Journal of Radioanalytical and Nuclear Chemistry, Articles, VoL 113, No.

1 (1987) 145-161

Comparators

A C C U R A C Y A N D APPLICABILITY O F T H E k o - S T A N D A R D I Z A T I O N METHOD

F. De CORTE, *+ A. SIMONITS,** A. De WlSPELAERE,* J. HOSTE*

*Institute for Nuclear Sciences, State University

Proeftuinstraat 86, B-9000 Gent (Belgium)
**Central Research Institute for Physics,
H-1525 Budapest, 114, P.O.Box 49 (Hungary)
(Received December 12, 1986)

The present paper deals with the accuracy and applicability of the ko-standardization technique
in NAA. Topics included are: user-oriented outline of the method, relevant nuclear data (ko, Q0,
~tc.), the non-1/E epithermal flux distribution, small detector separations and/or extended source
geometries, (n, 3') reactions with a Westcott.g :~ 1, primary interferences, subsequent (interrupted)
irradiations, the non-constancy of the neutron flux during irradiation, and a final account of the
accuracy. Although the paper is written in terms of the ko-methodology, a good deal of the
considerations can be transferred to most types of single-comparator standardization.

User-oriented outline of the k 0 - m e t h o d

The fundamental concept of the k0-method being elaborated previously in great

detail /I-3/, the present introduction will be restricted to a concise direc-
tions for use.
In terms of the k^-methodology, adopting the H~gdahl-oonvention /4/, the
concentration calculatlons are based on the fundamental equation :
Np/tm x
SDCW I f + ~(~) ~p (I)
- o ~ 9

Q~ppm = ""/NP/tm~* k0 f + Q0(~ ) p

ts--~vi
with k 0 defined as :
M 0. o 0 .y (2)
k0 9 x
M.0 .~0.Y
It has been indicated in previous papers /2, 3/ how these equations should be
modified in case of complicated reaction/decay schemes.
As mentioned below, k~-factors have been experimentally determined ver-
sus t97Au(n,y) tgSAu (Ey = ~11.8 keV), but they can be converted to any com-
parator which is found suited to be coirradiated with the sample. In Eqs (I)
and (2) :
M-atomic mass;
0-isotopic abundance;

+
Research associate of the National Fund for Scientific Research.

10 Elsevier Sequoia S. A , Lausanne

A kaddmiai Kiad6, Budapest
F. DE CORTE et al.: ACCURACY AND APPLICABILITY

00-2200 m.s -I (n,y) cross-section;

T-absolute gamma-intensity;
N -peak area corrected for pulse losses;
W$-sample weight in gram;
w -comparator weight in microgram;
S = l-exp(-%tirr); tirr-irradiation time; %-decay constant;
D = exp(-%td); td-decay time;
C = [l-exp(-%tm) ]/%tm; tm-measuring time;
f-thermal to epithermal neutron flux ratio;
Q0(~) = I0(~)/~0; I0(~ ) -resonance integral corrected for a non-ideal
(assumed I/E I+~) epithermal neutron flux distribution (see below);
g -Ge(Li) peak detection efficiency.
P
Mentioning only the parameters which are specific to the k0-standardiza-
tion, the user is confronted in prac~i2e with the following situation :
I. All relevant nuclear data (k0~ Q0' Er' decay scheme data, etc.) can be
found in a tabulated form or zn a computer library ;
2. Experimentally, one should :
a) determine a "reference" peak efficiency curve (log Ep versus log Ey)
for point sources at 15-20 cm detector distance. Although in our prac-
tice no significant variation with time was observed, it is advised
to check the Sp-CUrve once a year, e.g. by measuring some calibrated
point sources with low, medium and high gamma-energy (for instance
133
Ba, 137 Cs and 60 Co). In practice, when small source-detector sepa-
rations and/or extended source geometries are involved, the c_ re =-
curve should be converted; so as to guarantee a complete versat~l~ty,
this requires the use of a cylindric detector with specified dimen-
sions (see below) ;
b) determine f and ~. If the flux characteristics are known to remain
constant over a long period, this can be done "once and for all".
On condition that irradiation of a Cd-cover is allowed, use can be
made of the "Cd-ratio for multi-monitor" or "Cd-eovered multi-moni-
tor" method /5/ for s-determination (see also below), and of the
well-known Cd-ratio method for f-determination; Without Cd, ~ can be
obtained from the "bare multi-monitor" method /5/ and f from the
"bare dual-monitor" method. Obviously, the latter techniques are the
only possibility when ~ and f-determination should be repeated for
each irradiation, and this subject of instantaneous monitoring is
dealt with at this MTAA-7/1986 Conference by Simonits et al./7/.
In practice, it requires the coirradiation and counting of a 0 . 1 %
Au-AI wire (available with I% relative accuracy) and a thin Zr-foil.
The Au can at the same serve as the comparator [index ~ in Eq.(1)];
c) determine the peak-to-total curve (log P/T versus log Ey) for the
source-detector distances used in the analysis measurements, needed
for true-coincidence corrections (see below). This curve was s~own
to be linear /2/ and to be practically independent of source g:ometry
and composition. Thus, it suffices to measure 2 or 3 mono-gamma point
sources with a suitable energy-spread, e.g. z~ 137Cs and 65Zn;
3. Since many complex calculations are involved, the use of a computer program
is necessary. At Gent, the FORTKAN IV program SINGCOMP is operated on a
VAX 11/780 machine and a more general interactive computer code, extended
with gan~na-spectrum unfolding has been developed by Moens et al. Both prog-
rams are modified versions of that proposed at the MTAA-6/1981 Conference
IS/.

146
 F. DE CORTE et al.: ACCURACY AND APPLICABILITY

In the following subsections the most important parameters, which affect

the accuracy and the applicability of the ko-standardization technique, will
be examined in more detail. It should be emphasized that a good deal of the
statements and conclusions can be transferred integrally to other single-com-
parator methods, whether they are labelled "absolute", "monostandard", "para-
metric" or otherwise.

P ~ a m e t e ~ influencing accuracy and applicability

~,Au-factors
An experimental k0,Au factor is determined as /2,3/ :

Asp f + Q (~) g--P-P (3)

kO'Au = A ~ " f + Q0 (~) " gp
sp
with Np/tm
=
Asp SDCw ' (4)
choosing conditions Of accurately known f, ~ and e (quasi-point geometry at
reference distance). P
Per definition, the applicability of the ko-method is limited to the iso-
topes and gamma-energies for which ko-factors are available. As outlined pre-
viously /2,3/, a "recommended" ko-factor is the average of several experimental
determinations in the WWR-M reactor (Budapest) and the THETIS reactor (Gent)9
This implies different sample preparation, irradiation and counting conditions,
peak area integration, etc. In each reactor, irradiations were carried out in
at least two channels possessing considerably different f and ~, with 3-5
samples per channel. This enterprise, enabling detection and reduction of
systematic errors, leads to ko's with an accuracy better than 2% (average ~]%),
which as such is transferred ~o the analysis results. A k^ is reported but
9 . . U
not recommended if the standard devlatlon of the mean exceeds 2% or if it is
- for a particular gamma line of a given isotope - only the result of experi-
ments in one reactor; even then, it is the average of 3-5 experimental results
x 2 channels.
In 1980 /2/ and 1984 /3/ ko-tabulations were released for a total of 35
and 72 isotopes, respectively. Since then, the experimental determinations
were continued, and former values were revised and updated. For a number of
isotopes, the irradiations were extended to the highly thermalized channel
R4V4 (f = 320; ~ = 0.17 /9/) of the DR-3 reactor (Ris~, Denmark). This was
especially useful for the accurate k0-determination for isotopes with a very
high Q0-value, according to the Cd-subtraction method :

Asp-(Asp)CH/FcH g-P-P (5)

kO,Au [As~-(Asp)Cd/FCd]_ ~" Kp

with Fc~ = Cd-transmission factor for epithermal neutrons /10/. At the present
MTAA-77T986 Conference, the results for the extremely difficult case 96Zr(n,y)
9?Zr (Q0 = 248) are dealt with in detail by Simonits et al. /7/, As a new out-
put of ~he above mentioned efforts, the present paper is accompanied by a INW/
KFKI Interim Report /ii/ with a tabulation of k0=Au-factors for 94 analytical-
ly interesting isotopes. The Report also shows that, when calculating k O [Eq.
(2)3 from the data given in Refs /13,14/ [0,o~ and /15/ [y], the discrepancy
with the recommended ko-factorsis:

10" 147
F. DE CORTE et al.: ACCURACY AND APPLICABILITY

lower than 5%, for 37% of the investigated isotopes ;

-

between 5 and 10%, for 16% of the investigated isotopes ;

-

between I0 and 20%, for 22% of the investigated isotopes ;

-

- between 20 and 50%, for 20% of the investigated isotopes ;

- larger than 50%, for 5% of the investigated isotopes.
This gives an idea about the accuracy situation when performing absolute NAA-
standardization without data control.

Q_0-values
The accuracy requirements on the Q0-values to be introduced in Eq. (I) are
less stringent than on the k0-factors , since the term [f + Q~(e)]/ [f +
Q0 (~)]
causes an error reduction. Nevertheless, Qo-values often being inaccurately
known in the literature, a careful choice or an experimental redetermination
is required, especially for cases with high QO and for application to ENAA
/lO/.
Following a similar philosophy as described above for the Gent-Budapest
cooperative determination of k0-factors , tabulations with recommended Q~-va-
lues were released in 1979 /16/ and 1984 /17/ for resp. 13 and 57 analytical-
ly interesting (n,y) reactions. Recently, we have updated and extended this
work - including determinations in the R4V4 channel of the DR-3 reactor -,
reaching a total of 72 (n,y) reactions. The very difficult cases of Q0-deter-
mination for 94Zr(n,y)95Zr and 96Zr(n,y)97Zr are discussed by 8imonits et el.
/7/ at the present MTAA-7/1986 Conference (see also below). Recommended or
carefully evaluated Q0-values are also listed in the INW/KFKI Interim Report
/11/. As a continuatlon of the above cited 1979- and 1984-papers, a third Q0-
tabulation is in preparation.
Although it is difficult in general to predict the residual uncertainty of
the analysis result caused by the uncertainty in Qo - this being dependent on
the magnitude of QO versus f -, it has been shown 727/ that on the average a
value of I% can be assumed.

N0n-I/E epithermal neutron flux distribution

One of the major concerns in the course of our work has been the preservation
of the accuracy in the ko-factors and in the concentrations when the epither-
mal neutron flux distribution deviates from ideality, i.e. when it does not
follow the I/E-law. This effect influences the epithermal activation response,
and its magnitude is obviously determined by:
- nuclear reaction parameters, namely the ratio of the epithermal-to-thermal
cr0ss-section (i.e. QO, which influences the contribution of epithermal
response), and the energy-position of the neutron resonances ;
- experimental conditions, namely the thermal-to-epithermal flux ratio (also
influencing the contribution of the epithermal response), and - evidently -
the actual extent of deviation from the I/E-law.
In our search for a simple experimental technique to correct for this
effect with an accepnable accuracy, we have adopted the approach of Ryves
et el. /18, 19/, representing the epithermal neutron flux distribution 7y
~ ( E ) % I/E I+~, with ~ independent of E. Strictly associated to this concept
is=the introduction of the effective resonance energy Er' to a first approxi-
mation considered as s-independent :

inEr = ~ I Zi w i In Er, i (units eV) (6)

9 2
i 9
wlth w i = (gF~,Fn/F)i/Er i' g belng noW the statistical weight factor. Based
on these appr6xlmatlons'one arrives at the conversion formula :

148
 F. DE CORTE et al.: ACCURACYAND APPLICABILITY

Q0(~) = (~-0.429)/(Er)~ + 0.429/ [(2~ + i)(0.55) e] (7)

and this is the corrected Qo(~)-factor which figures in Eqs (I) and (3).
Postponing for a moment the discussion on_the accuracy of the Qo/Qo(~)
converffion, i.e. the accuracy of the I/E I+~ - E concept, it is clea9 that
two additional parameters should he known : thernuelear constant Er' and the
neutro__n flux parameter ~.
E -values can be calculated from Eq. (6), with the introduction of liter-
ature ~ata foX the relevant resonance parameters. Ryves' papers /18,19/ con-
taining only Er's for a few isotopes, Moens et al. /20/ calculated values for
96 (n,y) reactlons, based on the 1973-edition of BNL-325 /21/. At the present
MTAA-7/1986 Conference, Jovanovic et al. /22/ are presenting an updating and
extension for 127 (n,y) reactions, based on the recent compilations of Mughabg-
hab et al. /13,14/ and including a discussion of accuracy.
The parameter ~ should be experimentally determined, and simple tech-
niques have beendeveloped /5/, namely the "Cd-covered multi-monitor" method,
the "Cd-ratio for multi-monitor" method and the "bare multi-monitor" method.
In the latter, suited for instantaneous ~-determination, the minimum number
of monitors is three, and the use of ~Zr-96Zr-197Au has been proposed /5/,
with the Zr-pair serving at the same time for f-monitoring. At the present
MTAA-7/1986 Conference, Simonits et el. /7/ deal extensively with the use of
Zr as an e- and f-monitor, emphasizing recent accurate remeasurements of the
input nuclear data.
.+Let us consider now the crucial question of the accuracy of the adopted
I/E l ~-Er approximations. Although much can be said theoretically/23-26/,

Table 1
,,Standard" monitors and nuclear data for use in the "Cd.ratio for multi-monitor" method for a-determination. Er
and Q0 values are based on MUGHABGHABet al.13,~4 Fcd=Cd-transmissiongfactor for epithermal neutrons, to
be multiplied with RCd

Monitor Er, eV Q0 T

197Au(n,y) 198Au 5.65 + 0.40 15.71+0.28 2.695 d

(Fcd=~991 )
238u(n,7)239U 16.9 + 0.2 103.4+1.3 23.50 min
/239Np
2. 355 d
232Th(n,T)233Th 54.4 + 0.5 11.53 + 0.42 22.3 rain
/233pa
27.0 d
59Co(n,~60Co 136+ 7 1,990+0.054 5.271 y
98Mo(n,7)99Mo 241 + 48 53.1+3.4 66.02 h
/99mTc 6.02 h
55Mn(n,y)56Mn 468 + 51 1.053 + 0.028 2.5785 h
100Mo(n,T)lOIMo 672 + 94 18.84 + 0.81 14.6 min
/IO1Tc 14.2 min
64Zn(n,y)65Zn 2560 --
+ 260 1.908 + 0.094 244.0 d
I q

149
F, DE CORTE et al.: ACCURACY AND APPLICABILITY

9it looks more conclusive to consider it from a practical point of~view. Re-
cently we have performed e-determinations, based on the "Cd-ratioifor multi-
monitor" method /5/, in 5 irradiation positions of three differens reactors
with a largely diverging neutron thermalization : channel "MILA" in the WWR-
M reactor, channels 14, 7 and 16 in the THETIS reactor and channel R4V4 in
the DR-3 reactor. We have introduced the use of 8 suited monitors, for which
the adopted nuclear data (E , Q , T ) - to be considered as "standard" data
0 12
for this application - can ~e assume~ to have an acceptable accuracy (see
Table I).
Fig. I shows for each channel one example of the ~-results obtained with
197Au-23eU-9~Mo-l~176 The adequacy of the linear fits is expressed as

(og E'r" *c
I R C # - I ) Oo(~<1
WWR -M / CH. MILA
, .,=o.o,,;o.o,o _ x:=~
n-APR-85 ~ f = 36.01 ti3,112 "

r1620.0298.t 0 0 THETIS CH.I/,

0~-JAN-86 - ~ r= 9 089 , "z'. "

._z 0 4 - J U L - 8 5 ~ ~~n
3~35'~ " ~ I ~ ~ ~ X2 =O.~,TO

~ 0.00.

_o2.JuL.ss~o~ i ~P'~'''-" x~=

197Au 23BU 98Mo IOOMo B&Zn

"1 ,I I . I .I, . I I
1.0 2,0 3.0 I~ Er
Fig. 1. Experimental a,determination in Various channels of the WWR-M reactor (Budapest), the THETIS reactor
(Gent) and the DR-3 reactor (Risb). Use is made of the ,,Cd-rafic for multi-monitor" method (5) with some
,,standard" monitors and nuclear data of Table 1

150
 F. DE CORTE et al.:ACCURACY AND APPLICABILITY

2 l E ; averaging over the 5 channels one obtains = 0.904.

~ = ~:~ i\ si/ g-~
Note that the acceptability of the linear [log (Rcd_I)Q0(~)
r versus log Er ]
plots, with slope -~, corresponds to the acceptability of the @~(E) % I/E I+~
approximation. Although the linearity seems to hold for the 5 different chan-
nels, this does not absolutely guarantee the accuracy of 6he 5 ~-results,
which might be subject to a systematic error caused by the choice of the moni-
tors. Therefore Fig. 2 shows as an example for one of the considered channels,
a comparison of ~-results obtained on the one side with the above mentioned
monitors, on the other hand with the set 197Au-23aU-2a2Th-59Co-SSMn. For the
monitors of the latter set, there is even better reason to believe in the
accuracy of the relevant nuclear data. The negligible ~-difference revealed
in Fig. 2 is considered as a final proof for the accuracy of the ~-values,
i.e. of the I/EI+~-E approximations. Nevertheless, it is interesting to turn
now to practlce, and to check the accuracy of the Q0/Qn(~) converslon itse f
[Eq.(7)] , based on ~-determinations as described above: Probably the most
striking example is the determination of Q0-values from Rcd-measurements
(which primarily yield Q0(~) values) for the 94Zr(n,y)~SZr and 96Zr(n,y)97Zr
reactions [see Simonits et al./7/ at the present MTAA-7/1986 Conference]. The

Er- ~
log
(Rcd- I) Qo(~)

1 _z o 1
._
-- 04- JUL-1985 r *

I ~,,,~ THETIS CH,?

X~ 1852

199Au 238u 232Th 59Co 98Mo 55Mn100Mo 6/,Zn

i F I I I I t I.
1.0 2.0 3~ log Er

Fig. 2. Check of the accuracy of the ~-determination in channel 7 of the THETIS reactor (Gent) by using two
different "standard" monitor sets

151
F. DE CORTE et al.: ACCURACY AND APPLICABILITY

Table 2
Qo-values determined in 5 channels/3 reactors, based on ~-determinatinn according to the
"Cd-ratio for multi-monitor" method. "Qo" is obtained without any correction for

Reactor Channel 94Zr(n,y)95Zr 96Zr(n,y)97Zr

"Qo" Q0 "Q0" Q0

WWR-M "MILA" 5.53 5.34 + 0.64 251 245 + 26

THETIS 14 4.32 5.15 + 0.27 224 251 + 30
7 3.23 5.O2 ~ 0. t6 ]82 243 ~ 6
16 3.16 5.10 ~ 0.23 185 254 ~ 8
DR-3 R4V4 I. 88 4.97 + 0.22 127 251 + 7

-values are 338 eV for 96Zr(n,%) and 6260 eV for 9~Zr(n,7). Thus, these de-
r .
termlnatlons . are especlally
. . challenglng
. . the latter
for . reactlon, slnce It h as
to be assumed that the validity of the I/E I+~ approximation, shown to hold
up to 2560 eV [E_ (64Zn)], can be extrapolated to ~ 2.5 times higher neutron
energy. Without ~oing into detail, the final results of repeated determina-
tions are listed in Table 2, and the consistency of the results, after cor-
rection for ~, is striking.
Two practical remarks: ~/ ECd should be = 0.55 eV, especially for low-
QO monitors (Mn, etc.)/5/; thus, one should stick as close as possible to the
prescription: a quasi-point source centered in a large cylindric Cd-box with
I mm wall thickness and height/diam.= 2. B/ one should avoid different neu-
tron thermalization by polyethene spacers etc. in the containers for bare
and Cd-covered irradiation.
The propagation formula of the uncertainty on ~ towards the analytical ~
results has been given in a previous paper /3/. The residual uncertainty is
of course dependent on the flux parameters and on the isotope under conside-
ration, but on the average it amounts to ~ 2%. The residual uncertainty on
the analysis result, caused by the f-determination, was shown /27/ to be of
the order of 1.5%. A negligible residual uncertainty is induced by E , which
is, for isotopes with medium and high Q0-factors, usually known to w~thin 10%
accuracy.

Small source-detector separations and/or extended source geometries

When measuring samples with quasi-point geometry at large distance to a Ge-
detector (say 15-20 cm), the sn-values to be introduced in Eq.(1) can simply
be taken from a "reference" efficiency curve (log gp versus log ~ ) , which is
experimentally determined at this distance with callbrated and rezative point
. . . . 152 Z26 60 133 137
sources. A posslble set is for znstance Eu, Ra, Co, Ba, Cs,
57Co ' S4Mn ' S8y, Z41Am ' 182Ta ' 11~ 24Na, 72Ga and 22Na, yielding informa-
tion from ~ 55 keV to ~ 3000 keV with an uncertainty of I-2%, except in the
extremely low and high energy region. This uncertainty is somewhat reduced
(~ay to ~ I%) in the analysis results (dependSng on the difference between
E~ and Ey), since Eq. (I) contains only the ~p/~p-ratio.
In many practical applications, the gp,ref-eurve is no longer valid be-
cause use is made of small source-detector separations, where corrections for
true coincidence of cascade gamma-rays are needed as well, and/or of extended
source geometries, where moreover corrections for gamma-attenuation are ne-
cessary.

152
 F. DE CORTE et al,: ACCURACY AND APPLICABILITY

The solution of the true-coincidence problem was extensively dealt with

in Refs. /27,28/, was illustrated at the MTTA-6/1981 Conference /29/. It is
sufficient to mention here that, experimentally, the proposed method requires
only the determination of the peak to total curve (log P/T versus log E was
shown to be linear) with some mono-ga~mm emitters like 203Hg, 137Cs andY65Zn.
It was shown previously /2/ that, after correction for true-coincidence ef-
fects (which can be as high as 30%), the residual uncertainty on the analysis
results is of the order of 1.5%.
Conversion of e f values to other counting configurations, including
correction for g ~ m m ~ e n u a t i o n , has been worked out by Moens et al. /31,32/
both for Ge(Li) and HPGe detectors. The procedure is available as the com-
puter code SOLANG. Its applicability is bound to the following conditions :
I) The detector body must be cylindric and concentric with its housing, and
its geometric parameters must be known. This means in practice that, so as
to reach ~ 2% accuracy on the efficiency conversion, the detector diameter
should be known within I-2% whereas for the other parameters (detector
height, p-core dimensions, etc.) an uncertainty of 10-20% can betolerated;
the detector-Al window distance should be known to within 0.! man.
2) The method applies to cylindrically symmetrical sources (cylinders, disks,
points) with a rotation axis coincident with the detector axis and a ra-
dius less than or equal to the detector radius. The source-Al window dis-
tance should be measured to within 0. I mm. The source eomposition with
respect to the major elements should be known approximately.
3) The thickness and major element composition of all absorbing layers inter-
posed between the source and the ~eteetor body should be known (n-layer,
Al-window, polythene or plexiglass holders, etc.)
As to conditions 2) and 3) : in our practice dealing with a large variety
of samples with different chemical and physical structure, not any insuperable
situation has been encountered which was obstructing the applicability of the
ep-conversion. Much more serious is condition I) : the use of a cylindrical
detector with known geometric configuration. Since 1981, efforts have been
made to convince manufacturers about the need for this type of Ge-detectors;
this campaign involved a'INW/KFKI-Report /33/ sent to the different firms, a
paper by Moens et al. /34/ in the framework of the International Committee
for Radionuclide Metrology, and a good deal of discussions with company-repre-
sentatives. Obviously, these efforts were fruitful, since cylindrical detec-
tors with specified dimensions are nowadays available at a price hardly excee-
din~ that for other detectors of comparable quality. If such a detector is put
into operation, it is advised - according to our experience - to check the
e -conversion by counting some mono-gamma points sources (from low to high
P a t large and small distance to the detector. Minor differences between
Ey)
the measured and the calculated eD-ratios can then be easily eliminated by
slight adjustment - some trial anH error - of the specified data for the de-
tector-Al window distance and detector diameter.
It has been proved previously /31, 32/ that, if the above conditions are
ful filled, the residual uncertainty on the analytical results, originating
from experimental determinations (at reference distance) and from conversion
of s can be kept on the average as low as % 2%, and does not exceed 3-4%
for heavy counting geometries.

Isotopes with gWESTCOTT # I

Since the k0-methodology is written in the H~gdahl convention, inclusion of

(n,y) reactlons which do not exactly obey the ~(v) ~ I/v law up to I-2 eV will
lead to inaccuracies, the importance of which is related to the deviation of

153
 F, DE CORTE et al.:ACCURACY AND APPLICABILITY

the Westcott g-factor from unity. More precisely, the estimation of the error
introduced should be based on the variation of g with neutron temperature,
rather than on the g-value itself, and it is interesting to demonstrate this
statement in a simplified way with the example of 197Au(n,y) ISSAu, the ulti-
mate comparator. In general, a recommended k 0 ~_U -factor is the average of de-
terminations in several channels of the WWR-M and THETIS reactors, with neu-
tron temperatures from e.g. 20 to I00~ Thus, according to Ref./35/, gAu is
ranging from 1.0038 to i~0068. This variation of 0.3% (well within the expe-
rimental uncertainty) is - roughly speaking - transferred to the k O Au(eXp)
values. Hence, the average recommended k 0 A -factor is approximatel~ corres-
ponding to an average neutron temperature'o~ 60~ with gAu = 1.0053. If this
k^ 9 -factor is now used in an actual analysis at a neutron temperature he-
t~ 20 and 100~ the committed error on the resul~ing concentration turns
out to be maximum 0.15%, which is negligible. Similar cases are for instance
109 A
g(n,y) 11om~g~ 133 Cs(n,y) 134 Cs, I~8 Ba(n,y) I 3 9 ha, 181 Ta(n,y) 182 Ta, I8S W(n, )
187
W, 1 8 5 Re(n, T) ~ 8 6 Re, 2 3 2 Th(n,y) 2 3 3 m.h and 2 3 8 U(n,y) 2 3 8 U.
A somewhat more serious situation occurs for reactions like ~~
(see Table 3) with g-factors deviating a few percent from unity. Here, errors
of the order of I-2% are to be expected, which is still acceptable.
From analytical standpoint there are two cases where the g-factor is
drastically deviating from unity~ and thus significant errors will be commi-
ted : 1~IEu(n,y) and especially 176Lu(n,y) (see Table 3). In principle, de-
termination of Eu and Lu can also be performed via the iS~Eu(n,y) IS~Eu and
175 176m 9 .
Lu(n, T) Lu reactlons (for whlch recommended k0-factors are avallable).
However, for instance in non-destructive NAA of geological material, measure-
ment of 154Eu and 176mLu gives rise to poorer precision or even to a complete
loss of quantitative information (inherent poorer sensitivity for 154Eu; short
half-life and low gamma-energy for 176mLu), and this is - especially for the
rare earths - a regrettable situation.
Although up to now we have not performed any experimental work related to
the above problem, the solution is straightforward: one should change over to
the Westcott-convention, including a neutron temperature monitoring. The lat-
ter can be accomplished by the well-known technique of Lu-irradiation in two
irradiation positions: the one under investigation and a reference position
with known temperature. Note that this relative measurement was formerly re-
commended because of the uncertainty of the knowledge regarding the cross-
section for 176Lu(n,y)177Lu and the 177Lu decay scheme. In view of the recent-
ly re-evaluated data of interest [oQ = (2090+70) barn /14/; I0 = (1087+40) barn
/14/; y (208 keV) = (11.0+O.4)% /44f3, it might be interesting to expl~re the
possibility of an absolute T-monitoring with acceptable accuracy.
Finally, it is worthwile to dwell on the situation arising when a neu-
tron temperature monitoring would be performed. Since Lu would he coirradia-
ted, it can serve as a relative standard for Lu-determination, and the compli-
cation of T-monitoring and changeover to the Westcctt-convention is then only
necessary for the 151Eu(n,y) reactions. However, if recommended k~-factors
would be available for 152m Eu and 152 Eu (again, as above for Au, ~or T = 60 o C
and g = 0.8532), it appears from the g-factors of Table 3 - and follo~ing the
same reasoning as outlined above for Au - that the maximum committed error on
the Eu-concentration would be ~ 4.5%, which is in most cases acceptable for
chondrite normalization. Thus, it seems justified to determine the ~s2mEu and
~52Eu k0-factors, which - although physically not very meaningful - will lead
to reasonably accurate analytical results.

154
 F. DE CORTE et al.: ACCURACY AND APPLICABILITY
Table 3
Isotopes for which application of the ko-method gives rise to small or significant errors (see text);
(a) = WESTCOTT/36/, (b) = GRYNTAKIS et al./35/, (c) = ENDF/B-V/37/,
(d) = MOENS/38/, (e) assumed to show a limited deviation from g (20 ~

Isotope Isotope
measured measured 100~
20*C 100*C 20~

Subject to I-2% errors (e)

188(m)Re 0.9819 (c)
104(m)Rh 1.023 (a) 1.041 (a) 1921r 1.0326 (b) I. 0425 (b)
ll6mln 1.0175 (b) 1.0321 ( b ) 1941r 1.0218 (b) 1.0400 (b)
154Eu 1.0290 (b) 1.0074 (b)
subject to significant errors
165(m)Dy 0.9876 (c) (e)
169yb 1.050 (d) 1.092 (d) 152mEu 0.8936 (b) 0.8183 (b)
176mLu 0.9766 (c)
(e) 152Eu 0.9022 (b) 0.8336 (b)
186Re 1.0049 (e) (e) 177Lu 1.6914 (b) 2.2421 (b)

Table 4
Some important primary interferences in comparator-type and absolute NAA;
crosS-section data from MUGHABGHAB et al./13/(o0, Io) and CALAMAND/39/(~-; + estimated);
* - from THIS WORK; ** - from Ref./40/; *** - based on Q0 from Ref./41/

formed by
Produced
(n,y) (n,2n)
isotope
8, % ~0' barn I0, barn Er' eV 8, % ~, barn 8, % ~, barn

77mse 9.0 22 17 577 7.6 0.733 23.6 0.00018+

87msr 9.86 0.77x 3.17 795 7.00 0.112 82.58 0.00011+
lllmcd 12.49 0.14 3 125 12.80 0.228 24.13 0.00042
ll7msn 14.53 0.00596x 0.336m 128 7.68 0.095~m 24.22 0.00080+
135mBa 2.417 0.053 2.96~ 115 6.592 0.30~ 7.854 0.0011+
137%a 7. 854 O.OLO 0.68~x~ 545 11.i3 0.225 71.70 0.0024

Primary interferences
A problem inherent to many types of single-comparator NAA-standardization is
the ~ccurrence of primary interfering reactions of the type (n,n') and (n,2n),
causing a positive error if not corrected for. Some cases of practical impor-
tance are listed in Table 4, together with the relevant data for the isotopic
abundances and cross-sections.
The (n,n') interferences for 117msn and 135mBa were for the first time re-
cognized and elaborated during the course of our work. The (n,n') and (n,y)
cross-section values for the production of 135mBa were experimentally deter-
mined in exactly the same way as described previously for ~ T m s n /40/.
Table 5 shows the contribution from (n,y), (n,n') and (n,2n) to the ob-
served activity, for irradiation in three channels of reactor THETIS with

155
F. DE CORTE et al.: ACCURACY AND APPLICABILITY

Table 5
Contribution of (n, 7), (n, n') and (n, 2n) to the formation of TTmse, aTmsr, lllmCd, 11~mSn, laSmBa and
1a 7tuBa in three channels of reactor THETIS
...

THETIS Channel
Produced Formed 17 f 5
isotope by r162 = 15 Os/r = 42 r162 = 158
@s/r f = 1.6 ~s/r = 21 r162 = I18
= -0.028 = 0.052 = 0.11

77mse (n,y) 98.4% 99.87% 99.98%

(n,n') 1.6% 0.]3% 0.02%
(n,2n) ~0.001%

87msr (n,y) 95.3% 99.5% 99.91%

(n,n') 4.7% 0.5% 0.09%
(n,2n) ~0.0005%
F
: 1 t lmcd (n,y) 71.6% 94.6% 98.7%
(n,n') 28.3% 5.4% 1.3%
(n,2n) 0.1%

1]7msn (n,y) 49.5% 83.2% 94.3%

(n,n') 49.2% 16.3% 5.6%
(n,2n) 'M .3% 80.5% ~0.1%

135tuBa 35.1% 73.4% 90.2%

(n,%)
(n,n') 64.6% 26.5% 9.8%
(n,2n) '~0.3% ~0.1%

137tuBa (n,y) 23.0% 57.0% 80.7%

(n,n') 72.1% 40.3% 18.1%
(n,2n) 4.9% 2.7% 1.2%

low, medium and high thermalization. It is clear that the formation by (n,2n)
is negligible, except for 137mBa and for 117msn in a very hard neutron spec-
trum. On the other hand, the (n,n') interference is indeed a serious obstacle,
except for 77mse and 87msr. Nevertheless, corrections can of course be ap-
plied on condition that the fast flux component is known or is exPerimental-
ly determined; this cannot be considered as a serious restriction, sinc~ ~ -
monitoring is often necessary in N A A - whatsoever the standardization Fro--
cedure - so as to enable corrections for interfering (n,p) or (n,a) reac-
tions. In some favorable cases (high flux, low thermalization) it is in prin-
ciple possible to use Zr as a fast-flux monitor.Recently, the 238U spectrum
averaged cross-section for the reaction 9~ SgZr has been accurately
determined by two research groups, namely Sekine and Baba /42/ [(0, I04 +
0.005) mbarn] and Mannhart and Fabry /43/ [(0.103 + 0.004) mbarn]; 0the~ re-
lated nuclear data are : MZ~ = 91.22 ; @ (S~ = ~51.45 + 0.02)% /12/;
T (SSZr) = (78.43 ~ 0.08)h 744/; y (909.1 keV) (99.04_+--0.03)% /44/.

156
 F. DE CORTEet al.: ACCURACYANDAPPLICABILITY

Anyhow, a warning should be given concerning the obtainable accuracy of the

correction for (n,n') interferences, indeed, in v i e w o f the relatively low
threshold energy for (n,n') reactions, distortion of the fission sp4c~rum at
the low-energy side will lead to significant errors. Since this distortion
is mainly due to thermalization, the accuracy will, fortunately, be better
for hard neutron spectra - where the correction is the highest.
Apart from the above considerations, it should be realized that for the
determination of Se, St, Cd. Sn and Ba other alternativqs.exist : e.g. via
7s~=~, 8SSL,_lls~=Iz~sm~_~ut ~ul
~L~, 11~m~l117~='11Smln/11Sln,~j 11~m)sn/ll3mIn, 12Zmsn,
125 Sn, 131Ba~ 133mBa, l~gBa.

Subsequent (interrupted) irradiations

When performing N subsequent irradiations (I, 2, ... i .... N), the simple
equation for concentration calculation [(Eq. I)] is no longer valid. However,
on condition that the flux characteristics remain constant during each indi-
vidual irradiation, extension of the equation is simple. One should make a
distinction between the following situations :
A. flux characteristics (#s' f' ~) remain constant from irradiation to irra-
diation, i.e. ~s i = ~ fi = f and ~. = e. It suffices then to keep the
same comparator ~ith ~e sample durin~ the N irradiations, and to perform
one measurement of the accumulated activity. Eq.(1)can thus be transfer-
reed to :
Np/t m
CW Z S. D.
i l z 1 f + O~(cO E
P (8)
f + q0(~) " ep
O'ppm :{kCwiNp/tm
Z S Di)~ " ko0 "
\ i

B. flux characteristics (r f, ~) differ from irradiation to irradiation.

Then, one should coirra~iate each time new monitors, which should be mea-
sured individually, and the concentration calculation is performed as :

Np/tm 1 1 [E [A:p,i Si Di fi+Q0(~i ) __/__I]] -I

9 ~ . x (9)
0,ppm = cw " k0 Ep i fi+Q:(~i ) ep, I

Note that it is even not necessary to measure the single comparator eve-
r~ time in the same counting position; if it is done, then of course e~ =
Ep. p,i

No significant loss of accuracy will be induced on condition that proper

care is taken about the experimental work, which is of course more extensive
in situation B.

Non-constancy of neutron flux during irradiation

When during irradiation significant variations occur in the neutron flux (and
supposing that f and ~ remain constant), one should replace Eq.(1) by :

157
F. DE CORTE et al.: ACCURACY AND APPLICABILITY

Np/tm .......

WDC~0 tirr %(t'tirr) O E

F(t)%e dt f+Q~(~)
I p
(I0)
0,ppm = Np/t m " ~00 " f+Q0 (~) " ~p

cy0tirr ~(t-t. ~)
wD F(t)~e ir~ dt

where F(t) is the time-dependent neutron flux function. If F ( t ) i s indeed va-

riable, it should be introduced in Eq. (10), except for T = T x (which is the
case in classical relative standardization).
So as to have an idea about the inaccuracy caused by flux variations, it
is interesting to consider for instance a 10% linear flux increase during ir-
radiation, i.e. F(t) = F~ (I + 0.1 t/t. ). The % error induced by not ta-
9 irr
king into account this e~fect is then glven by :
Sx I00
%E= (~--B) x--~ (11)
with [S + 0. I (I-S/I tirr) ] ~
B = [S + 0. I (I-S/% tirr) ]

If Au (19SAu, T = 2.695 d) is used as the comparator for the determina-

tion of AI, Mn, Sb, Fe and Co, one obtains for t. = 7 h:
irr
AI[ZSAI ; T = 2.240 min] : %E = +4.6%
Mn[SGMn ; T = 2.5785 h ]: %E = +1.4%
Sb [t22Sb ; T = 2.70 d ]: %E = -1.1.10-4%
Sb [Iz~Sb ; T = 60.20 d ]: %E = -5.7.10-2%
Co [6~ ; T = 5.271 y ]: %E = -9.2.10-2%
The above results indicate that the effect should not be overdramatized. Any-
how, when a serious flux variation is presumed - and since F(t) is generally
not known, thus not allowing a correction - the constancy of the neutron flux
during irradiation is to be considered as the very limiting condition of ap-
plicability for any comparator-type or absolute standardization method. For-
tunately, the irradiation positions in most research reactors show a suffi-
cient stability with respect to neutron flux.

Final account of the accuracy

As a final conclusion of the above discussion with respect to the accuracy of

the k0-standardization, some grand mean can be instructive. Table 6 gives the
contrlbutions to the uncertainty on the analysis results, caused by the dif-
ferent relevant parameters, in not too extreme conditions of irradiation and
counting and for (n,y) reactions with medium Qo-values and with no special
difficulties (n,n' interferences, gwestcott # I, etc.). Following the recom-
mendations of the BIPM Working Group on the Statement of Uncertainties /45,
46/, quadratic summation leads to an overall uncertainty of less than 4%.
When comparing this to classical relative standardization, one should be a-
ware of the fact that also in the latter many practical problems are present.
Two of these are interesting to mention :

158
 F. DE CORTE et al.: ACCURACY AND APPLICABILITY

Table 6
Final account of the accuracy of k0-standardization in NAA; the overall uncertainty is obtained by quadratic
summation of the individual contributions

Uncertainty on analysis results

induced by contribution

k0 i%

Q0
2%
f 1.5%
eoine, corr. 1.5%
e -measur. and 2%
P conversion

Overall ~ 3.8%

- the general problem of how to prepare a standard with accurately known com-
position. According to our experience, systematic errors due to non-stoi-
chiometry of compounds or caused by pipetting of small volumes are no ex-
ception; they were detected and eliminated by our cooperative but indepen-
dent k0-determinations ;
- the problem of how to find or to prepare a standard suited for the analysis
of bulky samples which are measured close to the detector. Different Sp and
gamma-attenuation imposes in fact the same type of conversions as outllned
in the present paper.
Finally, it can be mentioned that the above estimated overall uncertain-
ty of < 4% was confirmed by actual analyses of various (standard) reference
materials /8, 47, 48/, showing at the same time the practical applicability
of the k0-standardization method.

The authors are highly indebted to L. MOENS (Gent), A. ELEK, E. SZABO (Budapest), K. HEYDORN, L. H.
CHRISTENSEN, J. JAKOBSEN, E. DAMSGAARD and U. JACOBSEN (Ris6) for their help in various ways. ~lanks
are due to M-L. MUNGHEN for the typographical work. The financial support of the Belgian National Fund for
Scientific Research is gratefully acknowledged.

References

1. A. SIMONITS, F. De CORTE, J. HOSTE, J. Radioanal. Chem., 24 (1975) 31.

2. A. SIMONITS, L. MOENS, F. De CORTE, A. De WISPELAERE, A. ELEK, J. HOSTE, J. Radioanal. Chem., 60
(1980) 461.
3. L. MOENS, F. De CORTE, A. De WlSPELAERE, J. HOSTE, A. SIMONITS, A. ELEK, J. SZABO, J. Radioanal.
Nucl. Chem., 82 (1984) 385.
4. O. T. HIDGDAHL, Report MMPP-226-1 Dec. 1962.

159
F, DE CORTE et al.: ACCURACY AND APPLICABILITY

5. F. De CORTE, K. SORDO-EL HAMMAMI, L. MOENS, A. SIMONITS, A. De WISPELAERE, J. HOSTE, J.

Radioanal. Chem., 62 (1981) 209.
6. A. SIMON1TS, F. De CORTE, J. HOSTE, J. Radioanal. Chem., 31 (1976) 467.
7. A. SIMONITS, F. De CORTE, A. De WlSPELAERE, J. HOSTE, paper presented at the MTAA-711986
Conference, Copenhagen, June 1986.
8. LIN XILEI, F. De CORTE, L. MOENS, A. SIMONITS, J. HOSTE, J. Radioanal. Nud. Chem., 81 (1984) 333.
9. A. SIMONITS, F. De CORTE, A. De WISPELAERE, K, HEYDORN, L. CHRISTENSEN, in preparation.
10. T. ELNIMR, F. De CORTE, L. MOENS; A. SIMONITS, J. HOSTE, J. Radioanal. Chem., 67 (198 I) 421.
11. F. De CORTE, A. SIMONITS, A. De WISPELAERE, J. HOSTE, A compilation ofko -factors and related nuclear
data for 94 radionuclides of interest in NAA, INWfKFKI Interim Report 1986.
12. P. De BI'EVRE, I. L. BARNES, Intern. J. Mass Spectrom. Ion Processes, 65 (1985) 211.
13. S. F. MUGHABGHAB, M. DIVADEENAM, N. E. HOLDEN, Neutron Cross Sections, Vol. 1, Neutron
Resonance Parameters and Thermal Cross Sections, Part A: Z = 1-60, Academic Press, N.Y., 1981.
14. S. F. MUGHABGHAB, Neutron Cross Sections, Vol. 1 Neutron Resonance Parameters and Thermal Cross
Sections, Part B : Z = 61-100, Academic Press N.Y., 1984.
15. G. ERDTMANN, W. SOYKA, The Gamma Rays of the Radionuclides, Verlag Chemie, Weinheim]New York,
1979.
16. L. MOENS, A. SIMONITS, F. De CORTE, J. HOSTE, J. Radioanal. Chem., 54 (1979) 377.
17. A. SIMONITS, F. De CORTE, T. ELNIMR, L. MOENS, J. HOSTE, J. Radioanal.Nuel. Chem., 81 (1984) 397.
18. T. B. RYVES, E. B. PAUL, J. Nucl. Energy, 22 (1968) 759.
19. T.B. RYVES, Metrologia, 5 (1969) 119.
20. L. MOENS, F. De CORTE, A. SIMONITS, A. De WlSPELAERE, J. HOSTE, J. Radioanal. Chem., 52 (1979)
379.
21. S.'F. MUGHABGHAB, D. I. GARBER, Neutron Cross Sections, VoI. 1, Resonance Paramters, BNL-325, June
1973.
22. S. JOVANOVIC, F. De CORTE, A. SIMONITS, L. MOENS, P. VUKOTIC, J. HOSTE, paper presented at the
MTAA.711986 Conference, Copenhagen, June 1986.
23. S. JOVANOVIC, F. De tORTE, L. MOENS, A. SIMONITS, J. HOSTE, J. Radioanal. Nucl. Chem., 82 (1984)
379.
24. J. Op de BEECK, J. Radioanal. Nucl. Chem., 89 (1985) 169.
25. J. Op de BEECK, J. Radioanal. Nucl. Chem., 90 (1985) 167.
26. F. De CORTE, L. MOENS, S. JOVANOVIC, A. SIMONITS, A. De WISPELAERE, J. Radioanal. Nucl. Chem., in
press.
27. L. MOENS, Ph.D. THESIS, University Gent, 1981.
28. LIN XILEI, Ph.D. Thesis, University Gent, 1981.
29. L. MOENS, F. De CORTE, A. SIMONITS, LIN XILEI, A. De WISPELAERE, J. De DONDER, J. HOSTE, J.
Radioanal. Chem., 70 (1982) 539.
30. L. MOENS, P. ROOS, A. De WISPELAERE, J. HOSTE, in preparation.
31. L. MOENS, J. De DONDER, LIN XILEI, F. De CORTE, A. De WlSPELAERE, A. SIMONITS, J. HOSTE, Nucl.
Instr. Methods, 187 (1981) 451.
32. L. MOENS, J. HOSTE, Int. J. Appl. Radiation Isotopes, 34 (1983) 1085.
33. F. De CORTE, L. MOENS, A. SIMONITS, The need for cylindrically shaped Ge(Li) and HPGe detectors with
well-defined geometric parameters, INW/KFKI Report, Dec. 1981.
34. L. MOENS, K. DEBERTIN, Nucl. Instr. Methods in Physics Research, A238 (1985) 180.
35. E.M. GRYNTAKIS, J. I. KIM, Radiochim. Acta, 22 (1975) 128.
36. C. H. WESTCOTT, Effective Cross Section Values for Well.Moderated Thermal Reactor Spectra, Report
CRRP-960 of the AECL, November 1, 1960 (reprinted 1962).
37. B. A. MAGURNO, R. R. KINSEY, F. M. SCHEFFEL, Guidebook for the ENDF]B-V Nuclear Data Files,
Topical Report BNL-NCS-31451, July 1982.
38. L. MOENS, private communication
39. A. CALAMAND, in: Handbook on Nuclear Activation Cross-Sections, IAEA Technical Reports Series No. 156,
IAEA, Vienna 1974.
40. F. De CORTE, L. MOENS, A. SIMONITS, A. De WlSPELAERE, J. HOSTE, J. Radioanal. Chem., 79 (1983)
255.
41. R. Van Der LINDEN, F. De CORTE, J. HOSTE, in: Nuclear Data in Science and Technology, Vol. II,
IAEA-SM-170/31, 1973, p. 241.

160
 F. DE CORTE et al.: ACCURACY AND APPLICABILITY

42. T. SEKINE, H. BABA, J. Inorg. Nucl. Chem., 43 (1981) 1427.

43. W. MANNHART, A. FABRY, in: Progress Report on Nuclear Data Research in the Federal Republic of
Germany, Report NEANDC(E)-262U Vol. V, 1985, p. 58.
44. D. C. KOCHER, Radioactive Decay Data Tables, Report DOEfflC-11026, 1981.
45. R. KAARLS (Rapporteur), Report of the BIPM Working Group on the Statement of Uncertainties (1 st meeting:
21-23 Oct. 1980) to the Comit~ International des Poids et Mesures.
46. J. W. Miiller, in: Precision Measurements and Fundamental Constants 11 B. N. TAYLOR and W. D. PHILLIPS
(Eds), Natl. Bur. Stand. (U.S.) Spec. Publ. 617, 1984, p. 375.
47. F. De CORTE, A. DEMETER, LIN XILEI, L. MOENS, A. SIMONITS, A. De WlSPELAERE, J. HOSTE,
Isotopenpraxis, 20 (1984) 223.
48. L. MOENS; F. De CORTE, A. SIMONITS, J. HOSTE, Proc. 5th Intern. Conf. on Nuclear Methods in
Environmental and Energy Research, J. R. VOGT, (Ed.), Mayaguez/Puerto Rico, CONF.840408, April 1984, p.
527.

11 161