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An investigation of some chemical aspects of precise isotope ratio measurement of uranium and neodymium
International Elsevier
AN
Journal of Mass Spectrometry
Scientific
Publishing
OF SOME
INVESTIGATION
MEASUREMENT O.J.
OF URANIUM
HEINONEN,
Technical Otakaari
Company,
CHEMICAL
AND
P. SALONEN
Research
Centre
3 A, SF-02150
-
397-400 in The Netherlands
Printed
ASPECTS
397
48 (1983)
and Ion Physics,
Amsterdam
OF PRECISE
ISOTOPE
RATIO
NEODYMIUM and
K. UUSHEIMD
of Finland,
Espoo
Reactor
Laboratory
15 (Finland)
ABSTRACT The investigation is a part of the studies treating the chemical aspects of The isotopic fractionation in a multiple filament thermal ionization source. dependence of the formation of uranium and neodymium and their oxide ions on various chemical and instrumental conditions are looked into. INTRODUCTION Accurate
and
knowledge
cosmochronofogy,
nology.
Several
of the
samples
ratios.
The
of uranium the
of the
mineralogy,
investigations
to tend
purpose
(ref.2)
behaviour
isotopic
of this
systematic
shown
instrument
Is needed
and nuclear
the
chemical
in the measured
errors
investigation
another
of elements
hydrology
biochemistry, (refs.l,il) have
to cause
with
composition
in geo-
fuel
tech-
conditions isotopic
was
to verify
the previous
and
to extend
the
results
investigations
to
of neodymium.
EXPERIMENTAL The MI-1309 filament
investigations and MI-1201 thermal
were
made
ionization
oxides
chlorides
by heating
measurements RESULTS
AND
were
sources
and
The
operating
samples
sulphates
the filaments made
USSR).
for
They
were
equipped
to uranium
or 10 minutes earlier
of types
with
voltages
and neodymium
converted
10 seconds described
spectrometers
at acceleratjng
of uranium
and were
in the manner
mass
triple
up to
were
loaded
and
neodymium
in open
air.
The
(ref.2).
DISCUSSION
The dependence chemical 235",238
two different
(V/O Techsnabexport,
3 kV and 5 kV, respectively. as nitrates,
using
form
of measured
of the
U ratios
were
isotopic
loading
solution
obtained
OO20-73al/83/00OCk-0000/$03.00
Q
for
ratios was
studied.
SRM-U-500
1983 Elsevier
on the filament The
material
following
samples.
Scientific
Publishing
Company
and the
measured
398 TABLE
1
Measured
235U/238U
ratios
Preparation
Tungsten
HNO3 HCl H2S04
1.0036 1.0078 I.0076
filament
-
1.0077 1.0085 1.0093
100
.-
filament f 0.0019 * 0.0010 f 0.0019
HN03
*
. .-
.
Rhenium
* 0.0015 f 0.0016 * 0.0020
1ocI- HN03 Rhenium
__
Rhenium
.
.
.
10
.
. 0
10
. +
v
.
0 0
:
0
l +
l
1
1
+
l .
CONVERSlON 0.5
100
1.0
10s
.
1-S 2.0
1
I
.
CONVERSION
2.5
3.0
HNO3
3.
1QC1.
Tungsten
10
0.5
1.0
1.5
INTENSITY, ARBITRARY
10 MIN 2.0
2.5
3.0
UNITS
10 .
- . .
1
1
**** U+ IONS 0000~ Uo’ IONS +*++ UO; IONS
-
l
.
l
CONVERSION
CURRENT,
IOMIN
,
1 I
I
0 5 1.0 1.5 2.0 253 0 35 L-0 L.5 5.0 5.5 60
Intensity distribution Fig.1. tion current (temperature) for spectrometer MI-1309.
r-
0.5
1.0
1.5
2.0
AMPERES 2.5
3.0 3,
of U+, UO+ and UO2+ ions as a function of ionizarhenium and tungsten filaments using mass
399 Bearing ratio
in mind
observed
for samples
ratios
the other
of the
samples
which
in turn
the overall
owes
ratios
of measured
isotopic
atic
slightly
error
The uranium The
results
on the atic
various
shown
cases
samples
of different
to metal Under ide ions. will
But
with
ratios
0
filaments
may be due a system-
ions of neodymium
conditions
were
may
composition
lead to considerable
reported
earlier
metal
the formation the oxide
and
investigated.
of the chemical
of neodymium
nitrate
system-
(ref.2).
ions
of oxide
increases ions
ion production
in all
is different.
with
respect
an -increasing temperature.
conditions of chloride
a few percent
of ions are
preparations
temperature.
.
Tungsten
which as was
, while
increasing
HNQ3
difference
bri-nging about
and oxide
out the effect
ion types,
neodymium
in the case an
ion currents observations
The systematic this
the
reproducibility
Similar
and rhenium
instrumental
the production
analyzing
with
tungsten
point
temperature
with
ions decreases typical
increase
1
the
lower
preparation.
filaments.
of metal
and
isotopic
in Fig.3
with
The
from
measurements.
in Figs.l-2
loaded
the isotopic
seem to differ
filament.
of the filaments,
chemical
in measured
As presented
In
between
sizes
would
system,
is due to the use of lower
in sample
of the formation
formation
errors
three
ratios
in temperature
under
sulphate
to the rhenium
different
dependence
on a tungsten
as uranyl
apply
of the analytical
as nitrates
to difficulties
on isotopic
to the
loaded
salt forms
loaded
precision
the production
Although
1
a0
loosened
as ox-
of oxide
the production
HN03
ions
of metal
. .
Tungsten
.
. - 0 s -
0.1
D
0 ++
+
0
+
l
4 + D
0,O’ +*
+
D +
+ +
+
D
tt*.
0,001
l
0
u+
UO+ ++++UO; 0000
IONS IONS IONS
0,001
. 0
3.~ 3.8 L.2 L.6 5.0 5-L
IIA)
t...
m
CClN";RSIONlOS QCUOI
l
0000
.
0.0001
' CONVERSION
++++
u+ IONS
UO+ IONS UO>
IONS
10MIN
2.8 3.2 3.6 4.0 A.4 4.8 5.2 I(A)
Fig.2. Intensity distribution of U+, UO+ and UO ' ions as a function of ionization current (temperature) for tungsten filamenzs using mass spectrometer FIX-1201.
HN03
lo0
,,
Tungsten
lq
. *LJ+
rNd+
Egsten oNdO+ s 0
0,l 0
0*
0
Ot, NdO’
00,1
CONVERSION 30
1.0
3.4
0
IOMIN
3-8 G-2 4.6
5.0 5.1
H2S04 Tungsten
0 ,Ol
I[ Al
l
.
0.1
CONVERSION
I 3.8
I I L.2 4.6 50
1OMIN I[A I
,” NdO+
00
0 0
800
0
000~0~‘~0~~~~51*~
Q,Ol
3.2 3.6
ions
is
case
is higher.
tion
was
lower
LO L.L 4.8
with
respect
sample
the
I[A] ions
the
investigations
in chloride and
I~MIN
5.2
to oxide
In earlier
observed the
“,
Intensity distribution Fig.3. of Nd+ and NdO+ ions as a function of ionization current (temperature) for tungsten filaments using mass spectrometer MI-7201.
*
between
I 3.:
‘Nd’ * a
2.8
I 3.0
media.
filaments
One which
overall
(ref.3)
ion production a higher
possibility calls
for
uranium
is a chemical further
in this ion
produc-
reaction
investigations.
REFERENCES 1 2 3
in N.R. Daly (Ed), Advances in Mass Spectrometry, Vol 7 A. P. de Bievre, Heyden & Son Ltd, London, 1978, 393 pp. O.J. Heinonen and R. Korhonen, Journal of Radioanalytical Chemistry, Vol 64 No.l-2(1981) 65-72. O.J. Heinonen, Chemical Aspects of the Precise and Accurate Determination of Uranium and Plutonium from Nuclear Fuel Solutions, Report Series in Radiochemistry 3/1981.
AN
Journal of Mass Spectrometry
Scientific
Publishing
OF SOME
INVESTIGATION
MEASUREMENT O.J.
OF URANIUM
HEINONEN,
Technical Otakaari
Company,
CHEMICAL
AND
P. SALONEN
Research
Centre
3 A, SF-02150
-
397-400 in The Netherlands
Printed
ASPECTS
397
48 (1983)
and Ion Physics,
Amsterdam
OF PRECISE
ISOTOPE
RATIO
NEODYMIUM and
K. UUSHEIMD
of Finland,
Espoo
Reactor
Laboratory
15 (Finland)
ABSTRACT The investigation is a part of the studies treating the chemical aspects of The isotopic fractionation in a multiple filament thermal ionization source. dependence of the formation of uranium and neodymium and their oxide ions on various chemical and instrumental conditions are looked into. INTRODUCTION Accurate
and
knowledge
cosmochronofogy,
nology.
Several
of the
samples
ratios.
The
of uranium the
of the
mineralogy,
investigations
to tend
purpose
(ref.2)
behaviour
isotopic
of this
systematic
shown
instrument
Is needed
and nuclear
the
chemical
in the measured
errors
investigation
another
of elements
hydrology
biochemistry, (refs.l,il) have
to cause
with
composition
in geo-
fuel
tech-
conditions isotopic
was
to verify
the previous
and
to extend
the
results
investigations
to
of neodymium.
EXPERIMENTAL The MI-1309 filament
investigations and MI-1201 thermal
were
made
ionization
oxides
chlorides
by heating
measurements RESULTS
AND
were
sources
and
The
operating
samples
sulphates
the filaments made
USSR).
for
They
were
equipped
to uranium
or 10 minutes earlier
of types
with
voltages
and neodymium
converted
10 seconds described
spectrometers
at acceleratjng
of uranium
and were
in the manner
mass
triple
up to
were
loaded
and
neodymium
in open
air.
The
(ref.2).
DISCUSSION
The dependence chemical 235",238
two different
(V/O Techsnabexport,
3 kV and 5 kV, respectively. as nitrates,
using
form
of measured
of the
U ratios
were
isotopic
loading
solution
obtained
OO20-73al/83/00OCk-0000/$03.00
Q
for
ratios was
studied.
SRM-U-500
1983 Elsevier
on the filament The
material
following
samples.
Scientific
Publishing
Company
and the
measured
398 TABLE
1
Measured
235U/238U
ratios
Preparation
Tungsten
HNO3 HCl H2S04
1.0036 1.0078 I.0076
filament
-
1.0077 1.0085 1.0093
100
.-
filament f 0.0019 * 0.0010 f 0.0019
HN03
*
. .-
.
Rhenium
* 0.0015 f 0.0016 * 0.0020
1ocI- HN03 Rhenium
__
Rhenium
.
.
.
10
.
. 0
10
. +
v
.
0 0
:
0
l +
l
1
1
+
l .
CONVERSlON 0.5
100
1.0
10s
.
1-S 2.0
1
I
.
CONVERSION
2.5
3.0
HNO3
3.
1QC1.
Tungsten
10
0.5
1.0
1.5
INTENSITY, ARBITRARY
10 MIN 2.0
2.5
3.0
UNITS
10 .
- . .
1
1
**** U+ IONS 0000~ Uo’ IONS +*++ UO; IONS
-
l
.
l
CONVERSION
CURRENT,
IOMIN
,
1 I
I
0 5 1.0 1.5 2.0 253 0 35 L-0 L.5 5.0 5.5 60
Intensity distribution Fig.1. tion current (temperature) for spectrometer MI-1309.
r-
0.5
1.0
1.5
2.0
AMPERES 2.5
3.0 3,
of U+, UO+ and UO2+ ions as a function of ionizarhenium and tungsten filaments using mass
399 Bearing ratio
in mind
observed
for samples
ratios
the other
of the
samples
which
in turn
the overall
owes
ratios
of measured
isotopic
atic
slightly
error
The uranium The
results
on the atic
various
shown
cases
samples
of different
to metal Under ide ions. will
But
with
ratios
0
filaments
may be due a system-
ions of neodymium
conditions
were
may
composition
lead to considerable
reported
earlier
metal
the formation the oxide
and
investigated.
of the chemical
of neodymium
nitrate
system-
(ref.2).
ions
of oxide
increases ions
ion production
in all
is different.
with
respect
an -increasing temperature.
conditions of chloride
a few percent
of ions are
preparations
temperature.
.
Tungsten
which as was
, while
increasing
HNQ3
difference
bri-nging about
and oxide
out the effect
ion types,
neodymium
in the case an
ion currents observations
The systematic this
the
reproducibility
Similar
and rhenium
instrumental
the production
analyzing
with
tungsten
point
temperature
with
ions decreases typical
increase
1
the
lower
preparation.
filaments.
of metal
and
isotopic
in Fig.3
with
The
from
measurements.
in Figs.l-2
loaded
the isotopic
seem to differ
filament.
of the filaments,
chemical
in measured
As presented
In
between
sizes
would
system,
is due to the use of lower
in sample
of the formation
formation
errors
three
ratios
in temperature
under
sulphate
to the rhenium
different
dependence
on a tungsten
as uranyl
apply
of the analytical
as nitrates
to difficulties
on isotopic
to the
loaded
salt forms
loaded
precision
the production
Although
1
a0
loosened
as ox-
of oxide
the production
HN03
ions
of metal
. .
Tungsten
.
. - 0 s -
0.1
D
0 ++
+
0
+
l
4 + D
0,O’ +*
+
D +
+ +
+
D
tt*.
0,001
l
0
u+
UO+ ++++UO; 0000
IONS IONS IONS
0,001
. 0
3.~ 3.8 L.2 L.6 5.0 5-L
IIA)
t...
m
CClN";RSIONlOS QCUOI
l
0000
.
0.0001
' CONVERSION
++++
u+ IONS
UO+ IONS UO>
IONS
10MIN
2.8 3.2 3.6 4.0 A.4 4.8 5.2 I(A)
Fig.2. Intensity distribution of U+, UO+ and UO ' ions as a function of ionization current (temperature) for tungsten filamenzs using mass spectrometer FIX-1201.
HN03
lo0
,,
Tungsten
lq
. *LJ+
rNd+
Egsten oNdO+ s 0
0,l 0
0*
0
Ot, NdO’
00,1
CONVERSION 30
1.0
3.4
0
IOMIN
3-8 G-2 4.6
5.0 5.1
H2S04 Tungsten
0 ,Ol
I[ Al
l
.
0.1
CONVERSION
I 3.8
I I L.2 4.6 50
1OMIN I[A I
,” NdO+
00
0 0
800
0
000~0~‘~0~~~~51*~
Q,Ol
3.2 3.6
ions
is
case
is higher.
tion
was
lower
LO L.L 4.8
with
respect
sample
the
I[A] ions
the
investigations
in chloride and
I~MIN
5.2
to oxide
In earlier
observed the
“,
Intensity distribution Fig.3. of Nd+ and NdO+ ions as a function of ionization current (temperature) for tungsten filaments using mass spectrometer MI-7201.
*
between
I 3.:
‘Nd’ * a
2.8
I 3.0
media.
filaments
One which
overall
(ref.3)
ion production a higher
possibility calls
for
uranium
is a chemical further
in this ion
produc-
reaction
investigations.
REFERENCES 1 2 3
in N.R. Daly (Ed), Advances in Mass Spectrometry, Vol 7 A. P. de Bievre, Heyden & Son Ltd, London, 1978, 393 pp. O.J. Heinonen and R. Korhonen, Journal of Radioanalytical Chemistry, Vol 64 No.l-2(1981) 65-72. O.J. Heinonen, Chemical Aspects of the Precise and Accurate Determination of Uranium and Plutonium from Nuclear Fuel Solutions, Report Series in Radiochemistry 3/1981.