Comparative evaluation of selenium accumulation by allium species after foliar application of selenium nanoparticles, sodium selenite and sodium selenate


Golubkina, N.A.; Folmanis, G.E.; Tananaev, I.G.

Doklady Biological Sciences 444: 176-179

2012


Accumulation and translocation intensity of selenium nanoparticles by natural selenium accumulators-perennial onions-is established and a decrease of these parameters is demonstrated in a sequence: Se<sup>+6</sup>> Se<sup></sup>> Se<sup>+4</sup>.

ISSN
0012-4966,
Doklady
Biological
Sciences,
2012,
Vol.
444,
pp.
176-179.
©
Pleiades
Publishing,
Ltd.,
2012.
Published
in
Russian
in
Doklady
Akademii
Nauk,
2012,
Vol.
444,
No.
2,
pp.
230-233.
GENERAL
BIOLOGY
Comparative
Evaluation
of
Selenium
Accumulation
by
Allium
Species
after
Foliar
Application
of
Selenium
Nanoparticles,
Sodium
Selenite
and
Sodium
Selenate'
N.
A.
Golubkinaa,
G.
E.
Folmanisb,
and
Corresponding
Member
of
the
RAS
I.
G.
Tananaevb
Received
December
28,
2011
Abstract
—Accumulation
and
translocation
intensity
of
selenium
nanoparticles
by
natural
selenium
accumu-
lators
—perennial
onions
—is
established
and
a
decrease
of
these
parameters
is
demonstrated
in
a
sequence:
Se
+6
>
Se
°
>
Se
+4
.
Key
words:
nanoparticles,
selenium,
perennial
onion.
DOI:
10.1134/S0012496612030076
Intensive
development
of
nanotechnology
and
for-
mation
of
absolutely
new
class
of
materials
causes
seri-
ous
apprehension
due
to
restricted
data
about
biologi-
cal
effect
and
possible
ecological
risks
connected
with
environmental
pollution
with
nanoparticles,
and
in
particular
with
selenium.
Degradation
of
such
com-
pounds
in
natural
conditions
and
consequences
of
such
pollution
are
unknown.
Extremely
high
surface
of
plant
shoots
lightens
nanoparticles'
absorption.
Besides
this
peculiarities
of
plants
epidermis
(for
instance,
tubes,
cuticle,
trichomes,
stigma)
induce
nanoparticles'
accumulation.
The
latter
are
shown
not
only
to
be
absorbed
on
the
leaves
surface,
but
also
may
penetrate
inside
plants
via
micropores
[1]
.
Soil
microorganisms
possess
an
active
role
in
sele-
nium
metabolism:
some
of
them
are
able
to
reduce
selenites
and
selenates
to
nanoparticles
of
elemental
selenium
[2]
,
the
others
—convert
selenium
nanopar-
ticles
to
more
labile
forms
(Se
and
Se
'
6
)
[3].
Though
elemental
selenium
is
considered
to
demonstrate
rela-
tively
low
toxicity,
the
possibility
of
this
form
utiliza-
tion
by
plants
is
poorly
studied.
The
earliest
works
devoted
to
selenium
accumula-
tion
by
plants
done
in
30-50
years
of
the
20th
century
showed
a
significant
accumulation
of
elemental
sele-
nium
by
Astragalus—well
known
selenium
accumula-
1
The
article
was
translated
by
the
authors.
a
Institute
of
Nutrition,
Russian
Academy
of
Medical
Sciences,
Moscow,
Russia
b
Boikov
Institute
of
Metallurgy
and
Material
Science,
Russian
Academy
of
Sciences,
Moscow,
Russia
tors
[4].
On
the
contrary
plants
-non
accumulators
of
selenium,
including
pasture
plants,
demonstrated
extremely
low
levels
of
selenium
accumulation
after
administration
of
Se°
into
soils
[5,
6].
The
sizes
of
such
particles
of
the
element
were
not
determined.
At
the
beginning
of
the
21st
century
the
possibility
of
intensive
fortification
of
H.
Tuberosus
tubers
with
selenium
nanoparticles
via
foliar
application
was
established
[7].
Another
work
demonstrated
an
increase
in
seeds
germination
intensity
of
several
agri-
cultural
plants
due
to
selenium
nanoparticles
[8].
Unfortunately
no
comparison
was
achieved
in
these
studies
between
the
effect
of
nano
selenium
and
well
known
selenates
and
selenites.
The
aim
of
the
present
work
was
to
evaluate
pecu-
liarities
of
different
chemical
forms
of
selenium
(Se°,
Se
and
Se
'
6
)
by
perennial
onion
as
a
result
of
foliar
application.
MATERIALS
AND
METHODS
Colloidal
water
solution
of
selenium
nanoparticles
was
produced
via
injection
under
high
energy
laser
impulse
[9].
Selenium
content
in
water
solution
was
determined
by
AAS
with
inductively
coupled
plasma.
Dynamic
light
emission
method
(Photocor
Complex,
laser
wave
length
-632.8
nm,
detector
diaphragm
diameter
-0.2
mm,
time
of
signal
accumulation
-30
s)
revealed
the
presence
of
particles
with
hydrodynamic
radius
about
1
nm.
In
2010-2011
perennial
onions:
A.
nutants
L.,
A.
Schoenoprasum
L.,
and.
A.
obliquum
L.
—were
plan-
ted
on
dernovo-podsol
heavy
loamy
soil
with
selenium
content
240
±
20
µg/kg.
Square
of
experimental
beds
was
1
m
2
with
fourfold
experiment.
In
the
middle
of
176
COMPARATIVE
EVALUATION
OF
SELENIUM
ACCUMULATION
177
Table
1.
Total
selenium
content
(µg/kg
dry
weight)
in
leaves
of
perennial
onion
as
a
result
of
foliar
fortification
with
differ-
ent
chemical
forms
of
the
element
Species
Se
°
(nanoparticles)
Se
4+
(sodium
selenite)
Se
6+
(sodium
selenate)
Control
A.
nutans
L.
720
±
27
410
+
5
1085
±
93
82
+
3
A.
schoenoprasum
L.
1109
±
57
565
±
8
2169
±
150
91
±
4
A.
obliquum
L.
1108
±
33
267
±
32
1215
±
87
153
±
13
July
a
single
foliar
application
was
achieved
with
(a)
selenium
nanoparticles,
(b)
sodium
selenate,
and
(c)
sodium
selenite
solutions
with
concentration
of
2.34
mg
Se/L
or
32
vtg
Se
per
plant.
To
protect
soil
from
selenium
contamination
it
was
covered
with
polyethylene
fi
lm
during
spraying.
Two
weeks
later
leaves
were
cut,
washed
with
water,
dried
at
room
tem-
perature
and
homogenized.
The
second
cutting
was
achieved
after
another
14
days.
The
total
selenium
content
and
concentration
of
water
soluble
forms
of
the
element
were
determined
by
fluorimetric
method,
using
wet
digestion
of
samples
with
a
mixture
of
HNO
3
-HC10
4
,
reduction
of
Se
to
Se
by
6
N
HC1
solution
and
formation
of
fluorescent
complex
between
Se
and
2,3-
diaminonaphtalene
[10].
Lyophilized
cabbage
powder
with
the
known
selenium
content
-150
µg/kg—was
utilised
as
a
ref-
erence
material
(Institute
of
Nutrition,
RAMS).
Statistical
analysis
was
achieved
using
Student
cri-
terion.
RESULTS
AND
DISCUSSION
Utilization
of
perennial
onions
for
fortification
with
different
chemical
forms
of
selenium
gives
signif-
icant
benefits
as
the
former
are
known
to
be
natural
selenium accumulators,
stable
to
extremely
high
con-
centrations
of
selenium
in
the
environment
(100
times
higher
than
those
being
tolerated
by
non
accumula-
tors)
that
excludes
the
possibility
of
plants
toxicosis.
Foliar
application
of
the
element
allows
also
to
exclude
the
effect
of
soil
microorganisms
on
selenium
nanoparticles
accumulation.
Table
1
demonstrates
a
significant
selenium
accu-
mulation
in
leaves
of
perennial
onions
as
a
result
of
foliar
application.
In
all
cases
with
one
and
the
same
concentration
of
the
element
in
spraying
solutions
the
degree
of
sele-
nium
enrichment
decreases
in
a
sequence:
sodium
sel-
enate
(Se
'
6
)
>
selenium
nanoparticles
(Se°)
>
sodium
selenite
(Se
'
4
)
(Fig.
1).
Higher
accumulation
of
sel-
enate
(Se
'
6
)
than
selenite
(Se
'
4
)
is
well
known
for
the
case
when
selenium
salts
are
added
into
soil
and
the
phenomenon
is
explained
by
light
formation
of
non
soluble
complexes
between
Se
with
ferrous
and
alu-
minum
oxides.
At
the
same
time
the
phenomenon
of
low
Se
accumulation
in
foliar
fortification
experi-
ments
still
waits
for
its
explanation.
Differences
between
selenite
and
selenate
accumulation
by
peren-
nial
onions
are
equal
to
2.6-4.6
folds
depending
on
the
Allium
species
investigated.
The
analogous
sele-
nium
fortification
level
for
carrot
is
found
to
be
1.6
folds
[11].
Enrichment
of
wheat,
rye-grass,
white
clover
and
Neptunia
amplexicaulis
(selenium
accumu-
lator)
with
(
75
5e)
selenite
in
water
culture
has
revealed
a
partial
reduction
of
Se
to
poorly
mobile
Se°
[6].
The
possibility
of
such
a
reduction
is
demonstrated
also
by
pick
coloring
of
stachis
pots
after
watering
in
sodium
selenite
solution
[12].
Se
'
4
may
be
partially
reduced
in
perennial
onion
by
ascorbic
acid
which
concentration
in
these
plants
is
rather
high
(60-
80
mg/100
g
of
fresh
leaves).
At
the
same
time
it
should
be
noted
that
the
above
facts
do
not
explain
dif-
ferences
in
the
total
selenium
accumulation
level
between
selenite
and
selenate
utilization.
Data
presented
in
Table
1
indicate
extremely
high
fortification
of
plants
with
selenium
via
nanoparticles
utilization,
exceeding
that
for
selenite
enrichment
1.75-4.15
times.
Besides
that
sensitivity
of
Allium
species
to
sele-
nium
containing
solutions
differs
considerably.
The
highest
values
of
enrichment
are
typical
to
A.
schoenoprasum,
the
lowest
—to
A.
ohliquum
(Fig.
1).
Fortification
value
compared
to
the
control
25
-
20
15
10
Nano
Se
L
Se
4+
Se
6+
Fig.
1.
Values
of
perennial
onion
fortification
with
sele-
nium
using
foliar
application
for:
the
1st
column
(white)
A.
nutans,
the
2nd
(grey)
—A.
schoenoprasum,
the
3rd
(black)
—A.
obliquum.
DOKLADY
BIOLOGICAL
SCIENCES
Vol.
444
2012
178
GOLUBKINA
et
al.
Water
soluble
90
-
80
-
70
-
60
-
50
-
40
-
30
-
20
-
10-
0
Se
content,
%
A.
nutans
A.
schoenoprasum
A.
obliquum
Fig.
2.
Content
of
water
soluble
selenium
forms
in
peren-
nial
onion:
the
1st
column
(white)
—Se
nanoparticles
(Se
°
),
the
2nd
(grey)
—sodium
selenite
(Se
+4
),
the
3rd
(black)
—sodium
selenate
(Se
+6
).
Different
levels
of
selenium
accumulation
by
three
Allium
species
investigated
may
be
connected
both
with
differences
in
leaves
surface
and
in
adhesion
value.
Nevertheless
one
can
indicate
significant
differ-
ences
between
perennial
onion
species
in
sensitivity
to
chemical
form
of
the
element.
Thus,
similar
primary
selenium
concentrations
in
solutions
used
result
in
2
fold
differences
between
enrichment
values
for
sel-
enate
and
nanoparticles
utilization
for
A.
schoenopra-
sum,
1.5
folds—forA.
nutans
and
no
effect
is
found
for
A.
obliquum
(Fig.
1).
Thus
the
higher
value
of
selenium
enrichment
is
observed
for
easily
available
Se
(sel-
enate),
more
significant
are
the
differences
in
accu-
mulation
levels
of
other
chemical
forms
of
the
ele-
ment.
Especially
interesting
are
the
data
of
water
soluble
selenium
forms
accumulation
(Fig.
2).
As
can
be
seen
from
Fig.
2,
there
are
no
differences
in
accumulation
levels
of
water
soluble
selenium
when
anionic
forms
of
selenium
(Se
and
Se
'
6
)
are
used
for
A.
nutans
and
A.
obliquum
(p
>
0.5).
Only
A.
schoenoprasum
demon
-
Table
2.
Selenium
accumulation
in
new
leaves
of
A.
schoe-
noprasum
after
the
first
cutting
Parameter
Se
°
Se
4+
Se
6+
Se
in
dry
weight
pg/kg
%
from
the
first
cutting
value
Se
connect
in
roots,
pg/kg
of
dry
weight
Se
leaves
147
±
12
13.3
152
±
23
0.97
96
±
3
17.0
117
+
8
0.82
546
±
48
25.2
309
+
26
1.77
Se
roots
rario
strates
significantly
higher
concentrations
of
selenium
soluble
in
water
(p
<
0.001).
Utilization
of
nanoparticles
results
in
a
large
decrease
of
mobile
forms
of
selenium,
soluble
in
water,
and
such
an
effect
is
more
pronounced
for
A.
obliquum
(1.9
folds)
and
is
the
lowest
forA.
schoenoprasum
(1.5-
1.6
folds).
Anomalously
small
ability
of
selenium
nanoparticles
to
form
water
soluble
forms
in
perennial
onions
compared
to
sodium
selenite
and
selenate
may
reflect
their
lower
metabolic
activity
or
a
significant
sorption
of
elemental
selenium
by
components
of
plant
cells.
Thus
a
specific
ability
of
plant
proteins
to
absorb
intensively
nanoparticles
is
documented
[13].
Mobility
of
selenium
water
soluble
forms
is
supposed
to
be
connected
with
their
biological
activity.
Indeed
water
soluble
forms
concentration
of
the
element
in
Chinese
cabbage
correlates
with
plants
tolerance
to
viral
diseases
[12].
A
direct
correlation
is
demon-
strated
for
Apiaceae
species
between
concentration
of
water
soluble
selenium
and
intensity
of
seeds
germina-
tion
[14].
Water
soluble
forms
of
nanoparticles
seem
to
par-
ticipate
in
the
element
migration
from
leaves
to
roots
and
translocation
of
the
element
back
to
young
leaves
after
the
first
cutting.
Evaluation
of
the
intensity
of
such
a
process
can
be
demonstrated
on
A.
schoenopra-
sum
due
to
large
amount
of
leaves
and
quick
leaves
growth.
Data
presented
in
Table
2
indicate
that
the
most
intensive
flow
of
selenium
takes
place
for
sodium
sel-
enate
utilization
(Se
'
6
).
Only
two
weeks
after
the
first
cutting
selenium
concentration
in
new
leaves
reaches
the
value
550
µg/kg.
This
process
is
1.9
times
slower
for
nanoparticles
and
1.5
times
slower
—for
sodium
selenite.
The
Se
leaves/Se
roots
ratio
may
also
be
a
good
indicator
of
selenium
migration
intensity.
As
can
be
seen
from
Table
2
data
this
parameter
decreases
in
a
raw:
Se
'
6
(selenate)
>
Se°
(nanoparticles)
>
Se
'
4
(selenite).
Thus
the
investigation
gives
the
first
data
about
the
intensity
of
accumulation
and
migration
of
selenium
nanoparticles
by
perennial
onions
(natural
selenium
accumulators)
and
reveals
a
decrease
of
these
parame-
ters
in
a
raw:
Se
>
Se°
>
Se
REFERENCES
1.
Dietz,
K
-J.
and
Herth,
S.,
Trends
Plant
Sci.,
2011,
vol.
16,
pp.
582-589.
2.
Mishra,
R.R.,
Prajapatic,
S.,
Dasc,
J.,
et
al.,
Chemo-
sphere,
2011,
vol.
84,
pp.
1231-1237.
3.
Dowdie,
P.R.
and
Oremland,
R.S.,
Environ.
Sci.
Tech-
nol.,
1998,
vol.
32,
pp.
3749-3755.
4.
Beath,
0.A.,
Epson,
H.E,
and
Gilbert,
C.S.,
J.
Am.
Pharm.
Assoc.,
1937,
vol.
26,
pp.
334-340.
5.
Ganje,
T.J.
and
Whitehead,
E.J.,
Proc.
S.
Dakota
Acad.
Sci.,
1958,
vol.
37,
pp.
85-88.
DOKLADY
BIOLOGICAL
SCIENCES
Vol.
444
2012
COMPARATIVE
EVALUATION
OF
SELENIUM
ACCUMULATION
179
6.
Peterson,
I.J.
and
Butler,
G.W.,
Nature,
1966,
vol.
212,
pp.
961-962.
7.
Bogachev,
V.N.,
Kovalenko,
L.V.,
Folmanis,
G.E.,
et
al.,
Persp.
Mater.,
2007,
no.
3,
pp.
37-40.
8.
Nikonov,
I.N.,
Ivanov,
L.I.,
Kovalenko,
L.V.,
and
Fol-
manis,
G.E.,
Persp.
Mater.,
2009,
no.
4,
pp.
54-57.
9.
Kazilin,
K.K.,
Markevich,
M.I.,
Konkin,
S.V.,
et
al.,
Persp.
Mater.,
2008,
no.
2,
pp.
60-63.
10.
Alfthan,
G.,
Anal.
Chim.
Acta,
1984,
vol.
65,
pp.
187-
194.
11.
Kapolna,
E.,
Hillestrom,
P.R.,
Laursen,
K.H.,
et
al.,
Food
Chem.,
2009,
vol.
115,
pp.
1357-1364.
12.
Golubkina,
N.A.
and
Papazyan,
T.T.,
Selen
v
pitanii.
Rasteniya,
zhivotnye,
chelovek
(Selenium
in
Nutrition:
Plants,
Animals,
Humans),
Moscow:
Pechatnyi
Gorod,
2006.
13.
Lin,
Z
-H.
and
Wang,
C.R.C.,
Mat.
Chem.
Phys.,
2005,
vol.
92,
pp.
591-595.
14.
Golubkina,
N.A.,
Kiseleva,
TV,
Viktorova,
E.V.,
et
al.,
Gavrish,
2010,
no.
3,
pp.
47-49.
DOKLADY
BIOLOGICAL
SCIENCES
Vol.
444
2012