS/N=3.4e3838

WP1+2 A

nalytical method developm

ent and analytical quality

food intakes

0,00200,00400,00600,00800,00

1000,001200,001400,001600,001800,002000,00

B CZ D I NL N S UK EU WHO

Countries

g pe

rson

day

01. Cereals & cereal products

02. Sweet products andsubstitutes 03. Vegetables and pulses, freshand processed04. Potatoes, starchy roots andtheir products06. Meat, meat products andsubstitutes07. Fish, seafood and theirproducts08. Eggs

09. Milk and dairy products

10. Fats (vegetable and animal)

11. Miscellaneous

12. Water and other non-alcoholicbeverages13. 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 dataBio-monitoring dataTKTD modelling

ISS

, Rom

e (I) and BfR

, Berlin (D

)

WP 3 + 6

0

200

400

600

800

1000

1200

1400

1600

B CR D I NL N SW UK WHO

EU Countries

Fo

od

in

tak

e (g

/p

ers

on

/d

ay)

01. Cereals & products 02. Sweets03. Vegetables and pulses 04. Potatoes, starchy roots 05. Fruit 06. Meat & products07. Fish, seafood 08. Eggs09. Milk and dairy products 10. Fats11. Miscellaneous 12. Water and non-alcoholic beverages13. Coffee, tea, infusions 14. Alcoholic beverages

Consumption data EUConsumption data EU

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

ISS

, Rom

e (I) and BfR

, Berlin (D

)

WP 3 + 6

PFOS dietary intake in EU COUNTRIES

0

5

10

15

20

25

30

35

40

BE CZ DE IT NL NO SE GB EU

EU Countries

Inta

ke (

ng/d

ay k

g-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

, Rom

e (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 listWere 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 ITLab 1 Lab2

Lab 3

01. Cereals 01. Cereals xRice X X 2

Wheat X X X X 4Oats X x 2

X x 2Barley X X 2Maize X 13 1

02. Sweets 02. SweetsSugar x X X 3 x

Sugar (cane) X 1Honey x X X X 4

Cocoa powder X 9 1

03. Vegetables and pulses

03. Vegetables and pulses

Leafy vegetables Leafy vegetables xlettuce and other

salads x X x X4

spinaches x X 2chicory x X 8 2 x

Stem vegetables Stem vegetables

Survey– Sampling + Distribution

NILU

Tromsoe (N

) Univ of A

ntwerp–

Antw

erp (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

7 5 cm

Schematic graph of lysimeterFraunhofer 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 min40°

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 observed 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 Lebensmit tel

Diffusion Verteilung Diffusion

Migration CLM,t? ?

?? ?

?Ct=0

Verpackung Lebensmit tel

Diffusion Verteilung DiffusionDiffusion VerteilungVerteilung Diffusion

Migration CLM,t? ?

?? ?

?Ct=0Migration CLM,t

? ?

?? ?

?Ct=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 of 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 treatmentadvanced oxidation (UV-peroxide, ozonisation) 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 PFOS0

25

50

75

100

%Dutch freshwater (n = 12)

PFHxA PFHpA PFOA PFBS PFHxS PFOS0

25

50

75

Inf. rainwater (n = 12)

PFHxA PFHpA PFOA PFBS PFHxS PFOS0

25

50

75

%

North Sea water (n = 8)

PFHxA PFHpA PFOA PFBS PFHxS PFOS0

25

50

75

WP4+5 Tracking Sources/ ProcessingPatterns of PFAS in infiltrated ground water

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

0 250 500 750 1000 12500

5

10

15PFOALinear

Branched

Con

c. (n

g/L)

0 250 500 750 1000 12500

5

10

15PFOS

Distance (m)

Con

c. (n

g/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.208Perfluorinated alkylated substancesSeries: Reviews of Environmental Contamination and Toxicology, Vol. 208 De Voogt, Pim (Ed.)1st Edition., 2010, 132 p. 34 illus., 17 in color., HardcoverISBN: 978-1-4419-6879-1Available 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.