PFAS Meeting Book MYM 2023

AOAC INTERNATIONAL PFAS Working Group AOAC Midyear Meeting & Exposition Gaithersburg Marriot Washingtonian Center Gaithersburg, Maryland

PFAS Session Sign In

Thursday, March 16, 2023 1:00pm EST – 4:00pm EST

Draft Agenda

Moderator: Susan Genualdi, PhD (US FDA) PFAS Working Group Chair

I. Welcome & Overview (Bahr) (1:00pm – 1:05pm) Constance Bahr (Coordinator, AOAC INTERNATIONAL) will open the meeting by welcoming attendees and reviewing the agenda. II. Current Status and Future Directions of the PFAS Working Group for the Development of a Standard Method Performance Requirement for PFAS in Food and Feed (Genualdi) (1:05pm – 1:25pm) Susan Genualdi, PhD (Research Chemist, US FDA) will provide an overview of PFAS and give an update on working group progress.

III. Overview of EURL PFAS Guidance Document (Riemenschneider) (1:25pm – 2:10pm)

Christina Riemenschneider, PhD (Food Chemist, EURL POPs/CVUA Freiburg) will give a presentation on the Guidance Document on Analytical Parameters for the Determination of PFAS in Food and Feed developed by the European Union Reference Laboratory (EURL) in collaboration with National Reference Laboratories (NRLs) for halogenated POPs in feed and food and other experts. Q&A will follow.

IV. Method Performance Parameter Discussion (Perinello, Theurillat) (2:10pm – 2:40pm)

Giampalo Perinello (Technical Project Manager, Mérieux NutriSciences ) and Xanthippi Theruillat, PhD (Specialist, Société des produits Nestlé) will each give a presentation to start the working group discussion regarding PFAS and method performance parameters.

V.

Working Group Discussion (Genualdi) (2:40pm – 3:55pm) Susan Genualdi, PhD (Research Chemist, US FDA) will lead the discussion to continue working group efforts.

VI.

Next Steps (Genualdi, Bahr) (3:55pm – 4:00pm) Susan Genualdi, PhD (Research Chemist, US FDA) and Constance Bahr (Coordinator, AOAC INTERNATIONAL) will wrap up the working group discussion with next steps.

VII.

Adjournment

Subject to change without notification.

Susan Genualdi, PhD Research Chemist, US FDA; WG Chair, AOAC PFAS Project

Susan Genualdi is currently a Research Chemist in the Center for Food Safety and Applied Nutrition at the Food and Drug Administration. Her research focuses on developing methods for the analysis of direct and indirect food additives in food and food packaging. For the last 5 years, she has focused primarily on the method development and analysis of PFAS in foods. Prior to her work at the FDA, she received her PhD in Analytical Chemistry at Oregon State University and was a postdoctoral fellow at Environment Canada.

Christina Riemenschneider, PhD Food Chemist, EURL POPs/CVUA Freiburg

Christina Riemenschneider is currently a lab leader in the pesticides and contaminants team at CVUA Frieburg and scientific expert at the EURL for pesticides in food of animal origin and the EURL for halogenated POPs in Freiburg Germany. Prior to her five years at EURL POPs and CVUA Freiburg she attended a traineeship in the pesticides department at European Foods Safety Authority (ESFA) in Parma, Italy and worked as a research scientist at Leibniz Institute for Tropospheric Research in Germany after obtaining her PhD in Analytical and Environmental Chemistry at Helmholtz-Centre for Environmental Research in Leipzig Germany. She also has a Master of Science and Bachelor ’ s degree in Food Chemistry

from the University of Gießen.

Giampaolo Perinello, PhD Technical Project Manager for GKA, Mérieux NutriSciences

Gaimpaolo Perinello is a senior scientist in analytical chemistry and works as a technical project manager for GKAs. He has a strong background in food testing and more than 15 years as Chemistry Lab Director at Mérieux NutriSciences Italia with expertise in food safety and food composition.

Xanthippi Theurillat Specialist - Food Safety & Analytical Sciences, Société des Produits Nestlé S.A.

Xanthippi Theurillat is an Analytical Chemist and a specialist in the Analytical Science Department in the field of food contaminants at Nestlé Research in Lausanne, Switzerland. In 2012, she joined the Regional Swiss Official Food Control Laboratory in Lausanne as a scientific expert in the contaminants section. Since 2015, she is working at the Nestlé Research in Lausanne with a specific focus on the method development in the domain of contaminants, like pesticides, emerging and process contaminants and lately PFAS. Moreover, she participated in projects for the mechanistic understanding of process contaminants which allowed to publish subsequently patent applications.

Draft Applicability Statement

• Quantitative analysis of 30 PFAS in produce, dairy products, seafood, and animal feed

AOAC INTERNATIONAL Midyear Meeting March 13 – 17, 2023 | Gaithersburg, MD

Current Status and Future Directions of the PFAS Working Group for the Development of a Standard Method Performance Requirement for PFAS in Food and Feed

Susan Genualdi USFDA

Proposed Scope

• Development of voluntary consensus standard(s) for a targeted list of PFAS compounds in selected foods with defined (matrix based) Limits of Quantification (LOQ)

AOAC INTERNATIONAL Midyear Meeting March 13 – 17, 2023 | Gaithersburg, MD

Per and Polyfluoroalkyl Substances (PFAS) • Perfluoroalkyl substances are fully fluorinated carbon chain molecules. (e.g. PFOS, PFOA).

• Polyfluoroalkyl substances are not fully fluorinated and fluorine atoms are attached to at least one carbon (but not all) atoms. (e.g. 6:2 FTS)

AOAC INTERNATIONAL Midyear Meeting March 13 – 17, 2023 | Gaithersburg, MD

Sources of PFAS to food

Environmental contamination from the aquatic environment: • Landfill leachate • Effluents from fluorochemical manufacturing facilities • WWTP (wastewater treatment plant) • Reclaimed water – agricultural fields • Contaminated biosolids – agricultural fields • AFFF (aqueous film forming foam) • Contaminated groundwater

Food packaging: • Migration from grease-proof food contact substance • Percent migration dependent on condition of use, time and temperature conditions

• Uptake into livestock • Uptake to agriculture

AOAC INTERNATIONAL Midyear Meeting March 13 – 17, 2023 | Gaithersburg, MD

EU Maximum Levels

Maximum Levels* *microgram ( μ g) per kg of wet weight

Current Regulations

Sum of PFOS, PFOA, PFNA, and PFHxS

Foodstuffs

PFOS PFOA PFNA PFHxS

Eggs, fishery products, bivalve molluscs

USA: • Maine PFOS action level

1

0.3

0.7

0.3

1.7

Muscle meat of fish, except those below (and those below for children Other fish meat Other fish meat (2) Crustaceans and bi valve molluscs, meat and edible offal Offal of bovine animals, sheep, pig, and poultry Meat of game animals, with the exception of bear meat Offal of game animals, with the exception of bear offal Meat of bovine animals, pig and poultry Meat of sheep

2

0.2

0.5

0.2

2

• 0.21 µg/kg milk • 3.4 µg/kg beef

7

1

2.5

0.2

8

35

8

8

1.5

45

3

0.7

1

1.5

5

0.3

0.8

0.2

0.2

1.3

EU: • Regulation (EC) 2022/2388 • Released December 2022 • Maximum levels allowed – effective 1/1/23

1

0.2

0.2

0.2

1.6

6

0.7

0.4

0.5

8

5

3.5

1.5

0.6

9

50

25

45

3

50

AOAC INTERNATIONAL Midyear Meeting March 13 – 17, 2023 | Gaithersburg, MD

Development of an SMPR

• Identify PFAS analytes of interest • Identify priority foods • Define LOQ • Determine required LOQs • Define analytical parameters o Reproducibility o Repeatability o Analytical range

AOAC INTERNATIONAL Midyear Meeting March 13 – 17, 2023 | Gaithersburg, MD

PFAS analytes of interest

Required analytes: PFBA, PFPeA, PFHxA, PFHpA, PFOA, PFNA, PFDA, PFUnDA, PFDoDA, PFTrDA, PFTeDA PFBS, PFPeS, PFHxS, PFHpS, PFOS, PFNS, PFDS, PFUnDS, PFDoDS, PFTrDS, FOSA 9Cl-PF3ONS, 11Cl-PF3OUdS, HFPO-DA, ADONA, 4:2 FTS, 6:2 FTS, 8:2 FTS, 10:2 FTS Optional analytes: diPAPs, monoPAPs, Capstone A&B, FTOHs

AOAC INTERNATIONAL Midyear Meeting March 13 – 17, 2023 | Gaithersburg, MD

Identify priority foods Produce • Fruits • Vegetables • Tubers • Fungi

Seafood • Fish • Shellfish • Crustaceans Meat products (raw, cooked, processed) • Meat (ex: beef, chicken, pork) • Edible offal Feed • Pet food • Animal feed (ex: grain, silage, corn, hay, finished feed product)

• Beverages (ex: fruit/vegetable juice, coffee) • Fruit and vegetable based infant foods Dairy • Milk • Powdered milk • Infant Formula • Eggs • Cheese • Adult milk-based powders (ex: protein powder - animal and plant based)

AOAC INTERNATIONAL Midyear Meeting March 13 – 17, 2023 | Gaithersburg, MD

Define LOQ AOAC definition - The minimum concentration or mass of analyte in a given matrix that can be reported as a quantitative result Preliminary starting point for discussion: • LOQ is determined as the lowest spiking level that meets the recovery and repeatability requirements. LOQ can be estimated based on extrapolation of signal to-noise (S/N) ratio obtained for a concentration level naturally present in the evaluated matrix to a concentration level that would correspond to S/N = 10

AOAC INTERNATIONAL Midyear Meeting March 13 – 17, 2023 | Gaithersburg, MD

Determine required LOQs

• Limit of Quantification for foods/analytes with maximum residue level/action level established • Example: o Codex – required LOQ is 2/5 of action level

• Limit of Quantification for foods/analytes without maximum residue level/action level established • Example o Meets certain performance criteria o Required analytical range

AOAC INTERNATIONAL Midyear Meeting March 13 – 17, 2023 | Gaithersburg, MD

Next Steps:

• Identify performance criteria for LOQ and method o Recovery % – How is recovery calculated?

– Different ranges for those with matching isotopically labeled standards? o Reproducibility (within lab) o Repeatability (within lab) o Required analytical range – different for those with action levels/without? o S:N requirement – how calculated? Peak to peak?

o Ion ratios o Trueness o SRM evaluation?

AOAC INTERNATIONAL Midyear Meeting March 13 – 17, 2023 | Gaithersburg, MD

Other challenges to be addressed:

• Incorporating blanks/background into LOQs/performance criteria • PFOS, PFHxS, PFOA standards linear/branched – how to quantify? • PFBA, PFPeA – analytes with one transition – how to confirm? • Targeted surrogate recoveries? Criteria? • How to deal with interferences? (e.g. cholic acids)

AOAC INTERNATIONAL Midyear Meeting March 13 – 17, 2023 | Gaithersburg, MD

Overview of EURL PFAS Guidance Document

Christina Riemenschneider, Alexander Schächtele, Bjorn Berendsen, Stefan van Leeuwen

AOAC Midyear Meeting, March 16, 2023

Core Working Group ‚PFAS‘

 formed in 2018

 consists of members of the EURL network (national reference laboratories andinvited experts) with relevant experience in PFAS analysis

 works on analytical methodologies , proposals for analytical criteria , European Commission requests , …

 meets once a year

AOAC Midyear Meeting - Overview of EURL PFAS Guidance Document

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Timeline of the EURL Guidance Document

May 2022

01 March 2022

2020

08 March 2022

23/24 November 2021 Presentation

12 October 2021 Final discussion on main points

May 2023

23 June 2021 1 st draft of guidance document

Publication of Annex on EURL POPs

Question naires on analytical criteria etc.

Publication of Version 1.0 on EURL website

Publication of updated Version 2.0

Publication of updated Version 1.1

of draft at EURL/NRL Workshop

website; updated Version 1.2

AOAC Midyear Meeting - Overview of EURL PFAS Guidance Document

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Aim and status of the Guidance Document

Aim :  harmonization of PFAS analysis in food and feed within the EU  supportslaboratories starting with PFAS analysis

Status :  not legally binding  Commission Implementing Regulation (EU) 2022/1428 Part B.1. „ The principles as described in the EURL Guidance Document […] shall be followed “  deviation allowed only for sound reasons

AOAC Midyear Meeting - Overview of EURL PFAS Guidance Document

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Content of the Guidance Document

 focus on analysis; no advice on sampling

 analytes of interest

 PFCAs (C4-C14), PFSAs (C4-C13), FOSA, selected substitutes (e.g. GenX)

 matrices



food (animal and plant origin) and feed

 aspects to avoid contamination

 e.g. PTFE products, teflon, aluminiumfoil , …

AOAC Midyear Meeting - Overview of EURL PFAS Guidance Document

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Content of the Guidance Document

 method performance requirements

 specificcriteria for trueness, precision, and LOQ  validation(parameters, criteria, andexample approach)  quantification



br-PFOS

 measurement

 interfering substances, peak identificationcriteria , …  reporting of results



rounding and measurement uncertainty

AOAC Midyear Meeting - Overview of EURL PFAS Guidance Document

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Annex of the Guidance Document

 provides practical information for laboratories who want to get started with PFAS analysis, or wish to look for alternative approaches Content:  Information on (internal) standards; reducing impact of background contamination (possible sources)  Modules on sample preparation  example approaches

AOAC Midyear Meeting - Overview of EURL PFAS Guidance Document

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1. Specific performance criteria

AOAC Midyear Meeting - Overview of EURL PFAS Guidance Document

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Specific performance criteria

Table 1: Validation parameters and performance criteria

Parameter

Compliance testing of maximum levels

Monitoring purposes

Trueness

±20%

±35%

Within-laboratory reproducibility (intermediate precision)

≤ 20 %

≤ 25 %

based on Commission Recommendation (EU) 2022/1431 Number 6. and 7.

LOQ

 LOQ = lowest content of the analyte which can be measured with reasonable statistical certainty, i.e. the lowest concentration or mass of the analyte that has been validated with acceptable accuracy by applying the complete analytical method and identification criteria

AOAC Midyear Meeting - Overview of EURL PFAS Guidance Document

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Specific performance criteria

Table 2: Mass spectrometric performance and peak identification criteria

(U)HPLC-LRMS

Unit mass resolution

Typical systems (examples)

MS/MS triple quadrupole, ion trap, Q-trap, Q-TOF, Q-Orbitrap

Acquisition

Selected or multiple reaction monitoring (SRM, MRM)

Minimum number of ions

2 product ions

Ion ratio from sample extracts should be within ± 30 % (relative) of average of calibration standards from same sequence.

Ion ratio

Signal to noise (S/N) ratio

≥ 3

The ratio of the chromatographic RT of the analyte to that of the IS (i.e. relative RT of the analyte) shall correspond to that of the calibration standard with a maximum deviation of 1 %. Analyte peaks from both product ions in the extracted ion chromatograms must fully overlap.

Retention time (RT)

Other

AOAC Midyear Meeting - Overview of EURL PFAS Guidance Document

16.03.2023

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Confirmation of results for PFBA, PFPeA, and FOSA

 PFAS with only one specific MS/MS transition (e.g. PFBA, PFPeA) should be verified using a second chromatographic separation method (i.e. the use of a secondary LC elution on a different analytical column and eluent) or another MS method (e.g. the use of high resolution MS )

AOAC Midyear Meeting - Overview of EURL PFAS Guidance Document

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2. Quantitation of branched isomers

AOAC Midyear Meeting - Overview of EURL PFAS Guidance Document

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Quantitation of branched isomers

Why?  historical production of PFAS using electrochemial fluorination yielded in

 70-80% L-PFOS  80-85% L-PFOA  ~ 95% L-PFHxS  remaining products are branched isomers  contribution to contamination of food is not negligible

 current version of Guidance Document focuses on PFOS, only  contribution of branched isomers highest for PFOS  PFOS is main compoundin food

AOAC Midyear Meeting - Overview of EURL PFAS Guidance Document

16.03.2023

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Quantitation of branched PFOS (br-PFOS)

How?  quantified using L-PFOS (native and ILIS)  mass transitions e.g. m/z 499>99, 499>80

AOAC Midyear Meeting - Overview of EURL PFAS Guidance Document

16.03.2023

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Quantitation of branched PFOS (br-PFOS)

Problem  response factors of isomers differ in MS/MS

 accurate quantification of br-PFOS is hardly possible in routine analysis

A1

A2

A3

A4

Chromatographic separation of all isomers

yes

no

no

no

Standards of individual isomers

L-PFOS br-PFOS 1)

T-PFOS 2)

Quantification using …

Accuracy of quantification

+++

+(+)

+(+)

-

Applicable in routine analysis?

+

+++

++(+)

++(+)

1) containing L-PFOS (78.8%) + branched isomers (21.1%)  analytical standard 2) containing L-PFOS (68.3%) + branched isomers (31.7%)  technical grade

?

most pragmatic approach balances between accuracy and efforts/costs

• •

AOAC Midyear Meeting - Overview of EURL PFAS Guidance Document

16.03.2023

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Quantitation of branched PFOS (br-PFOS)

A2

A3

br-PFOS 1)

Quantification using …

L-PFOS

+(+)

+(+)

• underestimation when applying transition m/z 499 → 99 • overestimation when applying transition m/z 499 → 80

• isomer pattern in food samples can vary

Accuracy of quantification

1) containing L-PFOS (78.8%) + branched isomers (21.1%)  analytical standard

AOAC Midyear Meeting - Overview of EURL PFAS Guidance Document

16.03.2023

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Thank you for your attention!

contact us at info@eurl-pops.eu

Bissierstraße 5 79114 Freiburg Germany

EURL forhalogenated POPs in Feed and Food

info@eurl-pops.eu

www.eurl-pops.eu

PFAS in food 2023

dr. Giampaolo Perinello

■ Senior scientist - analytical chemistry ■ Technical project manager for GKAs ■ Strong background in food testing

■ > 15 years as Chemistry Lab Director at MxNS ■ Expertise in Food safety & Food composition

Agenda

PFAS testing method on food: an example of what is feasible

▪ Our experience

▪ EU regulatory framework

▪ The analytical approach

PFAS MxNS experience

PFAS methods for waters

starting PFAS testing >10 years ago

routine activity > 3000/year

5

PFAS 1° method on food

Liquid milk => LOQs 5 ppt Other food => LOQs 50 ppt

MxNS first method ■ 2019-2020 ■ LC-HRMS (Orbitrap) ■ Accredited ■ PTs

PFBA, PFPeA, PFHxA, PFHpA, PFOA , PFNA , PFDA, PFUnA, PFDoA, L PFBS, L-PFPeS, L- PFHxS , L PFHpS, L- PFOS , L-PFDS

■ UNI EN 15662:2018: QuEChERS extraction ■ ISO 25101:2009 for waters ■ EPA 537.1 2018 for food

End of 2021: need for a new method

6

PFAS EU Regulatory framework

PFAS: Regulatory framework EU

Stockholm Convention and POP Regulation REACH Regulation

2017 PFOA and PFOS are classified as priority hazardous substances under the Water Framework Directive (EC, 2017; EU, 2000) 2020 EU Directive 2020/2184 on drinking water, sum of PFAS < 0,50 µg/l – analytical guidelines to be decided before 2024 (a list of PFAS is provided in the Annex). Directive to be adopted by Member States in 2023.

2020 EU regulation restricts PFOA, PFOA salts and related substances for production and placing on the market (a maximum of 25 ppb of PFOA including its salts or 1 000 ppb of one or a combination of PFOA-related substances) 2020 Denmark first European country to ban all organic fluorinated compounds in food contact paper and cardboard – reference limit 20 µg/g of paper 2022 Netherland bans PFAS included in the EFSA Opinion in food contact paper

2023 ECHA Published the list of 10 thousands PFAS for which Denmark, Germany, The Netherland, Norway and Sweden asked for restrictions.

8

PFAS: Regulatory framework

EU -FOOD

-Requested data on perfluoroalkyl substances in food - Call for continuous collection of chemical contaminants occurrence data in food and feed 2010-2016 ( PFAS included )

Regulation (EU) 2022/2388 regarding the Maximum Limits on PFOS , PFOA , PFNA and PFHxS in foodstuffs of animal origins, that amends the Regulation (EC) 1881/2006

-Call for continuous collection of chemical contaminants occurrence in food and feed ( PFAS included ) EC asked EFSA to reassess the risk PFAS pose to human health using data that has become available

2020

2012

2018

2022

2010

PFAS data evaluation

-Call for continuous collection of chemical contaminants occurrence data in food and feed ( PFAS included ) EFSA Opinion: - Risk to human related to the presence of perfluoroalkyl substances in food - PFAS in food: EFSA assesses risk and sets tolerable intake

EFSA Scientific Report Perfluoroalkylated substances in food: occurrence and dietary exposure

▪ Commission Recommendation (EU) 2022/1431 on the monitoring of a list of 28 PFAS in food matrices, for the following 4 years ▪ Implementing Regulation (EU) 2022/1428 regarging the PFAS sampling and analytical guidelines ▪ EURL-POPs Guidance Document

2012: https://efsa.onlinelibrary.wiley.com/doi/abs/10.2903/j.efsa.2012.2743 2020: https://www.efsa.europa.eu/en/efsajournal/pub/6223 2020: https://www.efsa.europa.eu/en/news/pfas-food-efsa-assesses-risks-and-sets-tolerable-intake

9

PFAS: Regulatory framework

EU -FOOD

Regulation (EU) 2022/2388

Recommendation (EU) 2022/1431

List of 28 molecules of PFAS Monitoring all the food matrices:

■ Food of animal origin ■ Food of plant origin

Introduction of Maximum Limits for: in animal origin foodstuffs (egg, meat and fish)

■ Baby food ■ Beverages Limits of quantification target: up to 1 ppt for some matrices.

PFOS

Perflorooctane sulfonic acid

PFOA

Perfluorooctanoic acid

PFNA

Pefluorononanoic acid

PFHxS

Perfluorohexane sulfonic acid

Sum of PFOS. PFOA, PFNA and PFHxS

10

PFAS Mérieux NutriSciences experience

The new analytical approach in food

PFAS testing

■ Cutting-edge analytical instrument capable of achieving the required sensitivity

Screening in line with EU recommendation

■ LC-MS/MS analytical technique

■ Dedicated line to the analysis of PFAS in food

● Branched isomers for the 4 main PFAS included ● Capstone A & capstone B included ● Fluorotelomers alcohol excluded ● Fluorotelomers sulfonates: 6:2 FTS ● Labelled internal standards

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The analytical approach in food

PFAS testing

Screening of 4 main PFAS: PFOS, PFOA , PFNA and PFHxS and their sum

One method declined in different packages

■ LOQs of the four main PFAS - 1 ppt ■ LOQs of the remaining PFAS - 10 ppt ■ LOQ of PFBA - 25 ppt

Extended Screening of PFAS , including the 4 main PFAS (PFOS, PFOA, PFNA e PFHxS) and their sum

Accredited Analysis (since Oct. 2022)

The developed method can detect PFAS in full compliance with the legal limits and the monitoring requirements of the Recommendation (target LOQs); the method was validated in >40 matrices. .

Sensitivity & Contamination

Cutting edge instrument (dedicated) Assess your own background Contain the risk of contamination

▪ Animal origin products (meats and derivatives, fish and derivatives, shellfish, egg) ▪ Plant origin products (including fruits and vegetables) ▪ Baby food ▪ Milk & dairy products ▪ Raw materials ▪ Feed

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PFAS and the impact on the food supply chain

Prevention

Root Cause Analysis

Testing speed

Previous method vs the actual analytical strategy

June 2021

July 2022 Oct 2022

today

PFAS food testing LC-HRMS LOQs 50 ppt

1000 samples 15% positive 0.5% OOS

● MxNS new method , Oct. 2022 ○ LC-MS/MS ○ LOQ 1 ppt ○ Food ■ finished products ■ raw materials ○ Feed

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Sample procedure guidelines

Implementing Regulation (EU) 2022/1428 Sampling

Sample collection ■ The analyst shall ensure that samples do not become contaminated during sample preparation ■ Equipments into contact with samples should NOT contain PFAS, thus replaced with:

Storage and transmission ■ Samples shall be placed in clean and inert containers , made of polypropylene, polyethylene or other PFAS-free material, able to

The person responsible for sampling shall: ■ NOT wearing clothing of gloves that contain fluoropolymer linings or that are treated with PFAS to improve water and stain repellence

preserve the integrity of the sample protecting from any contamination and possible changes

■ Glass container NOT suggested

■ ■ ■

stainless steel

■ NOT use PFAS containing

high density polyethylene

moisturizers, cosmetics, hand cream, sunscreens and related products at the sampling day

polypropylene

■ Clean with PFAS FREE water, detergent and solvent.

Finished Products must be sent in the original commercial packaging – A dedicated closed product must be destinated for PFAS analysis, if additional analysis are required

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Implementing Regulation (EC) 2022/1428 EURL-POPs: Guidance Document on Analytical Parameters for the Determinationof Per-and Polyfluoroalkyl Substances PFAS in Food and Feed

Mérieux NutriSciences’ appointments

2022

2023

22.02.2023

FREE WEBINAR New PFAS Regulation: instructions for food industries

17

Thank you Giampaolo Perinello giampaolo.perinello@mxns.com Phone – +39 0423 7177

MXNS Italy contact– food.italy@mxns.com Head Office – Via Fratta 25, 31023 Resana (TV) www.merieuxnutrisciences.com/it Copyright: The document and its entire content are subject to copyright law. They may not be copied other than for non-commercial purposes and internal use; appropriate reference shall always include copyright notices. Nothing contained herein shall be construed as conferring by implication or otherwise any license or right under any copyright of Mérieux NutriSciences Corporation, or any affiliated party. Disclaimer: This document contains information derived from third party published literature or other public resources for general information purposes only. This document and the information contained herein are provided “As Is”, and are not intended to be exhaustive. Consequently, Mérieux NutriSciences Corporation shall not be held liable for any errors, inaccuracies or omissions in the content of this document, which is not meant to be a substitute for the advice provided by experts or other professionals. Neither Mérieux NutriSciences Corporation nor any other party involved in creating, producing or delivering this document shall be held liable for any direct, indirect, incidental, consequential or special damage or punitive damages arising out of use of the document by any person. Photos: Shutterstock, Pixabay, Mérieux NutriSciences

Towards reliable determination of PFAS in food

Xanthippe Theurillat Société des Produits Nestlé, Nestlé Research, Lausanne, Switzerland

Interlaboratory study - Design ❑ 5 different laboratories in Europe (A – E), 4 out of 5 accredited ISO 17025.

❑ Based on LC-MS/MS analysis.

❑ Variable scope of analytes and LOQs among the labs.

❑ Dispatch 3 samples: portions of identical composite food – cereal-based ingredient: homogenization by cryo-milling and storage at -20 o C before shipping.

❑ Two trials:

❑ 1 st : September 2022 samples sent to all labs (A - E).

❑ 2 nd : November 2022 samples sent to 2 of them (A and D).

AOAC INTERNATIONAL Midyear Meeting March 13 – 17, 2023 | Gaithersburg, MD

Interlaboratory study - Results

AOAC INTERNATIONAL Midyear Meeting March 13 – 17, 2023 | Gaithersburg, MD

Methods in the literature – Background contamination

AOAC INTERNATIONAL Midyear Meeting March 13 – 17, 2023 | Gaithersburg, MD

Methods in the literature – Reported LOQs

LOQs expressed in  g/kg

AOAC INTERNATIONAL Midyear Meeting March 13 – 17, 2023 | Gaithersburg, MD

Methods in the literature – LOQ determination

AOAC INTERNATIONAL Midyear Meeting March 13 – 17, 2023 | Gaithersburg, MD

Take-home message • Today, risks of inconsistency in PFAS analysis.

• Method performance criteria is key.

AOAC INTERNATIONAL Midyear Meeting March 13 – 17, 2023 | Gaithersburg, MD

AOAC INTERNATIONAL PFAS Working Group

Reminder : The focus of this working group is to develop a voluntary consensus standard(s) for a targeted list of PFAS compounds in selected foods with defined Limits of Quantification (LOQ). SMPRs are to be used as a guide to method developers for the development of new methods and as the basis for AOAC method acceptance and approval. The scope of this working group does not include packaging materials and water.

AOAC INTERNATIONAL Midyear Meeting March 13 – 17, 2023 | Gaithersburg, MD

AOAC mid-year working group meeting

Discussion on analytical method parameters 3/16/23

Preliminary starting point for discussion:

• LOQ is determined as the lowest spiking level that meets the recovery and repeatability requirements. LOQ can be estimated based on extrapolation of signal-to-noise (S/N) ratio obtained for a concentration level naturally present in the evaluated matrix to a concentration level that would correspond to S/N = 10

EURL document • For the LOQ estimation in PFAS determinations, the lowest validated level approach is recommended. [25] This means that the LOQ is the lowest successfully validated level of an analyte, for which it has been demonstrated that the respective criteria for identification (see section 2.4.3), trueness and precision (see section 2.1.1 and 2.1.3) are met.

EURL document continued..

Pesticide document – SANTE/12682/2019

• Mean recoveries from initial validation should be within the range 70 – 120%, with an associated repeatability RSDr ≤ 20%, for all analytes within the scope of a method. • In exceptional cases, mean recovery rates outside the range of 70-120% can be accepted if they are consistent (RSD ≤ 20%) and the basis for this is well established (e.g. due to analyte distribution in a partitioning step),but the mean recovery must not be lower than 30% or above 140%.

PCBs - Commission Regulation (EU) 2017/644 of 5 April 2017

• The limit of quantification of an individual congener may be identified as (a) the concentration of an analyte in the extract of a sample which produces an instrumental response at two different ions to be monitored with a S/N (signal/noise) ratio of 3:1 for the less intensive raw data signalor, if for technical reasons the signal-to-noise calculation does not provide reliable results, • (b) the lowest concentration point on a calibration curve that gives an acceptable (≤ 30 %) and consistent (measured at least at the start and at the end of an analytical series of samples) deviation to the average relative response factor calculated for all points on the calibration curve in each series of samples.

EPA 1633 – SLV report – fish tissue

• Limit of Quantification Verification analysis – prepared at 2 times the LOQ • All target analytes were within the 70-130% interim recovery limits with two exceptions – PFDoS at 61.35% and MeFOSE at 237.5%. This method does not look for PFUnDS or PFTrDS • Seven EIS exceeded the interim acceptance criteria (50-200%) – 13 C 2 PFTeDA (47.9%), D3-NMeFOSAA, D5-NEtFOSAA, D7-NMeFOSE, and D9-NEtFOSE. The upper limit was exceeded for 13 C 2 -4:2 FTS (221.5%) and D5-NEtFOSAA • LOQs ranged from 0.3 ng/g to 10 ng/g for solids, sediments, biosolids and tissues (4, 6, and 10*LOQ are low, medium, and high spiking levels)

Summary

• Reproducibility • EURL

• Repeatability • EURL

• 80-120% for compliance • 65-135% for monitoring

• ≤ 20% for compliance • ≤ 25% for monitoring

• Pesticides

• Pesticides • ≤ 20% • EPA 1633 – PFAS in fish tissue • Everything was ≤ 20% except NMeFOSE • CODEX

• 70-120% • EPA 1633 – PFAS in fish tissue • 70-120 (PFDoS 62%) • CODEX

• 40-120% for 1 ppb method level • 60-115% for 10 ppb method level

• RSD r - 22% for 1 ppb method level • RSD r - 22% for 10 ppb method level • RSD R - 44% for 1 ppb method level • RSD R - 44% for 10 ppb method level

Method Performance Parameters for foods/analytes with maximum residue level/action level

Parameter

Produce

Dairy

Seafood

Meat

Feed

Analytical range (ppb)

Ex: 0.1-10

LOQ (ppb)

Ex: 2/5 of action level

LOD (ppb)?

Recovery % (for analyte with matching isotopically labeled standard) Recovery % (for analyte without matching isotopically labeled standard)

Ex: 40-120

Ex: 30-140

RSD r %

Ex: ≤ 20

RSD R %

Ex: ≤ 30

S:N ratio

Ex: 10

Method Performance Parameters for foods/analytes for monitoring purposes

Parameter

Produce

Dairy

Seafood

Meat

Feed

Analytical range (ppb)

Ex: 0.1-10

LOQ (ppb)

Ex: 0.1

LOD (ppb)?

Recovery % (for analyte with matching isotopically labeled standard) Recovery % (for analyte without matching isotopically labeled standard) RSD r %

Ex: 40-120

Ex: ≤ 20

RSD R %

Ex: ≤ 30

S:N ratio

10