p e warwick, i w croudace & t warneke southampton...
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Mass spectrometry inradionuclide analyses
P E Warwick, I W Croudace & T Warneke
Southampton Oceanography Centre
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Range of mass spectrometric techniques
• TIMS• SIMS• RIMS• AMS• ICPMS
- quadrupole ICPMS- HR-ICPMS- MC-ICPMS
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Advantages of mass spectrometry
• Often rapid analyses• Improved data quality
(e.g. 238U:235U ratios)• Permits analyses that are not possible
radiometrically (e.g. 239Pu and 240Pu separately)
• Improved sensitivity for long lived nuclides
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Comparison of mass spectrometric techniques
Method Urequiredfordetection
U requiredfor isotoperatios
Isotopes reported Typicalaccuracy
Typicalprecision(2σ)
HRGS 10 µg 1 mg 235U, 238U 10% 10%
Alpha spec 10 ng 10 µg 234U, 238U 10% 5%
Quad ICPMS 5 pg 1 µ g 235U, 236U, 238U 2% 5%
HRICPMS 50 fg 5 µ g 234U, 235U, 236U, 238U 1 – 8% 0.1 – 1%
TIMS 1 fg 1 ng 234U, 235U, 236U, 238U 0.1 – 2% 0.1 – 0.2%
SIMS 5 pg 5 ng 235U, 238U 1 – 5% 10%
MCICPMS 5-50 fg 1 pg 234U, 235U, 236U, 238U 0.1 – 0.2% 0.1 – 0.2%
Modified from Toole et al, 1997
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Sensitivity of ICPMS versus alpha spectrometry
0.00000010.0000010.000010.00010.0010.010.1
110
1001000
10000
1E-01 1E+01 1E+03 1E+05 1E+07 1E+09 1E+11
Half life (years)
Min
imum
act
ivity
(Bq)
2 x 106 years 232Th238U
235U
236U
237Np
242Pu234U
233U
230Th
239Pu
243Am/240Pu
226Ra
241Am
210Po228Th 208Po
238Pu
232U209Po
Assuming 10ppt limit5ml solution
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Sensitivity of MC-ICPMS versus alpha spectrometry
1E-111E-101E-091E-081E-071E-061E-05
0.00010.0010.010.1
1
1E-01 1E+01 1E+03 1E+05 1E+07 1E+09 1E+11
Half life (years)
Min
imum
act
ivity
(Bq)
ca . 300 years 232Th238U
235U
236U
237Np
242Pu234U
233U
230Th
239Pu
243Am/240Pu
226Ra
241Am
210Po228Th 208Po
238Pu
232U209Po
Assuming 5ppq limit1ml solution
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Challenges• Isobaric interferences (e.g. 99Ru on 99Tc)• Polyatomic interferences (e.g. 197Au40Ar on 237Np)• Peak tailing• Isotopic fractionation• Beam instability• Matrix effects• Method blanks
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High Precision Pu Isotope Ratio Measurements
Ian W. CroudaceThorsten Warneke
Phillip E. Warwick
Rex N. Taylor
J. Andy Milton
Geosciences Advisory Unit
Southampton Oceanography Centre
University of Southampton, UK.
www. gau.org.uk
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Analytical techniques used for 240Pu/239PuAnalytical techniques used for 240Pu/239Pu
METHOD ADVANTAGE DISADVANTAGE NOMINALPRECISION
2 sigma~50 fg
AlphaSpectrometry
Not suitable because alpha energies interfere
AMS Can measure ~50fg High potential cost ~ 18%
ICPMS Quad High ionisationefficiency
Ion beam instability > 30%
ICPMS Sector High ionisationefficiency
Better stability thanICPMS Quad
~ 3%
TIMS Stable ion beam • Low ionisationefficiency
• No internalinterelementfractionationcorrection
~ 10%
MC-ICPMS • Unstable ion beambut multicollectionnegates this effect
• Interelement massfractionationcorrectioncapability
• Can measure 5 fg
High ionisationefficiency
~ 1%
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Some applications for 240Pu/239Pu ratios
Source characterisation
Datingusing impulse and continuous events
Analogous to using 238Pu/239,240Pu but is a clearer discriminator
e.g. the 240Pu/239Pu in weapon’s testing depend on the parameters of each individual test . Therefore the 240Pu/239Pu in the fallout varies with time.
Similar to using 239,240Pu, 241Am or 137Cs
The 240Pu/239Pu versus time has significant features that can be attributed to certain years.
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Range of Pu isotope ratiosRange of Pu isotope ratios
0 0.2 0.4 0.6 0.8
Weapon (pre-1960 Los Alamos National Laboratories)
Weapon (modern - Los Alamos National Laboratories)
Weapon grade
Average weapon testChernobyl accident
Power reactors
240Pu/239Pu
GasCooledReactor
BoilingWater
Reactor
PresurisedWater
Reactor
AdvancedGas Cooled
reactor
Pressure Tube BoilingWater
Reactor
Sellafield discharge
1950s Recent
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6 x 0.7 cm i.d.Eichrom 1-X8 ANION RESIN
2 x 0.7 cm i.d.Eichrom UTEVA resin
U
Pu
Stage 1 piggy-back columns
1. Load sample in 10 ml 8M HNO3 with 1drop of concentrated HCl
2. Elute 20 ml 8M HNO3 followed by 30ml of 3M HNO3
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Anion UTEVA
Pu eluted with 50 ml offresh 1.2M HCl/H2O2
(50:1)
Pu U
PuU
30ml 3M HNO325ml 9M HCl to remove Th
U eluted with 10ml 0.02M HCl
Plus use a small 2nd anion clean-up column
Removal of any U remaining because 238Uhydride interferes with 239Pu measurement.
STAGE 2Separate the columns
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Plutonium isotope ratio measurementPlutonium isotope ratio measurement
Objective: To measure 240Pu/239Pu with a reproducibility and
accuracy <5% 2sd on samples containing <50fg Pu(<150 µBq), to enable the analysis of low-level environmental samples.
Method:Multicollector ICP-MS (Micromass IsoProbe) using :
Peak jump ion counting through a Daly detector with inter-peak normalisation to 236U.
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239.0
239Pu
238UH+
Acidblank
238Utail
238.5 239.5
100
200
300
0
counts.sec-1
m/z 239 composition using:
25 ppq Pu
30 ppb U
no 233+236U
Corrections required:
1. On-peak blank subtraction including detector zero
2. Tail from 238U at +1 a.m.u. (200 ppb)
3. 238UH+ interference at m/z 239 (5.5 ppm)
4. Pu addition from 236+233U spike (2 ppm)
5. Mass bias of U-Pu (0.6% amu-1)
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Axial Daly
Low 3 Faraday
Low 2 Faraday
239
Sequence1
238
Sequence2
242
236 (235)
Sequence3
240
233(234)
Detector and peak-jump array for Pu isotope ratios using U-double spike
Low 1 Faraday 236 (239)(237)
236
Taylor R.N., Warneke T., Milton J.A., Croudace I.W., Warwick P.E. and Nesbitt R.W. (2001) Plutonium isotope ratio analysis at fg to ng levels by multicollector ICP-MS. J. Anal. At. Spectrom., 16, 279-284.
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-0.7%
-0.6%
-0.5%
-0.4%
-0.3%
-0.2%
-0.7% -0.6% -0.5% -0.4% -0.3% -0.2%236U/233U mass bias amu-1
242Pu/239Pumass bias
amu-1
236U-233U (1:1) added to separated Pu solutions to correct for mass bias and instrument drift between Daly peak jumps
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MC-ICP-MS Site 1120.215
0.220
0.225
0.230
0.235
0.00001 0.0001 0.001 0.01 0.1239Pu Volts
240 Pu
/239 Pu
100fg ml-1
I
1pg ml-1
I
10pg ml-1
I
100pg ml-1
I
1ng 239Pu = 2.3 Bq Therefore only ~1g of a typical UK soil with fallout Pu of 0.3 Bq/Kg is neededfor a precise analysis of the Pu isotope ratio
Rothamstedgrass 1 gram
UK soil
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ICP AMS
TIMSTIMS
RIMS
ICP
this study MC-ICP PJD
0.14
0.16
0.18
0.20
0.22
0.24
0.26
1 10 100 1000 10000
femtograms (g.10-15) of Pu analysed
240Pu239Pu
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Accuracy for 240Pu/239Pu atom ratios
Measured 240Pu/239PuCertified 240Pu/239Pu
Atom ratio 0.5 ng/ml 5 ng/ml
NBL122 0.13200.1318 ± 0.001
(n=4)
0.1321 ± 0.0001
(n=3)
NBL 126 0.02090.0211
(n=1)
0.0204
(n=1)
NBL 128 0.0007 -0.0007
(n=1)
UK-Pu-5 0.9662 ± 0.0011 -0.9645 ± 0.0013
(n=7)
NBL –US New Brunswick National Laboratory; UK-Pu-5 - AEA Technology
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An application of the developed method
Establishing a northern latitude fallout record
1 Unique collection of herbage and soil since 1843. Samples collected and stored annually or bi-annually
Given permission to take 50 grams of dried grass from 1945 until 1990
Rothamsted Grass Archive (IACR Rothamsted, Harpenden)
2 Alpine ice core 116 m ice core, Mont Blanc
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Warneke et al. Warneke et al.Literature data
NTS June 1952Mike + NTS
US & USSR
France & PRC
ITB Treaty
Warneke, Croudace, Warwick & Taylor (2002) Earth Planetary Science Letters, 203, 1047-57
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Warneke, Croudace, Warwick & Taylor (2002) EPSL, 203, 1047-57
Uranium isotope - 238U/235U fallout record - Europe
2sd error 2sd error
-117-112-107-102-97-92-87-82-77-72-67-62-57-52
125 130 135 140238U/235U
dept
h (m
)
Alpine Ice Core
1945
1950
1955
1960
1965
1970
1975
1980
1985
1990
137 137.5 138 138.5238U/235U
year
RothamstedGrass (UK)
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Summary
MC-ICP-MS is a highly effective method to measure 240Pu/239Pu in environmental and other samples.
Precise measurements are possible at <10 fg Pu (<30 µBq).
Used to investigate fallout history, global and local nuclear events, sediment ages in estuarine environments, source of plutonium contamination.
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Other Possible Future Application
Has great potential in plutonium and uranium bioassay
Precise U isotopic analysis using only 50ml of sample
Typically 1-2 litres urine (bulked monthly) are analysed using alpha spectrometry
Clearly MC-ICPMS can greatly enhance these data quality