Environment International,
Год журнала:
2023,
Номер
180, С. 108240 - 108240
Опубликована: Сен. 28, 2023
Atmospheric
particulate
matter
(PM)
poses
great
adverse
effects
through
the
production
of
reactive
oxygen
species
(ROS).
Various
components
in
PM
are
acknowledged
to
induce
ROS
formation,
while
interactions
among
chemicals
remain
be
elucidated.
Here,
we
systematically
investigate
influence
Brown
carbon
(BrC)
surrogates
(e.g.,
imidazoles,
nitrocatechols
and
humic
acid)
on
hydroxyl
radical
(OH)
generation
from
transition
metals
(TMs)
simulated
lung
fluid.
Present
results
show
that
BrC
has
an
antagonism
(interaction
factor:
20-90
%)
with
Cu2+
OH
upon
interaction
glutathione,
which
concentrations
TMs
extent
antagonism.
Rapid
glutathione
is
observed
for
Fe2+,
formation
very
little
Fe3+.
The
compositions
antioxidants
ascorbate,
urate),
resembling
upper
lower
respiratory
tract,
respond
differently
(Cu2+,
Fe2+
Fe3+)
degree
complexation
equilibrium
constants
site
numbers
between
acid
were
further
analyzed
using
fluorescence
quenching
experiments.
Possible
products
TMs,
4-nitrocatechol
also
identified
quadropule-time-of-flight
mass
spectrometry.
suggest
atmospheric
widely
participate
human
fluid,
should
considered
evaluating
mediated
by
ambient
PM.
Environmental Science & Technology Letters,
Год журнала:
2024,
Номер
11(4), С. 315 - 322
Опубликована: Март 25, 2024
Particulate
matter
(PM)
emitted
from
road
traffic
causes
adverse
health
effects
upon
inhalation
and
respiratory
deposition.
Non-exhaust
emissions
will
eventually
become
the
dominant
source
of
PM
transition
to
electric
vehicles;
however,
non-tailpipe
is
currently
unregulated
as
its
impacts
are
still
unclear.
In
this
study,
we
generated
brake
wear
particles
(BWPs)
with
non-asbestos
organic,
ceramic,
semimetallic
pads
using
custom
dynamometers
measured
aqueous-phase
formation
reactive
oxygen
species
(ROS).
We
found
that
BWPs
do
not
contain
environmentally
persistent
free
radicals
(EPFRs),
all
types
generate
exclusively
·OH
in
water.
by
ceramic
brakes
during
heavier
braking
lead
higher
yields
compared
gentle
conditions,
suggesting
potential
ultrafine
BWPs.
Chemical
characterization
reveals
organic
elemental
carbon
correlated
positively
while
exhibiting
negative
correlations
abundant
metals
including
Fe
Mn.
suggest
thermal
decomposition
hydroperoxides
derived
phenolic
resin.
oxidative
quantified
dithiothreitol
(DTT)
assay
exhibited
a
positive
correlation
yield.
These
results
provide
critical
insights
into
toxicity
The Journal of Physical Chemistry A,
Год журнала:
2022,
Номер
126(40), С. 7361 - 7372
Опубликована: Окт. 4, 2022
Reactive
oxygen
species
(ROS)
and
environmentally
persistent
free
radicals
(EPFR)
play
an
important
role
in
chemical
transformation
of
atmospheric
aerosols
adverse
aerosol
health
effects.
This
study
investigated
the
effects
nitrogen
oxides
(NOx)
during
photooxidation
α-pinene
naphthalene
on
EPFR
content
ROS
formation
from
secondary
organic
(SOA).
Electron
paramagnetic
resonance
(EPR)
spectroscopy
was
applied
to
quantify
formation.
While
no
were
detected
SOA,
we
found
that
SOA
contained
about
0.7
pmol
μg-1
EPFR,
NOx
has
little
influence
concentrations
oxidative
potential.
α-Pinene
generated
under
low
conditions
form
OH
superoxide
aqueous
phase,
which
lowered
substantially
by
50-80%
for
high
conditions.
High-resolution
mass
spectrometry
analysis
showed
substantial
nitroaromatics
nitrates
a
environment.
The
modeling
results
using
GECKO-A
model
simulates
explicit
gas-phase
chemistry
radical
2D-VBS
treats
autoxidation
predicted
reduced
hydroperoxides
enhanced
due
reactions
peroxy
with
instead
their
HO2.
Consistently,
presence
resulted
decrease
peroxide
contents
potential
SOA.
Geoscientific model development,
Год журнала:
2023,
Номер
16(7), С. 2037 - 2054
Опубликована: Апрель 14, 2023
Abstract.
The
heterogeneous
chemistry
of
atmospheric
aerosols
involves
multiphase
chemical
kinetics
that
can
be
described
by
kinetic
multi-layer
models
(KMs)
explicitly
resolve
mass
transport
and
reactions.
However,
KMs
are
computationally
too
expensive
to
used
as
sub-modules
in
large-scale
models,
the
computational
costs
also
limit
their
utility
inverse-modeling
approaches
commonly
infer
aerosol
parameters
from
laboratory
studies.
In
this
study,
we
show
how
machine
learning
methods
generate
inexpensive
surrogate
for
model
surface
bulk
(KM-SUB)
predict
reaction
times
systems.
We
apply
compare
two
common
openly
available
generation
polynomial
chaos
expansion
(PCE)
with
UQLab
neural
networks
(NNs)
through
Python
package
Keras.
PCE
method
is
well
suited
determining
global
sensitivity
indices
KMs,
demonstrate
applications
enabled
or
accelerated
NN-suggested
sampling.
These
qualities
make
them
suitable
supporting
tools
work
interpretation
data
design
future
experiments.
Overall,
KM
investigated
study
fast,
accurate,
robust,
which
suggests
applicability
models.
Environmental Science & Technology,
Год журнала:
2023,
Номер
57(36), С. 13546 - 13558
Опубликована: Авг. 25, 2023
The
oxidative
potential
(OP)
of
particulate
matter
has
been
widely
suggested
as
a
key
metric
for
describing
atmospheric
particle
toxicity.
Secondary
organic
aerosol
(SOA)
and
redox-active
transition
metals,
such
iron
copper,
are
drivers
OP.
However,
their
relative
contributions
to
OP,
well
the
influence
metal-organic
interactions
chemistry
on
remains
uncertain.
In
this
work,
we
simultaneously
deploy
two
novel
online
instruments
first
time,
providing
robust
quantification
We
utilize
AA
(OPAA)
2,7-dichlorofluoroscein
(ROSDCFH)
methods
investigate
Fe(II)
Cu(II)
OP
secondary
(SOA).
addition,
quantify
OH
production
(OPOH)
from
these
mixtures.
observe
range
synergistic
antagonistic
when
mixed
with
representative
biogenic
(β-pinene)
anthropogenic
(naphthalene)
SOA.
A
newly
developed
kinetic
model
revealed
reactions
among
SOA
components,
ascorbate,
influencing
OPAA.
Model
predictions
agree
OPAA
measurements,
highlighting
metal-ascorbate
-naphthoquinone-ascorbate
important
simultaneous
application
multiple
assays
provides
new
insights
into
metal
Environmental Science Atmospheres,
Год журнала:
2023,
Номер
3(7), С. 1066 - 1074
Опубликована: Янв. 1, 2023
A
multiphase
kinetic
model
analysis
quantifies
effects
of
air
pollutants
on
reactive
oxygen
species
production
and
oxidative
stress
in
the
respiratory
tract.
Atmospheric chemistry and physics,
Год журнала:
2024,
Номер
24(1), С. 155 - 166
Опубликована: Янв. 5, 2024
Abstract.
Nitrogen
(N)-containing
compounds
have
a
significant
impact
on
the
optical
and
toxicological
properties
of
aerosols.
1,2,4-Trioxolanes,
known
as
secondary
ozonides
(SOZs),
i.e.,
key
products
from
ozonolysis
biogenic
terpenoids,
are
readily
taken
up
into
atmospheric
aerosols
act
oxidants,
potentially
interacting
with
amines
in
atmosphere.
In
present
work,
we
carefully
investigated
component
particles
produced
by
β-caryophyllene
(β-C)
presence
ethylamine
(EA),
methylamine
(MA),
dimethylamine
(DMA),
or
ammonia.
The
mass
spectrometric
results
show
that
SOZ
is
dominant
product
β-C.
It
reacts
EA
MA
but
has
inert
reactivities
toward
DMA
Similar
experimental
were
achieved
α-humulene
(α-H),
an
isomer
β-C,
was
used
place
Additionally,
D2O
H218O
solvents
for
characterization
products.
revealed
intriguing
phenomenon
where
β-C
α-H
reacting
same
amine
(EA
MA)
possessed
different
functional
groups,
despite
fact
they
isomerized
species
identical
chemical
structure
(1,2,4-trioxolane).
This
indicates
conformation
SOZs
strong
influence
how
react
amines.
For
first
time,
derived
reported
this
study;
may
represent
hitherto
unrecognized
source
N-containing
compound
production
Environmental Science & Technology,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 19, 2025
Fenton-like
reactions
between
organic
peroxides
and
transition-metal
ions
in
the
atmospheric
aqueous
phase
have
profound
impacts
on
chemistry,
composition,
health
effects
of
aerosols.
However,
kinetics,
mechanisms,
key
influencing
factors
such
remain
poorly
understood.
In
this
study,
we
synthesized
a
series
monoterpene-derived
α-acyloxyalkyl
hydroperoxides
(AAHPs),
an
important
class
formed
from
Criegee
intermediates
during
ozonolysis
alkenes,
investigated
their
with
iron
phase.
We
found
that
AAHPs
are
essentially
chemically
inert
to
Fe3+
but
highly
reactive
toward
Fe2+.
The
aqueous-phase
reaction
rate
constant
Fe2+
(kIIAAHP+Fe(II))
was
determined
range
11.0
±
0.8
150.0
3.3
M–1
s–1,
depending
positively
solution
pH
(1–3),
water
content
(50%–90%),
temperature
(8–25
°C).
Meanwhile,
kIIAAHP+Fe(II)
value
is
linearly
correlated
O/C
ratio
AAHPs,
which
allows
for
estimation
reactivity
based
oxygenation
level.
addition,
decomposition
via
predominantly
yields
alkoxy
(RO)
radicals
production
yield
OH
smaller
than
16%.
Similar
several
abundant
including
pinonic
acid-derived
AAHP
exhibit
high
low
dissolved
α-pinene
secondary
aerosol.
A
quantitative
analysis
measured
kinetics
suggests
even
dominant
drivers
behind
transformation
atmosphere,
would
significantly
affect
multiphase
chemistry
aerosol
impacts.
Journal of Cheminformatics,
Год журнала:
2024,
Номер
16(1)
Опубликована: Март 22, 2024
Abstract
Kinetic
process
models
are
widely
applied
in
science
and
engineering,
including
atmospheric,
physiological
technical
chemistry,
reactor
design,
or
optimization.
These
rely
on
numerous
kinetic
parameters
such
as
reaction
rate,
diffusion
partitioning
coefficients.
Determining
these
properties
by
experiments
can
be
challenging,
especially
for
multiphase
systems,
researchers
often
face
the
task
of
intuitively
selecting
experimental
conditions
to
obtain
insightful
results.
We
developed
a
numerical
compass
(NC)
method
that
integrates
computational
models,
global
optimization,
ensemble
methods,
machine
learning
identify
with
greatest
potential
constrain
model
parameters.
The
approach
is
based
quantification
output
variance
an
solutions
agree
data.
utility
NC
demonstrated
multi-layer
describing
heterogeneous
ozonolysis
oleic
acid
aerosols.
show
how
neural
network
surrogate
chemical
system
used
accelerate
application
comprehensive
mapping
analysis
conditions.
also
uncertainty
quantitative
structure–activity
relationship
(QSAR)
models.
calculated
molecules
extend
training
data
correlates
reduction
QSAR
error.
code
openly
available
Julia
package
KineticCompass
.
Graphical
Environmental Science & Technology,
Год журнала:
2025,
Номер
unknown
Опубликована: Март 25, 2025
Exposure
to
atmospheric
aerosols
threatens
human
health
and
is
yet
be
effectively
addressed
globally.
Aerosol
toxicity
strongly
depends
upon
components
whose
chemical
profiles
concentrations
can
constantly
evolve
throughout
transformation,
inhalation,
distribution,
metabolism,
excretion.
Despite
the
abundant
studies
on
aerosol
their
toxic
effects,
dynamics
in
component
related
biological
effects
from
air
body
remain
unclear.
Here,
we
propose
a
conceptual
toxicokinetic
framework
mathematically
deduce
bioavailable
concentration
changing
bulk
of
constituents
atmosphere.
The
single
or
multiple
are
further
predicted
via
toxicodynamic
modeling
according
concentrations.
Atmospheric
composition
turn
regulated
by
risk-based
guidelines,
aiming
alleviate
vivo
effects.
This
perspective
demonstrates
how
serial
toxicokinetic-toxicodynamic
equations
bridge
knowledge
gap
between
ambient
associated
bodies.
prediction
an
inhalation
also
allows
connecting
with
exposomes
aggregate
exposure
pathways.
We
call
for
development
model
validity
integrate
quantitative
adverse
outcome
pathways
apply
exposure-disease
modeling,
providing
novel
insights
into
quality
policymaking
public
management.
Environmental Science & Technology,
Год журнала:
2022,
Номер
56(14), С. 9978 - 9987
Опубликована: Июнь 25, 2022
Particulate
matter
(PM)
and
gaseous
hydrogen
peroxide
(H2O2)
interact
ubiquitously
to
influence
atmospheric
oxidizing
capacity.
However,
quantitative
information
on
H2O2
loss
its
fate
urban
aerosols
remain
unclear.
This
study
investigated
the
kinetics
of
heterogeneous
reactions
PM2.5
explored
how
these
processes
are
affected
by
various
experimental
conditions
(i.e.,
relative
humidity,
temperature,
concentration).
We
observed
a
persistent
uptake
(with
coefficients
(γ)
10-4-10-3)
exacerbated
aerosol
liquid
water
confirming
critical
role
water-assisted
chemical
decomposition
during
process.
A
positive
correlation
between
γ
values
ratio
dissolved
iron
concentration
suggests
that
Fenton
catalytic
may
be
an
important
pathway
for
conversion
under
dark
conditions.
Furthermore,
basis
kinetic
data
gained,
parameterization
was
developed
applied
into
box
model.
The
good
agreement
simulated
measured
uncovered
significant
plays
in
sink
atmosphere.
These
findings
suggest
composition-dependent
particle
reactivity
toward
should
considered
models
elucidating
environmental
health
effects
ambient
aerosols.