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Gianfranco Brambilla
Dirigente di Ricerca
Dipartimento Alimenti, Nutrizione e Sanità Pubblica Veterinaria
Istituto Superiore di sanità, Roma
Dipl. EBVS – EAVPT, Abilitazione Nazionale H7/04
Criteria supporting the planning of a Reference Material
for PFAS analysis in Environmental&Food matrices
INTERCIND ANNUAL MEETING BOLOGNA POP’S DAY: May 24, 2019
Acknowledgements:Grant MoH #IZS SA RC 2016«Development of target and untarget approaches for PFAS analysis»
Project leader:Cecilia Testa, IZS SA SS
Dorte Hertze NILU TromsoCarolina Barola IZS UM PGGianfranco Brambilla ISS RMGiannina Chessa IZS SA SSRoberta Galarini IZS UM PGGiulio Lora Agrolab VCSimone Moretti IZS UM PGDonatella Pietraforte ISS RMNicola Rubattu IZS SA SSSeveryn Salis IZS SA SSWerner Tirler Eco-Research BZGiulio Voto Eco-Research BZ
Sampling:Alessandro Dondo IZS PLVdA TOGiorgio Fedrizzi IZSLER BORocco Martoccia ASL PZWalter Mignone IZS PLVdA IMLaura Serracca IZS PLVdA SP
Outline
OECD perspective in PFAS
analysis
Analytical challenges in a
environment & health risk-driven
context
Evidence-based choices of
matrices proposed as Reference
Material:
a) wild boar liver;
b) leachate
Future developments:
- Criteria
- Interlab Studies
- PT
- Peer reviewed publications
The PFAS funnel: from (unknown) poly-fluorinated precursors
to known perfluorinated chemicals
from: Ross I, Hurst J, 2019. Managing Risks and Liabilities associated with PFASs. CL:AIRE TB 19.
Towards stricter Health-Based Guidance Values….
PFAS Agency HBGV
(ng/kg per giorno)
Toxicological
End Point
PFOS EFSA (2018) 1,8 (150 2008) dislipemia
FSANZ (2017) 20 developmental toxicity
US EPA (2016) 20 developmental toxicity
US ATSDR (2018) 2 developmental toxicity
PFOA EFSA (2018) 0,8 (1500 2008) dislipemia
FSANZ (2017) 160 developmental toxicity
RIVM (2016) 12,5 liver enlargment
US EPA (2016) 20 developmental toxicity
US ATSDR (2018) 3 developmental toxicity
Composto C (n) RRF
PFBS 4 0,001
PFHxS 6 0,6
PFOS 8 2,0
PFBA 4 0,05
PFHxA 6 0,01
PFOA 8 1,0
PFNA 9 10
PFUnA 11 4,0
PFDoA 12 3,0
PFTeDA 14 0,3
PFHxDA 16 0,02
PFOcDA 18 0,02
Gen X 6 0,06
…Probably framed within a cumulative toxicity approach…
Relative Response Factors (RRFs) of different PFAS with respect to liver toxicity (RIVM Opinion, 2018)
PROPOSED LIMITS (EU COMMISSION) TO TOTAL PFAS OF
TOXICOLOGICAL RELEVANCE IN THE REVISION OF DRINKING
WATER DIRECTIVE
http://www.europarl.europa.eu/sides/getDoc.do?type=REPORT&reference=
A8-2018-0288&format=XML&language=IT
UNDER DISCUSSION
PFAS - single 0.10 μg/L
PFAS = every per- and poli- fluorinated
chemical (CnF2n+1−R) of toxicological relevance
according to OECD definition
PFAS - Total 0.50 μg/L
Total PFAS – sum of PFAS chemicals of
toxicological relevance (CnF2n+1−R) according to
OECD definition
….Or extended to an overall sum of PFAS of toxicological relevance
and to their precursors.
TLPFOS TL PFOA Commodities
pg/g pg/g
13.04 56.52 Cereals
37.58 66.22 Vegetables
14.13 19.79 Fruit
21.92 21.92 Potatoes
29.09 14.55 Meat
541.2 58.82 Fish&Seafod
14.39 8.633 Dairy
77.42 51.61 Eggs
34.78 34.78 Oils and Fats
0.611 6.155 DW
10.00 10.00 Sweets
4.000 4.000 Wine and Spirits
Computed analytical
Threshold Levels (TL) for
the Italian Population –
Adults, based on food items
consumption, on their
relative contribution to the
PFAS intake, and on the
2018 HBGV proposed by
EFSA:
PFOS = 1.8 ng/kg bw per day
PFOA = 0.8 ng/kg bw per day
This would drive analytical LOQs towards ppt level in food matrices,
accounting for the HBGV for PFAS and the contribution/allocation of
each food commodity to the overall intake (drinking water included)
Requirement of a matrix candidate as Reference
Material for PFAS analysis
Fit-for-purpose presence of PFAS of toxicological
concern and their precursors
Suitable for post-acquisition and non-target analysis.
Suitable for the application of Total Organic Fluorine
(TOF) protocols to reveal the presence of precursors
of PFAS of toxicological relevance.
TOPA analysis
(Total Oxidable Precursors Assay)
(Houtz and Sedlak, 2012)
Free radical based cleavage of LC –PFAS)
>> C 8 >> C2 – C6
LC PFAS
LC PFAS
•OH
Why wild boar liver?
Sentinel of medium-long
chained PFAS bound to
Organic Carbon of top soil
Sentinel of short chained
PFAS uptaken by roots,
tubers.
Interference of Cholic Acids
with PFOS acquisition
Expected Ion Suppression
phospholipids mediated
Brambilla G, Testa C, Fedrizzi G, Dioxin 2016
Statistical descriptors of selected PFCAs and PFSAs
occurrence in muscle and liver of wild boars (N = 63),
in Italy. Values expressed as ng/g fresh weight
28 livers from adult wild
boars drawn by Official Vets
in a risk-oriented way, and
pooled.
Different geo-referenced
PFAS pressures accounted
for.
◊ PFAS Plant
○ Oil Drilling
♦ Biosolids as soil improvers
▼Anthropogenic pressures
░ Rainfalls
◊
○
♦▼
░ ▼
N
Pool of wild boar livers drawn at local slaughterhouses by Official Vet Inspectors of
the Italian national health system, from areas officially free from Africa Swine Fever.
Livers were ground together with ultraturrax, with the addition of 0.1% w/w of Beta
Hydroxy Toluene – BHT as preservative), poured in 40 mL glass jars, and sterilized
with steam (+120 °C, 20 min, 1.3 bar). Jars were then stored at Room Temperature,
in the dark.
analyte
Wild boar liver
Range (µg/kg)
1 PFBA (Perfluoro-n-butanoic acid) 0.1 – 1.0
2 PFPeA (Perfluoro-n-pentanoic acid) 0.01 – 0.1
3 PFBS (Perfluoro-1-butanesulfonate) 0.1 – 1.0
4 PFHxA (Perfluoro-n-hexanoic acid) 0.1 – 1.0
5 PFPeS (Sodium perfluoro-1-pentanesulfonate) 0.1 – 1.0
6 HFPO-DA (2,3,3,3-tetrafluoro-2-(1,1,2,2,3,3,3-heptafluoropropoxy)-propanoic acid) <0.01
7 PFHpA (Pefluoro-n-heptanoic acid) 1.0 - 10
8 PFHxS (Perfluoro-1-hexanesulfonate) 0.1 – 1.0
9 PFHpS (Sodium perfluoro-1-heptanesulfonate) 0.1 – 1.0
10 NaDONA (Sodium dodecafluoro-3H-4,8-dioxanonanoate) <0.01
11 PFECHS (Potassium perfluoro-4-ethylcyclohexanesulfaonate) <0.01
12 6:2FTS (Sodium 1H,1H,2H,2H-perfluorooctane sulfonate) 0.1 – 1.0
13 PFOA (Perfluoro-n-octanoic acid) 10 - 100
14 PFOS (Perfluoro-1-octanesulfonate) 20 - 200
15 PFNA (Perfluoro-n-nonanoic acid) 10 - 100
16 FOUEA (2H-Perfluoro-2-decenoic acid) 0.01 – 0.10
17 FOEA (2-Perfluorooctyl ethanoic acid) <0.01
18 9Cl-PF3ONS (Potassium 9-chlorohexadecafluoro-3-oxanonane-1-sulfonate) <0.01
19 FHpPA (3-Perfluoroheptyl propanoic acid) <0.01
20 8:2 PAP (Sodium 1H,1H,2H,2H-perfluorodecylphospate) 10 - 100
21 8:2FTS (Sodium 1H,1H,2H,2H-perfluorodecane sulfonate) 0.1 – 1.0
22 L-PFNS (Sodium perfluoro-1-nonanesulfonate) 0.01 – 0.1
23 PFDA (Perfluoro-n-decanoic acid) 1.0 – 10
24 N-MeFOSAA (N-methylperfluoro-1-octanesulfonamidoacetic acid) <0.01
25 PFDS (Perfluoro-1-decanesulfonate) <0.01
26 PFUdA (Perfluoro-n-undecanoic acid) 1.0 – 10
27 N-EtFOSAA (N-ethylperfluoro-1-octanesulfonamidoacetic acid) <0.01
28 11Cl-PF3OUdS (Potassium 11-chloroeicosafluoro-3-oxaundecane-1-sulfonate) <0.01
29 PFDoA (Perfluoro-n-dodecanoic acid) 1.0 – 10
30 PFDoS (Sodium perfluoro-1-dodecanesulfonate) 0.01 – 0.10
31 PFTrDA (Perfluoro-n-tridecanoic acid) 2.0 - 20
32 PFTeDA (Pefluoro-n-tetradecanoic acid) 1.0 - 10
33 PFHxDA (Perfluoro-n-hexadecanoic acid)* 0.1 – 1.0
34 PFODA (Perfluoro-n-octadecanoic acid) 0.01 – 0.10
Indicative range of
contamination
(ng/g fresh weight)
for 34 PFAS
considered in the
wild boar liver pool.
LC-HRMS analysis
Courtesy
Roberta Galarini
IZSUM, Perugia
0.01 - 0.10
0.10 - 1.00
1.00 - 10.0
10.0 – >100
ng/g
Review of PFAS occurrence in leachate. Hamid et al., 2018
Why a leachate?
Water-based
PFCAs/PFSAs
precursors
Untarget analysis
TOF protocols
Analytes generally
more concentrated
than in water
Leachate, from an urban waste landfill, kindly provided by a private lab in
charge of internal checks. Leachate was poured in glass bottles for
sterilization (+120 °C, 20 min, 1.3 bar), filtered on Whatman No. 5 filter, and
under stirring, aliquots of 12 mL each were prepared in 15 mL sterile PP vials.
Effects of persulfate and microbial fermentation on the release of
PFOA from precursors in a leachate.
Courtesy Werner Tirler, Eco-Tresearch Bolzano
Future developments:
Consolidation of homogeneity and stability tests on target materials
Proposition and discussion of analytical criteria for PFAS analysis in
food matrices within II.ZZ.SS/ISS network with respect to:
LOQs = 0.1 ppb
Identification Criteria
Chromatographic resolution
Linear vs branched isomers resolution and their quantification
Cholic acids interference
Ion Suppression
Procedural Blank contribution and its management in term of results
reporting
Internal Standards representative of a PFAS sub-group
Identification of unknows PFAS via mass loss/mass defects?
Development of a report format
Delivery of materials to interested labs for intercalibration study
Delivery of materials to an accredited PT provider
PFAS C ng/g ng/g
A B
PFBA C4 4.19 43.0
PFPeA C5 4.75 29.6
PFHxA C6 2.58 8.95
PFHpA C7 0.200 0.524
PFOA C8 2.05 9.77
PFNA C9 0.350 0.200
PFDA C10 1.95 9.64
PFBS C4 0.500 0.500
PFPeS C5 0.130 0.130
PFHxS C6 0.350 0.350
PFHpS C7 0.120 0.120
PFOS C8 1.80 9.11
PFNS C9 0.120 0.120
PFDS C10 0.200 0.200
Risultati di un recente
PT su PFCAs e PFSAs
in alimenti (A e B).
In grassetto i dati che
hanno potuto avere un
valore di consenso (22
– 30 labs)
Thank you for the kind attention
https://www.oecd.org/chemicalsafety/portal-perfluorinated-chemicals/
Help us to raise the awareness about PFAS
Contribute to the development of Risk Reduction
