Palaeontology,
Journal Year:
2019,
Volume and Issue:
63(1), P. 103 - 115
Published: Sept. 19, 2019
Fossils
are
a
key
source
of
data
on
the
evolution
feather
structure
and
function
through
deep
time,
but
their
ability
to
resolve
macroevolutionary
questions
is
compromised
by
an
incomplete
understanding
taphonomy.
Critically,
relative
preservation
potential
two
components,
melanosomes
keratinous
tissue,
not
fully
resolved.
Recent
studies
suggesting
that
preferentially
preserved
conflict
with
observations
preserve
in
fossil
feathers
as
external
moulds
organic
matrix.
To
date,
there
no
model
explain
latter
mode
melanosome
preservation.
We
addressed
these
issues
degrading
systematic
taphonomic
experiments
incorporating
decay,
maturation
oxidation
isolation
combination.
Our
results
reveal
production
mouldic
requires
interactions
oxidant
most
likely
occur
prior
substantial
maturation.
This
constrains
conditions
under
which
be
fossilized.
our
also
confirm
structures
have
higher
than
range
diagenetic
conditions,
supporting
hitherto
controversial
hypotheses
can
retain
degraded
structures.
Environmental Science & Technology,
Journal Year:
2021,
Volume and Issue:
55(18), P. 12136 - 12152
Published: Sept. 1, 2021
Manganese
(Mn)
is
a
biologically
important
and
redox-active
metal
that
may
exert
poorly
recognized
control
on
carbon
(C)
cycling
in
terrestrial
ecosystems.
influences
ecosystem
C
dynamics
by
mediating
biochemical
pathways
include
photosynthesis,
serving
as
reactive
intermediate
the
breakdown
of
organic
molecules,
binding
and/or
oxidizing
molecules
through
organo-mineral
associations.
However,
potential
for
Mn
to
influence
storage
remains
unresolved.
Although
substantial
research
has
demonstrated
ability
Fe-
Al-oxides
stabilize
matter,
there
scarcity
similar
information
regarding
Mn-oxides.
Furthermore,
Mn-mediated
reactions
regulate
litter
decomposition
pathways,
but
these
processes
are
constrained
across
diverse
Here,
we
discuss
ecological
roles
environments
synthesize
existing
knowledge
multiple
which
biogeochemical
intersect.
We
demonstrate
high
degrade
abiotic
microbially
mediated
oxidation
at
least
temporarily,
outline
priorities
needed
advance
understanding
Mn-C
interactions,
highlighting
gaps
address
key
uncertainties
soil
predictions.
Environmental Science & Technology,
Journal Year:
2020,
Volume and Issue:
54(14), P. 8801 - 8810
Published: June 17, 2020
Minerals,
natural
organic
matter
(NOM),
and
divalent
manganese
(Mn(II))
often
coexist
in
suboxic/oxic
environment.
Multiple
adsorption
oxidation
processes
occur
this
ternary
system,
which
are
coupled
to
affect
the
fate
of
both
OM
Mn
therein
alter
their
chemical
reactivity
toward
metals
other
pollutants.
However,
details
about
coupling
poorly
known
although
much
has
been
gained
for
binary
systems.
We
determined
mutual
influence
surface-catalyzed
Mn(II)
humic
acid
(HA)
a
Fe(III)
oxide
(goethite)-HA-Mn(II)
system
at
pH
5-8.
The
presence
substantially
increased
HA
whereas
greatly
impaired
extent
rate
by
O2
on
goethite
surfaces.
impacts
were
more
pronounced
higher
pH.
produced
β-MnOOH,
γ-MnOOH,
Mn3O4
turn
oxidized
HA,
producing
small
acids.
markedly
altered
composition
products
inhibiting
formation
β-MnOOH
while
favoring
production
γ-MnOOH
adsorbed
HA-mineral
assemblage.
Nonconducting
γ-Al2O3
exhibited
similar
but
weaker
effects
than
semiconducting
above
processes.
Our
results
suggest
that
Mn-oxidizing
microorganisms,
mineral
surfaces
can
drive
redox
cycle
with
NOM
oxidative
degradation
under
circumneutral/alkaline
conditions.
Environmental Science & Technology,
Journal Year:
2020,
Volume and Issue:
54(21), P. 14114 - 14123
Published: Oct. 23, 2020
Oxidative
decomposition
of
soil
organic
matter
determines
the
proportion
carbon
that
is
either
stored
or
emitted
to
atmosphere
as
CO2.
Full
conversion
CO2
requires
oxidative
mechanisms
depolymerize
complex
molecules
into
smaller,
soluble
monomers
can
be
respired
by
microbes.
Current
models
attribute
depolymerization
largely
activity
extracellular
enzymes.
Here
we
show
reactive
manganese
(Mn)
and
iron
(Fe)
intermediates,
rather
than
other
measured
characteristics,
best
predict
in
temperate
forest
soils.
Combining
bioassays,
spectroscopy,
wet-chemical
analysis,
found
surface
litters
was
most
significantly
correlated
abundance
Mn(III)
species.
In
contrast,
underlying
mineral
soils
Fe(II/III)
Positive
controls
showed
both
species
are
equally
potent
generating
activity,
but
imply
conventional
bioassays
have
a
systematic
bias
toward
Fe.
Combined,
our
results
highlight
coupled
biotic-abiotic
nature
mechanisms,
with
Mn-mediated
oxidation
dominating
within
Mn-rich
Fe-mediated
Fe-rich
These
findings
suggest
microbes
rely
on
different
strategies
depending
relative
availability
Fe
Mn
given
environment.
Environmental Science & Technology,
Journal Year:
2019,
Volume and Issue:
53(10), P. 5768 - 5777
Published: April 11, 2019
Dissolved
Mn(III)
species
have
recently
been
recognized
as
a
significant
form
of
Mn
in
redox
transition
zones,
but
their
speciation,
stability,
and
reactivity
are
poorly
understood.
Besides
acting
the
intermediate
for
chemistry,
can
undergo
disproportionation
producing
insoluble
oxides
aqueous
Mn(II).
Using
pyrophosphate(PP)
model
ligand,
we
evaluated
thermodynamic
kinetic
stability
complexes.
They
were
stable
at
circumneutral
pH
prone
to
(partial)
acidic
or
basic
pH.
With
an
initial
lag
phase,
kinetics
Mn(III)–PP
was
autocatalytic
with
produced
promoting
disproportionation.
X-ray
diffraction
average
oxidation
state
indicated
that
solid
products
not
pure
Mn(IV)
mixture
triclinic
birnessite
δ-MnO2.
Addition
synthetic
analogs
precipitates
eliminated
confirming
catalytic
roles.
Thermodynamic
calculations
adequately
predicted
regime
Mn(III)–PP.
The
present
results
refined
constant
Mn(PP)25–
formation,
which
allows
consistent
quantitative
prediction
equilibrium
speciation
Mn(III)–Mn(II)–birnessite
PP.
A
simple
robust
model,
incorporated
constraints,
rate
law,
verified
reaction
stoichiometry,
successfully
simulated
all
data.
ACS Earth and Space Chemistry,
Journal Year:
2023,
Volume and Issue:
7(9), P. 1592 - 1609
Published: Aug. 23, 2023
Reduction-oxidation
(redox)
reactions
underlie
essentially
all
biogeochemical
cycles.
Like
most
soil
properties
and
processes,
redox
is
spatiotemporally
heterogeneous.
However,
unlike
other
features,
heterogeneity
has
yet
to
be
incorporated
into
mainstream
conceptualizations
of
biogeochemistry.
Anoxic
microsites,
the
defining
feature
in
bulk
oxic
soils
sediments,
are
zones
oxygen
depletion
otherwise
environments.
In
this
review,
we
suggest
that
anoxic
microsites
represent
a
critical
component
function
appreciating
promises
advance
our
understanding
sediment
sections
1
2,
define
highlight
their
dynamic
properties,
specifically
microsite
distribution,
gradient
magnitude,
temporality.
section
3,
describe
influence
on
several
key
elemental
cycles,
organic
carbon,
nitrogen,
iron,
manganese,
sulfur.
4,
evaluate
methods
for
identifying
characterizing
5,
past
current
approaches
modeling
microsites.
Finally,
6,
steps
incorporating
heterogeneities
more
broadly
sediments.
Environmental Science & Technology,
Journal Year:
2022,
Volume and Issue:
56(13), P. 9806 - 9815
Published: June 20, 2022
Birnessite
(δ-MnO2)
is
a
layered
manganese
oxide
widely
present
in
the
environment
and
actively
participates
transformation
of
natural
organic
matter
(NOM)
biogeochemical
processes.
However,
effect
oxygen
on
dynamic
interface
processes
NOM
δ-MnO2
remains
unclear.
This
study
systematically
investigated
interactions
between
fulvic
acid
(FA)
under
both
aerobic
anaerobic
conditions.
FA
was
transformed
by
via
direct
electron
transfer
generated
reactive
species
(ROS).
During
32-day
reaction,
79.8%
total
carbon
(TOC)
solution
removed
conditions,
unexpectedly
higher
than
that
conditions
(69.8%),
suggesting
limitation
more
conducive
to
oxidative
δ-MnO2.
The
vacancies
(OV)
surface
were
exposed
thus
promoting
adsorption
as
well
regeneration
active
sites.
Additionally,
reaction
with
weakened
strongly
bonded
lattice
(Olatt),
released
Olatt
an
important
source
ROS.
Interestingly,
part
(OC)
preserved
forming
MnCO3,
which
might
be
novel
mechanism
for
preservation.
These
findings
contribute
improved
understanding
MnO2
provide
new
insights
into
effects
cycling
preservation
OC.