neutron activation analysis at the radiochemical laboratory, institute of nuclear techniques,...
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Neutron Activation Analysis
at the Radiochemical Laboratory, Institute of Nuclear Techniques,
Budapest University of Technology and Economics
N. Vajda, Zs. Molnár, M. Balla, D. Bódizs,
IWIRadBucharest, 20-21 June 2005
Contents
• Facility• INAA –accredited procedure
uncertainty budgetmethod validation
Application examples:geological samplesarchaeological samplesbiological samples
• RNAAanalysis of 129I
Equipment for the measurement of trace elements by NAA
γ spectrometer
training reactor pneumatic transport Фth= 2E12 /s/cm2 system
Radiochemical laboratories
for „high” activity samples
for low activity samples
hot cell facility for processing irradiated samples
• Training reactor vertical irradiation channels with several thermal irradiation positionsrabbit system with 2 irradiation positions
φth: 2.6E12/cm2/s (100 kW, thermal channel)φth/φepi: 26-33 (100 kW, thermal channel)
• HPGe detectors and MCAsefficiency: resolution:
well type Ge 14 % 1.95 keVPOP-TOP Ge 22 % 2.5 keV
• MCA: S100 (16k), Accuspec B (8k)
• SAMPO 90, Gennie 2000
NAA in numbers
INAA
• Comparator technique: Au comparator
Zr flux monitor
cx = korIk Ix
x sp
,
* = N
S DC
p
x x x
x
/N
SDCm k Mp
x
*
* * * */ /
1 1
,
Standard conditions: sample preparation
irradiation
measurement
standardization
Sample preparation:
weighing :sample, gold, Zr
humidity,
impurities of vials
Irradiation:
Measurement:
Standardisation
flux variation,
the,
irr. time
counting statistics,
geometry, dead time,
timing, background
canalyte
Uncertainty budget / major sources of uncertainty:
counting statistics: 0.2-30 %; k factors: 2-7 %
Uncertainties of k factors
Element EnergykeV
Uncertainty ofk-factors %
Element EnergykeV
Uncertainty ofk-factors %
Sm-153 103,18 3 Sb-122 563,93 2.5Ce-141 145,44 3 Sb-124 602,71 3Lu-177 208,36 3,7 Sb-124 1691,00 4Np-239 228,18 3,5 Cs-134 604,70 3Np-239 277,60 3,5 Cs-134 795,84 3Pa-233 311,98 2,8 Tb-160 879,36 5Cr-51 320,08 3 Sc-46 889,25 2,2Yb-175 396,32 3 Sc-46 1120,30 2,2Au-198 411,00 2 Rb-86 1076,60 6Hf-181 482,03 3 Fe-59 1099,20 3La-140 487,03 2.5 Fe-59 1291,50 3La-140 1596,50 2.5 Zn-65 1115,50 4,6Ba-131 496,00 4,5 Ta-182 1221,40 5Nd-147 91,00 7 Co-60 1332,50 3Nd-147 531,00 7 Co-60 1173,10 3As-76 559,10 3 Na-24 1368,50 3As-76 657,03 5 Eu-152 1408,00 3
FA S7 MS FA S7 MS FA S7 MSNo. ofmeasurements
9 3 15 9 3 15 9 3 15
As As As Ba Ba Ba Ce Ce CeCertified val. 145 13,4 5,8 1500 159 4400 168 61 92
15 0,8 0,8 40 30 200 8 8 8Meas. val. 138 13,3 6,18 1422 170 4455 170 61,0 93,6
2,59 0,36 0,71 90,51 8,02 191,87 9,82 1,00 4,27 1,9% 2,7% 11,4% 6,4% 4,7% 4,3% 5,8% 1,6% 4,6%u test 0,47 0,11 -0,36 0,78 0,36 0,20 0,14 0,00 0,18
Co Co Co Cr Cr Cs Cs CsCertified val. 43 8,9 76,7 196 58,4 10,4 5,4 9,4
2 1,2 1,2 6 1,3 0,8 0,7 0,7Meas. val. 42 8,67 71,1 193 58,5 10 5,43 8,66
0,51 0,38 2,07 6,19 2,33 0,21 0,21 0,32 1,2% 4,4% 2,9% 3,2% 4,0% 2,0% 3,8% 3,7%u test 0,66 0,19 2,36 0,30 0,05 0,04 0,05 4,23
Eu Eu Eu Fe Fe Fe Hf Hf HfCertified val. 3,5 1 5,3 9,4 2,57 4,6 7,2 5,1
0,3 0,3 0,3 0,1 0,1 0,1 0,5 0,5Meas. val. 3 0,94 4,84 10 2,69 4,43 7,16 5,13 4,45
0,10 0,09 0,14 0,20 0,08 0,13 0,49 0,47 0,20 2,9% 9,8% 2,8% 2,1% 2,8% 2,9% 6,8% 9,2% 4,6%u test 0,27 0,18 1,39 0,60 0,96 1,06 0,06 -0,05
La La La Lu Lu Lu Na Na % Na %Certified val. 79,1 28 67,8 1,075 0,3 1,46 1700 0,24 3,568
2 2,9 2,9 0,07 0,19 0,19 100 0,04 0,04Meas. val. 77,61 25,70 65,48 0,98 0,29 1,32 1730 0,22 3,21
1,97 0,70 2,34 0,04 0,01 0,07 80,09 0,00 0,09 2,5% 2,7% 3,6% 4,0% 4,0% 5,5% 4,6% 0,0% 2,8%u test 0,53 0,77 0,62 1,25 0,07 0,70 0,24 0,50 3,64
QC
Analysis of
SRMs
FA
fly ash,
S7
soil-7
MS
marine
sediment
FA S7 MS FA S7 MS FA S7 MSNd Nd Nd Rb Rb Rb Sb Sb Sb
Certified val. 75,7 30 91,8 131 51 97,3 6,15 1,7 1,85 2 3,9 3,9 2 2,6 2,6 0,6 0,35 0,35
Meas. val. 58,1 29,00 81,60 128 47,7 84 6,43 1,70 2,08 11,60 11,36 12,83 11,45 5,51 13 0,10 0,20 0,08
19,9% 39,2% 15,7% 9,0% 11,6% 15,5% 1,6% 11,8% 3,7%u test 1,49 0,08 0,76 0,29 0,55 1,02 0,45 0,00 0,64
FA S7 MS FA S7 MS FA S7 MSSc Sc Sc Sm Sm Sm Ta Ta Ta
Certified val. 38,6 8,3 25,6 17,2 5,1 21,5 1,93 2 2,9 2,9 1 1,3 1,3 0,07
Meas. val. 38,5 8,47 26,56 16,39 4,84 19,96 2 0,96 1,11 0,71 0,12 0,76 0,29 0,20 0,59 0 0,08 0,13
1,8% 1,4% 2,9% 1,8% 4,0% 2,9% 4,6% 0,09 0,11u test 0,04 0,06 0,32 0,78 0,20 1,08 1,25 11,31
Tb Tb Tb Th Th Th U U UCertified val. 2,53 0,6 3,4 24,7 8,2 13,9 10,2 2,6 1,98
0,04 0,3 0,3 1 1,1 1,1 0,3 0,47 0,47Meas. val. 2 0,67 3,18 24,45 8,07 13,45 10,1 2,63 1,83
0 0,07 0,20 0,53 0,47 0,58 0,18 0,15 0,43 8,9% 0,10 0,06 2,2% 5,9% 4,3% 1,8% 5,8% 23,6%u test 0,66 0,23 0,60 0,22 0,11 0,36 0,30 -0,07 0,23
Yb Yb Yb Zn Zn ZnCertified val. 7,5 2,4 9,8 220 104 160
0,13 1,1 1,1 10 3 3Meas. val. 8 2,29 9,88 241,5 106 194
0 0,11 0,37 45,03 15 25 2,7% 0,05 0,04 18,6% 14,4% 13,0%u test 0,18 0,10 0,07 0,47 0,15 1,34
u test (cref - cm) /SQRT (m2 + ref
2) 3.29
QC
Analysis of
SRMs
Ce 2000-2002
FA FAMS
MS
MSMS
MSMS
MS
MSMS S7 S7 S7
FAFA FA
FAMS
FA
FA
MS
MSMS
MS
MS
-4
-3
-2
-1
0
1
2
3
4
u t
est
Ce
Accuracy criteria:GBW 07313 Marine Sediment [ppm]:Element Reference
valueUncertainty Meas.value Uncertainty u test
As 5,8 0,8 5,42 0,60 0,38Ba 4400 200 4400 250 0Ce 92 8 86,37 3,30 0,65Co 76,7 1,2 73,82 2,50 1,04Cr 58,4 1,3 58,52 3,00 -0,04Cs 9,4 0,7 8,50 0,40 1,12Eu 5,3 0,3 4,82 0,18 1,37Fe 46000 1000 45300 1500 0,39Hf 4,38 0,22La 67,8 2,9 66,34 2,20 0,4Lu 1,46 0,19 1,37 0,06 0,45Na 35680 400 32600 1100 2,63Nd 91,8 3,9Rb 97,3 2,6 93,0 10 0,42Sb 1,85 0,35 2,05 0,10 -0,55Sc 25,6 2,9 26,9 0,70 -0,44Sm 21,5 1,3 18,32 0,60 1,12TaTb 3,4 0,3 3,24 0,21 0,44Th 13,9 1,1 13,60 0,50 0,25U 1,98 0,47
Yb 9,8 1,1 9,75 0,40 0,04Zn 160 3 224 25 -2,54
u test (cref - cm) /SQRT (m2 + ref
2)
Method
validation:
inter-
comparison
exercise
Precision criteria:
Five samples of GBW 07313 Standard Reference Material (Marine Sediment) were irradiated.
Precision index: SQRT((ref/cref)2 + (m/ cm)
2 25%
Concentrations in ppmElement Average conc. STDEV Uncertainty Precision
index %As 5,42 0,63 0,60 17,7Ba 4400 235 250 7,3Ce 89,9 1,4 3,30 9,4Co 73,8 1,81 2,50 3,7Cr 58,5 2,33 3,00 5,6Cs 8,50 0,31 0,40 8,8Eu 4,82 0,16 0,18 6,8Fe 45300 1000 1500 4,0Hf 4,38 0,13 0,22La 66,3 1,46 2,20 5,4Lu 1,37 0,06 0,06 13,7Na 32600 561 1100 3,6NdRb 93,0 10 10 11,1Sb 2,05 0,06 0,10 19,5Sc 26,94 0,62 0,70 11,6Sm 18,32 0,64 0,60 6,8TaTb 3,24 0,09 0,21 10,9Th 13,60 0,48 0,50 8,7U 0,30Yb 9,75 0,25 0,40 12Zn 224 15 25 11,3
Method
validation:
inter-
comparison
exercise
Sample 1 Sample 2 Sample 3 Element c c c Mn % 1,84 +- 0,1 1,89 +- 0,1 1,92 +- 0,1 Cu % 1,02 +- 0,2 1,13 +- 0,2 1,09 +- 0,2 V ppm 707 +- 50 695 +- 50 710 +- 50 Cr % 24,5 +- 1 24,6 +- 1 25,8 +- 1
Sb ppm 5,2 +- 0,2 4,9 +- 0,2 5,5 +- 0,2 As ppm 25,8 +- 0,7 23,9 +- 1 27,8 +- 1
Fe % 36 +- 1 36,3 +- 1 37,8 +- 1 Co ppm 370 +- 20 385 +- 20 390 +- 20
Ni % 28 +- 2 29 +- 2 29,5 +- 2 W ppm 68 +- 3 67 +- 3 72 +- 3 Mo % 3,05 +- 0,5 3,07 +- 0,5 3,26 +- 0,5
Sample 4 Sample 5 Sample 6 Element c c c Mn % Cu % V ppm Cr % 25,4 +- 1 26,3 +- 1 27 +- 1
Sb ppm 6,3 +- 0,8 As ppm
Fe % 37,6 +- 2 37,1 +- 2 40 +- 1,7 Co ppm 405 +- 20 415 +- 20 420 +- 20
Ni % 28,5 +- 2 30,4 +- 1 31,2 +- 1 W ppm Mo % 3,24 +- 0,5 +- 3,57 +- 0,5
Element Average σ (k=2)Mn % 1,88 +- 0,1
Cu % 1,08+- 0,2
V ppm 704 +- 50
Cr % 25,6+- 1
Sb ppm 5,2+- 0,3
As ppm 25,8 +- 2
Fe % 37,5 +- 1,5
Co ppm 398 +- 20
Ni % 29,4 +- 2
W ppm 69 +- 3
Mo % 3,24 +- 0,5
Analysis of steel BSS3 (intercomparison)
APPLICATION EXAMPLE: INAA
Analysis of archaeological samples
Fingerprinting of archaeological ceramic materials: Multivariate statistical methods using trace element data for provenance studies of ceramics.
Terra sigillataceramics used in Aquincumwere not locally manufactured.
Jan Gunneweg, MartaJan Gunneweg, Marta BallaBalla
The Provenance of Qumran Pottery by Instrumental Neutron Activation Analysis
COST G8 Qumran Meeting 21-23 May 2005
Main goalsMain goals
• to trace pottery by its chemistry to their place(s) of manufacture
• to establish the relation between pottery found in the settlement and the caves
• to study what pottery was locally made and which was brought in from elsewhere
• to learn the interregional contact between Qumran and its surroundings
COST G8 Qumran Meeting 21-23 May 2005
Sample selectionSample selection
1. Qumran reference samples
2. Clay and ceramic samples from Jericho, Jerusalem, Hebron, Callirhoe, ‘Ain Feshkha
3. 166 pottery samples from the settlement and the caves
COST G8 Qumran Meeting 21-23 May 2005
Analytical resultsAnalytical results evaluated by multivariate evaluated by multivariate statisticsstatistics
Data points in PC1-PC2 space
-40
-20
0
20
40
60
80
100
0 50 100 150 200 250 300 350
PC1
PC
2outlayers
group 5
group 1
group 2
group 3
group 4 ?
group 5 ?
group 2 - subgroup ?
group 3 ?
Conf. ellip. - group 5
Conf. ellip. - group 1
Conf. ellip. - group 2
Conf. ellip. - group 3
Conf. ellip. - group 4
PC1-PC2-PC3
-433 -389.4 -345.8 -302.2 -258.6 -215 -171.4 -127.8 -84.2 -40.6 3-54
-43.2
-32.4
-21.6
-10.8
0
10.8
21.6
32.4
43.2
54
centers for the iteration
Co - La projection
0
10
20
30
40
50
0 10 20 30
COST G8 Qumran Meeting 21-23 May 2005
Most important results and archaeological Most important results and archaeological conclusionsconclusions
• Qumran’s local chemical fingerprint has been defined• 5 chemically different groups of pottery were
determined and their probable provenance have been localized
• Analysis of clay and ceramic samples from other sites of the Dead Sea region provided reference data for workshop assignment
• Pottery serves as a connecting link between the settlement and the caves
COST G8 Qumran Meeting 21-23 May 2005
APPLICATION EXAMPLE: INAA
Analysis of geological samples mineral separates, bulk rocklanthanides and other incompatible trace elements
Element LD ppm
Element LD ppm
As 2,8 Nd 25 Ba 300 Rb 35 Ce 4,5 Sb 0,4 Co 2 Sc 6e-2 Cr 9 Sm 0,1 Cs 0,9 Ta 0,2 Eu 0,12 Tb 0,6 Fe 600 Th 0,7 Hf 0,8 U 1,7 La 0,5 Yb 0,7 Lu 0,1 Zn 20 Na 80
Typical detection limits:
Processes of igneous petrogenesis, paleotectonic and paleogeographic position of rocks
APPLICATION EXAMPLE: INAA
Analysis of biological samples brain biopsy samples to study Alzheimer deseasealkali metals + iodine
Uncertainties LD
INAA ICPMS ICPAES INAA ICPMS ICPAES
unc% STD% unc% STD% unc% STD%
Li(ng/g) - - 3 32 5 28 3 1
Na(ug/g) 1 2 5 8 40 2
K(ug/g) 5 3 2 6 1300 90
Rb(ug/g) 5 4 2 11 0,6 0,02
Cs(ng/g) 10 5 5 24 7 20
I(ng/g) 7
Good reproducibility in INAA!
RNAAfor the analysis of radionuclides
Methods:
α spectrometry
β spectrometry
γ spectrometry
RNAA
Long-lived„difficult to determine nuclides„ (DDN) in the nuclear fuel cycle
e.g. 129IT1/2=1.57E7
y 129I(n,γ)130IT1/2=12.4 h99Tc T1/2=2.13E5
y99Tc(n,γ)100TcT1/2=15.8 s
Too short!
Radiochemical separation procedure for the simultaneous separation of DDNs
Sample Tracers, carriers
DestructionNAA
pre-, post- irradiationseparation
Fe(OH)2 coprecipitation TBP extraction
γ spectrometry UTEVA TEVA129I
α spectrometry
NiDMG Ca oxalate 232Th,230Th,228Thprecipitation coprecipitation α spectrometry α spectrometry
239,240Pu, 238Pu 238U, 235U, 234U
DMG TRU LSC α spectrometry LSC241Pu 237Np 99Tc
Sr Resin TEVA
59Ni
X spectrometry
LSC LSC α spectrometry63Ni 90Sr, 89Sr 241Am, 244Cm, 242Cm
129I
99Tc
Pu-Np-UNi
Sr Am-Cm
APPLICATION EXAMPLE: RNAA
129I analysis:
- Ground level measurements in well water on the site of the future radioactive waste
disposal area: analysis of 100 L of water<μBq/L
- Analysis of nuclear wastes:evaporation concentrates: 10-100 mBq/Lspent ion exchange resins: 1-10 Bq/L
• γ spectrometry• Determination of Gamma Emitting Fission and Corrosion Nuclides in NPP Primary Coolant by Gamma Spectrometry • Determination of Activity Concentration of
Nuclear Power Waste by Gamma-Spectrometry• Determination of Activity Concentration of Environmental Samples by Gamma-SpectrometryNAA • NAA of geological and environmental samples • NAA of archaeological potteries α and β spectrometries• Analysis of Uranium, Plutonium, Americium, Curium, Nickel and Strontium Nuclides in Radioactive Wastes • Determination of Strontium and Plutonium Isotopes in Concentrates of Water Samples
Accredited procedures:
Staff: N. Vajda, Zs. Molnár, M. Balla, D. Bódizs,Gy. Csuday, J. Szabó, K. Jovicza
PhD students: A. Kerkápoly, Sz. Osváth, É. Kabai, D. Tar, G. Surányi
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