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Handbookof PromptGamma
ActivationAnalysis
with NeutronBeams
Edited by
Gábor L. Molnár
Chemical Research Centre,
Budapest, Hungary
:1.1..=
KLUWER ACADEMIC
PUBLISHERS
DORDRECHT / BOSTON / LONDON
Table of Contents
Preface (Zs.
Chapter 1.
l.
Principles of the PGAA method
(Zs. Révay,T. Belgya)
In t r oduct io n
2.
2. I Ch ar acte r is t icosf n e u t r o n s ..............
..............2
2. 2 F undam e n tapl r o c e s s e o
s c c u rr in gin PG A A
.................5
2. 2. I Rad ia tiv en e u t r o nc a p t u r eo, r ( n ,y )-r eacti o n......
....................5
2. 2. 2 Rad ia tiv en e u t r o nc a p t u r eo f e p it hennalneutr o ns................................5
2 . 2 . 3 A c t i v a t i o r.l . . . . . . . . . . . . .
...............6
2 . 2 . 4 I s o m e r i ct r a n s i t i o (nI T ) . . . . . . . . .
................6
2. 2. 5 N e u t r o nc a p tu r ewith c h a r g e dp a rti cl eemi ssi o n
...................6
2.2.6 Neutron inducedfission,or (n,f)-reaction......
.......6
2 . 2 . 1 E l a s t i cs c a t t e r i n g
...................6
2. 2. 8 T h e r m a liz a t io n
......7
2.2.9 Inelasticscatteringof fastneutrons,or (n,n')reaction
..........7
2.2.Í0 Nuclear reactionsof fastneutrons..
.......7
2. 2. 11 S e c o n d a r yr e a c tio n s
..............8
2. 3 P r obab ilitie o
s f n u c le a rr e a c tio n s .
.................8
2. 4 E ne r ge t ic so f th e c a p tu r ep ro c e s s ....
............14
2. 5 R e act i o nr a t ee q u a t io n s .........
......17
2. 5. 1 T hin s a m p lea p p ro x im a tio n
................18
2 . 5 . 2 " B l a c k " s a m p l ea p p r o x i m a t i o n . . . . . . . . .
..................19
2 . 5 . 3 R e a l s a m p l e .s. . . . . . . . . .
............19
a
J.
3. 1
3.2
3. 3
An al yt i c a lp r o p e rtie s ..............
Characterization
of promptgamma spectra
Dyn ami c r a n g ea n d d e t e c t io nlim it
.....20
................23
.............25
vi
Table of Contents
Chapter 2.
Beams and Facilities
(R.M. Lindstrom, Zs. Révay)
Basic parts of the PGAA
1.
1. 1 N e ut r o ns o u rc e s
I.2 Shapingand tailoringthe neutronbeam
I.2.1 Collimator..............
1.2.2 Neutron filters
1. 3 N e ut r o ng u id e sa n d f o c u s i.,g..........
1. 3. 1 S t r a ig h tg u id e s
1. 3. 2 Cu rv e d g u id e s
1. 3. 3 S u p e r m irr o gr u id e s
1. 3. 4 Ne u tr o nle n s e s
1. 3. 5 D if f r a c te db e a m s
1.4 Neutron absorbersand shieldins:materialsissues
1.5 Shutter....
..-............
1 . 6 B e a mt u b e . . . . . . . .
1 . 7 S a m p l eh o l d e r
1 . 8 B e a m s t o p. . . . . . . .
2.
..........
31
.....34
.............34
.....34
............35
....36
.....31
.............38
....38
.................40
......40
.....42
...........42
.............43
...........43
Neutron flux mapping and monitoring
2.I
2. 2
3.
Average neutronwavelengthand beam temperature............
Mon i t o rin ga n d m a p p in g
Additional shieldins and backsroundissues......
......43
............45
.............41
4.
References
Chapter 3.
Samples and Standards
(R.M. Lindstrom, Ch. Yonezawa)
S a m p l ec o n s i d e r a t i o n s . . . . . . . . .
1 . 1 S a m p l es i 2 e . . . . . . . . .
1 . 2 S a m p l es h a p e
Í . 2 . 1 N e u t r o ns e l f - a b s o r p t i o r r . . . . . . . . .
1. 2. 2 Ne u tr o ns c a t te r in with
in th e s a m p1e..............
g
1. 2. 3 G a m m a - ra ys e lf - a b s o r p t io n
S t a n d a r dasn d b l a n k s . . . . . . . . . . . . . .
2. 1
2.2
2. 3
P r e par a t io no f s t a n d a rd s .........
Referencematerials
S ui t ab leb la n k s .....
References
...........59
........59
..............60
.......'.....61
....62
................65
........66
.....66
....67
.......68
Table of Contents
Chapter 4.
Gamma-Ray Spectrometry
(T. Belgya,Zs. Révay)
l.
Introduction
2.
Basic
2. 1 De t e ct o rs
2.2 Electronios..............
2 . 2 . 1 A n a l o ge l e c t r o n i c s . . . . . . . . . . . . . .
2.2.2 Digital signalprocessing
2 . 3 D e a d t i m ea n d p i l e - u p . . . .
2.4 Responsefunctionof germaniumdetectors.........
Cal i br at i o np r o c e d u r e s ...........
3.
3. 1 E n e r gyre s o lu t io n
3 . 2 S y s t e r nn o n l i n e a r i t y . . . . . . . . . . . .
3.3 Detectorefficiency
3.3.1 Wide energyrangeefficiencycalibration
3. 3. 2 Int r in s ica n d g e o m e t r ice f f ic ie n c y . ......
3. 3. 3 G e o m e t r yf a c to rf o r c o llim a te dd e tecto r .........
s
3.3.4 Active and effectivevolume of the sample
3.4 Calibrationsources
4.
O pt i mi z at io no f d e t e c t io n
4.1
5.
vii
.....12
....74
................14
.....75
.............76
.......78
.........80
........80
........81
......83
...........83
................86
..................87
.........89
.....90
...............91
Spectralbackground
Mor e s oph is t ic a t edde te c t io ns y s te m s ..............
...............96
Compton suppressedand pair spectrometers
Compositegermaniumdetectors...........
Coi nci den c et e c h n iq u e ..........
s
Chopped-beam
PGAA
..............96
......99
....99
..............101
5.1
5.2
5. 3
5.4
6.
Chapter 5.
Quantitative Analysis
(Ch. Yonezawa)
1.
Introduction
2.
Elemental
3.
3.1
Table of Contents
v1l1
3. 2
3. 3
4.
R e l at i ves ta n d a rd iz a tio n ........
Int e mals t a n d a rd iz a tio n ........
S ou r ce sof er r o r ....
S pe ct r ali n te r f e re n c e ............
Gamma-raybackground
4. 1
4.2
Utilizationof short-liveddecay gamma rays .........
5.
Chapter ó.
Introduction...........
2.
Appl i cat i on sin C h e m is tr y
3.1
3.2
3.3
3. 4
3.5
3. 6
3. 1
4.
RelatedReferenceMaterials
Ores, Metal Alloys, and ConstructionMaterials.
F o s s i lF u e l s
Cat al ys ts .
Glass and Semiconductors
N ucl e ar T e c t u r o lo g yA p p lic a t io n s
Mat e r i alC o m p o s it io na n d Pr o c e s s in g .. ...........
Geology, Geochemistry,and Cosmochemistry
4. 1
4. 2
4. 3
5.
G e och e m ic a R
l e f e r e n c eM a te r ia lA n a ly s i s...........
G e ol ogy
Cosmoch e m is tr y
A r t a n dA r c h a e o l o g y . . . . . . . . . . . .
5.1
5.2
5. 3
5.4
6.
S t o n et o o l s
Ceramics
P i gme nt sa n d p a in tin g s ..........
Metalobjects.....
Food and Agriculture
6.1
6. 2
7.
An al ysi s o f C e rtif ie dR e f e re n c eM a te r ia l s.............
Isot opi ca n d C h e m ic a lC o m p o s it io nStu di es
Ch e mi ca lM a t r ix Stu d ie s
Applicationsand MaterialsScience
Industry-Related
3.
.........I27
.....I27
...........129
.......133
Applications of PGAA with Neutron Beams
(D.L. Anderson, Zs. Kasztovszky)
1.
2. 1
2. 2
2. 3
....116
.....118
Certificationof ReferenceMaterials.
An al ysi s o f Fo o d ...
E n vi r on me n t aSl tu d ie s ...........
.......137
............138
...138
............139
..........140
..................141
.....141
......I42
...............143
...144
........t45
............145
.........146
.............148
....148
....149
.......151
.........152
................I52
...153
...154
........154
....156
........
156
....157
.......158
Table of Contents
II
7. 2
At mos p h e r icG a s e sa n d Pa r tic le s ....... ....
W at e ran d S e d im e n tPo llu t io n ..........
Biology
8.
8.1
8. 2
Biological Matrix ReferenceMaterials
H uman a n d A n im a l Stu d ie s
Me di ci ne
9.
9.1
9.2
Boron NeutronCaptureTherapy
O t h e rM e d i c a l S t u d i e s
R e f e r e n c e.s. . . . . . . . . . . . .
Chapter 7.
I n t r o d u c t i o.n. . . . . . . . . .
2.
Evaluationof promptgamma-raydata
S our ce so f t h e e v a lu a t io n
in B u d a p e s t
Me asur e m e n ts
Evaluation.............
S pe ct r aan d t a b le sf o r e le m e n t s............
3.
3. 1
3.2
3.3
F or mato f th e e le m e n t asl p e c t r a .
Format of the elementaltables
Backgroundspectra
R e f e r e n c e.s. . . . . . . . . . . . .
3. 4
...158
........159
.........160
.....160
......161
.......162
..............162
..............163
. . . . . . . . . . . .1.6. .4.
Prompt Gamma-Ray Spectrum Catalog
(Zs. Révay,R.B.Firestone,T. Belgya, G.L. Molnár)
1.
2. 1
2. 2
2.3
ix
S pe ct r aa n d ta b le sf o r e a c he le m e n t...
.......113
.........174
..........114
.......\14
....175
........116
...............176
..179
.. 186
................186
.......186
Appendices Reference Data
(R.B. Firestone,G.L. Molnár, Zs. Révay)
l.
F undame n t acl o n s t a n t s ...........
.......365
2.
P r ope r t i e so f c h e m ic a le le m e n t s ............
.......367
3.
Isot opi cda t a .........
4.
Radioactivn
euc1ides..............
5.
X- r ay e n e rg ie sa n d in t e n s it ie s .........
..............390
6.
E n e r gyan d in te n s it ys t a n d a rd..........
s
...........393
.........31I
.......380
Table of Contents
1.
T he r malne u t r o nc a p tu r ed a t a .........
..............400
8.
Resonanceparametersand Westcottg factors
..............410
9.
Neutron capturecross sectionof elements.............
.......4I2
Preface
Prompt Gamma Neutron Activation Analysis (or the more common usage, Prornpt
Gamma Activation Analysis, abbreviatedas PGAA) is based on one of the most basic
nuclear reactions,the radiative capture of neutrons.This nuclear reaction takes place for
aHe. Therefore,in principle,
each isotope of every element,with the single exception of
a complete elemental and isotopic analysis can be performed using PGAA. Nevertheless
this versatile nuclear technique has mainly been used as a supplementary analytical tool
until recently. Many recent developments have been achieved at the leading laboratories
of this field that make it timely to summarize the results in the form of this handbook.
The creationof this book was possible thanks to the cooperationof many specialists:
radiochemists and physicists working in the fields of PGAA, traditional neutron activation analysis (NAA), gamma spectroscopy and nuclear data evaluation. The PGAA facility at the collimated thermal beam at NISI USA began operation in the early eighties
and has been mainly used for the analysis of biological samples by D. L. Anderson. A
second PGAA system was installed at a guided cold neutron beam at the same reactor
by R.M. Lindstrom towardsthe end of the 1980's.APGAAfacility operatingwith either the thermal or the cold beam was startedat JAERI in Japan under the leadership of
Chushiro Yonezawa in the early nineties.
The thermal neutron guides started operating at the Budapest Research Reactor in
1994.A PGAA facility of the Budapest Neutron Center was establishedin 1996. Since
that time thousands of PGAA measurementswere performed there for different fields of
application and to the development the PGAA technique. A cold neutron source was
installed at the reactor in 2000 at Budapest, improving the capabilities further.
The Departmentof Nuclear Research of the Instituteof Isotopes,led by Gábor L.
Molnár, proved to be an ideal laboratory for adopting and developing fuither the PGAA
method.Professor Molnár organizedthe cooperationof colleagues from many different
backgrounds to accomplish a very significant improvement in the methods and techniques of PGAA. Tamás Belgya developedy-y-coincidencetechniquesfor PGAA applications and has been responsible for the sophisticated electronics. Zsolt Kasztovszky
has been in charge of arrangingdifferentapplications,and I myself have establishedthe
PGAA analytical data library and developed data reduction programs and techniques.
The large number of gamma-ray peaks appearing in prompt gamma spectra requires
an accuratecalibration of the detectionsystem,and a reliable and reproducibleidentification of gamma lines. The principal reason that this useful technique did not become a
standardnuclear analytical method has been the lack of an accurate and complete analytical library. The poor reliability of available spectroscopic data discouraged many
scientistsfrom using the PGAA (Molnár 2000). In parallel with the new, precise library
xll
Preface
measurementsperformed in Budapest, a thorough databasewas constructed as part of a
Coordinated Research Program of the InternationalAtomic Energy Agency. The library
provided in this book results from the IAEA evaluation led by Richard B. Firestone
from Lawrence Berkeley National Laboratory (IAEA 2004). It combines the precise
Budapest elementalmeasurementswith detailed isotopic measurementsfrom the scientific literature.
Many review ar1icleswere published about PGAA and its applications(Anderson é/
al. 1982, Greenwood 1919, Lindstrom et al. 1997, Lindstrom et al. 1994, Paul and
Lindstrom 2000, Shaw 1999) and a dedicated book has also appeared (Alfassi and
Chung 1995). The idea of publishing a handbook that contains all up-to-dateinformation needed to perform reliable analysis with the PGAA method, was born in the Budapest group. This new handbook summarizes the experiencescollected at those PGAA
facilities equipped with Compton-suppressedHPGe detectorsand using cold and thermal neutron beams.This is the first time that an atlas of prompt gamma spectrawith a
data library for every naturally occurring element as measured with a high-resolution
germanium detector has been published. It is mainly intended for analytical applications; however the tables have been constructedin a way that they could be used in
other fields, as well.
In Chapter 1 the fundamentalsof the PGAA method are given. Chapter 2 discusses
beam and facility construction material considerations,and the most important facilities
are also described. Chapter 3 addresses sample preparation and the use of standards.
Chapter 4 is dedicatedto the spectroscopy,the setting up of the data acquisition electronics and the calibration proceduresrequired for the accurateanalysis.Chapter 5 outlines the process of PGAA quantitativeelemental analysis and discussesthe most important factors affecting the analytical results, and Chapter 6 gives examples of the
many applicationsof PGAA performedwith neutronbeams. Chapter 7 containsthe experirnental prompt gamma ray spectrum library measured in the Budapest thermal and
cold neutron beams, and lists up to 100 of the most prominent prompt and delayed
gamma rays. Tl-reappendix provides useful tables of frequently used nuclear and elemental data. The CD supplement contains high resolution drawings of the spectra (in
PDF format) and the complete library of prompt and delayed gamma rays.
Gábor Molrrár began tlre preparatiorrof this handbook in the year 2000. He designed
the content of the book, invited the co-authorsto participate and coordinated the project.
He planned to finish the book in 2003, but last fall his enthusiasmseemedto have deteriorated.He startedreviewing the manuscripts,made some changesin chapter3, gener'7
ated the headings in Chapter and thoroughly verified the data library and the atlas.
Unfortunately he could not finish this work and was unable to start writing the chapters
he was responsible for. Tragically, he passed away shortly after the Christmas holidays,
which were spent in hospital. The rest of the work on the Handbook was passed on to
his colleagues in the Departmentof Nuclear Research.Tamás Belgya and myself have
prepared the missing chapters,Zsolt Kasztovszky has undertakenthe updating of the
chapteron applicationsof the method,while I finished the editing of the book.
Gábor Molnár's contributionsto the developmentof the PGAA method were both
broad-basedand essential.In addition to this book, a special journal issue dedicatedto
his memory is also being edited,includes many paperson the projectshe took part in or
Preface
xlll
inspired in different laboratories.These papers, are cited throughout this book, and are
to be published in the Gábor Molnár memorial issue of the Journal of Radioanalytical
and Nuclear Chemistry, which is will appear at the end of 2004.
The authors hope that this handbook will contribute to the propagation of PGAA as
a powerful nuclear analytical technique.
Let me give special thanks for the valuable and friendly support of Richard LindStrom,Richard Firestone and also my colleague Tamás Belgya' who helped me considerably in solving numerous problems that arose while completing this book. The careful
proofreadingand the useful advice of Jesse L. Weil are also gratefully acknowledged.
Zsolt Révay
Budapest,
June 28, 2004.
References
Alr.esst, Z. B., CHtxG' C.' l995' Prompt Gamma NetúronActivation Analysis, (Boca Raton: CRC Press).
ANDERSoN, D.L.,Zot-rEn, W. H., GoRDoN, G. E., WALTEnS,W. B., LrNosrRoM, R. M., 1982,IleutronCapture Gamma-Ray Spectroscopy and Related Topics (lnst. Phys. Ser. 62), edited by Maier, B. (London:
Inst. Physics), Chapter: Neutron-Capture Prompt Gamma-Ray Spectroscopy as a Quantitative Analytical
M e t h o d ,p . 6 5 5 .
GnPENwooo, R. C., 1979, Proceedings ol the Third Internationctl Sympositrm on IYeutron-C-apttu'eGammaRay Spectroscopy and Related Tbpics, edited by Kane, W. R. (New York: Plenum), Chapter: Practical Applications of Neutron Capture Gamma Rays, p. 441.
LtNostRona, R' M., PAUL, R' L., Walrpns' w. B.' MolNÁn, G., |994' Capture Gamma-Ray Spectroscopy anc|
Related Tbpics,edited by Kern, J. (Singapore:World Scientifrc),Chapter:Analytical Applications of Cold
Neutron Capture and opportunitiesÍbrNuclear Physics, p. 955.
LtNosrRov, R. M., ANDERSoN, D. L., PAUL, R. L., 1997, Proc. 9th Internat. S1,mp.Capture Gamma-Ray
Spectroscopy and Related Topics, edited by G.L' Molnár' T. Belgya, Zs. Révay (Budapest: Springer), Chapter: Analy.tical Applications of Neutron Capture Gamma Rays, p. 693.
MolNÁn, G. L.' 2000' J. Radioanal. Nucl. Chem.,244.27.
Paul, R. L., LtNDStRoM, R. M., 2000, J. Radioanal. Nucl. Chem., 243, l8l.
S H a w "D . M . . 1 9 9 9 . J .N e u t r o nR e s . . 7 . 1 8 1 .