Science o he To al En i onmen 932 (2024) 172589
A ailable online 22 Ap il 2024
0048-9697/© 2024 Else ie B.V. All igh s ese ed.
De e mina ion o o ganic luo ina ed compounds con en in complex
samples h ough combus ion ion ch oma og aphy me hods: a way o de ine
a “To al Pe - and Poly luo oalkyl Subs ances (PFAS)” pa ame e ?
Baba ound´
e I.T. Idja on
a
,
b
, Anne Togola
a
,
*
, Jean Philippe Ghes em
a
, Lau a Kas le
a
,
S´
ebas ien B is eau
a
, Ma iska Ron el ap
c
,
d
, S ´
e an Colombano
a
, Nicolas De au
a
, Julie Lions
a
,
E ic D. an Hullebusch
b
a
BRGM, Di ec ion Eau En i onnemen P oc´
ed´
es e Analyses, 3 a . Claude-Guillemin - BP 36009, 45060 O l´
eans, F ance
b
Uni e si ´
e Pa is Ci ´
e, Ins i u de physique du globe de Pa is, CNRS, F-75005 Pa is, F ance
c
Del land Wa e Au ho i y, Phoenixs aa 32, he Ne he lands
d
TU Del , Wa e Managemen Depa men , S e inweg 1, Del , he Ne he lands
HIGHLIGHTS GRAPHICAL ABSTRACT
•De elopmen o To al (TF), adso bable
(AOF) and ex ac able (EOF) o ganic
luo ine me hods
•A obus AOF me hod de eloped and
alida ed o e y complex liquid
ma ices.
•AOF and EOF measu ed concen a ions
e y low compa ed o es ima ed OF.
•AOF and EOF mos ly comp ised o un-
known luo ina ed compounds
•Nei he AOF o EOF o TF a e ele an
as a p oxy o “ o al PFAS”.
ARTICLE INFO
Keywo ds:
PFAS
Combus ion ion ch oma og aphy
O ganic luo ine
En i onmen
Analysis
ABSTRACT
Eme ging con aminan s a e a g owing conce n o scien is s and public au ho i ies. The g oup o pe -
poly luo oalkyl subs ances (PFAS), known as ‘ o e e chemicals', in complex en i onmen al liquid and solid
ma ices was analysed in his s udy. The de elopmen o global analy ical me hods based on combus ion ion
ch oma og aphy (CIC) is expec ed o p o ide accu a e pic u e o he o e all PFAS con amina ion le el ia he
de e mina ion o ex ac able o ganic luo ine (EOF) and adso bable o ganic luo ine (AOF). The ob ained esul s
may be pu in o pe spec i e wi h o he me hods such as a ge ed analyses (LC-MS/MS). The impac o pH, he
p esence o dissol ed o ganic ca bon and suspended pa icles on AOF measu emen s we e explo ed. The e ec-
i eness o he washing s ep o emo e adso bed ino ganic luo ine (IF) has been p o en o samples con aining
up o 8 mgF.L
−1
. CIC-based me hods showed good epea abili y and ep oducibili y o he complex ma ices
s udied. En i onmen al applica ions o hese me hods ha e been es ed. AOF and EOF analyses could explain
be ween 1 % and 23 % and 0.1 % o 2 % o o al o ganic luo ine (TOF), espec i ely. The sum o PFAS
* Co esponding au ho .
E-mail add ess: [email p o ec ed] (A. Togola).
Con en s lis s a ailable a ScienceDi ec
Science o he To al En i onmen
jou nal homepage: www.else ie .com/loca e/sci o en
h ps://doi.o g/10.1016/j.sci o en .2024.172589
Recei ed 28 Decembe 2023; Recei ed in e ised o m 12 Ap il 2024; Accep ed 17 Ap il 2024
Science o he To al En i onmen 932 (2024) 172589
2
compounds exp essed as luo ine could explain om 0.2 % o 11 % and om 0.003 % o 5 % o AOF and EOF,
espec i ely. These esul s also sugges ha some luo ina ed compounds a e no adso bed o ex ac able and/o
los by ola ilisa ion du ing he applica ion o AOF and EOF analy ical p ocedu e. These indings highligh ha
AOF and EOF a e no en i ely e icien as p oxy o assess “ o al PFAS” o assessing en i onmen al con amina ion
by PFAS. Howe e , hese me hods could s ill be applied o gain a be e unde s anding o he sou ces and a e o
PFAS in he en i onmen .
1. In oduc ion
Called “ o e e chemicals” because o hei high chemical s abili y,
pe - and poly luo oalkyl subs ances (PFAS) a e almos ubiqui ous en i-
onmen al con aminan s (E ich e al., 2022). The de ini ion o PFAS has
been e ol ing o se e al yea s as new knowledge was acqui ed. The
mos ecen OECD Recommenda ions and P ac ical Guidance published
in 2021 indica es: “PFASs a e de ined as luo ina ed subs ances ha
con ain a leas one ully luo ina ed me hyl o me hylene ca bon a om
(wi hou any H/Cl/B /I a om a ached o i ), i.e. wi h a ew no ed ex-
cep ions, any chemical wi h a leas a pe luo ina ed me hyl g oup
(–CF
3
) o a pe luo ina ed me hylene g oup (–CF
2
–) is a PFAS.”
(Ba nabas e al., 2022; OECD, 2021; Sadia e al., 2023; Wang e al.,
2021), which co e s a wide ange o chemical p oduc s.
Since 1940, PFAS ha e been p oduced by he chemical indus y in
high quan i ies because o he high s abili y o he ca bon‑ luo ine
(C
–
F) bond and hei in insic p ope ies, such as he mal esis ance
( i e- igh ing oam, e c.), wa e epellence (wa e - and s ain- epellen
ex iles, medical de ices, e c.) and oil epellence (labo a o y supplies
and pe sonal hygiene p oduc s, e c.) (Codling e al., 2014; Raheem e al.,
2018). Because o he high di e si y o PFAS, he e is a signi ican
knowledge gap ega ding he quan i ies discha ged in o he en i on-
men . The wo k o Dalmijn e al. (2024) gi es he i s comple e in-
en o y o emissions o luo ina ed o ganic subs ances and PFAS om
he p oduc ion o luo opolyme s. They es ima e he quan i y o luo-
opolyme s and PFAS emi ed in 2021 by he p oduc ion o luo opol-
yme s in Eu ope o be 360 /y .
As a esul o hei in ensi e use, PFAS can be ound in incoming
was e s eams such as domes ic o indus ial was ewa e s as well as
land ill leacha es, and hus in was ewa e e luen ea men plan s,
which can become signi ican ga eways o PFAS o he en i onmen
(Lenka e al., 2021; Wang e al., 2020). O ganising PFAS by chemical
g oup, chain leng h o o he pa ame e s is complex, gi en he shee
numbe o desc ip o s (o e 2000) o >7 million PFAS co esponding o
he OECD, 2021 de ini ion (Buck e al., 2011; Kibbey e al., 2020;
Schymanski e al., 2023; Su and Rajan, 2021; Wang e al., 2017). They
a e no , consequen ly, a “single chemical amily” which can easily be
analysed by one analy ical me hod (Fiedle e al., 2021; Hue a e al.,
2022; James e al., 2023).
Mos PFAS a e no comple ely deg aded by con en ional physico-
chemical and biological wa e ea men p ocesses and, consequen ly,
was ewa e e luen s con ain PFAS om bo h domes ic and indus ial
sou ces (A ani i and S asinakis, 2015; Coggan e al., 2019; Hu e al.,
2016). Con en ional wa e ea men me hods can also gene a e PFAS
ans o ma ion p oduc s (Chen e al., 2018; Kim e al., 2020; Winchell
e al., 2022). Consequen ly, was ewa e ea men plan s (WWTP)
discha ge PFAS and ans o ma ion p oduc s ia se e al ou es: ea ed
was ewa e , sewage sludge and ai by ola ilisa ion (Bas ow e al., 2022;
Dauchy e al., 2017; Nguyen e al., 2019; Rewe s e al., 2018; Szabo
e al., 2023). Th ough indus ial o consume p oduc s, he ma e ials
con aining PFAS a e disposed o a land ill si es (Liu e al., 2022;
Rehns am e al., 2023), and PFAS a e pa ly ans e ed in o he land ill
leacha e (Lang e al., 2017). The e a e se e al housand o mo e o less
known PFAS, associa ed o unknown ans o ma ion p oduc s, dissem-
ina ing in o he en i onmen . The e is he e o e a need o be e cha -
ac e ise he a e o PFAS, hei le el o con amina ion in he a ious
sou ce s eams, ecep o en i onmen s and deg ada ion p ocesses. Fo
ha , adap ed analy ical ools a e needed as well as good cha ac e isa-
ion o he pa i ion o PFAS in he sample.
PFAS analysis aces many challenges, due o he housands o un-
known compounds, bu also due o he lack o s anda ds and obus
analy ical me hods o quan i ying hem using con en ional me hods o
a ge ed compounds. Fo his pu pose, he mos commonly used quan-
i a i e me hods a e liquid ch oma og aphy combined wi h mass spec-
ome y o he analysis o ionic PFAS (i.e. ca boxylic and sul onic
acids, PFCA and PFSA), and gas ch oma og aphy combined wi h mass
spec ome y me hods o he analysis o ola ile and semi- ola ile PFAS
(e.g. luo o elome alcohols, FTOH) (Al Amin e al., 2020; Ma in e al.,
2019; Rewe s e al., 2018). Bu he combina ion o all me hods con-
ce ning a ge ed PFAS analysis co e s <200 compounds, highligh ing
he need o mo e global pa ame e s such as o ganic luo ine con en o
he “TOTAL PFAS” pa ame e , in oduced in he D inking Wa e
Di ec i e 2020 (Cioni e al., 2023; DWD, 2020; Shojaei e al., 2022;
T ojanowicz e al., 2011; Ve wold e al., 2023).
Fo hese global pa ame e s, se e al app oaches ha e been p oposed.
Di e en ac ions o he sample can be iden i ied: TF ( o al luo ine),
EOF (ex ac able o ganic luo ine) o AOF (adso bable o ganic luo ine).
Remo al o ino ganic luo ine (IF) is needed o disc imina ing o ganic
luo ine om TF con en . Fig. 1 p o ides a comp ehensi e illus a ion o
he di e en o ms o luo ine compounds acco ding o hei ino ganic
o o ganic cha ac e as well as hei adso p ibili y o ex ac abili y
ea u es. Se e al me hods a e a ailable o measu ing o ganic luo i-
na ed compounds like high esolu ion-con inuum sou ce-g aphi e
u nace molecula abso p ion spec ome y (HR–CS–GFMAS) (Simon
e al., 2022), high- esolu ion mass spec ome y (HRMS) (Liu e al.,
2019; Wu e al., 2022) and combus ion ion ch oma og aphy (A o e al.,
2021b; Ga g e al., 2023; on Abe c on e al., 2019). Based on expe i-
ence wi h he de e mina ion o global adso bable o ganic halogens
(AOX) pa ame e , he combus ion ion ch oma og aphy (CIC) seemed o
be he mo e eliable me hod o PFAS compounds. Upon adso p ion,
ac i a ed ca bon is combus ed and luo ine is con e ed in o hyd ogen
luo ide (HF), which is hen adso bed in a apping solu ion. Subse-
quen ly, he analysis o luo ide is ca ied ou using an ion ch oma og-
aphy (IC) me hod (Geh enkempe e al., 2021; Wagne e al., 2013).
E en hough he analy ical p inciple o CIC is ela i ely simple,
di e en me hodological issues may a ise. Wi h CIC, i is impossible o
dis inguish be ween IF and OF a e combus ion. Hence he e is a need,
when measu ing he AOF and EOF pa ame e s, o ensu e ha IF has been
emo ed. A numbe o bo lenecks ha e been iden i ied, on which
esea ch wo k emains o be done. Fo AOF measu emen , he liquid
sample is loaded on ac i a ed ca bon and hen washed wi h a solu ion o
elimina e he IF (Han e al., 2021; on Abe c on e al., 2019). Howe e ,
he washing s ep e iciency and poo e en ion o sho -chain PFAS
compounds has been iden i ied as a majo challenge. Fo AOF mea-
su emen , he e a e no speci ic s udies based on e ec o dissol ed
o ganic ca bon (DOC) and suspended solids (SS). Reliabili y o he
me hods is a unc ion o PFAS molecula physico-chemical p ope ies
including pola i y, ca bon chain leng h, ype o unc ional g oup, and
en i onmen al ma ices o conce n (Winchell e al., 2021).
F om a egula o y poin o iew, d a s anda ds a e cu en ly being
d awn up o educe he dispa i ies obse ed in he p o ocols epo ed in
he li e a u e. Fo example, he d a ISO WD 18127 s anda d ocuses on
AOF measu emen . I is based on DIN 38409–59, an upda e o ISO 9562.
Fo EOF measu emen on solid ma ix, sample p epa a ion is gene ally
B.I.T. Idja on e al.
Science o he To al En i onmen 932 (2024) 172589
3
ca ied ou by ul asonica ion o he sample in di e en combina ion o
pola sol en s, a iable depending on samples (K¨
a man e al., 2021;
Miaz e al., 2020; Ruyle e al., 2023).
The objec i es o his s udy a e o alida e obus and eliable
me hods o measu ing global o ganic luo ine based on CIC analysis.
Pa ame e s a e TF and EOF o solid samples, AOF and TF o liquid
samples. Fo his pu pose, ep esen a i e PFAS a e selec ed o de elop
me hod o AOF. Complex ma ices such as compos , sewage sludge o
solid samples o WWTP in luen /e luen o liquid samples ha e been
analysed o ma ix e ec s o e alua e he impac o key ac o s such as
IF, suspended ma e and dissol ed o ganic ca bon con en s. Me hods
a e hen applied o eal samples and compa ed wi h PFAS a ge analysis
me hod o assess hei ele ance o be e unde s and he sou ces and
a e o PFAS in he en i onmen .
2. Ma e ials and me hods
2.1. Samples
A ange o di e en samples was collec ed om WWTP (e luen ,
in luen and sludge) and g ound wa e om di e en Eu opean coun-
ies, wi h a pa icula ocus on he by-p oduc s o sewage sludge as
sou ce o e ilise (SI1). These eco e ed by-p oduc s a e p oduced a
di e en s eps o he alo isa ion p ocess o a mix o sludge and ash in o
e ilise s. One li e and 500 g we e collec ed, espec i ely o liquid and
solid samples in high-densi y polye hylene (HDPE)/polyp opylene (PP)
con aine s. Samples we e s o ed a −20 ◦C un il analysis.
2.2. S anda ds and eagen s
81 PFAS s anda ds (59 Na i es and 22 Deu e a ed) we e pu chased
om Welling on (On a io, Canada), Chi on AS (T ondheim, No way),
Neochema (Da ms ad , Ge many), LGC (Manches e , US) and HPC
S anda ds (Cunne sdo , Ge many). Mo e de ails ega ding names and
CAS numbe s o he conside ed PFAS a e p esen ed in Supplemen a y
In o ma ion 2 (SI 2). The Milli-Q wa e used in he CIC sys em was
p oduced by a Milli-Q sys em A10 om Sa o ius (Me ck, Da ms ad ,
Ge many). Ul apu e wa e (HPLC g ade) and me hanol (op ima LC-MS
g ade) we e pu chased om Fishe Chemical (F ance). Ammonium ac-
e a e (pu i y 99 %) and glacial ace ic acid (pu i y 99 %) we e pu chased
om Me ck (Da ms ad , Ge many), ammonia solu ion (25 %, analy ical
eagen g ade) was pu chased om Fishe Scien i ic (F ance). The so-
dium luo ide solu ion (NaF, ACS eagen , ≥99 %) was pu chased om
Me ck (Da ms ad , Ge many). The 4- luo obenzoic acid (AFB) solu ion
(200
μ
gF.L
−1
) was pu chased om Neochema (Da ms ad , Ge many).
P e-packaged ac i a ed ca bon columns (AOX Pack / P emium Pack)
and combus ion essels a e om En i oscience (Dusseldo , Ge many).
The humic acid ( e : 041747.14) was pu chased om The mo ishe
Scien i ic (Da ms ad , Ge many). Glass ibe il e (Ac odisc, Sy inge
Fil e , 25 mm, 1
μ
m) used o il a ion o leacha e we e pu chased om
Wa e s (Guyancou , F ance).
2.3. Chemical analyses
2.3.1. LC-MS/MS analyses
This me hod was de eloped in he labo a o y (publica ion in p ep) and
include 56 PFAS om di e en chemical amilies (C
3
o C
20
) in a single
analy ical me hod. The me hod is inspi ed om p e iously published
me hods by Munoz e al. in 2018 and 2022. Addi ional and di e en
PFAS a e conside ed in he p esen s udy compa ed o Munoz e al.
(2018, 2022). The ins umen consis ed o an Acqui y I-Class Wa e s®
UPLC chain coupled o a Xe o TQXs Wa e s® andem mass spec ome e
in mul iple eac ion moni o ing (MRM) mode. The ch oma og aphic
sepa a ion was pe o med wi h a BEH C18 column (2.1 mm ×100 mm,
1.7
μ
m) Wa e s (F ance) hea ed a 35 ◦C. The delay C18 column (isola o
column 50 ×2.1 mm) Wa e s (F ance) was used o a oid PFAS
con amina ion om he ch oma og aphic sys em. The ins umen al
limi o quan i ica ion is anging om 2 o 10 ng/L o 54 PFAS com-
pounds and 100 ng/L o 2 o he compounds (i.e. 6:2FTCA and 8:2
FTCA). Injec ion olume was 10
μ
L and he mobile phase was a mix u e
o 2 mM Ammonium Ace a e in H
2
O (A) and 2 mM Ammonium Ace a e
in MeOH (B) a a 0.3 mL/min low. The g adien elu ion s a ed wi h
100 % A, and g adually changed up o 100 % B wi hin 23 min. This a io
was kep o 4 min and hen e e sed in o he ini ial condi ions o 3
min. The ionisa ion mode used was elec osp ay. The sou ce condi ions
we e se as he ollowing: desol a ion empe a u e 500 ◦C, desol a ion
gas low 1100 L/H , cone gas low 150 L/H , capilla y ol age −1000 V.
Quan i a i e analysis is ca ied ou using in e nal s anda ds. Samples
(ex ac om solid o wa e ) we e p epa ed o ob ain a inal a io o 20/
80 / ; wa e /me hanol; 0.3 % ace ic acid be o e analysis.
Fig. 1. O e iew o he di e en luo ine chemical species acco ding o hei ino ganic o o ganic cha ac e as well as hei adso p ibili y o ex ac abili y ea u es o
di e en ma ices (liquid o solid) (Modi ied om A o e al., 2021a, 2021b).
B.I.T. Idja on e al.
Science o he To al En i onmen 932 (2024) 172589
4
2.3.2. To al o ganic luo ine de e mina ion by IC me hods
The analy ical sys em is cons i u ed o an ASC-2700LS liquid au o
sample , an ABC-210 au oma ic boa con olle , an HF-210 ho izon al
o en and a GA-211 sample abso p ion uni , coupled o an ICS 6000 ion
ch oma og aphy uni (The mo Scien i ic). In he case o AOF, samples
a e p e-concen a ed on ac i a ed ca bon columns using he 5-channel
AD en ichmen module, all om En i osciences (Dusseldo , Ge -
many). Di e en ypes o analysis a e summa ized in Fig. 2.
Ion ch oma og aphy (IC) allows luo ide analysis om he luo ine
con en o he sample. Di ec combus ion o samples (100
μ
g o 100
μ
L)
be o e analysis p o ides o al luo ine (TF) con en , while di ec injec-
ion in he IC p o ides IF measu emen . The de e mina ion o o ganic
luo ine is possible a e p e ious sample p epa a ion such as sol en
ex ac ion ( o EOF) o solid phase ex ac ion ( o AOF). De ails on he
ope a ing condi ions a e desc ibed in he supplemen a y ma e ials ile
(SI 3 & SI 4). B ie ly, combus ion akes place acco ding o he pa ame-
e s shown in SI 3 & 4. A e luo ide abso p ion in 10 mL o wa e , 5 mL
a e injec ed in he AS 20 column a a low a e o 0.250 mL.min
−1
.
Fo EOF, he selec ed p o ocol o solid samples is an ex ac ion o 1 g
o d y solid wi h 3 consecu i e ex ac ion s eps: 10 mL o sol en ,
ul asonica ion o 20 min, cen i uga ion o 5 min (4612 g) and
ans e in o a polyp opylene 50 mL cen i uge ube. The 3 sol en s we e
MeOH wi h 10 mM NH
4
OH, MeOH wi h 100 mM CH
3
COONH
4
and 10
mL MeOH. The h ee ex ac s we e combined. An aliquo olume o 10
mL is educed unde ni ogen o 1 mL. One hund ed mic oli e is
collec ed and analysed by CIC o de e mine EOF.
DOC was measu ed o liquid sample cha ac e isa ion using he
“CELLULOSE” me hod ou lined in NF EN 1484 s anda d. In a eac o
ope a ing a 97 ◦C, a s ongly oxidising mix u e (K
2
SO
4
) is added o he
acidi ied sample. The CO
2
o med is ans e ed o he 1010 OI-
ANALYTICAL ca bon analyse by an ine gas.
2.3.3. Valida ion o he di e en pa ame e s o he AOF and EOF me hods
To assess di e ences be ween IF and OF o IC calib a ion, wo cal-
ib a ions anging om 0.005 mgF.L
−1
o 2.5 mgF.L
−1
o o ganic luo-
ine as 4- luo obenzoic Acid (FBA) and 0.005 mgF.L
−1
o 10 mgF.L
−1
o
IF as NaF we e compa ed.
To assess he impac o pH on solid phase ex ac ion (SPE) o AOF
p epa a ion s ep, an ul apu e wa e solu ion was spiked wi h 0.020
mgF.L
−1
o o ganic luo ine (PFOA, PFOS, PFBS o AFFF Technical mix).
The olume o he es sample was 100 mL. The pH o each solu ion was
adjus ed o pH 2 and pH 7 (de ails in SI4). This expe imen aims o
compa e he e ec o pH on he adso p ion o pe luo ina ed compounds
on o ac i a ed ca bon.
To assess he impac o a washing s ep du ing SPE o elimina e IF,
0.020 mgF.L
−1
o o ganic luo ine (PFOA, PFOS, PFBS o AFFF Tech-
nical mix) as PFAS was oge he wi h 2 mgF.L
−1
o IF in ul apu e wa e
solu ion adjus ed o pH 7. The washing s ep was pe o med wi h 25 and
15 mL o 0.01 mmol.L
−1
NaNO
3
insing solu ion. Tes s on eal samples
wi h high IF concen a ions (up o 8 mgF.L
−1
) ha e also been conduc ed.
To assess he impac o high DOC on AOF measu emen , ul apu e
wa e adjus ed a pH 7 was spiked wi h di e en concen a ions o
humic acid up o 150 mg.L
−1
. Tes s on na u al samples wi h e y high
DOC concen a ions (up o 3000 mg.L
−1
) ha e also been conduc ed.
Tes s we e conduc ed wi h di e en PFAS co e ing di e en mo-
lecula ea u es: ca bon chain leng h: a sho one wi h PFBS (C
4
) and a
long one wi h PFOS (C
8
); chemical g oups: ca boxylic (PFOA) and sul-
onic (PFOS) and a echnical mix wi h an aqueous ilm o ming oam
(AFFF) con aining mos ly 6:2 FTSA and 6:2 FTAB. The ul a-sho -chain
PFAS ha e been iden i ied as a majo challenge, bu he au ho s did no
analyse PFAS below C
4
.
Fo some was ewa e samples, he e ec s o he p esence o high-
suspended pa icles can be signi ican as PFAS can be so bed on sus-
pended pa icle ma e (SPM), which is why he impac o SPM has been
s udied. To educe he concen a ion o SPM, wo app oaches a e
possible: dilu ion o cen i uga ion. Dilu ion could elease adso bed
PFAS, while cen i uga ion would elimina e hem wi h SPM. Fo ha , a
eal sample WWTP In luen 1 (SPM 309 mg.L
−1
) was selec ed o pe -
o ming his es . The sample was di ec ly analysed in he i s condi ion;
in he second one dilu ed 3 imes wi h ul apu e wa e be o e cen i u-
ga ion ( he supe na an was hen analysed); and cen i uged ollowed by
3 imes dilu ion o he supe na an wi h HPLC wa e in he hi d. The se
o h ee esul s has been compa ed.
Fo mo e solid samples like sewage sludge and p oduc s de i ed om
i , as TF includes bo h OF and IF, leaching es s we e pe o med o
measu e IF con ibu ion. One g am o solid sample is mixed wi h 1 mL o
0.5 M NaNO
3
o ex o 30 s and il e ed h ough a glass il e . The inal
olume (≈1 mL) was dilu ed o a olume o 5 mL, and hen injec ed in o
he IC.
To assess he ele ance o he di e en de eloped me hods, appli-
ca ion o eal samples and compa ison wi h PFAS a ge analysis we e
conduc ed. Fo liquid ma ices, TOF, AOF and LC-MS/MS (56 a ge ed
PFAS compounds) analysis we e compa ed o he same sample. The
TOF alue was es ima ed by deduc ing he measu ed IF om he
Fig. 2. Ope a ing p inciple o he CIC and analysis p ocesses inspi ed by The mo Scien i ic applica ion n
◦73481 (US is ul asonica ion).
B.I.T. Idja on e al.
Science o he To al En i onmen 932 (2024) 172589
5
measu ed TF. These es s we e ca ied ou on di e en samples (e luen ,
in luen , land ill leacha e, ea ed land ill leacha e, g ound wa e ) wi h
a ying SPM, DOC and IF con en s (see SI 5). Fo solid ma ices, he
compa ison was done be ween TF (100 mg), EOF and LC-MS/MS a -
ge ed analysis. EOF and LC-MS/MS analyses a e ob ained on he same
ex ac . These es s a e ca ied ou on di e en samples o a ious ypes
(sludge, e ilise s and in e media es in he eco e y p ocess, see SI 6).
2.3.4. Quali y assu ance
Calib a ion con ols we e pe o med o each analy ical un. The 20
μ
gF.L
−1
(as IF) calib a ion le el is used in each sequence as a quali y
con ol (QC) o he e e ence calib a ion ange used o se e al analy -
ical uns. En i osciences, ac i a ed ca bon and combus ion essel blanks
we e ou inely pe o med be ween each analy ical un. The limi o
quan i ica ion (LOQ) o each me hod was calcula ed as he a e age
concen a ion measu ed in blank ex ac s plus 10 imes i s s anda d
de ia ion. Fo LC-MS/MS analyses, he con ols o he p ocedu al and
analy ical blanks a e in eg a ed in o each se ies o analyses and a e PFAS
ee.
2.3.5. Da a p ocessing
The p og am Ch omeleon o MassLynx, as applicable, immedia ely
inco po a es concen a ion and dilu ion pa ame e s. In o de o compa e
a ge analysis wi h o ganic luo ine con en , PFAS concen a ions a e
con e ed o luo ine equi alen s based on he pe cen age (%) o luo-
ine o e e y compound (Mola mass based). The ollowing o mula has
been applied:
To al [F] = Sum o ([PFAS] × %F )(1)
3. Resul s & discussion
3.1. IF and OF calib a ion
When he calib a ion cu es o IF and OF a e compa ed, he e is no
signi ican di e ence (see SI 7). These esul s di e om hose ob ained
by A o e al. (2021b) who showed ha in he same concen a ion ange,
he e is a signi ican di e ence ega ding he analy ical esponse o OF
and IF by a ac o o 0.3. When inc easing o 10 mg F.L
−1
, he IF cali-
b a ion cu e s ill co ela es well wi h he OF calib a ion cu e. Quali y
con ol solu ions o PFOA, PFOS, PFBS and AFFF analysed in his IF
ange con i med he co ec quan i ica ion. The e o e, an IF o OF
calib a ion can in a iably be used o calib a e he CIC using a poly-
nomial calib a ion cu e.
3.2. Op imising he ex ac ion me hods
3.2.1. AOF o liquid samples
3.2.1.1. SPE condi ions (pH and washing s ep). When compa ing he
e ec o pH (2 s 7) on he adso p ion o pe luo ina ed compounds on o
ac i a ed ca bon in he absence o ino ganic luo ine, pH 7 shows be e
pe o mance. The so p ion e iciency o o ganic luo ine on o ac i a ed
ca bon is impac ed by pH a ia ion, as shown in Fig. 3.
In o de o a oid an o e es ima ion o he o ganic luo ine concen-
a ion, he IF should be washed ou om he ac i a ed ca bon, as CIC
analysis do no allow o disc imina e he di e en ypes o luo ine a e
combus ion. The e iciency o he washing solu ion olume was es ed
o di e en PFAS ca bon chain leng hs and di e en chemical unc-
ions. When compa ing he esul s wi h 25 mL and 15 mL washing so-
lu ion, he wo olumes showed equi alen esul s wi h no pa icula
loss o PFAS, including sho chain compounds (i.e. pe luo obu ane
sul onic acid (PFBS)). These esul s a e compa able o hose epo ed by
Fo s e e al. (2023). The washing me hod assessmen on a eal sample
con aining a high concen a ion o IF (7.8 mgF.L
−1
) showed ha a
washing solu ion olume o 15 mL is e ec i e (Fig. 4), showing same
esul s on h ee (3) di e en le els o sample dilu ion (i.e. no o e -
es ima ion due o p esence o IF). Addi ionally, Fig. 4 demons a es ha
he AOF pe o ms well o indi idual solu ions spiked wi h o ganic
luo ine (i.e. PFBS, PFOS, PFOA and AFFF). These esul s a e simila o
he ones epo ed in he d a o ISO 18127 s anda d, ha does no
p opose acidi ica ion as o o he AOX (Cl, B , e c.).
3.2.1.2. Impac o concen a ion o dissol ed o ganic ca bon (DOC). The
i s es pe o med wi h humic acid did no show any impac on he AOF
measu emen s up o 150 mgC.L
−1
DOC. The same p ocess was applied o
wo eal samples (wi h DOC concen a ions o 2135 and 3167 mgC.L
−1
),
and he high DOC concen a ion esul ed in a 2 o 4- old signal ex inc-
ion, espec i ely (Fig. 5). This is no e y high compa ed wi h he in-
c ease in DOC concen a ion, which is 14 o 21 imes g ea e han he
maximum concen a ion es ed wi h humic acid. Howe e , i con i ms
he necessi y o dilu ing liquid samples con aining high concen a ions
o DOC.
Conside ing he in luence o sample p e- ea men in case o he
p esence o high SPM con en , he esul s showed ha he a iabili y in
AOF quan i ica ion was below 10 %, wha e e he p o ocol, which is no
signi ican . Fo his liquid sample (WWTP In luen 1, see SI 1), dilu ion
be o e o a e cen i uga ion had no s a is ically signi ican di e ence
on AOF measu emen . Howe e , he ac ha he esul s o hese wo
condi ions a e also simila o hose o he di ec sample shows ha he e
Fig. 3. Impac o pH a ia ion on he adso p ion mechanism o O ganic Fluo ine on o ac i a ed ca bon (n =3). 90 % and 110 % is he accep abili y limi s o
ex ac ion e iciencies.
B.I.T. Idja on e al.
Science o he To al En i onmen 932 (2024) 172589
6
Fig. 4. (A) Measu ed concen a ion o AOF in spiked wa e wi h di e en PFAS exp essed in
μ
gF.L
−1
depending on washing olume (n =3). (B) E iciency o washing
s ep on eal liquid sample analysed by AOF a 3 le els o dilu ion ( esul s a e co ec ed by he dilu ion ac o ). [IF] concen a ion in each sample is exp essed in mg F.
L
−1
. (Only washing 15 mL o PFOS a e ealise).
Fig. 5. (A) Measu ed concen a ion o AOF in spiked wa e wi h AFFF mix, exp essed in
μ
gF.L
−1
depending on [DOC] (n =1). (B) Measu ed concen a ions o AOF in
land ill leacha es (LL1 and LL2) be o e (di ec ) and a e dilu ion. [DOC] indica ed below each alue ( o di ec sample) is exp essed in mgC.L
−1
.
B.I.T. Idja on e al.
Science o he To al En i onmen 932 (2024) 172589
7
is no con ibu ion o o ganic luo ine by he SPM, which explains he
inconclusi e na u e o he expe imen . New es s should he e o e be
ca ied ou wi h di e en samples.
3.2.2. Analysis on solids
Analysis o IF in he leachable ac ion highligh s e y low concen-
a ions. Fo example, in he sample “SS Ash” low IF concen a ion was
measu ed (0.2 mgF.kg
−1
) compa ed wi h TF (661.5 mgF.kg
−1
), ha can
be conside ed insigni ican . Leachabili y o all IF ac ions is no gua -
an eed by he selec ed p o ocol. In pa allel, he equi emen o dilu e he
liquid ac ion (1 mL) o analysis (5 mL) esul s in an enhancemen o
he LOQ o 0.025 mgF.kg
−1
, which can make low concen a ions un-
de ec able. Conside ing hese esul s, we ha e chosen o conside ha TF
and TOF we e equi alen in all expe imen s.
3.3. Quali y assu ance
To ensu e he quali y o he analy ical wo k se e al blanks we e
analysed. A p o ocol o cleaning he combus ion-abso p ion ube o he
CIC was ca ied ou be o e each se ies o analyses. Pa icula a en ion
was paid o he memo y e ec a e elu ing a highly concen a ed
sample, which equi es a blank analysis a e each sample. The addi ion
o a sys ema ic blank a e wa ds elimina es he esidual e ec o high
luo ide concen a ions.
Mul iple assays on he analysis o indi idual consumables ( eused
boa , new boa , ac i a ed ca bon) ha e shown ha con amina ion le el
o he analy ical pa s is <0.21 ±0.06
μ
gF.L
−1
o combus ion boa and
0.47 ±0.12
μ
gF.L
−1
o en i e p ocess (combus ion boa +ac i a ed
ca bon).
Simila ly, mul iple es s o AOF blanks including en i e p o ocol
(ex ac ion and analysis) be o e and a e eal samples we e ca ied ou
wi h HPLC wa e . They demons a ed excellen epea abili y (<12 %, n
=11) and good con ol o esidual con amina ion (by cleaning en ich-
men module a e each sample elu ion) leading o a backg ound le el o
luo ide o 0.88 ±0.11
μ
gF.L
−1
, called “p ocedu al blank” which con-
s ains he limi s o quan i ica ion (LOQ) o he di e en
measu emen s.
Conside ing LOQ om appa a us sensi i i y (5
μ
gF.L
−1
) and
analy ical pa ame e s o each me hod, heo e ical LOQ o AOF will be
0.5
μ
gF.L
−1
o 100 mL sample, 500
μ
gF.kg
−1
o TF (sample mass o
100 mg) and 500
μ
gF.L
−1
o EOF ex ac injec ed (sample olume o
100
μ
L).
Fo AOF, calcula ion o LOQ based on esidual con amina ion leads
o 1.98
μ
gF.L
−1
. Then he LOQ se as 2
μ
gF.L
−1
o 100 mL sample is
he e o e d i en by he sys em blank. Fo TF and EOF, he me hod blank
alue was 136 ±29
μ
gF.kg
−1
, leading o a LOQ o 500
μ
gF.kg
−1
o TF
(sample 100 mg) and 500
μ
gF.L
−1
o EOF (sample 100
μ
L ex ac
injec ed). The LOQ o IF in he leacha e om solid is 0.025 mgF.L
−1
.
3.4. Compa ison o in o ma ion by me hod
3.4.1. Liquid ma ices
Fo liquid samples, IF was de e mined by di ec injec ion in o he IC.
TF was used o calcula e TOF by deduc ing measu ed IF om TF. Fig. 6
p esen s he compa ison be ween TOF and AOF o liquid samples. The
p opo ion o TOF explained by AOF is s ill low, wi h a high a iabili y
be ween analysed samples. F om 1 % o 23 % o TOF can be explained by
he AOF. These esul s a e compa able o hose o Geh enkempe e al.
(2021), Han e al. (2021), on Abe c on e al. (2019).
The di e ence be ween TOF and AOF could be due o he ul asho
chain PFAS, such as i luo oace ic acid (TFA), pe luo op opionic acid
(PFP A) o i luo ome hane sul onic acid (TFMS) which a e poo ly
adso bed on o ac i a ed ca bon, abou 9 % acco ding o (Pan and Hel-
bling, 2023). These ul asho chain PFAS a e used in indus y o a e
gene a ed om he deg ada ion o longe chain PFAS in WWTP, o in he
en i onmen (Wu e al., 2022). O he compounds such as luo ina ed
ionic liquids can also explain he gap be ween AOF and TOF (Neuwald
e al., 2020).
Conside ing he a ge ed PFAS quan i ica ion by LC-MS/MS, Fig. 6
highligh s he compa ison be ween AOF and sum o PFAS exp essed in F.
Excep o one sample whe e LC-MS/MS explained 74 % o he F con-
ained in AOF, all he o he s we e explained om 0 % o 11 %.
The di e ence be ween AOF and he PFAS exp essed in luo ine is
due o uniden i ied PFAS, which a e no conside ed by he a ge ed
analysis me hods. E en i 56 PFAS conside ed as he mos ele an and
abundan we e analysed, he esul s show ha o he PFAS a e likely
p esen in he sample. O he luo ina ed compounds can also be so bed
on o ac i a ed ca bon ha a e no PFAS, making in e p e a ion mo e
complex.
3.4.2. Solid ma ices
Fig. 7 shows high a iabili y be ween samples whe e 0.1 % o 2 % o
he TF can be explained by he EOF. The gap be ween TF and EOF could
be a ibu ed o he loss o ola ile PFAS (e.g. luo o elome alcohol,
FTOH) du ing e apo a ion's s ep, as demons a ed by Pan and Helbling
(2023), Weed e al. (2022). I may also be due o he p esence o luo-
ina ed o ganic compounds ha a e s ongly adso bed on o he SPM and
hen no co ec ly ex ac ed by he analy ical me hod used (Koch e al.,
2020).
On eal solid samples, he same ex ac has been used o LC-MS/MS
and CIC measu emen s. The Fig. 7 shows he compa ison be ween EOF
and sum PFAS exp essed in
μ
gF.L
−1
. Excep o one sample whe e LC-
MS/MS explained 20 % o he luo ine con ained in he EOF, all he
o he s we e explained om 0.003 % o 5 %. These esul s a e compa-
able o hose o A o e al. (2021a), He zke e al. (2022), K¨
a man e al.
(2021) and Swedish Chemicals Agency (2021).
The di e ence be ween he EOF and he sum o PFAS can be
explained, as o AOF, by occu ence o unknown PFAS, o o he luo-
ina ed o ganic compounds no conside ed in a ge analysis.
4. P ac ical applicabili y o he de eloped me hods
The p esen esul s aise he ques ion o whe he AOF and EOF a e
e ec i e pa ame e s o assessing he occu ence o global PFAS
con amina ion. Because he AOF and EOF a e no exhaus i e, hey do
no accu a ely ep esen he luo ine con amina ion de e mined by TOF
o TF. The compa ison demons a es ha he e is s ill a la ge gap be-
ween AOF o EOF and TOF. AOF and EOF do no ake in o accoun all
PFAS (such as ul a-sho chain, ola ile, non-adso bable…). Especially
Fig. 6. Compa ison be ween TOF, AOF and ∑PFAS analysed by LC-MS/MS
exp essed as
μ
gF.L
−1
on liquid samples. (LL: Land ill Leacha e; E : E luen ; I :
In luen ; GW: G ound wa e ). Pe cen ages associa ed co espond, o AOF, o
he pe cen age o TOF explained by AOF and o ∑PFAS, he pe cen age o AOF
explained by ∑PFAS.
B.I.T. Idja on e al.
Science o he To al En i onmen 932 (2024) 172589
8
because TF in ol es he combus ion o all luo ina ed compounds
wi hou disc imina ion, hese pa ame e s include o ganic luo ina ed
compounds o he han hose co e ed by he de ini ion o PFAS (OECD,
2021). In pa allel o solids, a non-leachable IF ac ion can occu ha
lead o he o e es ima ion o TOF.
As he AOF does no in ege all PFAS, o he solid phase ex ac ion
(SPE) me hods can be ca ied ou using o he polyme ca idges and/o
ac i a ed ca bon. These me hods can a ou he inclusion o a g ea e
numbe o compounds and ill he gaps be ween TOF/AOF and TF/EOF
measu emen s (Koch e al., 2020; Ruyle e al., 2023).
As he compa ison o CIC and LC-MS/MS analyses highligh s he
impo an pa o unknown compounds, o he analy ical app oaches can
be conside ed.
To al Oxidisable P ecu so s Assay (TOP Assay) de eloped o e
se e al yea s by (Hou z e al., 2013) has been applied in a la ge a ie y
o applica ions. By including his me hod, he gap be ween he global
CIC pa ame e s and LC-MS/MS can be be e explained (Al Amin e al.,
2023; An ell e al., 2023; A eia e al., 2023; Dauchy e al., 2017; Janda
e al., 2019; Tsou e al., 2023).
Ano he sou ce o in o ma ion can be non- a ge analysis (HRMS) o
iden i y luo ina ed compounds no ye included in a ge analysis (Al
Amin e al., 2023; Bangma e al., 2023; Bugsel and Zwiene , 2020;
Cha bonne e al., 2022)The e o e, i is necessa y o combine se e al
analy ical app oaches (CIC, LC-MS/MS, LC-HRMS) o ob ain a comp e-
hensi e sc eening o PFAS (A o e al., 2021a; Geh enkempe e al., 2021;
Koch e al., 2020; Wang e al., 2016). Winchell e al. (2021) p oposes
app oaches o in eg a e di e en analy ical wo k lows.
5. Conclusion
To p o ide mo e accu a e sus ainable emedia ion o eme ging
con aminan s and educe he sp ead o PFAS in he en i onmen o
achie e ze o pollu ion a ge s, his pape de eloped and compa ed
di e en analy ical app oaches o moni o ing PFAS in complex sample
ma ices. Robus and eliable me hods ha e been de eloped o bo h
liquid and solid ma ices. In pa icula , AOF me hod demons a es a
good ac i a ed ca bon adso p ion e iciency o selec ed PFAS, as well as
obus ness wi h bo h high DOC and SPM concen a ions. I also shows an
e ec i e emo al o IF in complex liquid ma ices con aining up o 8
mgF.L
−1
. All es ed me hods show good ep oducibili y. Fo AOF, he
objec i e o a LOQ o 2
μ
gF.L
−1
is eached bu canno be lowe ed
because o he p ocedu al blank.
The p esen s udy compa es measu emen s o TOF, AOF and he
amoun o o ganic luo ine explained by a ge ed analysis o complex
liquid samples. Fo complex solid samples, he same compa ison was
pe o med on measu emen s o TF, EOF and he amoun o o ganic
luo ine explained by a ge ed analysis.
When conside ing he li e a u e e iew and he esul s o he p esen
s udy he ollowing conclusions can be d awn:
The AOF and EOF measu ed concen a ions a e low compa ed o
TOF/TF measu ed concen a ions. The e o e, he e is cu en ly no
me hod ha esponds alone o he “ o al PFAS” pa ame e .
The a ge analysis o 56 PFAS by LC-MS/MS allow o quan i y a e y
small ac ion o he luo ina ed compounds con ained in AOF/EOF,
depending on he complex ma ices s udied. The ul a-sho -chain PFAS
ha e been iden i ied as a majo challenge and i would be impo an o
u u e s udies o ake hem in o accoun in o de o assess hei po en ial
con ibu ion.
The di icul y o disc imina ing he IF con en is a limi a ion o
de e mining he eal TOF ac ion.
In iew o he p esen esul s, hese alida ed analy ical me hods will
be implemen ed o s udy he a e o PFAS in WWTP ou pu s eams and
will o m pa o an o e all obus moni o ing s a egy o de e mining
he PFAS ans e ac o s om sewage sludge o di e en eco e ed
p oduc s including e ilise s o o ganic amendmen s.
Acknowledgmen s and unding
The Au ho s would like o hank he PROMISCES p ojec pa ne s
who p o ided he samples analysed in his s udy and labo a o y ech-
nicians and enginee s o suppo and analysis. The esea ch leading o
hese esul s has ecei ed unding om he Eu opean Union H2020
P og amme (H2020/2014-2020) unde g an ag eemen n◦101036449.
Fig. 7. Compa ison be ween TOF, EOF and ∑PFAS analysed by LC-MS/MS exp essed as
μ
gF.kg
−1
on solid samples. (AP: Ammonium phospha e; PR: Phospho us
Reco e y; SS: Sewage Sludge). Pe cen ages associa ed co espond o EOF, o he pe cen age o TF explained by EOF and o ∑PFAS, o he pe cen age o EOF
explained by ∑PFAS.
B.I.T. Idja on e al.
Science o he To al En i onmen 932 (2024) 172589
9
CRediT au ho ship con ibu ion s a emen
Baba ound´
e I.T. Idja on: W i ing – e iew & edi ing, W i ing –
o iginal d a , Me hodology, In es iga ion, Fo mal analysis, Da a cu a-
ion. Anne Togola: W i ing – e iew & edi ing, Valida ion, Supe ision,
Me hodology, Funding acquisi ion, Concep ualiza ion. Jean Philippe
Ghes em: W i ing – e iew & edi ing, Valida ion, Me hodology. Lau a
Kas le : Resou ces, Da a cu a ion. S´
ebas ien B is eau: Resou ces,
Concep ualiza ion. Ma iska Ron el ap: W i ing – e iew & edi ing,
Da a cu a ion. S ´
e an Colombano: W i ing – e iew & edi ing, Me h-
odology, Da a cu a ion. Nicolas De au: Me hodology, Concep ualiza-
ion. Julie Lions: P ojec adminis a ion, Funding acquisi ion. E ic D.
an Hullebusch: W i ing – e iew & edi ing, Valida ion, Me hodology,
In es iga ion, Concep ualiza ion.
Decla a ion o compe ing in e es
The au ho s decla e ha hey ha e no known compe ing inancial
in e es s o pe sonal ela ionships ha could ha e in luenced he wo k
epo ed in his pape .
Da a a ailabili y
Da a will be made a ailable on eques .
Appendix A. Supplemen a y da a
Supplemen a y da a o his a icle can be ound online a h ps://doi.
o g/10.1016/j.sci o en .2024.172589.
Re e ences
Al Amin, M., Luo, Y., Shi, F., Yu, L., Liu, Y., Nolan, A., Awoyemi, O.S., Megha aj, M.,
Naidu, R., Fang, C., 2023. A modi ied TOP assay o de ec pe -and poly luo oalkyl
subs ances in aqueous ilm- o ming oams (AFFF) and soil. F on ie s. Chemis y 11.
Al Amin, Md., Sobhani, Z., Liu, Y., Dha ma aja, R., Chadala ada, S., Naidu, R.,
Chalke , J.M., Fang, C., 2020. Recen ad ances in he analysis o pe - and
poly luo oalkyl subs ances (PFAS)—a e iew. En i on. Technol. Inno . 19, 100879
h ps://doi.o g/10.1016/j.e i.2020.100879.
An ell, E.H., Yi, S., Oli a es, C.I., Ruyle, B.J., Kim, J.T., Tsou, K., Dixi , F., Al a ez-
Cohen, L., Sedlak, D.L., 2023. The To al Oxidizable p ecu so (TOP) assay as a
o ensic ool o pe - and Poly luo oalkyl subs ances (PFAS) sou ce appo ionmen .
ACS EST Wa e . h ps://doi.o g/10.1021/acses wa e .3c00106.
A o, R., E iksson, U., K¨
a man, A., Chen, F., Wang, T., Yeung, L.W.Y., 2021a. Fluo ine
mass balance analysis o e luen and sludge om No dic coun ies. ACS EST Wa e
1, 2087–2096. h ps://doi.o g/10.1021/acses wa e .1c00168.
A o, R., E iksson, U., K¨
a man, A., Rebe , I., Yeung, L.W.Y., 2021b. Combus ion ion
ch oma og aphy o ex ac able o gano luo ine analysis. iScience 24, 102968.
h ps://doi.o g/10.1016/j.isci.2021.102968.
A ani i, O.S., S asinakis, A.S., 2015. Re iew on he occu ence, a e and emo al o
pe luo ina ed compounds du ing was ewa e ea men . Sci. To al En i on.
524–525, 81–92. h ps://doi.o g/10.1016/j.sci o en .2015.04.023.
A eia, M., Chiang, D., Cashman, M., Acheson, C., 2023. To al Oxidizable P ecu so (TOP)
Assay
–
Bes P ac ices. En i on. Sci. Technol. Le , Capabili ies and Limi a ions o
PFAS Si e In es iga ion and Remedia ion. h ps://doi.o g/10.1021/acs.
es le .3c00061.
Bangma, J., McCo d, J., Gi a d, N., Buckman, K., Pe ali, J., Chen, C., Ampa o, D.,
Tu pin, B., Mo ison, G., S yna , M., 2023. Analy ical me hod in e e ences o
pe luo open anoic acid (PFPeA) and pe luo obu anoic acid (PFBA) in biological
and en i onmen al samples. Chemosphe e 315, 137722. h ps://doi.o g/10.1016/j.
chemosphe e.2022.137722.
Ba nabas, S.J., B¨
ohme, T., Boye , S.K., I me , M., Ru kies, C., We he bee, I., Kondi´
c, T.,
Schymanski, E.L., Webe , L., 2022. Ex ac ion o chemical s uc u es om li e a u e
and pa en documen s using open access chemis y oolki s: a case s udy wi h PFAS.
Dig. Dis. 1, 490–501. h ps://doi.o g/10.1039/D2DD00019A.
Bas ow, T.P., Douglas, G.B., Da is, G.B., 2022. Vola iliza ion po en ial o pe - and Poly-
luo oalkyl subs ances om ai ield pa emen s and du ing ecycling o asphal .
En i on. Toxicol. Chem. 41, 2202–2208. h ps://doi.o g/10.1002/e c.5425.
Buck, R.C., F anklin, J., Be ge , U., Conde , J.M., Cousins, I.T., de Voog , P., Jensen, A.A.,
Kannan, K., Mabu y, S.A., an Leeuwen, S.P., 2011. Pe luo oalkyl and
poly luo oalkyl subs ances in he en i onmen : e minology, classi ica ion, and
o igins. In eg . En i on. Assess. Manag. 7, 513–541. h ps://doi.o g/10.1002/
ieam.258.
Bugsel, B., Zwiene , C., 2020. LC-MS sc eening o poly- and pe luo oalkyl subs ances in
con amina ed soil by Kend ick mass analysis. Anal. Bioanal. Chem. 412, 4797–4805.
h ps://doi.o g/10.1007/s00216-019-02358-0.
Cha bonne , J.A., McDonough, C.A., Xiao, F., Schwich enbe g, T., Cao, D., Kase zon, S.,
Thomas, K.V., Dewap iya, P., Place, B.J., Schymanski, E.L., Field, J.A., Helbling, D.
E., Higgins, C.P., 2022. Communica ing con idence o pe - and Poly luo oalkyl
subs ance iden i ica ion ia high- esolu ion mass spec ome y. En i on. Sci.
Technol. Le . 9, 473–481. h ps://doi.o g/10.1021/acs.es le .2c00206.
Chen, S., Zhou, Y., Meng, J., Wang, T., 2018. Seasonal and annual a ia ions in emo al
e iciency o pe luo oalkyl subs ances by di e en was ewa e ea men p ocesses.
En i on. Pollu . 242, 2059–2067. h ps://doi.o g/10.1016/j.en pol.2018.06.078.
Cioni, L., Plassmann, M., Benskin, J.P., Coˆ
elho, A.C.M.F., Nøs , T.H., Rylande , C.,
Niki o o , V., Sandange , T.M., He zke, D., 2023. Fluo ine mass balance, including
To al luo ine, ex ac able o ganic luo ine, Oxidizable p ecu so s, and a ge pe -
and Poly luo oalkyl subs ances, in pooled human se um om he T omsø popula ion
in 1986, 2007, and 2015. En i on. Sci. Technol. h ps://doi.o g/10.1021/acs.
es .3c03655.
Codling, G., Vog , A., Jones, P.D., Wang, T., Wang, P., Lu, Y.-L., Co co an, M., Bonina, S.,
Li, A., S u chio, N.C., Rockne, K.J., Ji, K., Khim, J.-S., Naile, J.E., Giesy, J.P., 2014.
His o ical ends o ino ganic and o ganic luo ine in sedimen s o Lake Michigan.
Chemosphe e 114, 203–209. h ps://doi.o g/10.1016/j.chemosphe e.2014.03.080.
Coggan, T.L., Moodie, D., Koloba ic, A., Szabo, D., Shime a, J., C osbie, N.D., Lee, E.,
Fe nandes, M., Cla ke, B.O., 2019. An in es iga ion in o pe - and poly luo oalkyl
subs ances (PFAS) in nine een Aus alian was ewa e ea men plan s (WWTPs).
Heliyon 5, e02316. h ps://doi.o g/10.1016/j.heliyon.2019.e02316.
Dalmijn, J., Glüge, J., Sche inge , M., Cousins, I.T., 2024. Emission in en o y o PFASs
and o he luo ina ed o ganic subs ances o he luo opolyme p oduc ion indus y
in Eu ope. En i on. Sci.: P ocesses Impac s. h ps://doi.o g/10.1039/D3EM00426K.
Dauchy, X., Boi eux, V., Bach, C., Colin, A., Hema d, J., Rosin, C., Munoz, J.-F., 2017.
Mass lows and a e o pe - and poly luo oalkyl subs ances (PFASs) in he was ewa e
ea men plan o a luo ochemical manu ac u ing acili y. Sci. To al En i on. 576,
549–558. h ps://doi.o g/10.1016/j.sci o en .2016.10.130.
DWD, 2020. DIRECTIVE (UE) 2020/2184 DU PARLEMENT EUROP´
EEN ET DU CONSEIL
du 16 d´
ecemb e 2020 ela i e `
a la quali ´
e des eaux des in´
ees `
a la consomma ion
humaine. [WWW Documen ]. URL h ps://eu -lex.eu opa.eu/legal-con en /FR/
TXT/HTML/?u i=OJ:L:2020:435:FULL (accessed 12.14.23).
E ich, M.G., Da is, M.J.B., McCo d, J.P., Ac ey, B., Awke man, J.A., Knappe, D.R.U.,
Linds om, A.B., Spe h, T.F., Tebes-S e ens, C., S yna , M.J., Wang, Z., Webe , E.J.,
Hende son, W.M., Washing on, J.W., 2022. Pe - and poly luo oalkyl subs ances in
he en i onmen . Science 375, eabg9065. h ps://doi.o g/10.1126/science.
abg9065.
Fiedle , H., Kennedy, T., Hen y, B.J., 2021. A c i ical e iew o a ecommended
analy ical and classi ica ion app oach o o ganic luo ina ed compounds wi h an
emphasis on pe - and Poly luo oalkyl subs ances. In eg . En i on. Assess. Manag. 17,
331–351. h ps://doi.o g/10.1002/ieam.4352.
Fo s e , A.L.B., Zhang, Y., Wes e man, D.C., Richa dson, S.D., 2023. Imp o ed o al
o ganic luo ine me hods o mo e comp ehensi e measu emen o PFAS in
indus ial was ewa e , i e wa e , and ai . Wa e Res. 235, 119859 h ps://doi.o g/
10.1016/j.wa es.2023.119859.
Ga g, A., She i, N.P., Basu, S., Nadagouda, M.N., Aminabha i, T.M., 2023. T ea men
echnologies o emo al o pe - and poly luo oalkyl subs ances (PFAS) in biosolids.
Chem. Eng. J. 453, 139964 h ps://doi.o g/10.1016/j.cej.2022.139964.
Geh enkempe , L., Simon, F., Roesch, P., Fische , E., on de Au, M., P ei e , J.,
Cossme , A., Wi we , P., Vogel, C., Simon, F.-G., Mee mann, B., 2021.
De e mina ion o o ganically bound luo ine sum pa ame e s in i e wa e
samples—compa ison o combus ion ion ch oma og aphy (CIC) and high esolu ion-
con inuum sou ce-g aphi e u nace molecula abso p ion spec ome y (HR-CS-
GFMAS). Anal. Bioanal. Chem. 413, 103–115. h ps://doi.o g/10.1007/s00216-020-
03010-y.
Han, Y., Pulikkal, V.F., Sun, M., 2021. Comp ehensi e alida ion o he Adso bable
o ganic luo ine analysis and pe o mance compa ison o cu en me hods o To al
pe - and Poly luo oalkyl subs ances in wa e samples. ACS EST Wa e 1, 1474–1482.
h ps://doi.o g/10.1021/acses wa e .1c00047.
He zke, D., Niki o o , V., Yeung, L.W.Y., Moe, B., Rou i, H., Nygå d, T.,
Gab ielsen, Gei .W., Hanssen, L., 2022. Ta ge ed PFAS analyses and ex ac able
O gano luo ine – enhancing ou unde s anding o he p esence o unknown PFAS in
No wegian wildli e. En i on. In . 107640 h ps://doi.o g/10.1016/j.
en in .2022.107640.
Hou z, E.F., Higgins, C.P., Field, J.A., Sedlak, D.L., 2013. Pe sis ence o Pe luo oalkyl
acid p ecu so s in AFFF-impac ed g oundwa e and soil. En i on. Sci. Technol. 47,
8187–8195. h ps://doi.o g/10.1021/es4018877.
Hu, X.C., And ews, D.Q., Linds om, A.B., B u on, T.A., Schaide , L.A., G andjean, P.,
Lohmann, R., Ca ignan, C.C., Blum, A., Balan, S.A., Higgins, C.P., Sunde land, E.M.,
2016. De ec ion o poly- and Pe luo oalkyl subs ances (PFASs) in U.S. d inking
wa e linked o indus ial si es, mili a y i e aining a eas, and was ewa e
ea men plan s. En i on. Sci. Technol. Le . 3, 344–350. h ps://doi.o g/10.1021/
acs.es le .6b00260.
Hue a, B., McHugh, B., Regan, F., 2022. De elopmen and applica ion o an LC-MS
me hod o he de e mina ion o poly-and pe luo oalkyl subs ances (PFASs) in
d inking, sea and su ace wa e samples. Anal. Me hods 14, 2090–2099.
James, A., G¨
ockene , B., Gonzalez-Gaya, Belen, Kause, R., Bandow, N., Yeung, L.,
Labadie, P., Flanagan, K., Jacobs, G., 2023. 2023 PFAS Analy ical Exchange TOP
Assay Me hod Compa ison. h ps://doi.o g/10.13140/RG.2.2.25600.71681.
Janda, J., N¨
odle , K., Scheu e , M., Happel, O., Nü enbe g, G., Zwiene , C., Lange, F.T.,
2019. Closing he gap – inclusion o ul asho -chain pe luo oalkyl ca boxylic acids
in he o al oxidizable p ecu so (TOP) assay p o ocol. En i on. Sci.: P ocesses
Impac s 21, 1926–1935. h ps://doi.o g/10.1039/C9EM00169G.
K¨
a man, A., Y. Yeung, L.W., M. Spaan, K., Thomas Lange, F., Anh Nguyen, M.,
Plassmann, M., de Wi , C.A., Scheu e , M., Awad, R., P. Benskin, J., 2021. Can
B.I.T. Idja on e al.
