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.
Tellus B,
Год журнала:
2022,
Номер
74(1), С. 24 - 24
Опубликована: Март 25, 2022
This
review
presents
how
the
boreal
and
tropical
forests
affect
atmosphere,
its
chemical
composition,
function,
further
that
affects
climate
and,
in
return,
ecosystems
through
feedback
processes.
Observations
from
key
tower
sites
standing
out
due
to
their
long-term
comprehensive
observations:
The
Amazon
Tall
Tower
Observatory
Central
Amazonia,
Zotino
Siberia,
Station
Measure
Ecosystem-Atmosphere
Relations
at
Hyytiäla
Finland.
is
complemented
by
short-term
observations
networks
large
experiments.
discusses
atmospheric
chemistry
observations,
aerosol
formation
processing,
physiochemical
aerosol,
cloud
condensation
nuclei
properties
finds
surprising
similarities
important
differences
two
ecosystems.
concentrations
are
similar,
particularly
concerning
main
components,
both
dominated
an
organic
fraction,
while
ecosystem
has
generally
higher
of
inorganics,
influence
long-range
transported
air
pollution.
emissions
biogenic
volatile
compounds
isoprene
monoterpene
regions,
respectively,
being
precursors
fraction.
modeling
studies
show
change
deforestation
such
carbon
hydrological
cycles
Amazonia
changing
neutrality
precipitation
downwind.
In
Africa,
so
far
maintaining
sink.
It
urgent
better
understand
interaction
between
these
major
ecosystems,
climate,
which
calls
for
more
observation
sites,
providing
data
on
water,
carbon,
other
biogeochemical
cycles.
essential
finding
a
sustainable
balance
forest
preservation
reforestation
versus
potential
increase
food
production
biofuels,
critical
services
global
stability.
Reducing
warming
vital
forests.
Chemical Reviews,
Год журнала:
2023,
Номер
123(4), С. 1635 - 1679
Опубликована: Янв. 11, 2023
Organic
peroxides
(POs)
are
organic
molecules
with
one
or
more
peroxide
(−O–O−)
functional
groups.
POs
commonly
regarded
as
chemically
labile
termination
products
from
gas-phase
radical
chemistry
and
therefore
serve
temporary
reservoirs
for
oxidative
radicals
(HOx
ROx)
in
the
atmosphere.
Owing
to
their
ubiquity,
active
gas-particle
partitioning
behavior,
reactivity,
key
reactive
intermediates
atmospheric
multiphase
processes
determining
life
cycle
(formation,
growth,
aging),
climate,
health
impacts
of
aerosol.
However,
there
remain
substantial
gaps
origin,
molecular
diversity,
fate
due
complex
nature
dynamic
behavior.
Here,
we
summarize
current
understanding
on
POs,
a
focus
identification
quantification,
state-of-the-art
analytical
developments,
molecular-level
formation
mechanisms,
chemical
transformation
pathways,
well
environmental
impacts.
We
find
that
interactions
SO2
transition
metal
ions
generally
fast
PO
pathways
liquid
water,
lifetimes
estimated
be
minutes
hours,
while
hydrolysis
is
particularly
important
α-substituted
hydroperoxides.
Meanwhile,
photolysis
thermolysis
likely
minor
sinks
POs.
These
distinctly
different
fates,
such
reaction
OH
radicals,
which
highlights
need
understand
By
summarizing
advances
remaining
challenges
investigation
propose
future
research
priorities
regarding
fate,
Environmental Science & Technology,
Год журнала:
2020,
Номер
54(5), С. 2615 - 2625
Опубликована: Янв. 17, 2020
Among
the
nitrated
and
oxygenated
polycyclic
aromatic
hydrocarbons
(NPAHs
OPAHs)
are
some
of
most
hazardous
substances
to
public
health,
mainly
because
their
carcinogenicity
oxidative
potential.
Despite
these
concerns,
concentrations
fate
NPAHs
OPAHs
in
atmospheric
environment
largely
unknown.
Ambient
air
18
NPAHs,
5
quinones,
other
were
determined
at
two
urban
one
regional
background
sites
central
Europe.
At
sites,
total
(gas
particulate)
Σ10OPAHs
10.0
±
9.2
ng/m3
winter
3.5
1.6
summer.
The
gradient
site
exceeded
1
order
magnitude.
Σ18NPAH
typically
magnitude
lower
than
OPAHs.
OPAHs,
9-fluorenone
(9,10)-anthraquinone
abundant
species,
accompanied
by
benzanthrone
winter.
(9,10)-Anthraquinone
represented
two-thirds
quinones.
We
found
that
a
large
fraction
target
substance
particulate
mass
was
carried
submicrometer
particles.
derived
inhalation
bioaccessibility
PM10
size
is
be
≈5%
ambient
concentration
up
≈2%
for
NPAHs.
For
(9,10)-anthraquinone,
86
18%,
respectively,
rural
site.
Our
results
indicate
water
solubility
could
function
as
limiting
factor
inhaled
without
considerable
effect
surfactant
lipids
proteins
lung
lining
fluid.
Atmospheric chemistry and physics,
Год журнала:
2020,
Номер
20(9), С. 5197 - 5210
Опубликована: Май 4, 2020
Abstract.
The
capability
of
ambient
particles
to
generate
in
vivo
reactive
oxygen
species
(ROS),
called
oxidative
potential
(OP),
is
a
metric
for
evaluating
the
health
effects
particulate
matter
(PM)
and
supported
by
several
recent
epidemiological
investigations.
Studies
using
various
types
OP
assays
differ
their
sensitivities
varying
PM
chemical
components.
In
this
study,
we
systematically
compared
two
health-relevant
acellular
that
track
depletion
antioxidants
or
reductant
surrogates:
(i)
synthetic
respiratory-tract
lining
fluid
(RTLF)
assay
tracks
ascorbic
acid
(AA)
glutathione
(GSH)
(ii)
dithiothreitol
(DTT)
DTT.
Yearlong
daily
samples
were
collected
at
an
urban
site
Atlanta,
GA
(Jefferson
Street),
during
2017,
both
DTT
RTLF
performed
measure
water-soluble
PM2.5
mass
major
components,
including
metals,
ions,
organic
elemental
carbon
also
analyzed.
Correlation
analysis
found
as
measured
AA
(OPDTT
OPAA,
respectively)
correlated
with
organics
some
metal
species,
whereas
from
GSH
(OPGSH)
was
exclusively
sensitive
Cu.
These
moderately
each
other
due
common
contribution
ions.
OPDTT
OPAA
Pearson's
r=0.55
0.56,
respectively,
OPGSH
exhibited
lower
correlation
(r=0.24).
There
little
seasonal
variation
levels
all
weak
seasonality
OP-associated
species.
Multivariate
linear
regression
models
developed
predict
measures
particle
composition
data.
Variability
not
only
attributed
concentrations
ions
(mainly
Fe
Cu)
compounds
but
antagonistic
metal–organic
metal–metal
interactions.
change
Cu
brown
(BrC),
proxy
humic-like
substances.
Atmospheric chemistry and physics,
Год журнала:
2021,
Номер
21(7), С. 5549 - 5573
Опубликована: Апрель 12, 2021
Epidemiological
studies
have
consistently
linked
exposure
to
PM2.5
with
adverse
health
effects.
The
oxidative
potential
(OP)
of
aerosol
particles
has
been
widely
suggested
as
a
measure
their
toxicity.
Several
acellular
chemical
assays
are
now
readily
employed
OP;
however,
uncertainty
remains
regarding
the
atmospheric
conditions
and
specific
components
that
drive
OP.
A
limited
number
simultaneously
utilised
multiple
OP
wide
range
concurrent
measurements
investigated
seasonality
In
this
work,
filter
samples
were
collected
in
winter
2016
summer
2017
during
pollution
human
Chinese
megacity
campaign
(APHH-Beijing),
was
analysed
using
four
methods:
ascorbic
acid
(AA),
dithiothreitol
(DTT),
2,7-dichlorofluorescin/hydrogen
peroxidase
(DCFH)
electron
paramagnetic
resonance
spectroscopy
(EPR).
Each
assay
reflects
different
oxidising
properties
PM2.5,
including
particle-bound
reactive
oxygen
species
(DCFH),
superoxide
radical
production
(EPR)
catalytic
redox
chemistry
(DTT/AA),
combination
these
provided
detailed
overall
picture
at
central
site
Beijing.
Positive
correlations
(normalised
per
volume
air)
all
mass
observed,
stronger
compared
summer.
contrast,
when
values
normalised
for
particle
mass,
days
higher
concentrations
(μgm-3)
found
lower
mass-normalised
measured
by
AA
DTT.
This
finding
supports
total
alone
may
not
always
be
best
indicator
Univariate
analysis
an
extensive
additional
measurements,
107
total,
composition,
gas-phase
composition
meteorological
data,
insight
into
processes
determine
variability.
Multivariate
statistical
analyses
highlighted
associations
responses
varying
both
mass-
volume-normalised
data.
DTT
well
predicted
small
set
linear
regression
(MLR)
models
indicated
fossil
fuel
combustion,
vehicle
emissions
biogenic
secondary
organic
(SOA)
influential
sources
response.
Mass
MLR
associated
compositional
source
profiles
almost
models,
illustrating
influence
on
particle-level
multivariate
showed
cover
spaces,
through
comparison
data
we
demonstrate
provides
more
nuanced
drivers
analysis.
study
constitutes
one
most
comprehensive
datasets
currently
available
unique
opportunity
explore
variations
how
they
affect
species.
Environmental Science & Technology,
Год журнала:
2019,
Номер
53(23), С. 13949 - 13958
Опубликована: Окт. 25, 2019
It
has
been
hypothesized
that
the
cytotoxicity
of
secondary
organic
aerosols
(SOA)
is
mediated
through
formation
reactive
oxygen
species
(ROS)
in
exposed
cells.
Here,
lung
epithelial
cells
(A549)
residing
at
air-liquid
interface
were
to
proxies
anthropogenic
and
biogenic
SOA
photochemically
aged
under
varying
nitrogen
oxide
(NOx)
concentrations
an
oxidation
flow
reactor.
The
total
peroxides
ROS
radical
content
quantified
by
iodometric
spectrophotometric
method
continuous-wave
electron
paramagnetic
resonance.
effect
exposure
was
evaluated
measuring
cell
viability
cellular
production
following
exposure.
results
demonstrate
absence
NOx
contained
more
than
fresh
toxic
toward
cells,
while
conditions
had
no
significant
influence
on
levels
their
toxicity.
Analysis
using
cytometry
showed
a
similar
trend
with
SOA.
This
study
provides
first
direct
observation
such
association.
Atmospheric chemistry and physics,
Год журнала:
2021,
Номер
21(11), С. 9089 - 9104
Опубликована: Июнь 15, 2021
Abstract.
Air
pollution
by
particulate
matter
in
China
affects
human
health,
the
ecosystem
and
climate.
However,
chemical
composition
of
aerosol,
especially
organic
fraction,
is
still
not
well
understood.
In
this
study,
aerosol
samples
with
a
diameter
≤2.5
µm
(PM2.5)
were
collected
January
2014
three
cities
located
northeast,
east
southeast
China,
namely
Changchun,
Shanghai
Guangzhou.
Organic
(OA)
PM2.5
was
analyzed
an
ultrahigh-performance
liquid
chromatograph
(UHPLC)
coupled
to
high-resolution
Orbitrap
mass
spectrometer
both
negative
mode
(ESI-)
positive
electrospray
ionization
(ESI+).
After
non-target
screening
including
assignment
molecular
formulas,
compounds
classified
into
five
groups
based
on
their
elemental
composition,
i.e.,
CHO,
CHON,
CHN,
CHOS
CHONS.
The
CHON
CHN
present
dominant
signal
abundances
81
%–99.7
%
spectra
majority
these
assigned
mono-
polyaromatics,
suggesting
that
anthropogenic
emissions
are
major
source
urban
OA
all
cities.
characteristics
varied
between
different
degree
aromaticity
number
polyaromatic
substantially
higher
from
which
could
be
attributed
large
residential
heating
(i.e.,
coal
combustion)
during
wintertime
northeast
China.
Moreover,
ESI-
analysis
showed
H/C
O/C
ratios
for
Guangzhou
compared
indicating
undergoes
more
intense
photochemical
oxidation
processes
lower-latitude
regions
and/or
affected
larger
biogenic
sources.
sulfur-containing
(CHOS
CHONS)
aliphatic
low
degrees
unsaturation
aromaticity.
Here
again,
show
greater
similarity
but
differ
largely
those
Changchun.
It
should
noted
conclusions
drawn
study
mainly
comparison
formulas
weighted
peak
abundance
thus
associated
inherent
uncertainties
due
efficiencies
species.
Atmospheric chemistry and physics,
Год журнала:
2021,
Номер
21(3), С. 1565 - 1580
Опубликована: Фев. 4, 2021
Abstract.
Mass
accommodation
is
an
essential
process
for
gas–particle
partitioning
of
organic
compounds
in
secondary
aerosols
(SOA).
The
mass
coefficient
commonly
described
as
the
probability
a
gas
molecule
colliding
with
surface
to
enter
particle
phase.
It
often
applied,
however,
without
specifying
if
and
how
deep
has
penetrate
beneath
be
regarded
being
incorporated
into
condensed
phase
(adsorption
vs.
absorption).
While
this
aspect
usually
not
critical
liquid
particles
rapid
surface–bulk
exchange,
it
can
important
viscous
semi-solid
or
glassy
solid
distinguish
resolve
kinetics
at
surface,
transfer
across
interface,
further
transport
bulk.
For
purpose,
we
introduce
novel
parameter:
effective
αeff
that
depends
on
penetration
depth
function
coefficient,
volatility,
bulk
diffusivity,
particle-phase
reaction
rate
coefficient.
Application
traditional
Fuchs–Sutugin
approximation
mass-transport
interface
yields
SOA
results
are
consistent
detailed
kinetic
multilayer
model
(kinetic
interactions
clouds,
KM-GAP;
Shiraiwa
et
al.,
2012)
two-film
solutions
(Model
Simulating
Aerosol
Interactions
Chemistry,
MOSAIC;
Zaveri
2014)
but
deviate
substantially
from
earlier
modeling
approaches
considering
influence
related
parameters.
highly
particles,
show
remains
similar
case
low-volatility
compounds,
whereas
decrease
by
several
orders
magnitude
semi-volatile
compounds.
Such
effects
explain
apparent
inconsistencies
between
studies
deriving
coefficients
experimental
data
molecular
dynamics
simulations.
Our
findings
challenge
approach
models
using
fixed
regardless
state
depth.
introduced
study
provides
efficient
new
way
accounting
reactions
well
regional
global
air
quality
models.
limitations
may
planetary
boundary
layer
(PBL),
likely
amorphous
free
upper
troposphere
(FT–UT)
PBL
low
relative
humidity
temperature.