Development of a Nontargeted Algorithm for Per- and Polyfluoroalkyl Substances in the FT-ICR Mass Spectra of Complex Organic Mixtures
Analytical Chemistry,
Год журнала:
2025,
Номер
unknown
Опубликована: Март 6, 2025
The
unrivaled
mass
resolving
power
and
subppm
error
enable
the
application
of
Fourier
transform
ion
cyclotron
resonance
spectrometry
(FT-ICR
MS)
for
nontargeted
screening
per-
polyfluoroalkyl
substances
(PFAS).
Few
automated
FT-ICR
MS
methods
exist
analysis
PFAS
in
solutions
containing
other
dissolved
organic
matter.
In
this
study,
isotopic
pattern
dynamic
homologous
series
inspection
were
complementarily
employed
FTMSDeu
algorithm
to
simultaneously
assign
chemical
formulas
molecules,
with
an
overall
assignment
accuracy
91.2%
1,802
unique
their
11,634
formulas.
negative
effects
fluorine-related
isobaric
isotopes
sub-mDa
differences
on
formula
natural
matter
addressed
by
empirical
F/(H
+
X)
rule
adoption
a
threshold
number
plus
number.
There
203
one
novel
formula,
C9H6O4S1I1F11,
identified
fluoropolymer
industry-impacted
river
water
sample
using
our
analyzing
spectra.
Overall,
results
study
highlighted
great
potential
updated
high-throughput
spectra
complex
mixtures
from
real
environmental
samples.
Язык: Английский
Determination of 12 halogenated organic pollutants in edible fish by ultra performance liquid chromatography-high resolution mass spectrometry combined with ultrasound-assisted extraction and gel permeation chromatography purification
Chinese Journal of Chromatography,
Год журнала:
2025,
Номер
43(1), С. 68 - 77
Опубликована: Янв. 1, 2025
Halogenated
organic
pollutants
(HOPs)
have
attracted
considerable
attention
owing
to
their
persistence,
bioaccumulation,
and
toxicity.
The
development
of
methods
detect
HOPs
in
fish
is
challenging
the
compositional
complexity
matrices,
which
contain
high
levels
lipids
relatively
low
concentrations
HOPs.
In
addition,
lipophilicity
most
renders
extraction
difficult.
Moreover,
simultaneous
determination
multiple
achieve
high-throughput
screening
these
analytes
complex.
this
study,
a
reliable
efficient
pretreatment
method
based
on
ultrasound-assisted
extraction,
gel
permeation
chromatography
purification,
ultra
performance
liquid
chromatography-high
resolution
mass
spectrometry
(UPLC-HRMS)
was
developed
for
12
edible
fish.
procedures
sample
purification
LC-HRMS
detection
parameters
were
optimized
improve
method.
Fresh
samples
thoroughly
rinsed
with
water,
non-edible
parts,
including
skin,
bones,
phosphorus,
removed.
weighed,
cut
into
small
pieces,
vacuum
freeze-dried
48
h.
Subsequently,
freeze
grinder
used
grind
dried
fine
powder.
Exactly
2
g
powder
fortified
isotope-labeled
internal
standards
HOPs,
allowed
stand
5
min.
Methanol-acetonitrile
(1∶1,
v/v)
then
added,
followed
by
vortex
mixing
ultrasonication.
After
centrifugation,
supernatant
transferred
fresh
tube.
process
repeated
twice
all
extracts
combined.
extract
evaporated
under
gentle
nitrogen
flow
redissolved
mixture
ethyl
acetate-cyclohexane
v/v).
cleaned
using
chromatography,
eluate
collected
concentrated
flow.
Sample
residuals
reconstituted
water-methanol
prior
instrumental
analysis.
Chromatographic
separation
performed
an
ACQUITY
UPLC
BEH
C18
column
(100
mm×2.1
mm,
1.7
μm).
Water
containing
mmol/L
NH4Ac
acetonitrile
as
mobile
phases,
gradient
elution
program
applied.
Isotope
dilution
standard
quantify
An
electrospray
ionization
source
operated
negative
mode
applied
ionize
full
scan
together
data-dependent
acquisition
(DDA)
HRMS.
Excellent
linearities
(R2>0.99)
obtained
quantification
range
1.0-1000.0
ng/mL.
limits
0.5
ng/g.
analytical
validated
pooled
HOP
(4,
40,
400
ng/g).
recoveries
67.6%-133.8%,
corresponding
RSDs
0.5%-15.6%.
A
total
27
commercially
available
analyzed
method,
results
revealed
presence
fish,
indicating
practicability
real-world
samples.
rapid,
accurate,
precise,
suitable
detecting
This
study
provides
useful
approach
environmental
monitoring
food
safety
assurance
enabling
accurate
analysis
commonly
consumed
Given
increasing
global
concerns
over
will
provide
practical
technical
support
consumers
aiming
reduce
exposure
adverse
impacts
via
Язык: Английский
Nontarget Analysis and Characterization of a Group of Abundant Polyfluoroalkyl Substances─Fluorinated Benzoylurea Pesticides and Their Analogues and Transformation Products in Fish by LC-HRMS and Chemical Species-Specific Algorithms
Journal of Agricultural and Food Chemistry,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 13, 2025
Poly-
and
perfluoroalkyl
substances
(PFASs)
are
a
large
class
of
fluorinated
chemicals
used
in
various
industrial
agrochemical
products
such
as
benzoylurea
(FBU)
pesticides.
Initiated
from
an
incidental
preliminary
finding
three
high-abundance
FBUs
fish,
this
study
implemented
nontarget
analysis
characterization
for
together
with
their
analogues
transformation
(TPs)
fish
using
liquid
chromatography,
high-resolution
mass
spectrometry,
chemical
species-specific
algorithms.
A
total
23
FBU-relevant
compounds
were
found
tentatively/accurately
elucidated
structures,
including
18
PFASs
5
non-PFAS
compounds,
which
4
original
FBUs,
8
FBU
analogues,
11
FBU-TPs.
The
concentrations
0.8–1919.3
ng/g
the
samples.
strategy
data-processing
algorithms
can
be
extended
to
other
fluorine-containing
pesticides,
results
provide
new
understanding
PFAS
pollution
unveil
important
source
pollutants,
utilization
FBUs.
Язык: Английский
Molecular characteristics of emerging perfluoroalkyl and polyfluoroalkyl substances (PFAS) and dissolved organic matter (DOM) in surface waters around fluorine-related industries in a Chinese Megacity
Environment International,
Год журнала:
2025,
Номер
198, С. 109444 - 109444
Опубликована: Апрель 1, 2025
Fluorine-related
industrial
discharges
are
the
main
source
of
per-
and
polyfluoroalkyl
substances
(PFAS)
contamination
in
surrounding
surface
waters,
but
long-term
environmental
impacts
their
residual
PFAS
interactions
between
dissolved
organic
matter
(DOM)
field
waters
have
rarely
been
discussed.
In
this
study,
concentrations
32
target
were
quantified,
50
identified
semi-quantified
by
suspect
nontarget
screening,
molecular
characteristics
DOM
analyzed
water
Shanghai.
Concentrations
∑PFAS
284
∼
3018
ng/L.
Perfluorobutane
sulfonate
acid
(PFBS)
perfluorooctanoic
(PFOA)
remained
predominant
compounds
at
most
sampling
sites,
hexafluoropropylene
oxide
trimer
(HFPO-TA)
exhibited
extremely
high
values
a
few
specific
sites.
Near
historical
fluorotelomer
manufacturer
which
was
closed
2017,
concentration
still
high-level
1800
Thirteen
including
7
iodinated
perfluoroalkyl
acids
(IPFAAs)
100
%
samples.
A
total
8134
formulas
identified.
For
elemental
composition,
CHOS
(24
%)
has
highest
percentage,
while
for
species,
lignin
(36
proportion
molecules.
When
assignment
fluorine
included
analysis,
percentage
fluorine-containing
reached
to
55
%,
suggesting
anthropogenic
influences.
Emerging
PFAS,
i.e.,
perfluoropentanoic
(PFPeA)
dimer
(HFPO-DA)
negatively
related
(p
<
0.05)
due
microorganism
activities.
This
study
revealed
persistent
impact
fluorine-related
industries
behavior
aquatic
environments,
providing
support
systematic
comprehensive
evaluation
health.
Язык: Английский
Accurate Detection and High Throughput Profiling of Unknown PFAS Transformation Products for Elucidating Degradation Pathways
Water Research,
Год журнала:
2025,
Номер
282, С. 123645 - 123645
Опубликована: Апрель 15, 2025
Язык: Английский
Comparative Analysis of UV-initiated ARPs for Degradation of the Emerging Substitute of Perfluorinated Compounds: Does Defluorination Mean the Sole Factor?
Journal of Hazardous Materials,
Год журнала:
2024,
Номер
474, С. 134687 - 134687
Опубликована: Май 21, 2024
Язык: Английский
Nontarget analysis and characterization of p-phenylenediamine-quinones and -phenols in tire rubbers by LC-HRMS and chemical species-specific algorithm
Analytica Chimica Acta,
Год журнала:
2024,
Номер
1326, С. 343123 - 343123
Опубликована: Авг. 22, 2024
Язык: Английский
Optimized liquid chromatography–tandem mass spectrometry protocol for enhanced detection of 45 pesticides in water and soil samples
Rapid Communications in Mass Spectrometry,
Год журнала:
2024,
Номер
38(21)
Опубликована: Сен. 2, 2024
Rationale
The
development
of
analytical
screening
techniques
for
pesticides
is
crucial
preventing
and
mitigating
environmental
contamination.
Mass
spectrometry‐based
methods
differ
based
on
the
complexity
sample
matrix
diversity
target
compounds.
One
major
challenges
balancing
cost
reduction
in
extraction
process
with
optimization
results.
This
protocol
introduces
a
universal
efficient
scheme
qualitative
quantitative
schemes
45
within
single
run.
Methods
Water
samples
were
extracted
using
an
SPE
column,
pH
adjusted
to
7.
Soil
processed
modified
QuEChERS
method.
pretreatment
water
emphasized
selecting
appropriate
columns
optimizing
pH,
while
soil
samples,
focus
was
choosing
suitable
solvents
salt
packages.
enriched
then
analyzed
liquid
chromatography–tandem
mass
spectrometry
(LC–MS/MS).
method
evaluated
accuracy,
precision,
detection
limits,
effects.
Results
enabled
simultaneous
15‐minute
analysis
period.
recoveries
ranged
from
56.1%
118.8%.
Instrumental
limits
varied
between
0.02
1
pg,
extended
0.05
18.47
ng/l
matrices.
approach
successfully
applied
pesticide
concentration
ranging
0.1
ng/L
38
μg/L.
Conclusions
substantially
enhances
characterization
quantification
achieving
remarkable
by
order
magnitude
compared
previous
research.
enables
both
matrices
system,
addressing
separate
systems
different
media.
Furthermore,
this
provides
theoretical
foundation
managing
safeguarding
against
pollution.
Язык: Английский
Unravel the in-Source Fragmentation Patterns of Per- and Polyfluoroalkyl Substances during Analysis by LC-ESI-HRMS
Environmental Science & Technology,
Год журнала:
2024,
Номер
unknown
Опубликована: Дек. 12, 2024
In-source
fragmentation
(ISF)
was
inevitable
during
electrospray
ionization
(ESI)
of
per-
and
polyfluoroalkyl
substances
(PFAS)
when
analyzed
by
liquid
chromatography
coupled
with
mass
spectrometry
(LC-MS),
resulting
in
reduced
response
molecular
ions
misannotation
MS
features.
Herein,
we
82
PFAS
across
12
classes
to
systematically
identify
the
structures
ISF
potentials
reveal
pathways.
We
found
up
100%
for
38
six
classes,
which
all
contain
carboxylate
(CO
Язык: Английский
Identification of Novel Iodinated Polyfluoroalkyl Ether Acids and Other Emerging PFAS in Soils Using a Nontargeted Molecular Network Approach
Environmental Science & Technology,
Год журнала:
2024,
Номер
unknown
Опубликована: Дек. 31, 2024
Despite
advancements
in
high-resolution
screening
techniques,
the
identification
of
novel
perfluoroalkyl
and
polyfluoroalkyl
substances
(PFAS)
remains
challenging
without
prior
structural
information.
In
view
this,
we
proposed
implemented
a
new
data-driven
algorithm
to
calculate
spectral
similarity
among
PFAS,
facilitating
generation
molecular
networks
screen
for
unknown
compounds.
Using
this
approach,
81
PFAS
across
12
distinct
classes
were
identified
soil
samples
collected
near
an
industrial
park
Shandong
Province,
China,
including
first
reported
occurrence
iodine-substituted
PFAS.
Among
them,
standards
four
polyfluorinated
ether
sulfonates
(I-PFESA)
successfully
synthesized,
enabling
confirmation
subsequent
quantitative
analysis.
Although
median
concentration
∑I-PFESA
(0.74
ng/g
dw)
was
lower
than
that
∑H-PFESA
(hydrogen-substituted,
61.96
∑Cl-PFESA
(chlorine-substituted,
2.98
dw),
embryotoxicity
assays
zebrafish
revealed
6:2
I-PFESA
exhibited
greater
toxicity
compared
Cl-PFESA
same
chain
length.
This
highlights
need
closer
examination
toxic
effects
I-PFESA.
Notably,
algorithm,
based
on
similarity,
provides
perspectives
environmental
behavior
transformation
I-PFESA,
although
further
investigation
is
required
elucidate
underlying
mechanisms
their
toxicity.
Язык: Английский