Atmospheric chemistry and physics,
Год журнала:
2022,
Номер
22(3), С. 1989 - 2009
Опубликована: Фев. 11, 2022
Abstract.
Reactive
oxygen
species
(ROS),
such
as
OH,
HO2
and
H2O2,
affect
the
oxidation
capacity
of
atmosphere
cause
adverse
health
effects
particulate
matter.
The
role
transition
metal
ions
(TMIs)
in
impacting
ROS
concentrations
conversions
atmospheric
aqueous
phase
has
been
recognized
for
a
long
time.
Model
studies
usually
assume
that
total
TMI
mass
measured
bulk
aerosol
or
cloud
water
samples
is
distributed
equally
across
all
particles
droplets.
This
assumption
contrary
to
single-particle
measurements
have
shown
only
small
number
fraction
contain
iron
other
TMIs
(FN,Fe<100
%),
which
implies
also
not
droplets
TMIs.
In
current
study,
we
apply
box
model
with
an
explicit
multiphase
chemical
mechanism
simulate
formation
cycling
simulations
are
performed
range
1
%
≤
FN,Fe
100
constant
pH
values
3,
4.5
6
concentration
(10
50
ng
per
cubic
meter
air).
results
compared
two
sets
FN,Fe<100
(FeN<100)
(FeBulk).
We
find
largest
differences
between
OH
/
O2-
at
=
6.
Under
these
conditions,
subsaturated
because
its
high
effective
Henry's
law
fast
loss
reactions
radical
anion.
As
main
reduction
process
Fe(III)
reaction
O2-,
show
subsaturation
leads
Fe(II)
Fe(total)
ratios
lower
by
factor
2
approaches.
trend
largely
independent
concentration,
both
source
sink
rates
scale
concentration.
compare
model-derived
reactive
uptake
parameters
γOH
γHO2
full
FN,Fe.
While
affected
distribution,
calculated
from
0.0004
0.03
%,
respectively.
Implications
findings
discussed
application
lab-derived
models
present
on
aerosols.
conclude
distribution
(FN,Fe)
should
be
taken
into
account
estimate
potential
matter
might
overestimated
sampling
Our
study
suggests
iron-containing
may
more
important
than
determining
budgets
water.
Environmental Science Atmospheres,
Год журнала:
2023,
Номер
3(3), С. 581 - 594
Опубликована: Янв. 1, 2023
Wildfire
particulate
matter
contains
high
amounts
of
environmentally
persistent
free
radicals
and
generates
reactive
oxygen
species
with
implications
for
air
quality
public
health.
Environmental Science & Technology,
Год журнала:
2021,
Номер
56(11), С. 7234 - 7243
Опубликована: Окт. 1, 2021
Respiratory
deposition
of
secondary
organic
aerosols
(SOA)
and
iron
may
lead
to
the
generation
reactive
oxygen
species
free
radicals
in
lung
fluid
cause
oxidative
stress,
but
their
underlying
mechanism
formation
kinetics
are
not
well
understood.
Here
we
demonstrate
substantial
surrogate
(SLF)
by
mixtures
Fe2+
SOA
generated
from
photooxidation
isoprene,
α-terpineol,
toluene.
The
molar
yields
measured
be
0.03–0.5%
SLF,
which
5–10
times
higher
than
water.
We
observe
that
enhances
radical
dramatically
a
factor
20–80,
can
attributed
Fe2+-facilitated
decomposition
peroxides,
consistency
with
positive
correlation
between
peroxide
contents
yields.
Ascorbate
mediates
redox
cycling
ions
sustain
decomposition,
as
supported
kinetic
modeling
reproducing
time-
concentration-dependence
additional
experiments
observing
ascorbate
Fe3+.
•OH
superoxide
found
scavenged
antioxidants
efficiently.
These
findings
have
implications
on
role
damage
lipid
peroxidation.
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
Environmental Science & Technology,
Год журнала:
2022,
Номер
56(23), С. 17029 - 17038
Опубликована: Ноя. 17, 2022
Oxidative
stress
mediated
by
reactive
oxygen
species
(ROS)
is
a
key
process
for
adverse
aerosol
health
effects.
Secondary
organic
aerosols
(SOA)
account
major
fraction
of
fine
particulate
matter,
and
their
inhalation
deposition
into
the
respiratory
tract
causes
formation
ROS
chemical
cellular
processes,
but
relative
contributions
are
hardly
quantified
link
to
oxidative
remains
uncertain.
Here,
we
superoxide
generation
9,10-phenanthrenequinone
(PQN)
isoprene
SOA
using
chemiluminescence
assay
combined
with
electron
paramagnetic
resonance
spectroscopy
as
well
kinetic
modeling.
We
also
applied
imaging
techniques
study
mechanism
release
damage
on
cell
membranes.
show
that
PQN
activate
NADPH
oxidase
in
macrophages
massive
amounts
superoxide,
overwhelming
aqueous
reactions
epithelial
lining
fluid.
The
activation
dose
2
orders
magnitude
lower
than
SOA,
suggesting
quinones
more
toxic.
While
higher
exposures
trigger
antioxidant
response
elements,
released
induce
membrane
through
lipid
peroxidation.
Such
mechanistic
quantitative
understandings
provide
basis
further
elucidation
effects
matter.
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.
Environmental Science & Technology,
Год журнала:
2022,
Номер
56(8), С. 4882 - 4893
Опубликована: Март 31, 2022
Organic
peroxides
play
a
vital
role
in
the
formation,
evolution,
and
health
impacts
of
atmospheric
aerosols,
yet
their
molecular
composition
fate
particle
phase
remain
poorly
understood.
Here,
we
identified,
using
iodometry-assisted
liquid
chromatography
mass
spectrometry,
large
suite
isomer-resolved
peroxide
monomers
(C8-10H12-18O5-8)
dimers
(C15-20H22-34O5-14)
secondary
organic
aerosol
formed
from
ozonolysis
most
abundant
monoterpene
(α-pinene).
Combining
isothermal
evaporation
experiments
multilayer
kinetic
modeling,
bulk
were
found
to
undergo
rapid
particle-phase
chemical
transformation
with
an
average
lifetime
several
hours
under
humid
conditions,
while
individual
decompose
on
timescales
half
hour
few
days.
Meanwhile,
majority
isomeric
exhibit
distinct
behaviors,
highlighting
importance
characterization
reactivity.
Furthermore,
reactivity
increases
water
content
faster
low
relative
humidity
(RH)
range
than
high
RH
range.
Such
non-uniform
effects
imply
more
important
as
plasticizer
reactant
influencing
The
its
striking
dependence
should
be
considered
modeling
chemistry
effects.
The Journal of Physical Chemistry A,
Год журнала:
2023,
Номер
127(24), С. 5209 - 5221
Опубликована: Июнь 7, 2023
The
photochemical
aging
of
biomass-burning
organic
aerosols
(BBOAs)
by
exposure
to
sunlight
changes
the
chemical
composition
over
its
atmospheric
lifetime,
affecting
toxicological
and
climate-relevant
properties
BBOA
particles.
This
study
used
electron
paramagnetic
resonance
(EPR)
spectroscopy
with
a
spin-trapping
agent,
5-tert-butoxycarbonyl-5-methyl-1-pyrroline-N-oxide
(BMPO),
high-resolution
mass
spectrometry,
kinetic
modeling
photosensitized
formation
reactive
oxygen
species
(ROS)
free
radicals
in
mixtures
benzoquinone
levoglucosan,
known
tracer
molecules.
EPR
analysis
irradiated
solutions
showed
dominant
hydroxyl
(•OH),
which
are
products
reaction
triplet-state
water,
also
yielding
semiquinone
radicals.
In
addition,
hydrogen
(H•)
were
observed,
not
detected
previous
studies.
They
most
likely
generated
decomposition
irradiation
levoglucosan
led
substantial
carbon-
oxygen-centered
radicals,
became
prominent
higher
fraction
levoglucosan.
High-resolution
spectrometry
permitted
direct
observation
BMPO-radical
adducts
demonstrated
•OH,
derived
from
oxidation
Mass
superoxide
radical
(BMPO-OOH)
that
did
appear
spectra.
Kinetic
processes
successfully
reproduced
time
evolution
observed
BMPO
•OH
H•
EPR.
model
was
then
applied
describe
would
occur
absence
BMPO,
predicting
generation
HO2•
due
dissolved
oxygen.
These
results
imply
photoirradiation
containing
photosensitizers
induces
ROS
secondary
chemistry
drive
atmosphere.
ACS Earth and Space Chemistry,
Год журнала:
2021,
Номер
5(5), С. 1150 - 1162
Опубликована: Апрель 19, 2021
Cooking
emissions
contribute
significantly
to
organic
aerosol
in
urban
areas,
but
the
evolution
of
physicochemical
properties
and
health
impacts
upon
atmospheric
aging
remain
poorly
understood.
In
this
study,
detailed
chemical
composition
oxidative
potential
(OP)
primary
(POA)
secondary
(SOA)
from
heated
cooking
oils
(canola,
olive,
peanut)
were
characterized.
Results
acellular
measurements
indicate
an
enhanced
OP
photochemically
aged
SOA
compared
that
POA,
which
is
accompanied
by
increasing
abundance
reactive
oxygen
species
(ROS)
measured
using
electron
paramagnetic
resonance
(EPR)
spectroscopy.
canola
oil,
total
ROS
production
(by
a
factor
26)
coincides
with
increased
particle-phase
peroxide
content
(from
15
26%)
across
six
different
photooxidation
conditions
(up
2
days
equivalent).
Positive
correlations
found
among
abundance,
content,
average
carbon
oxidation
state
oil
along
aging.
Photooxidation
representative
volatile
compounds
shows
unsaturated
aldehydes
are
dominant
contributors
peroxides
during
aging,
degree
unsaturation
aldehyde
precursor
linked
ROS/peroxide
SOA.
The
abundant
OH
radicals
suggest
major
radical
source
SOA,
likely
initiated
homolytic
cleavage
oxygen–oxygen
single
bond.
Our
study
bridges
shedding
light
on
their
dynamic
toxicity
atmosphere.
Environmental Science & Technology,
Год журнала:
2023,
Номер
57(41), С. 15546 - 15557
Опубликована: Авг. 30, 2023
Unsaturated
triglycerides
found
in
food
and
skin
oils
are
reactive
ambient
air.
However,
the
chemical
fate
of
such
compounds
has
not
been
well
characterized
genuine
indoor
environments.
Here,
we
monitored
aging
oil
coatings
on
glass
surfaces
over
a
range
environmental
conditions,
using
mass
spectrometry,
nuclear
magnetic
resonance
(NMR),
electron
paramagnetic
(EPR)
techniques.
Upon
room
air
exposure
(up
to
17
ppb
ozone),
characteristic
ozonolysis
products,
secondary
ozonides,
were
observed
near
cooking
area
commercial
kitchen,
along
with
condensed-phase
aldehydes.
In
an
office
setting,
is
also
dominant
degradation
pathway
for
films
exposed
enclosed
spaces
as
drawers,
depleted
flow
makes
lipid
autoxidation
more
favorable
after
induction
period
few
days.
Forming
hydroperoxides
major
primary
this
radical-mediated
peroxidation
behavior
accelerated
by
direct
sunlight,
but
initiation
step
dark
settings
still
unclear.
These
results
accord
radical
measurements,
indicating
that
photooxidation
facilitates
formation
surfaces.
Overall,
many
intermediate
end
products
oxygen
species
(ROS)
may
induce
oxidative
stress
human
bodies.
Given
these
can
be
widely
both
household
surfaces,
their
toxicological
properties
worth
further
attention.
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.