Environmental Science & Technology,
Год журнала:
2024,
Номер
58(25), С. 11162 - 11174
Опубликована: Июнь 10, 2024
Thermal
treatment
has
emerged
as
a
promising
approach
for
either
the
end-of-life
or
regeneration
of
granular
activated
carbon
(GAC)
contaminated
with
per-
and
polyfluoroalkyl
substances
(PFAS).
However,
its
effectiveness
been
limited
by
requirement
high
temperatures,
generation
products
incomplete
destruction,
necessity
to
scrub
HF
in
flue
gas.
This
study
investigates
use
common
alkali
alkaline-earth
metal
additives
enhance
mineralization
perfluorooctanesulfonate
(PFOS)
adsorbed
onto
GAC.
When
treated
at
800
°C
without
an
additive,
only
49%
PFOS
was
mineralized
HF.
All
tested
demonstrated
improved
mineralization,
Ca(OH)2
had
best
performance,
achieving
efficiency
98%
air
N2.
Its
ability
increase
reaction
rate
shift
byproduct
selectivity
suggests
that
role
may
be
catalytic.
Moreover,
reduced
gas
instead
reacting
additive
form
inorganic
fluorine
(e.g.,
CaF2)
starting
waste
material.
A
hypothesized
mechanism
is
proposed
involves
electron
transfer
from
O2–
defect
sites
CaO
intermediates
formed
during
thermal
decomposition
PFOS.
These
findings
advocate
GAC
disposal
reuse,
potential
reduce
operating
costs
mitigate
environmental
impact
associated
incinerating
PFAS-laden
wastes.
Environmental Science & Technology,
Год журнала:
2021,
Номер
55(14), С. 9885 - 9894
Опубликована: Июль 8, 2021
In
this
study,
we
investigated
thermal
decomposition
mechanisms
of
cationic,
zwitterionic,
and
anionic
polyfluoroalkyl
substances,
including
those
present
in
aqueous
film-forming
foam
(AFFF)
samples.
We
novel
evidence
that
substances
gave
quantitative
yields
perfluoroalkyl
different
chain
lengths
during
treatment.
The
results
support
a
radical-mediated
transformation
mechanism
involving
random-chain
scission
end-chain
scission,
leading
to
the
formation
carboxylic
acids
such
as
perfluorooctanoic
acid
(PFOA)
from
certain
amides
sulfonamides.
Our
also
direct
(chain
stripping)
on
nonfluorinated
moiety
sulfonamides,
resulting
perfluorooctanesulfonic
(PFOS)
other
structurally
related
compounds.
Thermal
8:2
fluorotelomer
sulfonate
occurred
through
recombination
reactions,
successively
yielding
PFOS.
All
studied
began
degrade
at
200-300
°C,
exhibiting
near-complete
≥400
°C.
Using
high-resolution
parent
ion
search
method,
demonstrated
for
first
time
low-temperature
treatments
AFFF
samples
led
generation
fluoroalkyl
perfluoroheptanesulfonamide,
sulfonic
acid,
N-methyl
perfluorooctane
sulfonamide,
previously
unreported
compound
N-2-propenyl-perfluorohexylsulfonamide.
This
study
provides
key
insights
into
fate
processes.
Environmental Science & Technology,
Год журнала:
2022,
Номер
56(10), С. 6647 - 6657
Опубликована: Май 6, 2022
Hydrothermal
alkaline
treatment
(HALT)
can
effectively
degrade
per-
and
polyfluoroalkyl
substances
(PFASs)
present
in
aqueous
film-forming
foam
(AFFF).
However,
information
is
lacking
regarding
the
of
PFASs
actual
groundwater
soil
from
AFFF-impacted
sites,
especially
for
complex
matrices.
Given
lack
studies
on
direct
PFAS
destruction,
we
herein
applied
HALT
to
two
samples
three
sites
characterized
destruction
using
high-resolution
mass
spectrometry.
Results
showed
that
148
identified
all
collected
field
samples,
including
10
cationic,
98
anionic,
40
zwitterionic
PFASs,
were
mostly
degraded
nondetectable
levels
within
90
min
when
treated
with
5
M
NaOH
at
350
°C.
The
near-complete
defluorination,
as
evidenced
by
fluoride
release
measurements,
confirmed
complete
PFASs.
While
many
structures,
perfluoroalkyl
carboxylic
acids
polyfluorinated
substances,
readily
degraded,
sulfonates
(PFSAs,
CnF2n+1–SO3–),
most
notably
short
chain
lengths
(n
=
3–5),
more
recalcitrant.
Rates
PFSA
similar
those
measured
laboratory
water
solutions,
but
reactions
slow,
presumably
due
base-neutralizing
properties
soil.
Further,
degradation
groundwaters
soils
was
found
be
a
function
reaction
temperature,
concentration,
time.
These
findings
have
important
implications
remediation
sites.
Environmental Science & Technology,
Год журнала:
2023,
Номер
57(23), С. 8796 - 8807
Опубликована: Май 17, 2023
In
this
study,
we
investigated
the
thermal
decomposition
mechanisms
of
perfluoroalkyl
ether
carboxylic
acids
(PFECAs)
and
short-chain
(PFCAs)
that
have
been
manufactured
as
replacements
for
phased-out
per-
polyfluoroalkyl
substances
(PFAS).
C-C,
C-F,
C-O,
O-H,
C═C
bond
dissociation
energies
were
calculated
at
M06-2X/Def2-TZVP
level
theory.
The
α-C
carboxyl-C
energy
PFECAs
declines
with
increasing
chain
length
attachment
an
electron-withdrawing
trifluoromethyl
(-CF
Environmental Science & Technology,
Год журнала:
2023,
Номер
57(13), С. 5231 - 5242
Опубликована: Март 22, 2023
A
comprehensive,
generalized
approach
to
predict
the
retention
of
per-
and
polyfluoroalkyl
substances
(PFAS)
from
aqueous
film-forming
foam
(AFFF)
by
a
soil
matrix
as
function
PFAS
molecular
physiochemical
properties
was
developed.
An
AFFF
with
34
major
(12
anions
22
zwitterions)
added
uncontaminated
in
one-dimensional
saturated
column
experiments
mass
retained
measured.
described
using
an
exhaustive
statistical
generate
poly-parameter
quantitative
structure–property
relationship
(ppQSPR).
The
relevant
predictive
were
molar
mass,
fluorine,
number
nitrogens
molecule,
poorly
crystalline
Fe
oxides,
organic
carbon,
specific
(BET-N2)
surface
area.
anionic
nearly
independent
largely
hydrophobicity,
size
fluorinated
side
chain
main
predictor.
Retention
nitrogen-containing
zwitterionic
related
metal
oxides
carbon
content.
Knowledge
extent
which
suite
may
respond
variations
properties,
developed
here,
paves
way
for
development
reactive
transport
algorithms
ability
capture
dynamics
source
zones
over
extended
time
frames.
Journal of environmental chemical engineering,
Год журнала:
2023,
Номер
11(6), С. 111588 - 111588
Опубликована: Ноя. 29, 2023
The
treatability
of
perfluorocarboxylic
acids
(PFCA)
(perfluorobutanoic
acid
(PFBA),
perfluorohexanoic
(PFHxA),
perfluorooctanoic
(PFOA)
and
perfluorodecanoic
(PFDA))
perfluorosulfonic
(PFSA)
(PFBS,
Perfluorooctanesulfonic
PFHxS
(PFOS))
via
a
bubble
column
with
non-thermal
plasma
discharges
in
the
argon
headspace
were
investigated
individual
solutions
from
surface
water
sourced
contaminated
site.
High
degradation
(>90%)
could
be
achieved
for
PFOA,
PFOS
within
40
min
treating
water.
Overall,
correlated
length
perfluorinated
carbon
chain,
decrease
associated
reduction
backbone.
Experiments
prepared
PFAS
at
initial
concentrations
10,
25
50
μg/L
found
higher
PFCA
PFSA
faster
rates
suggesting
treatment
efficiency
was
limited
by
mass
transfer
PFAS.
Negligible
breakdown
observed
PFBA
any
trialled,
indicating
limitations
when
more
hydrophilic
PFAS,
which
may
require
combining
this
approach
polishing
step,
such
as
nanofiltration.
Environmental Science & Technology Letters,
Год журнала:
2023,
Номер
10(5), С. 425 - 430
Опубликована: Апрель 10, 2023
Granular
activated
carbon
(GAC)
adsorption
is
the
most
common
technology
applied
to
treat
water
contaminated
with
per-
and
polyfluoroalkyl
substances
(PFASs),
but
rapid
exhaustion
of
media
necessitates
frequent
replacement
costly
off-site
thermal
regeneration.
Here,
we
extend
application
hydrothermal
alkaline
treatment
(HALT),
which
uses
strong
alkali
near-critical
temperatures
pressures
(e.g.,
350
°C,
16.5
MPa,
1
M
NaOH)
degrade
mineralize
PFASs,
regeneration
spent
GAC.
Mass
balance
experiments
wherein
a
known
mass
perfluorooctanesulfonate
(PFOS)
was
adsorbed
onto
GAC
prior
showed
that
HALT
achieved
>99%
destruction
PFOS
96
±
4%
defluorination
no
observed
fluoro-organic
intermediates
[167
g
L–1
GAC,
NaOH,
trxn
=
400
min,
10–15
mg
(g
GAC)−1].
Treatment
collected
from
field
pilot
study
also
effective
range
PFASs.
Moreover,
repeated
cycles
did
not
significantly
affect
specific
surface
area,
similar
isotherms
for
perfluoropentanoic
acid
were
recorded
virgin
HALT-treated
These
findings
suggest
promising
strategy
on-site
PFAS-contaminated
other
adsorbent
may
be
an
alternative
practices.