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Enhancing the ability to detect and monitor PFAS

Author: Arp, Hans Peter H.
Publisher: Zenodo
DOI: 10.5281/zenodo.17684814
Source: https://zenodo.org/records/17684814/files/Arp_Keynote_Detection_Monitoring.pdf
This p ojec has ecei ed unding om he Eu opean Union’s Ho izon 2020
esea ch and inno a ion p og amme unde g an ag eemen No 101036756.
Enhancing he abili y o
de ec and moni o PFAS.
Wa e Resilience Wo kshop
EUROPEAN COMMISSION
DIRECTORATE-GENERAL FOR RESEARCH
AND INNOVATION
Di ec o a e B –Heal hy Plane
B.4 –Oceans, Seas and Wa e s
B ussels, No embe 21, 2025
Hans Pe e H. A p
No wegian Geo echnical Ins i u e (NGI)
No wegian Uni e si y o Science and Technology (NTNU)
Con ac : hans.pe e .a [email protected]
PFAS con amina ed si es in Eu ope
22,934 known con amina ion si es
21,426 p esump i e con amina ion si es
231 known PFAS use s
20 PFAS manu ac u ing acili ies
Sou ce: Fo e e Pollu ion P ojec
o e e pollu ion.eu
Co dne e al. En i on. Sci. Technol.2024, 58, 15, 6616-6627
The Flow
•Ad ancing De ec ion
Ad ancing Moni o ing
Ad ancing Public-P i a e Pa ne ships
•Ad ancing De ec ion
Types o PFAS Analysis P inciple
Limi a ions
Ta ge PFAS analysis High sensi i e me hods o selec ed PFAS
(LOD pg/L –ng/L)
Only small ac ion o PFAS analysed
To al oxidizable p ecu so
(TOP) Assay
Oxidize p ecu so s o a ge PFAS o a ge
PFAS
No good o ola iles, ul a-sho PFAS and
polyme s (bu me hods imp o ing, e.g dTOP
and Pho oTOP)
Ex ac able
o gano luo ine (EOF)
Ex ac able o gano lou ine in a sol en o
solid phase, quan i y “F-” a e des uc ion
Same as TOP, does no di e en ia e PFAS
and non-PFAS o gano lou ine and
luo idized me als, high LOD
Adso bable
o gano luo ine (AOF)
Adso bable o gan luo ine on a solid phase
(e.g. ac i a ed ca bon), ollwed by «F-»
quan i ica ion
Same as EOF, gene ally highe LOD
Non- a ge PFAS and 19-
NMR
Good o s uc u al elucida ion o non-
a ge PFAS
No quan i a i e ( hough semi-quan i i i e
me hods eme ging). Expensi e
Smi h e al. ES&T 2024
h ps://pubs.acs.o g/doi/10.1021/acs.es .3c10617

Ex ac able eTOP s Di ec dTOP p o ocols, e. g. o soil
Lange e al., 2024
T EAC 44, e00242
Disc imina ion o
•non-oxidizable PFAS
•non-ex ac able PFAS
• ola iles
•ul asho -chain
PFAAs (TFA, PFP A)
Lowe ma ix e ec s
(eTOP) s mo e PFAS
(dTOP)
TOP assay o a echnical p oduc
Liquid p oduc wi h a side-chain luo ina ed ac yla e-based
polyme o ex ile coa ing
Analysis o na i e sample accoun s o
only 0.02 % o he TOP assay esul .
eTOP assay analysis o he d ied
p oduc accoun s o only 1.44 % o
dTOP assay esul .
dTOP is needed o polyme diges ion!
ΣF(PFAS) = 1.18 %
Supplie in o ma ion: 1.2 %
0
10
20
30
Na i e TOP dTOP
µmol/kg
TFA
PFP A
PFBA
PFPeA
PFHxA
PFHpA
Da a om Lange e al. 2025, Mi . Umwel chem. Öko ox. 31/2, 33-37
F
F
F
F
F
F
F
F
F
F
F
F
F
C osslinke
o ex ile
Non-
luo ina ed
side chain
Poly-
luo ina ed
side chain
Polyac yla e
chain
O
OO
OO
OO
O
F
F
F
F
F
F
F
F
F
F
F
F
F
eTOP dTOPNa i e
Wha is special abou TFA in TOP assay? TFA ma e s!
Wild boa li e Co n lea es
Conc. in µg/kg d.m.
Su ace uno
be o e TOPA
a e TOPA
a) 6:2 FTSA, b) 4:2 FTSA, c) Fluopicolide,
d) T i osul u on, e) Tembo ione, ) Flu enace ,
g) Fluopy am, h) Flu amone, i) Fluoxe ine,
j) Si aglip in, k) Bisphenol AF, l) 4-Chlo o-3-
ni obenzo i luo ide, m) 4-chlo obenzo i luo ide
And many, many mo e… and:
They a e PFASs!!!
P ecu so s galo e (millions)!
Rupp e al. 2023, Sci. To al En i on. 871, 162028. Janda 2019, Pola e Pe luo alkylca bonsäu en, Ph.D. hesis
(wine-g owing a ea)
Chemical- ee TOP al e na i e wi h good pe spec i e
Because TFA needs o be included and
any disc imina ion by sample p e- ea men (i.e. ex ac ion) should be
a oided, a pe sul a e- ee di ec TOP assay is needed!
Online senso s o PFAS: he limi s o
selec i i y and sensi i i y
Colo ime ic PFAS De ec ion
Colo ime ic senso s use ca alys s like Cu-CN o de ec PFOS ia isible colo changes caused by ca aly ic si e blockage.
Pape -Based Analy ical De ices
Low-cos pape de ices wi h me hylene g een dye de ec PFAS by changes in spo diame e on wax-pa e ned pape .
Fluo escen Senso s
Fluo escen senso s like pe ylene diimide de i a i es show quenching when PFOS binds, enabling e y sensi i e de ec ion.
Su ace-Enhanced Raman Spec oscopy
SERS uses plasmonic nanos uc u es o de ec PFOS a ul a-low le els, showcasing ad anced op ical sensing echnology.

Limi a ions o senso echnology
•Ta ge PFAS h esholds a e a he ng/L
(e.g. o PFOS)
•To da e no senso has been his sensi i e,
pa icula ly in complex ma ices
•Highe he concen a ion, he mo e
po en ial o senso echnology.
Albe and Süs en uss, En i on. Sci. Technol. Le . 2024, 11, 10, 1090-1095
Ad ancing Public-P i a e Pa ne ships
P i a e-public collabo a ions acc oss
supply chains
EEA 2025
h ps://www.eea.eu opa.eu/en/analysis/pu
blica ions/p as-polyme s-in- ocus
P oduc es ing o supply chain
componen s/p oduc s
0
10
20
30
Na i e TOP dTOP
µmol/kg
TFA
PFP A
PFBA
PFPeA
PFHxA
PFHpA
Da a om Lange e al. 2025, Mi . Umwel chem. Öko ox. 31/2, 33-37
F
F
F
F
F
F
F
F
F
F
F
F
F
C osslinke
o ex ile
Non-
luo ina ed
side chain
Poly-
luo ina ed
side chain
Polyac yla e
chain
O
OO
OO
OO
O
F
F
F
F
F
F
F
F
F
F
F
F
F
eTOP dTOPNa i e
1) Make a ne wo k o wa e shed
ep esen a i es
2) Wa e companies moni o o PFAS
subs ances
3) Ups eam in es iga ion o ind sou ces
4) Ne wo k wo ks oge he wi h emi ing
sou ces o collabo a e on ( inancial)
solu ions
Regional/na ional au ho i ies
coo dina e and co-c ea e a he
wa e shed le el whe e:
•S ong leade ship
•Clea policy
•Ci izen pa icipa ion
•Socioeconomics
•En i onmen al sociologis s
De ec ion and Moni o ing o PFAS Needs Wa e shed
Managmen Thinking

Closing he mass balance o ea men
echnology de elopmen
Xiao e al. En i on. Sci. Technol.
Le .2021, 8, 4, 364-365 Radjeno ic e al. En i on. Sci. Technol.2020, 54, 23,
14815-14829 Xu e al. En i on.Sci.Technol.2025,59,21567−21578
The modes uc ion Elec olysis Biodeg ada ion
Example: Elec olysis
Scale: 10 L
So d inking wa e κ≈ 600 µS/cm
I = 1.5 A
Ini ial PFAS conc.: 100 µg/L each
Heico Schell e al. In p ep
Example: Sludge biodeg ada ion
Li e al Wa e Resea ch
Volume 189,1 Feb ua y 2021,
116583
Public-p i ia e collabo a ion o o lowe he
ene gy needed o PFAS mine aliza ion om
he mal me hods
Abou-Khalil ES&T (2024), 58-11162-11174
h ps://doi.o g/10.1021/acs.es .3c09795