DK1838 - ch07 Chapter 7 (Seven) Handbook of X Ray Spectrometry

7
Radioisotope-Excited X-ray Analysis
Stanislaw Piorek*
Niton Corporation, Billerica, Massachusetts
I. INTRODUCTION
Radioisotope x-ray uorescence (XRF) and x-ray preferential absorption (XRA) techni-
ques are used extensively for the analysis of materials, covering such diverse applications
as analysis of alloys, coal, environmental samples, paper, waste materials, and metalli-
ferous mineral ores and products (Rhodes, 1971; Rhodes and Rautala, 1983; Watt, 1978
and 1983; Watt and Stener, 1985; Piorek 1997). Many of these analyses are undertaken in
the harsh environment of industrial plants and in the eld. Some are continuous on-line
analyses of material being processed in industry, where instantaneous analysis information
is required for the control of rapidly changing processes.
Radioisotope x-ray analysis systems are often tailored to a specic but limited range
of applications. They are similar and often considerably less expensive than analysis
systems based on x-ray tubes, but these attributes are often gained at the expense of
exibility of use for a wide range of applications.
Operators making analyses in the eld or in industrial plants are usually less skilled
than those working in the laboratory with x-ray tube systems. Manufacturers of radio-
isotope x-ray analysis systems compensate for this by producing simple semiautomated or
fully automated systems whose output, calibrated for the specic application, is given
directly in terms of concentrations of elements required or in terms of a simple pass=fail-
type decision.
Radioisotope x-ray techniques are preferred to x-ray tube techniques when simpli-
city, ruggedness, reliability, and cost of equipment are important, when minimum size,
weight, and power consumption are necessary, when a very constant and predictable x-ray
output is required, when the use of high-energy x-rays is advantageous, and when short
x-ray path lengths are required to minimize the absorption of low-energy x-rays in air.
Also of signicant analytical importance is the fact that the radioisotope excitation is
usually monoenergetic (monochromatic) as opposed to polyenergetic (polychromatic)
excitation characteristic for x-ray tubes.
*Previous aliation: Metorex Inc., Princeton, New Jersey.
Copyright 2002 Marcel Dekker, Inc.

X-ray uorescence techniques based on the x-ray tubeBragg crystal spectrometer
are considerably more sensitive than those based on radioisotope sources. This high
sensitivity is due to the excellent x-ray resolving power of the crystal spectrometer, which is
superior to that of the gas-lled or solid-state detector typically used with radioisotopes.
Radioisotopes cannot be used with crystal spectrometers because of the low geometrical
eciency of this spectrometer coupled with the fact that the x-ray photon output of
radioisotope sources is relatively very low, about six orders of magnitude less than that of
x-ray tubes used with crystal spectrometers.
Presently, the bulk of use of XRF analysis is in portable and on-line equipment.
Portable systems outnumber on-line installation, and the gap increases from year to year.
A signicant number of radioisotope benchtop XRF systems have been installed for
quality control applications, as o-line auxiliary instruments. These, however, are very
quickly yielding the eld to XRF systems based on low-power x-ray tubes.
For some applications, x-ray preferential absorption (XRA) and x-ray scattering
(XRS) techniques are preferred to XRF techniques, particularly when coarse particulate
material is to be analyzed. Radioisotopes are the only practical source of x-rays for these
applications, because to penetrate deep into the material, high energy, usually above
100 keV, x-rays are required. The most important applications of XRA and XRS tech-
niques are the on-line analysis of particulate material on conveyors.
Some of the terminology used in this chapter is now briey dened. The element
whose concentration in the sample is to be determined is the analyte and the other ele-
ments of the sample are the matrix elements, or simply the matrix.
Sensitivity of an analytical method for a given analyte is dened as net change (in-
crease) of the measured signal of the analyte per unit concentration change (increase) of
that analyte. This term is notoriously, but wrongly, used in place of minimum detectable
level. A minimum detectable level (DL) for a given analyte is understood as that amount of
analyte in a sample that produces spectral signal equal to or greater than three standard
deviations of a signal obtained on a sample with no analyte present. The DL improves
when sensitivity of analysis improves.
The common link between all techniques and applications discussed here is the de-
pendence of the analysis primarily on the absorption of x- and g-rays. Compton and
coherent scattering are the other important interactions taking place in the sample. The
terms x-ray and g-ray can often be used interchangeably. The term x-ray is always used
when discussing uorescent x-rays. Radioisotope sources emit either g-rays directly from
the nucleus or uorescent x-rays emitted following the ejection of an atomic electron.
g-Rays emitted by radioisotopes usually have energies greater than 50 keV. X-ray uor-
escence analysis depends on both x-ray and g-ray excitation, but most XRA and XRS
analyses are based on the use of g-rays. The term high-energy g-ray is used when the
g-ray interaction in the sample is essentially entirely due to Compton scattering (typically
above 300 keV) which is being used to determine either the bulk density or mass per unit
area of the sample. The term low-energy g-ray is used when photoelectric interactions
are important to the analysis.
This chapter reviews radioisotope-excited x-ray uorescence, preferential absorp-
tion, and scattering techniques. The characteristics of radioisotope sources and x-ray
detectors are described, and then the x-ray analytical techniques are presented. The choice
of radioisotope technique for a specic application is discussed along with major factors
aecting the overall accuracy of analysis. This is followed by a summary of applications of
these techniques, with a more detailed account given of some of the most representative
applications, particularly those of considerable industrial importance.
II. BASIC EQUATIONS
The basic equations for x-ray analysis are given in Chapter 1. Some additional equations
used for XRF, XRA, and XRS analyses are presented here. The typical geometries (Watt
and Stener, 1985; Jenkins et al., 1981 b) of the radioisotope source, sample, and detector
used are shown in Figures 1 and 2.
Figure 1 The three geometries for radioisotope-excited x-ray fluorescence analysis: (a) annular
source, (b) central source, and (c) side source. (From Jenkins et al., 1981b.)

Figure 2 Arrangement of radioisotope g-ray source, collimators, and scintillation detector used in
x-ray preferential absorption analysis. (From Watt and Steffner, 1985.)
A. Absorption of X-rays
The intensity, I, of a narrow beam of monoenergetic x- or g-rays transmitted through a
sample (already shown in Chapter 1) is given by
I I0 emrt 1
where
X
n
m Wi mi 2
i1

and
X
n
Wi 1 3
i1
I0 is the intensity of x-rays detected without the sample. m and t are the mass absorption
coecient and path length of x-rays in the sample, respectively, r is the bulk density of the
sample, and mi and Wi are the mass absorption coecient and weight fraction of the ith
element in the sample, respectively.
Equation (1) also holds for broad beams of x-rays when the cross section for pho-
toelectric absorption is much greater than that for Compton and coherent scattering [i.e.,
particularly for low-energy x-rays and high-atomic-number (Z) elements]. This assump-
tion can be veried by reference to Appendices VIVIII of Chapter 1.
B. Fluorescent X-ray Intensity

When a monoenergetic beam of x-rays excites the K shell x-rays of the analyte i in an
innite-thickness sample and both the incident and emitted x-rays are normal to the
sample surface, the detected intensity Ii of the Ka x-rays of analyte i is given approximately
by Eqs. (94) and (90) in Chapter 1, namely
GeEi ai E0 I0 E0
Ii 4
mE0 mEi
where
G Geometrical constant
eEi Intrinsic eciency of the detector to the x-rays of the analyte i
ai E0 Wi t0i E0 oi ri 1 1=ji
I0 E0 The source emission (photons=s)
mE0 ; mEi Mass absorption coecients for the exciting radiation with energy
E0 and the characteristic radiation with energy Ei , respectively, in
the sample (cm2/g)
t0i E0 Total photoelectric mass absorption coecient for the ith element
at energy E0 (cm2/g)
oi The K shell uorescent yield for the analyte i
ri Relative transition probability for Ka lines of analyte i
ji Jump ratio
Enhancement eects (discussed in Chapter 5, Sec. II.B.2) have been assumed to be
negligible.
The intensities of L and M shell uorescent x-rays can be calculated from equations
similar to Eq. (4). For radioisotopes emitting x-rays of more than one energy, Ii can be
separately calculated for each emitted energy and the total uorescent x-ray intensity
determined by summing the products of Ii and the probability of emission of the given
x-ray energy from the radioisotope.
C. Scattered X-ray Intensities

X-rays are scattered from the sample and its surroundings to the detector by a mechanism
of coherent and Compton (or incoherent)-scattering interactions. There is no loss of
energy of incident radiation during coherent scattering. The energy E of the Compton-
scattered x-ray is given by [Eq. (52) of Chapter 1]
E0
E 5
1 g1 cos y
where E0 is the energy (in the units of keV) of the incident x- or g-ray, g E0 =511, and y
is the scattering angle. The scattering angle y, measured from the direction of the incident
x-ray, in most radioisotope XRF systems (Fig. 1) is in the range 90 150 . The loss in
energy of the incident x-ray due to Compton scattering at 90 , 120 , and 150 is shown in
Figure 3 and can be seen to be relatively very small at energies below 20 keV. The de-
tected intensity Is of x-rays scattered from an innitely thick sample to the detector is
given by
P
GI0 E0 Ts es msi yWi
Is P 6
mi msi Wi
where G; I0 E0 , and Wi are the same as in Eq. (4), Ts is the transmission of the scattered
x-rays through the lter and the detector window; es is the eciency of the detector for the
scattered x-rays; msi y is the dierential scattering cross section for the x-rays scattered by
the ith element toward the detector, and msi is the mass absorption coecient of the
scattered x-rays for the ith element of the sample.
Equation (6) holds for both coherent and Compton scattering when the appropriate
scattering cross section [Eqs. (73) and (65) of Chapter 1] is used. It assumes that the
photoelectric absorption cross section of the x-rays in the sample is much greater than
that for scattering and that incident and emergent x-rays are normal to the sample
surface.
The dierential and total Compton-scattering cross sections per atom are propor-
tional to Z=A, where A is the atomic weight of the atom, and, except for hydrogen, are
almost independent of the atomic number of the atom. Hence, the scattered intensity is
approximately inversely proportional to the sum of the mass absorption coecients in the
sample of the incident and emerging x-rays.
Figure 3 Loss in energy of x-rays in Compton scattering at angles 90 , 120 , and 150 .

The cross section for coherent scattering is highest for small scattering angles, low-
energy x-rays, and high-atomic-number atoms. For angles greater than 90 , the cross
section is low and varies by only a factor of about 2.
D. X-ray Fluorescence Analysis

The concentration of the analyte in the sample is determined from measurement of the
intensity of its uorescent x-rays, often combined with measurements of the intensities of
the uorescent x-rays of matrix elements and=or the Compton-scattered x-rays. Often the
denominator of Eq. (4) is proportional to that of Eq. (6); that is,
X
mE0 mEi / mi msi Wi 7
Hence, Eqs. (4) and (6) can be combined to give
Ii
Wi k 8
ICom
where k is a constant. Note that the intensity of scattered radiation, Is , is replaced here by
ICom , because Eq. (6) holds for both coherent and Compton scattering when the appro-
priate scattering cross section is used. If a major matrix constituent, a, has an absorption
edge energy between the energy of the characteristic x-rays of the analyte and the energy of
the incoherently (Compton) scattered primary radiation, then

1
Wi kIi k1 ma Wa 9
ICom
where k1 is a constant and the subscript a refers to the major matrix constituent. Equa-
tions (8) and (9) can be checked for accuracy for any specic application by substituting
mass absorption coecients (see Appendices VIIIX of Chapter 1) and elemental con-
centrations into Eqs. (4) and (6).
Relation (8) has a great analytical signicance; in many applications, it linearizes the
calibration curve for a given analyte, thus making analysis more accurate and robust.
Analysis of Eqs. (4) and (3) reveals that the intensity of the characteristic x-rays of a
given analyte is a function not only of this analyte concentration but also of the con-
centrations of all the other elements in the sample. This poses diculty in solving this
equation directly for Wi . However, by adopting, for example, a simple approximation
proposed by Lucas-Tooth and Price (L-TP) (1962), this problem can be solved. The L-TP
approximation states that because the x-ray intensities of elements are functions of their
respective concentrations, one can substitute their measured x-ray intensities for con-
centrations of matrix elements. In this way, Eq. (4), via Eq. (3), can be solved for Wi ,
which is now expressed, for each analyte, by all measured x-ray intensities of the elements
in the sample:
!
X
jn
W i b1 I i k 0 kij Ij 10
j6n
The I s are the x-ray intensities of the elements measured, kij are correction coecients
determined by multivariable linear least-squares tting, and Wi is concentration of the
analyte i. There are as many of this equations as there are analytes to be measured.
The L-TP model allows for the calibration of an x-ray analyzer with the suite of
calibration samples without the necessity of knowing assays for any element but the
desired analyte. Due to its simplicity and ruggedness, this approach is often used in the
calibration of benchtop and portable x-ray analyzers; the analyzer measures x-ray in-
tensities of the important interfering elements in calibration samples and then develops a
calibration equation for the analyte(s) by multivariable, linear least-squares tting.
E. X-ray Preferential Absorption Analysis

X-ray preferential absorption analysis is based on the measurement of the intensities of
two or more monoenergetic x-rays transmitted through the sample (Fig. 2). Sensitivity of
analysis depends on the selective absorption of the transmitted x-rays by the analyte
compared with absorption by the sample matrix. The greater the dierence (or contrast)
between the mass absorption coecients of the analyte and matrix for the transmitted
x-rays, the better the sensitivity of analysis for that analyte. From Eqs. (1)(3), the
concentration of the analyte is given by
lnI0 =I=rt mM
Wi 11
mi mM
where mi is the mass absorption coecient of the x-rays in the analyte and mM is the ab-
sorption coecient of the matrix, given by
X
n
mM mj Wj 12
j6i
and the subscript j refers to the matrix elements and S Wj 1 Wi . The concentration of
the analyte can thus be determined if the product of the bulk density and thickness of the
sample is known and the mass absorption coecients of the matrix elements are ap-
proximately equal or the composition of the matrix does not vary.
In practice, XRA analysis usually involves measurements of transmission of narrow
beams of x-ray, at two x-ray energies, through the sample (Watt and Stener, 1985). This
is called dual-energy (x- or g-ray) transmission (DUET) analysis. The beams are usually
coincident and thus not dierently aected by heterogeneity of the sample in the beam
path (Fig. 2).
From Eq. (11), the concentration Wi of the desired analyte is
m0M Rm00M
Wi 13
m0i m0M Rm00i m00M
where
lnI0 =I0
R 14
lnI0 =I00
and
m0M m0i m0M Wi m0
R 15
m00M m00i m00M Wi m00
The prime and double prime refer to the rst and second x-ray energies, respectively. The
concentration is thus determined independently of the density and thickness of the sample
through which the coincident x-ray beams pass.
The sensitivity of analysis is high when m0i m0M and when rt is large. The analysis is
accurate when the ratio m0M =m00M is constant, independently of variations in composition of
the sample matrix. This ratio is approximately constant when the x-ray energies of the
transmitted x-ray are just above and below the K shell absorption edge energy of the
analyte and at higher energies when, at each x-ray energy, the mass absorption coecients
of all matrix elements are about the same. In the latter case, the energy of the higher-
energy x-ray is usually chosen so that the mass absorption coecients of the analyte and
matrix elements are the same, the transmission measurement thus determining the mass
per unit area of sample in the x-ray beam.
The uncertainty in determination of R [Eq. (14)] caused by counting statistics is
s
2 2
R dI=I0 dI=I00
dR 16
rt m0 m00
where
0 2 0 2 0 2
dI dI dI
00 0 17
I I0 I
and
00 2 00 2 00 2
dI dI0 dI
00 00 18
I I0 I
and where dI=I is the relative counting statistical uncertainty and m is the mass absorption
coecient of the x-ray in the sample. The corresponding uncertainty in determining the
concentration of the analyte can be found by substituting R dR for R in Eq. (13).
The uncertainty in the determination of the concentration of the analyte, caused by
an increase in the concentration (dC) of one matrix element k replacing another matrix
element l, can be calculated by increasing the mass absorption coecient of the sample
matrix by
mM new mM old mk ml dC 19
and substituting the new mass absorption coecient into Eq. (13).
These equations accurately predict all aspects of XRA analysis (Watt and Stener,
1985) except when the sample is so highly heterogeneous that within the beam of x-rays,
there are signicant dierences in absorption of the x-rays.
F. X-ray Scattering Analysis

Of the two x-ray scattering methods of analysis, one relies on comparison of the detected
intensities of the Compton-scattered and coherent scattered x-ray (Schatzler, 1979),
whereas the other one is based on determination of the intensity of the Compton-scattered
x-rays (Fookes et al., 1975). The former method is essentially a measure of the ratio of the
dierential scattering cross sections of the two components, which is proportional to
between Z and Z2 (Siegbahn, 1965). The latter methods depends on the absorption of
x-rays in the sample, which, in the photoelectric region, is proportional to between Z4=A
and Z5=A (Siegbahn, 1965). Thus, the method is very similar to XRA analysis and is
considerably more sensitive than the Compton-scattered to coherent scattered ratio x-ray
method. Both methods are accurate only when the changes in detected x-ray intensities
caused by changes in the concentration of the analyte are much greater than those caused
by changes in the concentration of the matrix elements.
The sensitivity of both techniques and uncertainties due to variations in con-
centrations of matrix constituents can be predicted using Eq. (6), where the photoelectric
absorption cross section in the sample is much greater than the scattering cross section.
Dual-energy scattering techniques (Outokumpu Mintec, 1986), analogous to dual-
energy preferential absorption techniques, are used to minimize the eects of sample
heterogeneity. The x-ray scattering techniques are used in applications in which only one
side of the sample is accessible and thickness of the sample is too great to allow sucient
penetration of x-rays. Compared with DUET analysis, the main disadvantage is that
narrow beams of x-rays cannot often be used because of the lower geometrical eciency of
the source, sample, and detector. Hence, multiple scattered x-rays are detected with a
consequent loss in accuracy of analysis.
III. RADIOISOTOPE X-RAY SOURCES AND DETECTORS
The characteristics of radioisotope x-ray sources and detectors are described here. A full
understanding of the dierent characteristics of scintillation, proportional, and solid-state
detectors is essential because of the need to tailor their use to specic applications and to
environmental conditions in the eld and in industrial plants.
A. Radioisotope Sources
There are only a few radioisotope sources that are used frequently for x-ray analysis; these are
listed with their most important characteristics in Table 1. Also included are two radio-
isotopes that emit high-energy x-rays and they are used most frequently with the x-ray
sources to correct for changes in sample mass per unit area, thickness, or bulk density.
The activity of radioisotopes is specied in terms of the rate of disintegration of the
radioactive atoms [i.e., decays per second, or becquerel (Bq)]. One becquerel (Bq), an SI
unit, is dened as one disintegration per second. The unit of becquerel replaces the non-SI
unit, the curie (Ci), which equals 3.761010 becquerel. Unfortunately, the unit of becquerel
is not very practical. For example, a typical, useful activity of 100 mCi has to be expressed
in gigabecquerels (GBq). A practical conversion relation between the two units is
100 mCi 3:7 GBq
The typical number of x- or g-rays emitted per disintegration by the given radioisotope is
listed in Table 1 so that the essential parameter of the radioisotope source, the number of
x-rays or g-rays emitted per second, can be calculated. The emission rate of radioisotope
decreases with time according to the law of natural decay, the number of radioisotope
atoms decaying from N0 to N after an elapsed time t being given by
N N0 e0:693t=T1=2 20
where T1=2 is the so-called half-life of the radioisotope. The source decays to half of its
original emission rate during the time equal to its half-life. The radioisotope source is
usually replaced after one to two half-lives.
The physical size of radioisotope x-ray sources is small. Figure 4 shows the en-
capsulations of typical cylindrical and annular sources of 109Cd (Amersham, 1986).
Cylindrical sources used in portable analyzers are usually 8-mm-diameter by 5-mm-thick
Table 1 Properties of Radioisotope Sources Used for XRF, XRA, and XRS Analysis and
Determination of Bulk Density r, Mass per Unit Area (rt), and Thickness t in X-ray Analysis
Dose at 1 m
Radio- Half-life X- or g-ray Photons per from 1 GBq Analytical
isotope (years) energy (keV) disintegration (27 mCi) (mSv=h) technique
55
Fe 2.7 MnK x-rays (5.9, 6.5) 0.28 a XRF
238
Pu 88 UL x-rays (1330) 0.13 a XRF
244
Cm 17.8 PuL x-rays (1421) 0.08 a XRF
109
Cd 1.3 AgK x-rays (22, 25) 1.02 a XRF
g-rays at 88 0.04
125
I 0.16 g-rays at 35 0.07 2.7 XRF
TeK x-rays (2732) 1.38
241
Am 433 g-rays at 59.5 0.36 3.6 XRF, XRA, XRS
153
Gd 0.66 EuK x-rays (4148) 1.10 27 XRA
g-rays at 97 0.30
g-rays at 103 0.20
57
Co 0.74 g-rays at 122 0.86 24 XRF, XRA, XRS
g-rays at 136 0.11
133
Ba 10.8 g-rays at 81 0.34 65 XRA, XRS,
g-rays at 276 0.07 rt
g-rays at 303 0.18
g-rays at 356 0.62
0.09
137
Cs 30.2 g-rays at 662 0.85 83.7 rt
a
It is difcult to assign a radiological protection meaning to the dose of low-energy x-rays.
capsules and are often referred to as pellets. When economics justies it, a special source
may be designed for a particular type of the analyzer. A so-called lollipop source, de-
signed specically for light-element analysis probes made by Metorex Int. is such an ex-
ample (Amersham IEC.600 series). It is made in a form of a at copper ring, 1 mm thick,
15 mm in diameter, with a 8-mm opening. One side of this at copper annulus is elec-
troplated with a 55Fe isotope, over which a few-micrometer-thick Ni ashing is applied.
Such source geometry allows for a very close coupling between sample and a proportional
detector window. Consequently, the quantitative analysis of light elements, down to A1, is
possible without the nuisance of helium purge or vacuum.
There are international codes for the safe use of radioisotopes, and a simple in-
troduction to radiation protection has been published (Martin and Harbison, 1986). Each
organization using radioactive substances is required to hold a license, issued in most
countries by a government health department or atomic energy authority. The Interna-
tional Commission on Radiological Protection (ICRP, 1985) recommends that, for
members of the public, it would be prudent to limit exposures to radiation on the basis of a
lifetime average annual dose of 1 millisievert (mSv). Table 1 lists the approximate, typical
dose rates at 1 m from each radioisotope source, assuming no absorption of the emitted
radiation within the source or by air. The x-ray dose is inversely proportional to the square
of the distance from the source. X-ray doses received during the operation of x- and g-ray
instrumentation and gauges are trivial compared with the maximum permitted doses be-
cause of the low x-ray output of radioisotope sources, careful design of operating tech-
niques, and x-ray shielding.
109
Figure 4 Encapsulation of disk and annular Cd g-ray sources. Dimensions are in millimeters.
(From Amersham, 1986.)

The International Organization for Standardization (ISO, Geneva) has produced a
system for classifying sealed radioisotope sources based on safety requirements for typical
uses (Amersham, 1986). Prototype sealed radioisotope sources undergo temperature, ex-
ternal pressure, impact, vibration, and puncture tests (Table 2), which increase in severity
as the class designation increases from 1 to 6. The ISO classies the test requirements for
specic types of application of the sealed sources. The classication for low-energy g-ray
gauges and XRF analysis instruments used in industry is C33222 [i.e., from Table 2, the
rst classication 3 is temperature ( 740 C and 180 C), the second classication 3 is
25 kPa to 2 Mpa, and so on]. This classication, which meets the minimum requirements,
is marked in Table 2 by shaded areas. Most radioisotope sources are designed and
manufactured to have a greater integrity than required by this classication. For example,
the 109Cd sources (Fig. 4) are coded C64344 and C33344 according to the ISO classi-
cation, compared with C33222 required.
The use of radioisotope-containing devices is regulated in each country by the ap-
propriate government agency, which may require the user to just register the device with it
or obtain special license to posses and use the device.
B. X-ray and g-ray Detectors

Scintillation, proportional, and solid-state detectors arein this ascending order of im-
portanceextensively used in radioisotope x-ray analysis. The important characteristics of
these detectors are x-ray energy resolution, eciency, the ratio of the full energy peak to
total detection eciency, the spectrum of x-rays not in the peak, the sensitive area and
thickness of the detector, the count rate capability of detector and associated electronics,
the complexity of the detector and associated electronics, the robustness of the overall
system, andlast but not leastits cost. An excellent source on all aspects of detectors of
nuclear radiation can be found in the work of Knoll (1999).
The complexity and associated cost of equipment is greatest for solid-state detectors
and least for scintillation detectors. The need to use liquid nitrogen (LN2) with solid-state
detector systems and their relative complexity and cost have proven to be a cost penalty
but not a limiting factor, even for applications of on-line analysis in industry. Successful
application of thermoelectric cooling (Peltier eect) for semiconductor detectors, speci-
cally those based on the structure of p-i-n junction (diode), allowed the abandonment of
LN2 cooling without compromising analytical performance of those detectors (Amptek,
1977; EPA, 1997; Shefsky, 1997).
1. Energy Resolution of the Detector

Energy resolution is the detector parameter by which dierent detectors are compared to
each other. For detectors of x-rays and low-energy g-rays, the energy resolution is dened
as the full width of the MnKa peak measured at half of its maximum (a so-called FWHM),
when the detector is irradiated directly by the collimated beam from the 55Fe radioisotope,
at a total count rate in the whole spectrum not exceeding 1000 counts=s (see Fig. 5).
Usually, also a shaping time constant of the amplier is specied to be not less than 10 ms.
For semiconductor detectors, their energy resolution is expressed directly in units of en-
ergy (eV). For gas-lled proportional and scintillation detectors, their energy resolution is
customarily expressed as percent relative to the energy of the MnKa peak (5895 eV). For
example, the best gas-lled detectors may reach FWHM of about 700 eV, which, when
related to 5895 eV of the peak energy, equals about 12% relative. On the other hand,
semiconductor detectors such as Si(Li) crystals feature energy resolution better than 3%
Table 2 Classication of Performance Standards for Sealed Radioisotope Sources as per ISO.2919a
Class
Test for
resistance to 1 2 3 4 5 6
Temperature No test 740 C (20 min.), 740 C (20 min.) 740 C(20 min.), 740 C (20 min.), 740 C (20 min.),
80 C (1 h) 180 C (1 h)
400 C (1 h) and
600 C (1 h), 800 C (1 h)
thermal shock thermal shock from thermal shock from
from 400 C to 20 C 600 C to 20 C 800 C to 20 C
External No test 25 kPa absolute to 25 kPa absolute to 25 kPa absolute 25 kPa absolute 25 kPa absolute to
pressureb atmospheric pressure 2 MPa absolute to 7 MPa absolute to 70 MPa absolute 170 MPa absolute
Impactc No test 50 g from 1 m 200 g from 1 m 2 kg from 1 m 5 kg from 1 m 20 kg from 1 m
Vibrations No test 30 min, 25500 Hz at 30 min, 2550 Hz at 90 min, 2580 Hz
5gn peak amplitude 5gn peak amplitude; at 1.5 mm amplitude
5090 Hz at 0.635 mm peak-to-peak;
amplitude peak-to-peak; 802000 Hz at 20gn
90500 Hz at 10gn
Punctured No test 1 g from 1 m 10 g from 1 m 50 g from 1 m 300 g from 1 m 1 kg from 1 m
a
Details of the testing procedures are given in ISO.2919 and BS.5288. A further class X can be used when a special test procedure has been adopted.
b
External pressure 100 kPa 1 atm (approximate).
c
The source, positioned on a steel anvil, is struck by a steel hammer of the required weight; the hammer has a at striking surface, 25 mm in diameter, with the edges
rounded.
d
The source, positioned on a hardened steel anvil, is struck by a hardened pin, 6 mm long and 3 mm diameter, with a hemispherical end, xed to a hammer of the required
weight.
Note: The shaded cells of the table when read from top to bottom will correspond to class C33222, which is the minimum requirement for low-energy g-ray and x-ray sources
used in XRF instrumentation and g-ray gauges.

Figure 5 Definition of energy resolution, FWHM, of an x-ray detector, which is measured at the
half height of MnKa peak. Note the shaded area, which indicates the width of background window.
relative, and its is therefore more convenient and accurate to express their FWHMs in
units of energy rather than percent. Energy resolution, expressed as the full width at
half(peak)-maximum (FWHM) and shown for each type of detector as continuous line in
Figure 6, was calculated from equations given by Jenkins et al. (1981d). It is important to
remember that practical energy resolution for any detector is always worse than that
quoted by 10% to sometimes 20% relative. This is because the spectra measured from real
samples usually contain large amounts of backscattered radiation, and, additionally, the
intensities of the analytes may be very high.
As mentioned earlier, the energy resolution of solid-state detectors is superior to that
for proportional and scintillation detectors (see Fig. 26 in Chapter 2). Figure 7 shows the
calculated energy spectrum for the detection of 8-keV x-rays in each detector and also the
energies of the Ka x-rays in the 69-keV energy range. Figure 8 shows the dierence in
energy of Ka x-rays between adjacent atomic number elements.
Table 3 compares the dierence in Ka x-ray energies with the energy resolution for
aluminum, iron, and tin based on data given in Figures 6 and 8. Solid-state detectors are the
only detectors that can fully resolve Ka x-rays of adjacent Z elements. The factors aecting
their resolution are discussed in detail in Chapter 3 (Sec. III.D). Proportional detectors have
an energy resolution less than twice the energy dierence in Ka x-rays of adjacent Z elements.
Hence, their energy-resolving power is useful even if there are adjacent Z elements in the
sample. Scintillation detectors (see Chapter 2, Sec. III.F.2) have such limited resolving power
that other techniques must be used to discriminate between adjacent Z elements, such as
balanced lters. This achieved, however, at the expense of some loss in sensitivity of analysis.
Figure 9 illustrates the resolving capabilities of detectors by showing calculated energy
spectra for identical concentrations of Fe and Ni in the same sample.
Figure 6 X-ray energy resolution (FWHM) of scintillation, proportional, and solid-state
detectors. The continuous lines are calculated (data from Jenkins et al., 1981d), the silicon detector
results being based on a small detector (10 mm263 mm): The (diamonds) resolutions are for various
solid-state detectors (EG&G Ortec, 1986); () typical and (6) best for the high-resolution
proportional detectors (Metorex, 1986); and (open circles) typical and (solid circles) best resolutions
for specific NaI scintillation detectors (Harshaw).
2. Energy Resolution of Detector and Minimum Detectable Level

The energy resolution of the detector not only determines its ability to resolve the x-rays of
adjacent elements but also decides about the minimum quantity of the element that can be
detected by the detector, a so-called minimum detection limit, or the detection limit (DL).
The better the resolution (i.e., the narrower the x-ray peak), the better (i.e., smaller) the
minimum detectable quantity of element. The detection limit is frequently dened by
r
3 Ibgd
DL 21
S t
where S is the sensitivity (in counts=s per unit concentration of analyte), Ibgd is the
background intensity measured in the analytes integration window, and t is the mea-
surement time.
Figure 7 The calculated energy spectra for the detection of 8 keV x-rays in scintillation,
proportional, and solid-state detectors. (From Watt, 1983.)
The background intensity, Ibgd , is measured in the same window as the intensity
of a given x-ray peak. The width of the window is usually set equal to the peak
FWHM. If a sample containing a certain percentage of the analyte is measured with a
detector of energy resolution E1 (where E1 FWHM), it will generate in its FWHM-
wide window a certain intensity, I1. If the detector resolution now degrades to, say, E2
(i.e., the analytes x-ray peak is now wider), the intensity I2 will still be equal to I1 (as
long as the measurement window is FWHM-wide). This is because the energy de-
posited by the photon in the detector is represented by the area of the whole peak.
Therefore, if the peak is wider, it has to be smaller, and if it is narrower (better re-
solution), it has to be tallerfor the area of the peak to remain constant (see Fig. 5).
However, the background intensity will be larger in the case of a worse energy re-
solution, E2, than in the case of E1, because the integration window for the back-
ground intensity is wider in the case E2 than in the case E1. Then, it follows from
Eq. (19) that the DL for the E2 case will be larger (worse) than in the case of E1
energy resolution. Therefore, for the best DLs, it is of paramount importance to use
the detector with the best energy resolution.
3. Detector Efficiency for X-rays and Detector-Sensitive Area

Figure 10 shows the calculated eciencies of scintillation and solid-state detectors over
the energy range 1150 keV (see also Chapter 3). At low energies, the decrease in ef-
ciency is due to the absorption of x-rays in the beryllium window at the front of the
detector.
Table 3 Difference in Energy of the Ka X-rays of Adjacent Atomic Number Elements,
and the Energy Resolution of Three Types of Detector
Energy resolution of detector, FWHM (in eV)
Atomic No. Energy of Dierence in Solid Gas-lled

of element Ka x-rays (eV) Ka energies (eV) state proportional Scintillation
13 (Al) 1,490 253 117 425 3,000

26 (Fe) 6,400 527 160 660 6,200
50 (Sn) 25,300 1087 275 1,750 12,200
The eciency of the detector for registering the x-rays at high x-ray energies is
determined by the probability that the x-ray interacts with atoms in the sensitive volume of
the detector. The most ecient detectors are those with a high atomic number and a high
mass per unit area. For x-ray energies above about 40 keV, solid-state detectors made of
germanium are preferred to those made of silicon. Also, of the two detectors made of the
same material, the thicker one will have a better eciency for high-energy x-rays. This is
why even the smallest Si(Li) detector (usually at least 3 mm thick) is superior to the
siliconp-i-n diode detector, which is usually not thicker than 0.5 mm. The eciency of
Figure 8 The energy difference between the Ka x-rays of adjacent atomic number elements.

Figure 9 Comparison of energy resolution of Si(Li) (FWHM 160 eV) and gas proportional
detector (FWHM 660 eV). The solid line is spectrum of the 1-to-1 ratio of iron and nickel collected
with the Si(Li) detector. The dotted spectrum is generated with a gas proportional detector for the
same sample.
Figure 10 Calculated efficiencies of NaI scintillation detector and silicon and germanium solid-
state detectors used in XRF analysis.

proportional detectors depends on the type and pressure of the lling gas and the diameter
of the detector (Fig. 11).
The sensitive area for scintillation detectors is usually from 1000 to 2000 mm2; for
proportional detectors, it ranges from about 500 to 1000 mm2; for silicon solid-state de-
tectors, it is 10100 mm2; and for the commercially available silicon p-i-n diode detectors,
Figure11 X-ray detection efficiencies of Metorex International (formerly Outokumpu Electronics)

proportional detectors with different types of gas fillings. The number code below each graph is gas
pressure, bar (1), window thickness (in mm) (2), gas mixture (3), low background (4), high efficiency
(5) long lifetime (6), high count rate (7), and high resolution (8). The ratings shown are excellent
(xxx), good (xx), fair (x).

it is currently 313 mm2. Hence, in general, count rates are highest for the poor-
er-resolution detectors. The sensitive area of the detector determines the type of mea-
surement geometry that can be used with each detector type. Central source geometry
(Fig. 1b) is normally used with scintillation and proportional detectors, because the large
sensitive area compensates for the shadowing eect of the centrally located source. An
annular source geometry (Fig. 1a) is characteristic for Si(Li) solid-state detectors and
especially for their stationary installations. A side source geometry (Fig. 1c) is the only
choice for the small-area detectors, specically the most recent semiconductor detectors
such as HgI2, silicon p-i-n-diode, CdTe, CdZnTe, and so forth. The eciency of solid-state
detectors is discussed in some depth in Chapter 3 (Sec. III.F).
4. Ratio of Full-Energy Peak toTotal Spectrum

The ratio of the area of the full-energy peak to the total area of the x-ray spectrum is
critical to the sensitivity of XRF analysis. The spectrum outside the full-energy peak is
caused by many factors.
The rst and most important is the occurrence of the so-called escape peak
(Jenkins et al., 1981c), resulting from incomplete photoelectric absorption of the incident
x-ray in the detector material followed by escape of some of its uorescent x-rays from
the detector. For example, if an x-ray photon of iron energy 6.4 keV enters the active
volume of the detector, its energy is being absorbed by the detector material also by the
mechanism of excitation of characteristic x-rays of the detector material, such as Si, Ar,
and so forth. If, in turn, the excited x-ray photon of, say, silicon, of energy 1.74 keV, is
not absorbed in the detector but wanders outside of it, then the total energy deposited in
the detector by the original iron photon will be smaller by the energy of silicon x-ray
photon which escaped from the system. The energy left in the detector equals the
dierence in energy of the x-ray entering the detector and that of the escaping uor-
escent x-ray. This will give rise to the small peak always located left to the original x-ray
peak, at a distance equal to the energy of characteristic x-rays of the detector material.
Thus, for example, for silicon-based detectors, the escape peak may be observed
1.74 keV left to any original photopeak. The escape peak is greatest for the higher-Z
detectors. The ratio of x-rays in the escape and full-energy peaks is highest for pro-
portional detectors with gas llings of Xe (Ka x-ray of 29.7 keV), Kr (12.6 keV) and Nal
(iodine Ka of 28.5 keV) scintillation detectors. However, even silicon (1.74 keV) has
about 12% of the detected counts in the escape peak when excited by 2 keV or higher-
energy x-rays. The magnitude of the escape peak is also strongly dependent on the size,
shape, and geometry of the detector itself. The smaller the detector, the more likely the
escape of the characteristic x-ray of detector material is, because it is more likely for the
photon to be generated at the wall of the detector. Also, escape peaks are more intense
for more intense original photopeaks.
Other factors that lead to incomplete absorption of the energy of the x-ray in the
detector are Compton scattering of the incident x-ray in the detector, with the scattered
x-ray or Compton electron escaping from the sensitive volume; alternatively, the incident
x-ray may be photoelectrically absorbed in the detector, but the photoelectron escapes
from the sensitive volume of detector before losing all its energy. These phenomena, which
are dierent manifestations of the escape mechanism, result in the contribution to the
spectrum at energies dierent from the energy of the original x-ray photon. The full-energy
peak to total spectrum is highest for the high-Z detector materials and for low-energy
x-rays. It is lowest for the low-Z gases used in some proportional detectors.
Apart from the phenomena taking place within the detector itself, the total spectrum
is also a function of the instrument design. For example, typically most of the radiation
reaching the detector is not characteristic x-ray radiation from elements in the sample, but
primary radiation from the source scattered on sample and its environment. It is, there-
fore, very important that the design of the instrument be focused on minimizing and
optimizing of measurement geometry in order to reduce to absolute minimum any para-
sitic radiation reaching the detector.
5. Comments on the Characteristics of Proportional Detectors

The characteristics of proportional detectors vary considerably with type of lling gas and
its pressure and are much more variable than the characteristics of scintillation and solid-
state detectors. The best energy resolution is obtained by using Penning mixtures as gas
llings of these detectors (Jarvinen and Sipila, 1984b). Although the improvement in en-
ergy resolution is relatively small (Fig. 6), it is critically important for applications in the
atomic number range 2630 (iron to zinc). The low average ionization energy of Penning
mixtures also leads to other important advantages (Jarvinen and Sipila, 1984b): the vol-
tage required is lower, hence the gas pressure can be higher. This leads to a higher e-
ciency of detection, fewer wall eects, and smaller escape peaks and, consequently, to a
higher ratio of peak to total spectrum. The life of the detector is also increased to more
than 1013 counts because of the use of only noble gases.
The characteristics of proportional detectors supplied by Metorex International
(formerly Outokumpu Oy) are summarized in Figure 11. The recommended gas llings for
proportional detectors depend on the specic analysis application. The eciency of de-
tection of low-energy x-rays is limited by the absorption of the x-rays in the beryllium
window. Proportional detectors with lower gas pressures are used in the detection of low-
energy x-rays because the thinner windows do not withstand high pressures. For those
low-energy x-rays, the detectors lled with neon gas and tted with Be windows as thin as
13 mm are commercially available.
6. Developments in Solid-State Detectors

The solid-state detector (SSD) is the best type of x-ray detector for XRF analysis, but,
until recently, its potential has not been fully realized, particularly in industrial and eld
use, because of the need for liquid-nitrogen cooling. The only successful exceptions have
been pioneering and notable Kevex designs, known as AnalystTM Model 6700a factory
oor modeland X-SITETMa very rst portable, solid-state detector alloy analyzer
(Spiegel and Horowitz, 1981; Kevex Corp.). Both of these models featured a traditional
Si(Li), liquid-nitrogen-cooled detector and either annular or capsule-type radioisotope
source(s). Perhaps the best testimonial to the success of these designs of the early eighties is
the fact that owners of quite a few still working systems spare no eort and ingenuity to
keep them alive, despite a total abandonment by the original manufacturer.
There has been much promising research into mercuric iodide, cadmium telluride
and gallium arsenide SSDs (Cuzin, 1987) which can operate at or near ambient tem-
peratures. The eld-eect transistor (FET) of the low-noise charge preamplier associated
with these detectors must be cooled to at least 720 C and stabilized at this lower tem-
perature in order to reduce electronic noise. This is achieved with the Peltier element; the
one-stage Peltier cryostat can reduce the temperature of cooled object by about 20 C. Over
the last decade, the Peltier-cooled mercuric iodide detector has been used in the com-
mercially available, portable x-ray analyzers (Berry and Voots, 1989; Piorek, 1997).
However, production yields for these detectors are still problematic, and the same applies
to other semiconductor detector materials such as CdZnTe. It is reasonable to say that
should the demand for those detectors be as high as for silicon in the electronics industry,
we would most likely had mastered the technology of these promising semiconductor
materials a long time ago. Developments have led to the production of silicon-lithium-
drifted detectors that can be operated at temperatures much higher than that of liquid
nitrogen (195 C). Madden et al. (1986) used these silicon detectors cooled in a Peltier
cryostat. The front-end assembly, mounted in the cryostat, contains a silicon detector and
a FET and is mounted on a four-stage Peltier cooling cell. With the assembly under high
vacuum, a temperature of 774 C is achieved with a cell power of 4.3 W. For a
16-mm262-mm-thick detector, an energy resolution of 190 eV at 5.9 keV was achieved. As
the rst commercial manufacturer, Kevex Corp. announced the development of a Peltier-
cooled silicon detector system with x-ray energy resolutions of 155, 180, and 240 eV (at
6 keV) respectively for 10-, 30-, and 80-mm2 detectors, which is as good as have been
achieved for liquid nitrogen cooling. Other organizations have developed silicon detectors
and Peltier cryostats that also give good energy resolutions for x-rays (Tractor X-Ray,
now Spectrace). Systems based on these detectors are available as either laboratory or
benchtop versions.
It should not come as surprise that the most recent room-temperature detector is
a silicon p-i-n diode, manufactured using well-known technologies of silicon wafer and
chip fabrication. Two U.S. companies manufacture these detectors commercially. These
truly silicon (no lithium doping) detectors are supplied in a TO-8 package, containing a
detector element, a FET, a feedback loop, and a Peltier element. Typically, the detector is
a tiny, 713-mm2 area by 0.3-mm-thick silicon diode, with energy resolution currently
reaching below an impressive barrier of 190 eV (Amptek, 1997). These small detectors are
predominantly used in portable designs. Their main drawback is relatively high power
consumption (12 W on average) by Peltier cooler, which in the case of a portable,
battery-operated device is not desirable. The small thickness of these detectors (0.5 mm
appears to be maximum these days) makes them inecient for the detection of x-rays
above 25 keV. However, these Peltier-cooled systems did indeed replace liquid-nitrogen-
cooled systems and opened the way for the widespread use of silicon detectors in
industry.
A very good insight into the current status of research in solid-state detectors is
provided by Schlesinger and James (1995). From this reference, one may infer that the next
major development in detector technology may come from gallium arsenide. This semi-
conductor material is very important for semiconductor electronic and optoelectronic
industry and, therefore, is a subject of serious research. The windfall of this research may
be a new detector material for x-rays.
C. Electronics
The electronics used with the various detectors are discussed in Chapters 2 (Sec. III.F) and
in 3 (Sec. IV) and are also covered in detail by Jenkins et al. (1981a). The limits to accuracy
and sensitivity of XRF analysis are usually determined by the limitations of the detector in
energy resolution, eciency of detection, and maximum count rate, for example, rather
than of the electronics. With the excellent gain stabilization electronics now available and
the reliability of low-power, surface-mount components, it is rare that the electronics
system is a signicant limiting factor even in the harsh environmental conditions of
industrial plants.
IV. X-RAYAND g-RAY TECHNIQUES
The range of radioisotope x- and g-ray techniques used for analysis is far more extensive
than the range based on x-ray tube techniques. Almost all x-ray tube systems are based on
the high-energy resolution of wavelength-dispersive (the crystal spectrometer) or energy-
dispersive (the solid-state detector) devices. With this high resolving power, there is less
need to tailor a technique to the specic application. Radioisotope x-ray systems, espe-
cially those involving scintillation or proportional detectors, usually must be carefully
matched to the specic application. This disadvantage is more than compensated for by
such attributes as mechanical ruggedness, simplicity, and portability, which are so im-
portant in industrial and even more so in eld applications.
The selection of the radioisotope source to analyze dierent elements depends on
many factors, including whether the energy of the radioisotope x- or g-rays is sucient to
excite the element, the energies of the x-rays scattered by the sample, and the energy re-
solution of the detector. Figure 12 is an approximate guide and, although prepared for
proportional detectors (courtesy of Metorex Int., formerly Outokumpu Oy), can be used
for solid-state detectors and to a more limited extent for scintillation detectors. The iso-
topes of 238Pu and 244Cm, emitting x-rays similar in energy, can be used interchangeably
although curium is preferred for safety reasons. A 57Co isotope can be used with scintil-
lation detectors or germanium solid-state detectors for the K shell XRF analysis for high-
Z elements, such as uranium, gold, and lead.
This section reviews the radioisotope XRF techniques used with solid-state, pro-
portional, and scintillation detectors, x-ray preferential absorption techniques that are
normally based on the use of scintillation detectors, and x-ray scattering techniques that
are often based on use of scintillation detectors. An example of the application of each
technique is also given.
A. XRF Techniques Based on Solid-State Detectors

The analysis of samples of copper ores taken from the process streams of three dierent
mineral concentrators is used to illustrate XRF analysis with a solid-state detector
(Gravitis et al., 1974). The ore samples were excited by x-rays from a 3.3-GBq (or about
90 mCi) 238Pu source and the uorescent x-rays were detected by a 28-mm263-mm-thick
silicon-lithium-drifted [Si(Li)] detector. The x-ray spectrum (Fig. 13) of one of the samples
shows well-resolved peaks of Ka x-rays from iron, copper and zinc, and La; Lb, and Lg
x-rays from lead and the complex spectra of the Compton-scattered and coherently
scattered x-rays. The count rates of the copperKa x-rays (Fig. 14a) lie within three bands,
separated from each other because of the large dierence in absorption of x-rays in the
sample matrix caused by the widely dierent iron concentrations (5, 20 and 50 wt%) of the
dierent ores. The use of the scattered x-ray component in the calibration equation for
copper corrects for matrix absorption and reduces the overall uncertainty to better than
0.15 wt% copper (Fig. 14b).
Solid-state detectors are the only type of detector for which the x-ray energy re-
solution (Fig. 6) is sucient to resolve the uorescent x-rays of adjacent Z elements
(Fig. 8). There are minor problems of overlap in some cases in which the energy of the Ka
x-ray of the analyzed, Z element, overlaps the energy of the Kb x-ray of another, usually
Z 7 1, element in a sample. These overlaps can easily be identied from the energies of
uorescent x-rays as a function of Z (see Appendix II of Chapter 1). Fluorescent x-rays
can also overlap slightly if the concentration of an interfering, adjacent Z element is much
Figure12 Appropriate radioisotope x-ray source for use with proportional or solid-state detectors
to gain a high sensitivity of XRF analysis for elements in a specified atomic number range. The
principal energies of the x-rays emitted by each source are indicated above the x axis. The diagonal
lines are the K and L shell absorption-edge energies. K and L shell excitation is required to gain a
wider coverage of atomic number elements using the same radioisotope source and, in some cases,
for high-atomic-number elements.
Figure13 The spectrum of x-rays from a copper, lead, and zinc ore sample excited by 238Pu x-rays
and detected by a Si(Li) solid-state detector.

Figure 14 XRF analysis of copper in flotation feed samples from three mineral concentrators,
based on the intensity of (a) copper Ka x-rays and (b) the ratio of the intensities of copper Ka and
scattered x-rays. The analysis was based on a 238Pu source and silicon solid-state detector.

higher than that of the analyte. The extent of this overlap can be calculated using the
uorescent x-ray energies and x-ray energy resolution (FWHM) of the detector. The
overlaps of this type, which are known as spectral overlaps or spectral interferences,
can be easily corrected either mathematically or empirically.
The small sensitive area and, consequently, small solid angle are the main limitations
of solid-state detector compared with proportional and scintillation detectors. With solid-
state detectors, it takes longer to obtain the same counting statistics. It is not always
possible to use higher-activity sources to overcome this limitation because of self-ab-
sorption of x-rays in the source and, for some radioisotopes, the cost of the source. On the
other hand, the relatively small solid angle limits the amount of scattered x-rays reaching
the detector, which reduces the spectral background considerably and improves the de-
tector peak-to-background ratio.
Figure 15 shows the 3s minimum detection limits for low concentrations of various
elements in a low-Z matrix (Homann, 1986; Spatz and Lieser, 1977). The counting time
was 600 s. The measurements with 109Cd (185 MBq or 5 mCi), 241Am (370 MBq or
10 mCi), and 57Co (370 MBq or 10 mCi) were made using a 30-mm265-mm-thick silicon-
lithium-drifted, solid-state detector (FWHM of 250 eV at 6.4 keV), and the sample matrix
was silica gel. The measurements with 125I isotope (185 GBq or 5 Ci) were made using a 50-
mm263-mm silicon detector (FWHM 250 eV) and a matrix of average atomic number 10.
The measurements with 133Ba isotope (370 GBq or 10 Ci) were made using an 800-
mm2613-mm germanium detector (FWHM 590 eV at 122 keV) and a water matrix. The
detection limits using one source vary greatly with atomic number; hence, to maintain low
detection limits over a wide atomic-number range, several radioisotope sources, emitting
x-rays of dierent energies, must be used. In this case, detection limits less than 10 mg=g are
achieved for many elements. Iron-55 can be used to extend the range of sensitive detection
down to Z 15. Similar detection limits for elements in a soil matrix were reported using a
portable, Si(Li)-detector-based x-ray analyzer (Piorek, 1994).
B. XRF Techniques Based on Proportional Detectors

The main advantages of proportional detectors over classical, Si(Li) solid-state detectors
are the larger sensitive area, simpler equipment, and no need for cooling the detector to a
very low temperature. The higher count rates possible with these detectors lead to shorter
analysis times, except for those applications in which the energy resolution (Fig. 6) limits
the sensitivity of analysis. Many important XRF applications are not limited by the poorer
energy resolution, and many do not involve adjacent Z elements.
Selection of the appropriate type of proportional detector for the specic XRF
application is very important. The best type of detector is determined by optimizing the
various characteristics summarized in Figure 11 for a specic application. In practical
terms, it means proper matching of the detector gas ll, its pressure, and type and
thickness of detector window, with given analytical requirements. For example, in order to
analyze the fraction of percent of zinc and phosphorus in oil, one can select a single probe
with a detector, which will usually compromise eciency for both analytes. On the other
hand, a much higher eciency of detection and, hence, better analytical sensitivity for
these two analytes can be achieved by using two dierent probes, each with the detector
matched to the analyte; neon lling and thin window detector for phosphorus and a high-
pressure argon detector for zinc.
Figure 16 shows the spectra of x-rays, taken with 4-mm-thick samples of pure water
and water containing 100 mg=g of both iron and zinc, measured with a 244Cm source and a
Figure 15 Detection limits (3s) determined with various radioisotope x-ray sources and a solid-
state detector. [Data from Hoffman (1986) and Spatz an Lieser (1977).]
proportional counter lled with a neonargon Penning mixture gas to a pressure of 7 bar
(Jarvinen and Sipila, 1984b). The detection limits are comparable to those obtained with a
silicon solid-state detector with x-ray tube excitation (Jarvinen and Sipila, 1984b). If other
elements in the atomic number range 2630 had been present, however, there would have
been incomplete resolution of the K x-rays emitted and, hence, poorer sensitivity of
analysis.
Figure 17 shows detection limits for the elements in water (Jarvinen and Sipila,
1984a; other data courtesy of Asoma Instruments), normalized to a common counting
time of 100 s. The low detection limits were obtained by careful choice of lling gas and
pressure in relation to the exciting x-ray energy used. The issue of proper match of the
detector with the energy of exciting radiation is much more important for gas-lled pro-
portional detectors than for the solid-state ones. This is because of the much greater
uniform detection eciency of the solid-state detector for x-rays than that of the gas-lled
one. For most, except low-atomic-number elements, the detection limits were less than
10 mg=g, which is similar to the results for solid-state detectors (Fig. 15); however, they
were achieved in a time six times shorter than before. These low detection limits were
achieved using dierent proportional-counter gas llings, and, as a consequence, the
technique is less exible than that based on the solid-state detector. If adjacent Z elements
had been present, the detection limits for the proportional counter would have been
considerably worse, but for the solid-state detector, they would have been much less
changed.
Figure 16 Spectrum of x-rays from a pure water sample and from water spiked with 100 mg/g of
iron and zinc as determined using a (Ne Ar)-filled proportional detector and excited by x-rays from
a 244Cm source. (From Jarvinen and Sipila, 1984b.)
The relatively modest improvement in energy resolution of the high-resolution

gas-lled detector over standard proportional detectors leads to considerable im-
provement in the accuracy of analysis in some applications. Hietala and Viitanen
(1978) indicated that an improvement in resolution from 16% to 10% at 8 keV results
in the relative standard deviation for determination of zinc in copperzinc tailing,
containing 0.1 wt% of both copper and zinc, to be reduced from 0.40% to 0.05%
relative.
C. XRF Techniques Based on Scintillation Detectors

The energy resolution of scintillation detectors is so poor (Fig. 6) that the detector cannot
be used in most applications to resolve the K x-rays of the analyte and matrix elements.
Selectivity to the analyte is obtained with lters and radiators and by a proper choice of
the energy of the x-rays exciting the sample (Watt, 1983). Scintillation-detector XRF
systems have been used extensively in eld work and in industrial plants because of their
simplicity, high x-ray detection eciency, portability, ruggedness of the detector and
electronics, and low cost. These systems are simpler than those based on proportional
detectors and hence, if suciently sensitive and selective to the desired analyte, are the
preferred system. They are best used for applications requiring the determination of the
concentration of one or two elements only. Applications involving the determination of
Figure 17 Minimum detectable levels (3s) for low concentrations of elements in water using
proportional detectors and 100 s counting time. The measurements with the argon detector (gas
pressure, 5 bar) were made with 9-mm-thick water samples and 111 MBq of 109Cd, 2.2 GBq of
244
Cm, and 1.67 GBq of 241Am, with the neon detector (1 bar pressure and a 0.05-mm-thick
beryllium window), with 20-mm-thick water samples and 3.7 GBq of 55Fe, and with the xenon
detector (1 bar) with 110 MBq of 109Cd. (Data from Jarvinen and Sipila, 1984a; Asoma
Instruments.)

more elements are best undertaken with proportional and solid-state detector systems. The
detection limits of scintillation techniques are at least a factor of 10 higher (i.e., worse)
than those for solid-state detectors.
Three types of head unit are used with scintillation detectors: direct excitation, g-
rayx-ray source excitation, and detectorradiator (Fig. 18). Filters can be used with all
three assemblies.
1. Filters
Filters placed between the sample and detector (Fig. 18) increase the sensitivity of analysis
by ltering out a higher proportion of uorescent x-rays of matrix elements than those of
the analyte. Zinc, for example, may be the analyte in samples also containing iron. Cal-
culations based on Eq. (1) and mass absorption coecients [see Eq. (76) in Chapter 1]
show that a 27-mg=cm2 aluminum lter transmits 27% of the Ka x-rays of 8.6 keV but
only 4.5% of the iron Ka x-rays of 6.4 keV (Fig. 19); that is, it reduces the intensity of iron
K x-rays relative to the zinc K x-rays by a factor of 6. If the sample also contains lead,
however, about 55% of the lead La x-rays (10.5 keV) would be transmitted, twice that of
the zinc Ka x-rays. In this case (Fig. 19), an absorption-edge-type lter of copper (22.4 mg/
cm2) could be used to reduce the lead La x-ray transmission to only 1 % and also to reduce
the iron K x-ray peak. This selective enhancement of the zinc compared with the iron and
lead x-ray components partly compensates for the limitation of the poor resolution of the
scintillation detector. Although some iron and lead uorescent x-rays will still be detected
within the pulse-height channel set about zinc Ka x-ray peak, in many applications this
component will have been suciently reduced to make the analysis possible.
If the measurement with one absorption-edge lter does not give sucient selectivity
to the desired elements uorescent x-rays, balanced lters are used (Fig. 20). The in-
tensities of x-rays in the uorescent x-ray channel are measured separately, rst with one
lter and then with the other (with up and down lter). The atomic numbers of the
two lters are chosen so that their K shell absorption-edge energies are just above and
below the energy of the Ka x-rays of the analyte. The masses per unit area of the two lters
are chosen so that the product mrt [Eq. (1)] is practically identical for both lters, except
Figure 18 Three types of radioisotope XRF assembly based on scintillation detectors.

Figure 19 X-ray transmission through aluminum and copper filters.
Figure 20 X-ray transmission through balanced filters of copper (6) and nickel (solid circle).
Count-rate measurements made first with one and then with the other filter are subtracted to give a
count rate proportional to the intensity of zinc Ka x-rays from a sample.

within the energy window enclosing the Ka x-ray energy of the measured element. Hence,
the dierence in the count rates using the two lters is proportional to the intensity of
uorescent x-rays of the analyte. An excellent example of the balanced-lter application
has been MetallurgistTM, Model 9266, by TN Technologies (Spiegel and Horowitz,
1981). The portable analyzer used a series of balanced lters to quantitatively analyze
stainless steels, nickel, copper, and cobalt alloys.
It needs to be mentioned here that lters are also used with some low-energy-
resolution gas proportional detectors and also with x-ray tube excitation (Oxford In-
struments). A rather unique application of a single absorption-edge lter has been
reported for analysis of Mn in Hatled steels using a gas-lled proportional detector
(S. Piorek, personal communication, 1987). There, a MnKa peak is wedged between in-
tense CrKa and FeKa peaks. By placing a Cr lter over the detector window, the FeKa x-
ray intensity is reduced by a factor of 6 relative to MnKa x-ray, thus enabling quantitative
analysis of Mn. However, because manufacturing of the lters and necessary mechanics is
rather expensive, the practice of using lters becomes less and less common, in favor of
using systems with better energy resolution.
Figure 20 shows the transmission of x-rays by copper and nickel lters, which are
chosen when the analyte is zinc (Rhodes, 1966). Except in the energy window enclosing the
zinc Ka x-rays, the transmission is the same for the two lters. The balanced-lter tech-
nique is thus highly selective to the zinc Ka x-rays. The count rates, measured separately in
the uorescent x-ray channel with the two lters, are usually high and the dierence in
count rates can be quite small, often resulting in high relative uncertainties of measure-
ment. This is one of the main disadvantages of the balanced-lter technique.
There are two other disadvantages of lter techniques: The sensitivity of analysis is
poor when the uorescent x-rays of the main interfering matrix element have an energy
just below that of uorescent x-rays of the analyte (Fig. 19), and the sensitivity is
considerably less than the obtained with detectors that have the inherent resolving power
to isolate the uorescent x-rays of desired and matrix elements. These losses in sensitivity
result from the only partial absorption of interfering x-rays in the lter and, for absorp-
tion-edge lters, from the detection of lter K x-ray in the channel of the analyte. The
latter is a direct consequence of the use of the broad-beam geometries of radioisotope
XRF system. The lter K x-rays are mainly excited by the source radiation scattered from
the sample.
2. DirectExcitation Assemblies
The directexcitation technique (Fig. 18) is the most widely used of the three scintillation
detector assemblies. The energy of the radioisotope x-ray is usually chosen so that the
uorescent and backscattered x-rays are resolved by energy analysis (Fig. 21). The in-
tensity of the backscattered x-rays is used to correct for the absorption of the analytes
uorescent x-rays by the sample matrix [Eq. (8) or (9)]. The lter enhances the sensitivity
and selectivity of analysis.
Direct-excitation assemblies are used extensively in industry (e.g., in laboratory and
portable elemental analyzers (Rhodes, 1971) and in on-line (in-stream) analysis of mineral
slurries (Watt, 1983).
3. DetectorRadiator Assemblies
The detectorradiator assembly (Fig. 18) discriminated well against interfering x-rays of
energy just below that of the uorescent x-rays of the measured element (Watt, 1972). The
basis of this discrimination is that the atomic number of the radiator element can be
chosen so that, of the two x-ray components with nearly similar energies, only the higher
of the two has sucient energy to excite the K x-rays of the radiator element. The detector
is shielded from the sample and, hence, sees only the x-rays emitted by the radiator. Ba-
lanced-radiator techniques, analogous to balanced-lter techniques, can also be used to
improve selectivity to the analyte if there is another matrix element, in this case emitting
uorescent x-rays of energy higher than those of the analyte. The count rates obtained
with detectorradiator assemblies are about 5% of those obtained with direct-excitation
assemblies, using a source of the same activity, because of the additional excitation stage
of the radiator.
The intensity of higher-energy x-rays scattered by the sample can be measured si-
multaneously in the one assembly by use of a second radiator element of atomic number
considerably higher than that of the rst radiator. The x-ray energies of the two com-
ponents are well resolved and similar to that shown in Figure 21.
Detectorradiator systems are much less widely used than balanced-lter techni-
ques. They are less versatile than balanced-lter systems. Applications include the de-
termination of lead in zinc concentrates, in which the zinc Ka x-rays (8.6 keV) from the
high concentration of zinc (e.g., 50 wt%) swamp the lead L x-rays (10.514.8 keV) from
the low concentration of lead (e.g., 0.5 wt%). A radiator of zinc (absorption-edge energy
of 9.66 keV) is excited by the lead L but not by the zinc K x-rays. This radiator technique
238
Figure 21 Typical spectrum of x-rays from copper ore slurry excited by a Pu source and
measured using a scintillation detector.

improves the sensitivity to lead to that of zinc by a factor of about 20. However, the
absolute signals from the analytes when using the radiator technique may be up to an
order of magnitude smaller than when excited directly.
4. -Ray-Excited X-ray Assemblies

A limited number of x- or g-ray energies are emitted by radioisotope sources (Table 1).
A secondary x-ray source, in which g-rays from a radioisotope source excite the uorescent
x-rays of a target material, can be used to obtain essentially monoenergetic x-rays of
energy determined by the atomic number of the target element (Fig. 18). Hence, the energy
of the x-rays incident on the sample can be chosen to suit the specic XRF application.
The g-ray-excited x-ray assembly (Watt, 1983) makes use of lters, including balanced
lters, similarly to the direct excitation assembly. The count rates using the secondary
excitation source assembly are only about 5% of the count rate of a direct excitation
assembly using the same activity source.
A balanced-energy technique, in which separate measurements are made with two tar-
gets (in the secondary source) whose uorescent x-rays straddle the K shell absorption-edge
energy of the wanted element, can be used to obtain more selectivity to the analyzed element.
The g-ray-excited x-ray assembly is used as an alternative to direct excitation when
no suitable energy x-ray is emitted by radioisotope source. One application is in the de-
termination of the coating mass of tin on steel by the detection of the tin K x-rays. If
60-keV g-rays from 241Am isotope are used to excite the tin, K x-rays from both sides of
the steel are detected; by choosing the energy of the exciting radiation to be just above that
of the tin K shell absorption edge, tin K x-rays from only the one side are detected because
of the high absorption of the lower-energy excitation radiation in the steel.
D. X-ray Preferential Absorption Techniques

X-ray preferential absorption analysis is often based on the dual-energy g-ray transmission
technique (Fig. 2) because of important industrial applications involving the analysis of
coarse and heterogeneous materials, such as coal (Fookes et al., 1983; Gravitis et al., 1987)
and metalliferous mineral ores. Low-energy g-rays must be used in these applications to
obtain sucient transmission through the material, so that the only practical approach is
to use radioisotope sources. Scintillation detectors are used to ensure ecient detection of
the g-rays, with pulse-height analysis to separate the two energies.
Figure 22 illustrates the results using the DUET technique to determine the lead
content of zinc concentrate and residue (tailings) samples (Ellis et al., 1969). The radio-
isotopes 241Am and 153Gd were used. Their g-ray energies, 60 keV of 241Am and 97 and
103 keV of 153Gd, envelope the K shell absorption-edge energy of lead (88 keV). A com-
mon calibration curve is obtained despite the great dierence in absorption by the matrix
of the concentrates (with about 50 wt% zinc) and of the tailings, also called residues (with
about 0.6 wt% zinc).
This technique becomes more complicated when the g-ray transmission measure-
ments are made on material on fast-moving conveyors, as for the on-line determination of
the ash content of coal (Fookes et al., 1983; Gravitis et al., 1987). Equations (13) and (14)
hold only for time intervals during which there is little change in mass per unit area,
whereas there would be a linear summing of count rates in time although the correct re-
sponse is logarithmic [Eq. (14)]. This problem can be addressed by counting for shorter
intervals during which the mass per unit area changes little and summing the logarithms of
the counts during many of these intervals (Gravitis et al., 1987).
Figure 22 g-Ray preferential absorption analysis for lead, showing (left) the transmission of 153Gd g-rays ( 100 keV),
and (right) the combination of the separate transmission measurements for 153Gd and 241Am (59.5 keV) g-rays.

E. X-ray Scattering Techniques
The single most important applications of x-ray scattering techniques are in the on-line
systems, such as for the continuous analysis of particulate material on conveyors and
sample bylines in industrial plants. There is often no need to crush the material before
analysis because of the penetration of the g-rays in the material. Americium-241 g-ray has
been used to determine the ash content of coal both in a sample byline (Fauth et al.,
1986) and, when sucient thickness of coal is available, directly on a conveyor belt
(Cierpicz 1986). Dual-energy g-ray scattering has been used in ore-sorting applications
(Outokumpu Mintec Oy, 1986), in which the thickness of the ore lumps is too great for
XRA techniques.
F. Count Rates and Calibration

The count rates, or intensities, of uorescent and backscattered x-rays from the sample are
determined by many factors [Eqs. (4) and (6)]. Activities of the radioisotope sources used
range from 100 MBq to 10 GBq (or 3300 mCi), the higher activities being used mainly
with solid-state detectors, which have a smaller eective area than scintillation and pro-
portional detectors. For x-ray preferential absorption analysis, higher activities of
110 GBq (30300 mCi) are used for industrial on-line applications in which high count
rates are essential with the rapidly changing mass per unit area and where distances be-
tween analyzed medium and detector are relatively large. The source activities used for
x-ray scattering analysis are approximately the same as those for XRA analysis.
X-ray uorescence analysis is, as is the vast majority of other analytical methods, a
comparative analytical technique. Radioisotope x-ray systems are usually calibrated by
comparing the measured count rates with analyses of the same samples by more con-
ventional techniques. The coecients linking the count rates and chemical analysis are
determined by linear multiple regression. This empirical in nature method of calibration is
essential in most applications, especially when the materials to be analyzed have an un-
known particle size. For the calibration to be valid, it is essential to calibrate with ma-
terials covering the full range of variations in elemental composition and particle size. In
some industrial applications, these factors may change slowly with time and, hence, the
calibration must be regularly updated.
The widespread use of room-temperature solid-state detectors as well as availability
of microcomputers made so-called standardless methods of calibration a realistic alter-
native to the empirical ones. These standardless methods are variations of the funda-
mental parameters (FP)-based approaches, in which the concentrations of analytes are
deduced iteratively by combining spectral information from the sample with that of one
known standard and=or with fundamental equations of x-ray physics. It is to be noted,
however, that any empirical calibration based on a good set of standards will always be
more accurate than that derived with the FP algorithm.
V. FACTORS AFFECTING THE OVERALL ACCURACY OF XRF ANALYSIS
The choice of a radioisotope x-ray analysis technique for a specic application depends on
several interacting factors: the overall accuracy of the sampling and analysis required, the
time available to achieve this accuracy, technique available to obtain a suciently
representative sample of the material being analyzed, and the sample preparation
requirements, such as grinding, pressing, and so forth. The inuence of each of these
factors on the accuracy of XRF analysis is discussed here.
A. Overall Accuracy and Time for Analysis

The overall accuracy of analysis depends on uncertainties in calibration, sampling, sample
preparation, and x-ray analysis. The requirements of a good accuracy of analysis stay in
striking contrast with the time allotted for analysis. The maximum acceptable time must
include not only the time for the x-ray analysis but also the time for sampling and sample
preparation. Uncertainties due to nonrepresentative sampling are too often under-
estimated in industrial and eld applications, resulting in the accuracy of the overall
analysis often being compromised.
The total uncertainty of analysis, stot , can be expressed as the sum of all contributing
uncertainties:
q
stot s2instr s2stat s2het s2cal s2samp:plac: s2matrx s2part:size s2?? 22
where
sinstr Instrumental component such as thermal drift
sstat Uncertainty due to statistics of counting
shet Uncertainty reecting sample heterogeneity
scal Reects uncertainties contributed by reference analysis and calibra-
tion t
ssamp:plac: Uncertainty due to sample placement
smatrx Uncertainty associated with matrix eects
spart:size Uncertainty caused by varying particle size of analyzed material
s?? Any other potential, unidentied uncertainty
This formula assumes that all uncertainties included are random and normally distributed
and that systematic uncertainty (bias) is negligible. Under these assumptions, the stot can
be regarded as a good measure of the accuracy of analysis.
The rst two uncertainty components, sinstr and sstat , are often treated together
as main constituents of instrument precision (repeatability), whereas all the other
uncertainties identied in Eq. (22) can be regarded as contributing to user or application
related uncertainty. Thus, Eq. (22) can be written as follows:
q
stot s2instr:precis: s2applic: 23
where
q
sinstr:precis: s2instr s2stat 24
and
q
sapplic: s2het s2cal s2samp:plac: s2matrx s2part:size s2?? 25
Some of the uncertainties can be identied and easily controlled or minimized by the
analyst, such as uncertainty due to statistics of counting, or calibration uncertainty. For
example, the statistical uncertainty of counting, sstat , can be easily reduced by extending
the measurement time, whereas the uncertainty associated with calibration, scal , can be
reduced by using more accurately analyzed calibration samples and by selection of a better
calibration equation.
Sample placement uncertainties, ssamp:plac: , can be reduced by always following the
same procedure for preparing and loading the sample into the measuring chamber of the
analyzer, orpartiallyby spinning the sample during measurement.
Uncertainties due to matrix variability, smatrx , and particle size, spart:size , can be sig-
nicantly reduced by proper sample preparation techniques such as matrix dilution
(Jenkins et al., 1981a) and by grinding, pelletizing, or fusing the sample with spectrometric
ux, respectively.
Although all these uncertainty minimization techniques are valid and readily ap-
plicable in laboratory environments, they are an unattainable luxury in eld and industrial
applications where grinding, fusing or any type of sample preparation is simply out of the
question.
This is why the accuracy of analysis in eld and industrial environments tend to be
governed by the application-related uncertainties rather than by the usually much smaller
contribution from the instruments precision. It is also for this reason that the measure-
ment time may often be selected from the point of view of process throughput rather than
overall uncertainty of analysis; usually, good instrumental precision allows the analyst to
shorten the measurement time without sacricing the former. Nevertheless, the mea-
surement time is always a compromise between the throughput of the process and ana-
lytical requirements.
In the coating industry, the time for the determination of the coating mass of tin
and zinc on steel must be less than a few seconds if the result is to be useful; hence
continuous analysis directly on the main coating line is essential. In mineral con-
centrators, rapid changes in the grade of ore entering the plant and the time taken for
the ore to pass through the plant (about 15 min) make it essential for the process
slurries to be analyzed within 5 min. This can be achieved by continuous analysis either
directly in stream or on slurries in sampling loops (bylines). In scrap yards, alloys must
be sorted into dierent types in short periods: otherwise the sorting operation is not
economical. The lower the price per pound of scrap, the faster the sorting has to be. In
this case, it is essential to have analysis equipment that is both portable and capable of
producing rapid results.
It is important to realize that XRF analysis does require some nite time period
within which a meaningful measurement can take place. The consequence of this fact is
that XRF analysis results in process control applications are, most of the time, the average
rather than point estimates of the process parameters such as coating thickness, sulfur
concentration of diesel fuel, and so forth.
B. Uncertainties of Sampling and Sample Presentation

Uncertainties originated by sampling processes are probably one of the most signicant
contributors to the overall analytical uncertaintythe point we attempted to make in the
previous subsection. This is especially true for eld and industrial applications of XRF
methods, where sample preparation and conditioning is nonexistent, and which, as we
stated in the Introduction to this chapter, are mostly radioisotope based. That is also why
we devote so much space in this section to this issue.
All analyses involve sampling, some more than others. In the continuous on-line
measurement of material on conveyors or in process slurry streams, the analysis is
averaged over large quantities of material, but still has the potential for sampling un-
certainties because not all of the material on the belt or in the slurry stream is viewed. If
material is continuously sampled from the main stream and fed through a sampling loop
past the x-ray analyzer, the uncertainties in sampling the main stream and in viewing only
part of the sample loop must both be considered.
A mathematical approach to sampling of a particulate media has been detailed by
Gy (1982) and Pitard (1993). The most readily accessible information on sampling is given
in the various international standards for the sampling of process material from moving
conveyors and from slurry streams (ISO, Geneva). These describe preferred sampling
practices and estimate the accuracies of sampling, including the eects of dierent top sizes
and the number and mass of sample increments taken. These standards are regularly
amended.
Sampling uncertainties are of critical importance to the exploration for and assess-
ment of deposits and the mining of both metalliferous ores and coal. After all, it is possible
to analyze only a very small proportion of the ore. There are established practices for
choosing where to sample (e.g., on a regular spaced grid), the number of samples to be
taken, and the weight of each sample to be taken. This complex eld of sampling geo-
statistics is thoroughly covered in textbooks (David, 1971; Ingamells and Pitard, 1986;
Isaaks and Srivastava, 1989).
1. Uncertainty Due to Sample Heterogeneity

Samping uncertainties, specically in analysis of particulate type of material, are mainly
caused by heterogeneity of the measured medium. Should the analyte be uniformly
distributed throughout the mass=volume of the measured material, any sample taken
for analysis would contain the same concentration of the analyte. However, even this
ideal condition would be compromised by the morphology of the sample. If the sample
is liquid, then the dissolved analyte can, indeed, be homogeneously dispersed in a
liquid matrix. However, if the analyzed medium is ore or soil, or any other powder, the
chances of nonuniform distribution of the analyte in matrix increase dramatically. Not
only might the grains of the analyte not mix well with grains of the matrix, but any
handling of the sample will promote tendencies for segregation of one type of grain
from the other. A very important contributing factor is the size of the sample taken for
XRF analysis. The smaller sample is likely to emphasize its heterogeneity as compared
to a larger sample. The main consequence of heterogeneity of the material analyzed is
the fact that the sample of this material taken for analysis may not be representative of
the material.
If the uncertainty cannot be minimized, the next best way of dealing with it is to
estimate its magnitude. It is rather easy to evaluate the contribution of material hetero-
geneity factor to the total uncertainty. The only requirement is the availability of a suf-
cient quantity of analyzed material. Two series of measurements are required. In the rst,
a sample of material to be analyzed is measured in x-ray analyzer for at least seven times,
without being disturbed in any way. This series of measurements will yield a standard
deviation, which will correspond to stot , as per Eq. (20), except for the shet , that being
equal to zero because only one sample was measured. Next, at least seven dierent samples
of the same material are measured under the same conditions as before (i.e., the same
measuring cup, counting time, etc.). This second series of results will yield a standard
deviation, which will correspond to stot , exactly as per Eq. (20), now including the het-
erogeneity factor, shet . By subtracting the squared standard deviation of the rst series
from that of the second and taking the square root of the dierence, a numerical value of
shet is readily obtained. For example, in soil analysis for lead, the two standard deviations
obtained were 25 and 65 mg=kg, respectively. Therefore, after subtraction, the shet was
60 mg=kg, a signicant contribution to the total uncertainty.
It is very important to realize the fact that in the majority of analyses of granular or
particulate material, its heterogeneity determines the overall accuracy of analysis. This is
true not only for XRF, which by its nature is a surface measurement method, but also for
other instrumental techniques such as atomic absorption or inductively coupled plasma,
as long as an aliquot analyzed is not representative of the material from which it was
taken. It is therefore of paramount importance that good homogenization is applied to
analyzed material and that the amount of sample taken is sucient to be representative of
it, especially if verication or validation of XRF results with other analytical techniques is
required.
2. Sample Heterogeneity and Detection Limits

A detection limit (DL) for a given analyte is understood to be that amount of analyte in a
sample that produces a spectral signal equal to or greater than three standard deviations of
a signal obtained on a sample with no analyte present.
The authors own data and values cited in literature indicate that a typical DL for lead
in soil is about 50 kg=kg when a 109Cd isotope and semiconductor detector are used for
analysis. The 109Cd isotope x-rays reach to a depth of about 1.3 cm into a silica-based soil.
However, if there is lead in this sample, the excited lead L series x-rays can reach the surface of
soil only if they are generated at a depth not greater than 0.20.3 cm, as measured from the
soil surface. A 50-mg=kg DL for lead means, in practice, about 650 mg of total lead as po-
tentially seen by the analyzer in a soil cylinder of 13 g mass (cylinder base area of 5 cm2 by
1.3 cm high by 2 g=cm3 of assumed specic density of silica soil). However, the lead x-rays
reach the detector from a depth of only 0.3 cm and, therefore, the eective mass of total lead
seen is only 150 mg. This mass of lead translates into a 0.030-cm (or 12 mils)-diameter
sphere of pure lead. Even in a form of an oxide, the size of the lead oxide grain would not be
much more. If this small, by all means, lead grain happens to be within the rst 3 mm of soil,
the XRF analyzer will be able to measure it. However, if the lead grain ends up at deeper layer
of soil, it will never be noticed. Obviously, depending on its characteristic x-rays energy and
excitation source, any other element will be similarly aected by its location in the sample.
This perhaps extreme but simple example illustrates how illusionary and misleading the
concept of detection limit may be in case of granular material.
C. Choice of Radioisotope X-ray Technique

The choice of the most appropriate radioisotope x-ray technique for a specic application
depends on the requirements of accuracy of sampling and x-ray analysis and the time
available for the analysis. The simplest radioisotope x-ray technique that satises these
requirements is usually chosen.
In the laboratory, where many dierent types of analyses can be performed, XRF
analysis with a solid-state detector is the most exible method. For industrial and eld
applications, there is often a more restricted range of analyses paired with a greater need
for simple and reliable equipment, the cost of which may also be an important con-
sideration. X-ray uorescence analysis based on scintillation or proportional detectors is
often, but not always, the best approach. These considerations lead to the use of a much
wider range of radioisotope x-ray techniques in industry than in the laboratory. The choice
of technique is more complicated. Should an ore sample be ground before analysis and L
shell XRF be used for a high-Z element, such as uranium, or can K shell XRF techniques
determine the concentration with sucient accuracy despite the heterogeneity of the
sample? Should the analysis technique be chosen to make a direct measurement on-line, in
a sampling loop of the process stream, or on a sample taken to a laboratory? Should XRF
techniques even be used in an on-line application, given the inaccuracies introduced by the
heterogeneity of the material to be analyzed? The practical alternative may be to use XRA
or XRS techniques or a nuclear technique, based on more penetrating radiation, such as
high-energy g-rays or neutrons. The applications discussed in the next section indicate the
preferred solutions to some important analysis applications, particularly in industry.
VI. APPLICATIONS
Table 4 lists some important applications of radioisotope x-ray techniques based on XRF
equipment, usually referred to as laboratory or portable elemental analyzers. The analysis
techniques involve the use of scintillation, proportional, and semiconductor detectors.
These analyzers are in widespread use in many application areas and in many industries
(Rhodes, 1971; Rhodes and Rautala, 1983). The total number used worldwide probably is
about 10,000. Some major suppliers of radioisotope based instruments are listed in Table 5.
A photograph of a portable model of an x-ray analyzer for alloys, build around a silicon
p-i-n diode detector is shown in Figure 23 and a laboratory model based on gas-lled
proportional detectors is shown in Figure 24. Many solid-state detector systems are also in
routine use in laboratories.
Table 6 lists types of on-line analysis systems in routine use. These include systems
for the on-line analysis of mineral slurries, owing powders, coal, coal slurries, paper,
determination of sulfur in oil and petroleum products, and analysis of coatings. Most of
the analysis systems tend to be based on scintillation and proportional detectors, but some
of the more recently developed systems also use solid-state detectors. Table 6 is also an
attempt to list some commercial suppliers of the on-line equipment. Example of the ap-
plication of these techniques are now discussed in details, with emphasis given to appli-
cations of industrial importance. Some examples illustrate the interaction of sampling and
sample presentation with the selection of the appropriate radioisotope technique.
A. Identification of Alloys
Historically, the rst applications of portable XRF analyzers were in mining and pro-
specting. It was only with the advent of the on-board memory and microprocessors that the
portable XRF analyzers found wider acceptance and use for analytically more demanding
alloy identication and analysis. Since then, several thousand of these analyzers have been
sold, making alloy sorting and analysis a agship application for portable XRF analy-
zers. These analyzers can assay the alloy and=or identify it by its grade or common name.
Rapid sorting of alloys is required in many areas of the metals industry, such as
smelting, fabrication, inventory and incoming material control, and the sorting of scrap
(Piorek and Rhodes, 1986; Berry, 1981; Piorek, 1989). Some common alloy groups include
nickel alloys, copper alloys, stainless and high-temperature steels, and carbon and chro-
miummolybdenum steels. Although 4050 elements are involved in the alloying process,
in any given alloy there are only 1020, and of these, only about 10 are required for the
identication of specic alloy.
Table 4 Some Typical Applications of Radioisotope Based Laboratory and Portable
Elemental Analyzers
Application Typical examples
Alloy sorting and Low-alloy steels; stainless steels; nickel alloys; high-temperature alloys;
identification titanium, aluminum alloys; specialty alloys; metal scrap
Mining and mineral Copper, lead, zinc, tin, arsenic, molybdenum, nickel, iron, chromium,
bismuth, and uranium in commercial-grade ores, concentrates,
and tailings; titanium and iron in silica sand; silicon, potassium,
titanium, and iron in clays; phosphate rock
Pulp and paper Thickness of silicone coatings on paper and polymer membranes; calcium,
titanium, filler in paper
Environmental Soil screening for metals (Cr, Cu, Ni, Pb, Zn, As, Cd, Hg, Sb); hazardous
materials (e.g., lead, arsenic, chromium, or cadmium in waste sludge);
trace elements in wastewater discharge; metals in air particulates on
filters; chlorine (halogens) in waste oil; sulfur in diesel fuel
Fibers, films and Copper, zinc, tin, gold, silver and chromium plating thicknesses; metals
coatings in plating solutions; silver in photographic film; manganese coating
thickness on magnetic tape; titanium on glass; ruthenium on electrodes
Chemicals and Lead, titanium, and zinc in paint; sulfur, iron, alumina, silica, and calcium
process control in cement; vanadium in catalysts; palladium and gold coatings on silica
spheres uses as catalysts; zinc, chromium, nickel in plating baths
Plastics Calcium, lead, tin, and chlorine in PVC; zinc and bromine in polystyrene;
chlorine in urethane rubbers; bromine and chlorine in butyl rubbers;
silicon in polythene; TiO2 in nylon; bromine in Styrofoam
Agricultural Fertilizers (calcium, phosphates, potassium); copper, chromium, and arsenic
in wood preservatives and treated wood; bromine in almonds; ironzinc
ratio in meat for grading; minerals in cattle feed; titanium in fillers
Cosmetics Titanium, iron, lead in powders
Pharmaceutical Metals in vitamin pills; zinc in insulin
Petroleum products Lead, calcium, sulfur, vanadium, and chlorine in gasoline or oil;
sulfur in petroleum coke; sulfur and ash in coal; lubricating oils additives
The main requirements of analytical equipment for alloy identication are port-
ability, speed and reliability of identication, and an ability to be used by unskilled
operators. Balanced-lter techniques have two main disadvantages. Concentrations of at
least several elements must be determined; hence, separate measurements must be made
with several sets of balanced lters. The sensitivity of analysis is insucient for the lower
concentrations of some specic elements in the alloys.
Piorek and Rhodes (1986) showed that by using XRF analysis based on a 111-MBq
(3 mCi) 109Cd source and a high-resolution proportional detector, many alloys can be
identied in one measurement. Measurement is rst made to identify the alloy by group.
The spectrum of the unknown alloy is then compared with the key features of spectra of
known alloys in the group, which are stored in a memory chip in the equipment. This so-
called grade-identication mode of analysis is particularly useful because it does not
require the operator to be procient in the specics of alloy composition. In the grade-
identication mode, the analyzer uses a pattern-recognition algorithm to compare the
x-ray intensities of the measured sample with those of the stored references of alloy
standards. This approach is very fast, taking about 35 s to identify a single alloy. In
Table 5 Manufacturers and Suppliers of Radioisotope-Based Laboratory and Portable
Elemental Analyzers
Manufacturera Analyzer type Detector type
Amdel Laboratory Scintillation

ASOMAb Laboratory Gas proportional
BRGM Laboratory Solid-state Si(Li)
Metorex Int.b Portable, laboratory High-resolution gas
proportional; solid state:
Si(Li) or silicon p-i-n diode
Niton Corp. Portable Solid state: silicon
p-i-n diode, CdZnTe
Outokumpu Electronics, Oy Portable, laboratory High-resolution
gas proportional;
solid state: Si(Li)
Oxford Instrumentsb Laboratory Gas proportional
Radiation Monitoring Devices Portable Solid state: CdTe
TN Technologies Portable Solid state: mercuric
iodide, HgI2
a
See the list of manufacturers and their addresses in the Appendix of this chapter.
b
These manufacturers reacted to the dynamics of the market and industry by switching from isotope-based
instrumentation to x-ray-tube-excited devices.
Figure 23 The Metorex Int. portable alloy analyzer based on high-resolution silicon p-i-n diode
detector, MetalMasterTM 2000. (Courtesy Metorex Int.)

Figure 24 A laboratory, benchtop, elemental analyzer based on a high-resolution proportional
counter, X-METTM 820. (Courtesy of Outokumpu Electronics.)
comparison, assaying the alloy may take up to 4 min in order to maintain low measure-
ment uncertainty. Table 7 shows the identication results for dierent alloys by group,
obtained with the analyzer pictured in Figure 23. The probability of correct identication
is satisfactory for all alloys except the carbon steels. The results in Table 7 were generated
by measuring each alloy sample for 5 s for at least 10 times and comparing its spectral
features against the library of about 145 dierent alloys. The number of correct identi-
cations ratioed to the total number of trials for a given alloy group was then recorded in
Table 7 as a measure of probability of correct identication. Some of the identication
failures are for alloys very close in composition, for which the main alloying elements
dier in concentrations by less than 1%. The most dicult identication is for carbon
steels in which the concentrations of alloying elements are very low in the presence of
almost 100% iron, and the dierence in concentrations of the same elements between two
grades approaches the sensitivity of the XRF technique. Therefore, the XRF is not a
method of choice for identication of carbon steels, for which better techniques, such as
optical emission spectrometry, exist (Piorek et al., 1997).
By using a silicon p-i-n diode detector in place of a gas proportional one, it has been
possible to extend positive identication to such specic alloys as B1900 and B1900Hf,
which dier from each other by less than about 1% Hf, in the presence of several percent
of W and Ta and a balance of nickel.
Overall, the portable alloy analyzers oer a much simpler approach to identication
of alloys, with a reliability of identication as good as that for more complex techniques.
Despite the signicant dierences in design, the portable alloy analyzers exhibit si-
milar performance in the assay mode; that is, they oer measurement precisions ranging
from 0.01% to 0.5% absolute depending on the element, its concentration range, and the
Table 6 On-line Analysis Systems Based on Radioisotope X-ray Sourcesa
Application Analytical technique, detectorb Manufacturerc
Metal content of XRF/XRA, s and ss, in-stream Amdel

mineral slurries XRF, p, sample line Asoma
XRF, ss, sample line Outokumpu Mintec, Oy
XRF, ss, in-stream Texas Nuclear
XRF, ss, sample line Ramsey
Metal content of clay XRF, p, sample line Asoma
and mineral powders XRF, ss, sample line Outokumpu Mintec, Oy
Iron and chromium in Dual-energy XRS, s, on-line Outokumpu Mintec, Oy
ore on converyors
Ore sorting Dual-energy XRS, s, on-line Outokumpu Mintec, Oy
Ash in coal on conveyor Dual-energy XRS, s, on-line MCI; Harrison Cooper; SAI
XRS, s, on-line EMAG
XRS, s, sample line Humboldt-Wedag
XRS, p, sample-line Sortex
Solids weight fraction and XRF, neutron, and g Amdel
ash in coal in slurries transmission, s, on-line
Tin content of galvanizing XRS, p Rigaku
solutions
Calcium in cement raw mix XRF, s Rigaku; Outokumpy Mintec,
Oy
Sulfur in oil, diesel fuel, XRF, ion chamber, Yokogawa
gasoline sample line
XRF, p, sample-line Mitsubishi; Metorex Int.
Lead in gasoline XRF, p, sample-line Metorex Int.
Metals in plating bath XRF, p, sample-line Asoma; Metorex Int.
solutions (Ni, Cu, Cr, Ta, etc.)
Cement analysis for XRF, p, sample-line Metorex Int.
Ca, Si, Mg, Al, S, Fe
Corrosion products (Cr, Fe) in XRF, p, sample-line Detora Analytical
steam generator feedwater
of nuclear power plants
Ash content and/or mineral XRA, p, b-rays Sentrol; Yokogawa;
filler material in paper transmission, on-line Paul Lippke
XRF, p, on-line Sentrol
Coating mass of: Zn, Sn/Cr, XRF, p, on-line Data Measurement; FAG;
Sn/Ni, Zn/Fe, Sn/Pb on steel Gammametrics
and other substrates
a
X-ray tube techniques can be used in some of these applications.
b
Detectors: s scintillation, p gas proportional, ss solid state [usually Si(Li)].
c
See the list of manufactures and their addresses in the Appendix of this chapter.
matrix. Several references treat this subject in greater detail (Fookes et al., 1975; Jenkins
et al., 1981c, 1981d; Piorek and Rhodes, 1986; Piorek 1989; Spiegel and Horowitz, 1981;
Berry, 1981). Table 8 shows typical performance data for a contemporary portable XRF
alloy analyzer, such as illustrated in Figure 23.
Table 7 Performance of a Portable X-ray Analyzer in Alloy Identication
Identication results
Alloy group Measured elements (% feasible)
Nickel and cobalt alloys Ti, Cr, Fe, Co, Ni, Cu, Nb, Mo, W, Hf, Ta 100
Copper alloys Mn, Fe, Ni, Cu, Zn, Pb, Sn 90100; 98100
Stainless steels and Ti, Cr, Mn, Fe, Co, Ni, Cu, Nb, Mo 90100; 100
high-temperature alloys
Cr/Mo steels Cr, Fe, Ni, Mo 90100; 100
Low-alloy steels Cr, Mn, Fe, Ni, Cu, Nb, Mo 6580; 90100
Titanium alloys Ti, V, Mn, Cr, Zr, Mo, Sn 95100;
Aluminum alloys Mn, Fe, Cr, Cu, Zn 90100; 95100
Note: If two results are given, the rst refers to a gas-lled proportional detector, and the second to a solid state,
silicon p-i-n diode detector.
Source: From Piorex et al., 1997.
B. Determination of Uranium and Gold in Ore

During the exploration of mining of metalliferous ores, large numbers of ore samples must
be analyzed to compensate for the inherent variability of expression of the ore. The ore
may be analyzed in the laboratory or, for higher-Z elements, at the mine face or in situ in
boreholes.
K shell XRF techniques are often preferred for the analysis for uranium; because of
the penetration of the uranium K x-rays in the ore, little or no crushing of samples is
required and, additionally, the uranium concentration is averaged over much larger
samples. Uranium can be determined down to 20 mg=g or about 0.7 oz.=ton (1s) in 30 s
using a 222-MBq (6 mCi) 57Co and a 28-mm265-mm germanium detector (EG&G Or-
tec, 1986). This technique was used routinely to survey samples for uranium and other
Table 8 Standard Performance Data for a Typical, Contemporary, Commercially

Available Portable XRF Alloy Analyzer
Alloy group Ti Cr Mn Fe Co Ni Cu Zn Nb/Mo Sn Pb
Low-alloy steels 0.01 0.04 0.1 0.25 0.25 0.10 0.05 0.10 0.006 0.15 0.15
0.02 0.1 0.2 0.50 0.25 0.15 0.01
Stainless, hi-temp steels 0.015 0.20 0.10 0.20 0.20 0.20 0.06 0.20 0.01 0.30 0.05
0.03 0.30 0.20 0.30 0.30 0.10 0.03 0.30
Ni/Co alloys 0.10 0.20 0.10 0.12 0.10 0.20 0.05 0.30 0.02 0.30 0.15
0.50 0.30 0.50 0.50 0.50 0.30 0.08
Cu alloys, brass/bronze 0.02 0.10 0.02 0.02 0.05 0.05 0.15 0.07 0.01 0.008 0.20
0.06 0.06 0.08 0.40 0.30 0.20 0.30
Aluminum alloys 0.02 0.05 0.10 0.05 0.05 0.04 0.05 0.06 0.003 0.005 0.01
0.20 0.10 0.005 0.20 0.02
Titanium alloys 0.40 0.10 0.10 0.06 0.05 0.05 0.02 0.02 0.008 0.005 0.01
Notes: The values listed are typical precision ranges in percent absolute for total assay time per sample not longer
than 60 s. The differences are due to the analyzer model and/or the radioisotope(s) used.
Precision data listed are obtained with a 185-MBq (5 mCi) 109Cd and 1.48-GBq (40 mCi) 55Fe sources.
Source: From Piorek et al., 1997.

high-Z elements (Z
40) in the laboratory by the Australian company Geopeko in the
extensive exploration programs that found the large Ranger uranium deposit at Jabiru in
the Northern Territory, Australia (G. Sherrington, personal communication, 1987). It is
also used for borehole logging, with detection limits of 0.04 wt% (1s) for uranium,
tungsten, and lead and 6 mg=g for gold in 120 s counting time using a 518-MBq (14 mCi)
57
Co source and a small silicon detector in a 32-mm-diameter borehole probe (Scitech
Corp. undated).
An analysis system has been developed for the in situ determination of gold in ore at
the mine face (Hill and Garber, 1978). The hand-held probe consists of a 4.4-GBq
(120 mCi) 109Cd (88-keV g-rays) source, a 200-mm267-mm-thick germanium detector,
and a small Dewar ask containing liquid nitrogen, which must be replenished after 6 h of
operation. The sensitivity to gold has been optimized by careful choice of the incident
g-ray energy and by measuring gold Kb x-rays whose energy is greater than the energies of
most of the Compton-scattered g-rays. The precision for a 30-s scan time is 20 mg=g (1s)
and 2 mg=g for 100630-s scans. The technique is suitable for use in high-grade gold mines
but has insucient sensitivity to be applied widely in gold mining, in which 0.3 mg=g or
0.01 oz.=ton (1s) is normally required.
C. On-Line Determination of Coating Mass

Tin on steel (tinplate), zinc on steel (galvanized iron), zinc and aluminum on steel (zin-
calum), iron oxide on plastic (magnetic tape), and silicon coating on paper are only a few
examples of coated products manufactured in large quantities. The coatings are applied at
high speed. Accurate control of the coating mass per unit area is essential to economize the
operation.
Two XRF techniques can be used to determine the mass of the coating. Fluorescent
x-rays of the coating element can be excited and their intensity measured. The intensity of
the coating element x-rays increases with coating thickness. Alternatively, uorescent
x-rays of element in the base material can be excited. Their intensity decreases with the
increase in coating mass because of the absorption of the incident and excited x-rays in the
coating. Both radioisotopes and x-ray tubes are used as the source of x-rays, with
radioisotope sources preferred, except for those applications requiring very fast response,
such as 0.1 s.
Radioisotope XRF techniques for the on-line determination of coating mass are
based on the use of proportional detectors. These are preferred to scintillation detectors
because of their better energy resolution and because they can be used at the relatively high
temperatures that occur above the hot tin and galvanized iron coating processes. In
commercially available systems (Table 6), the analysis head unit continuously scans across
the width of the strip so that coating mass can be controlled across the whole strip. These
commercial systems are used worldwide in most high-throughput coating operations. They
can also be used to determine the separate coating masses of multiple coatings.
Coated products are usually sold with a specied minimum coating mass. The ac-
curate coating mass determination has led to coatings being controlled much closer to the
minimum specication. The variations in coating mass obtained on the zinc galvanizing
line of John Lysaght Pty. Ltd., Port Kembia, Australia, corresponding to no gauge, gauge
with manual control, and gauge with automatic control are shown in Figure 25. In 1977,
improved control of zinc coating mass led to savings of A$300,000 per year per line; si-
milarly, at the nearby Australian Iron and Steel Pty. Ltd., savings of A$1 million per year
(Watt, 1978) were made for tinplate.
Figure 25 The frequency distribution for product zinc coating mass before and after installation
of an on-line zinc coating mass gauge at John Lysaght Pty. Ltd. Product minimum specification is
300 g/m2. (From Watt, 1978).
Another typical coating mass application for XRF instruments is measurement of

zinc phosphate coating on steel (Johnson et al., 1989), where phosphorus x-ray intensity is
used rather than zinc to increase the sensitivity of analysis. A precision of 2 mg=cm2 was
achieved in a 30 s with gas-lled proportional detector and a 1.5 GBq (40 mCi) 55Fe source,
for up to 450 mg=cm2 coating mass.
D. On-Stream Analysis of Metalliferous Mineral Slurries

Most metalliferous minerals are concentrated from their ores by froth otation. The grade
of ore fed to the concentrator can vary rapidly; hence, to control the otation process, the
concentrations of valuable minerals in the plant process slurries should be determined
continuously. The concentrations, in the slurry solids, of such base metal minerals as
nickel, copper, zinc, and lead are usually in the range of 0.315 wt% for feed streams, tens
of weight % in concentrate streams, and 0.030.3 wt% in tailings (residue) streams. The
solids weight fraction is in the range of 1550 wt%. The time for analysis (less than 5 min)
is too short for laboratory analysis of samples taken from the process streams.
A radioisotope x-ray based on the use of scintillation detectors was introduced
in 1973 (Watt, 1985). Cesium-137 g-ray transmission is used to determine the bulk density
of the slurry and, hence, the solid weight fraction. X-ray uorescence techniques based
on direct excitation and detectorradiator assemblies (Fig. 18) are used to determine the
concentration of all but some high-Z elements, such as lead, which are determined by
153
Gd g-ray (about 100 keV) transmission. In each case, the x- or g-ray measurements are
combined with the solids determination to obtain the concentration of elements in the
slurry solids. These techniques are suciently sensitive for all but a few tailing streams
containing very low concentrations of valuable mineral. This limitation was overcome
later by the introduction of a solid-state detector probe.
The radioisotope x-ray system (Fig. 26) is based on probes, each containing a
radioisotope source and a detector, which are immersed directly into the plant process
slurries (Watt, 1985). Electrical signals from the probes are fed to an analyzer unit and its
output to a central computer. Thus, not only is there no need for sampling from the plant
process streams, but all streams are analyzed continuously rather than sequentially.
This radioisotope x-ray system is very dierent from x-ray tube and crystal spec-
trometer systems for on-stream analysis. These systems were developed in the 1960s to
scan slurries sequentially in up to 14 simple sampling loops (Leppala et al., 1971). Analysis
of the slurries involved sampling from the main process stream, running slurries through
long sections of sampling loops to the central analyzer, and subsampling from the sam-
pling loops before presentation to the analyzer. This is a complex and expensive system.
X-ray tube analysis systems developed in the 1980s sequentially route the slurries from up
to ve process streams through a common ow cell viewed by an XRF analyzing unit
(Saarhilo, 1983). The analyzer is mounted in the plant near the process streams and thus
overcomes much of the mechanical complexity of the 14-stream system just discussed.
Both the x-ray tube crystal spectrometer system and the radioisotope XRF solid-state
detector system are routinely used with this new sample loop system. Both systems can
also be used for the continuous analysis of ne powders. The radioisotope system is
capable of determining elements of atomic number as low as 14 (silicon), because with the
short x-ray path length, the absorption of the low-energy x-rays in air is minimized.
The development of dierent systems for the on-stream analysis of mineral slurries
illustrates the strong inuence of sampling and sample presentation on the type of XRF
analysis system used. Various radioisotope (Table 6) and x-ray tube systems are now in
use, with about several hundred plant systems being installed in concentrators throughout
the world. The radioisotope systems, both in stream (Watt, 1985; Berry et al., 1983) and
using short sample loop, and the ve-stream x-ray tube system, are preferred for new
installations because they cost less and are mechanically less complex. Improvements in
plant control based on this analysis information have led to an increase in the recovery of
valuable minerals (Fig. 27), decreased reagent addition, and reduced need for assay and
sampling sta (Watt, 1985). Total savings per concentrator vary in the range from
US$100,000 to several million dollars a year.
E. On-Line Determination of the Ash Content of Coal

Continuous on-line determination of the ash content of coal on conveyors is required for
the control of coal mining, blending, sorting, and preparation operations. The coal is
carried by the conveyors, usually at the rate of 100600 tons=h, the speed of the conveyor
Figure 26 A system for the on-stream analysis of mineral slurries. The microcomputer outputs solids weight fraction and concentrations of
valuable minerals in the solids of each stream. (Courtesy of AMDL.)

Figure 27 Improvements in recovery of mineral concentrators after installation of on-stream
analysis systems. The symbols refer to tin (diamonds), lead (square), zinc (circles) and copper
(asterisks).
is about 3 m=s, and the coal particle top size is in the range 10150 mm, depending on the
application. The process requirement for analysis time varies from 1 or 2 s for the fast
sorting of coal to 10 min for the steady-state control used in coal preparation plants.
Three x-ray or low-energy g-ray techniques have been developed: backscatter of
x-rays (H. Fraenkel, private communication, 1987), backscatter of low-energy g-rays
(Fauth et al., 1986; Cierpicz, 1986), and dual-energy g-ray transmission (Fookes et al.,
1983; Gravitis et al., 1987). Each relies on the photoelectric eect, which depends on
atomic number, and on the fact that ash (mainly SiO2 and Al2O3 with smaller con-
centrations of Fe2O3) has an eective atomic number, Z, greater than that of the coal
matter (carbon, hydrogen, nitrogen and oxygen).
The x-ray technique (H. Fraenkel, private communication, 1987) depends on the
scatter of approximately 17-keV x-rays from 238Pu (or 244Cm) source in the coal and, at
the same time, excitation of iron K x-rays in the coal to correct for the high absorption per
unit mass by Fe2O3 compared with Al2O3 and SiO2. Because the low-energy x-rays pe-
netrate only thin layers of coal, the coal is sampled from the conveyor, subsampled, and
ground to 5-mm top size particles, partially dried, and then presented in a moving stream
of controlled geometry to the radioisotope x-ray analysis system. This system compensates
for the eect of variations in Fe2O3 in the ash, a signicant source of uncertainty in some
applications. However, it involves complex sampling, sample handling and processing,
and blockages occur when the coal is very wet.
The low-energy g-ray technique, using an 241Am (60 keV) source, depends on mea-
surement of the intensity of g-ray scattered from thick layers (< 15 cm) of coal. It was rst
used on a high-throughput sample line (Fauth et al., 1986). Although coal must be
sampled, there is no need for the coal to be subsampled and crushed because of the high
penetration of g-rays in the coal. The technique has been adapted for use on-line (Cierpicz,
1986), the analysis head unit riding on a raft that is spring loaded so that it is always
touching the top of the coal on the conveyor. Its use is restricted to conveyor speeds of less
than 2 m=s and to minimum thickness of 15 cm of coal on the conveyor compared to the
normal practice of 520 cm.
The dual-energy g-ray transmission technique (Fookes et al., 1983; Gravitis et al.,
1987) measures coal directly on the conveyor belt (Fig. 28), eliminating the need for
sampling the coal. The ash content is determined independently of vertical segregation
of coal on the belt, and if segregation across the belt occurs, the narrow beam of g-rays can
be made to scan across the belt to obtain a representative sample. The coal mass per unit
area in the g-ray beam must be < 3 or 4 g=cm2 to achieve sucient sensitivity of analysis.
Variations of iron in the ash limits the accuracy of ash determination in some applications.
The choice of a suitable x- or g-ray analysis technique is highly inuenced by the
complexities in sampling of the coal on the conveyor and the subsequent subsampling and
grinding. Radioisotope techniques that measure directly on-line are preferred to those
involving sampling, and if sampling is necessary, preference is given to those that minimize
sampling and sample presentation.
Dual-energy g-ray transmission is now the preferred technique for the on-line
determination of ash content of coal, except for applications in which unacceptable un-
certainties in ash are caused by variations in iron in the ash. In this case, a high-energy
g-ray technique, which is based on the pair production interaction and is much less sen-
sitive to variations in iron, is preferred. Its main disadvantages are cost and that it must
operate on a sample line (Sowerby, 1986).
F. On-Line Analysis of Paper

Continuous on-line analysis of paper is required for control of the production process.
Paper consists of cellulose, water, and mineral llers. The characteristic and the quality of
various types of paper are, to a great extent, dependent on the quality, quantity, and
distribution of ller materials. These ller materials occupy the spaces between bers and
improve the printing properties of the paper. Filler materials include CaCO3, kaolin, talc,
and TiO2, and the concentrations of each may vary.
The analysis may be achieved by a combining XRF, XRA, and b-ray transmission
techniques (Kelha et al., 1983). The mass absorption coecients of x-rays in the 110-keV
region are shown in Figure 29, with abrupt changes in the K shell absorption-edge energies
of calcium (4.04 keV) and titanium (4.96 keV). X-ray preferential absorption measure-
ments are made at x-ray energies of 5.9 (55Fe), 4.51 (TiKa x-rays), and 3.69 keV (CaKa
x-rays), the latter two energies being contained by exciting a secondary target material
with 55Fe x-rays (Fig. 30). The total mass per unit area of the paper is determined by b-ray
transmission. The distribution of the ller material through the paper is determined by
making XRF measurements, using 55Fe x-rays to excite calcium K x-rays, to give the
dierence in CaCO3 concentrations near the surface on each side of the paper. These
techniques can be used to determine the concentrations of cellulose, kaolin or talc, CaCO3
and TiO2.
G. Determination of Sulfur and Chlorine in Oil

Sulfur in oil is a source of air pollution. Strict environmental controls are applied to limit
sulfur release into the atmosphere. Oil in sample lines from main pipelines is monitored
Figure 28 System for on-line determination of the ash content of coal based on dual-energy g-ray
transmission techniques.
routinely by one of two radioisotope x-ray techniques. One technique combines XRF
(55Fe and a proportional detector) and b-ray transmission. The other combines XRA,
using 22-keV silver K x-rays that are absorbed equally per unit weight by both carbon and
hydrogen, with a nonnuclear technique to determine the density of the oil. In Japan alone,
more than 100 of the former gauges and several hundred of the latter are used (Table 6).
More recently, this application received an application boost from regulatory agencies
such as U.S. Environmental Protection Agency. Since October of 1993, no on-highway
diesel fuel the United States can contain more than 500 mg=kg of sulfur. This regulation
forced sulfur monitoring for compliance at reneries, distributorships, and local suppliers.
A proportional detector with neon gas lling and a thin, 13-mm Be window, coupled with a
1.48-GBq (40 mCi) 55Fe isotope allows sulfur analysis in diesel fuel down to 50 mg=kg,
with a precision of 8 mg=kg (1s), in 300 s measurement time (Piorek and Piorek, 1993).
Figure 29 Mass absorption coefficients of the most frequently used filler materials, water and
cellulose, relating to the manufacture of paper. (From Kelha et al., 1983.)
A factor of 5 better results may be obtained by using low-power x-ray tube in the place of
the isotope. The issue of sulfur measurement in petroleum products for compliance with
the EPA regulations has been addressed by American Society for Testing and Measure-
ment (ASTM), with two ASTM Standard Test Methods, D2622 and D4294. Similar
regulations for sulfur in petroleum products for on-highway use are being implemented in
Europe and Asia.
Spent engine oil is burned as fuel in industrial boilers and home heating furnaces.
Because chlorinated solvents have routinely been mixed with much of this oil, there is a
danger that hazardous levels of these compounds or their derivatives will be released into
the atmosphere. The U.S. Environmental Protection Agency has banned the sale of used
oil for fuel if the total halogen level (interpreted as total chlorine level) exceeds 1000 mg=g.
If the total halogen level is more than 4000 mg=g, such oil has to be considered as
Figure 30 Measuring principle used in the on-line analysis of paper: (a) XRF, (b) XRA, and (c) b-ray absorption. (From Kelha et al.,
1983.)

hazardous waste and cannot be reused. However, if the total halogen level is greater than
1000 but less than 4000 mg=g, it may be diluted with less contaminated oil to reduce the
halogen content below 1000 mg=g, after which it can be burned as fuel. Piorek and Rhodes
(1987) and Gaskill et al. (1987) showed that a portable XRF analyzer, with a high-
resolution proportional detector and a 0.74-GBq (20 mCi) 55Fe source, can be used to
analyze for chlorine in oil. The used oil also contains phosphorus, sulfur, potassium, and
calcium, and the intensities of the K x-rays from all these elements were incorporated into
the calibration so that the measured chlorine K x-ray intensity could be properly corrected
for spectral overlap. The analysis time was 30 s per sample, and the overall accuracy
achieved was quite adequate.
H. Analysis of Environmental Samples

Perhaps the second most important group of applications well served by XRF is in the
analysis of a variety of environmental samples. This is especially true of portable XRF
analyzers, which, in a very natural way, drifted from mineral prospecting to soil screening for
metals; the two applications virtually dier only by name. Successes of XRF in analysis of
thin lms and coatings have been parlayed into measurement of air particulates collected on
lter media. Even much more analytically demanding analysis of water can also be per-
formed with XRF using ion-exchange membranes. All these applications will be discussed.
1. Air Particulates in Ambient Air

The concentrations of particulates suspended in ambient air are determined to identify
sources of air pollution. The air particulates are collected by drawing large volumes of air
through a lter paper, which is then submitted to multielements analysis. Rhodes et al.
(1972) and Florkowski and Piorek (1974) showed that energy-dispersive XRF analysis
based on radioisotope sources and a silicon solid-state detector is a simple and cost-
eective method for determining the elemental concentrations on the lter paper. The
advantage of the solid-state detector is that simultaneous multielement analysis is achieved
with excellent sensitivity and short analysis time.
Analyses were made using 4.44 GBq (120 mCi) 55Fe, 14.8 GBq (400 mCi) 238Pu, and
444 MBq (12 mCi) 109Cd, a 80-mm264-mm-thick silicon detector (energy resolution of
180 eV at 5.9 keV), and counting for 10 min per lter paper with 238Pu and 109Cd and 5 min
with 55Fe. The detection limit (3s of the background under the relevant peak) for the 19
elements measured varied in the range from 0.03 to 0.24 mg=cm2. This is more than adequate
for levels required in environmental pollution analysis. Rhodes and Rautala (1983) have
since shown that the same radioisotopes, with activities of 111370 MBq (310 mCi), can be
used with a high-resolution proportional detector to determine the same elements with de-
tection limits (3s) between 0.4 and 12 mg=cm2 in 4 min. The main competitive techniques are
energy-dispersive techniques using x-ray tubes and solid-state detectors (Chapter 3) and
particle accelerators in proton-induced x-ray emission (PIXE) techniques (Chapter 12). The
energy-dispersive XRF have been used for the last 20 years by various governmental and
international institutions for routine monitoring of ambient air pollution.
2. Air Particulates Monitoring in Stack Emissions and Workplace Air

The dierence between ambient air monitoring and stack emission or workplace air is
only in the levels of concentrations to be measured and frequency of sampling. As in
analysis of ambient air by ltering the air onto a thin membrane substrate, a signicant
preconcentration of the sample is realized, resulting in improved sensitivity of the XRF
analysis. Although the concentrations of metals in stack emissions and in workplace air
are much higher than in ambient air, they can only be sampled and analyzed for short
periods of time. Nevertheless, despite these restrictions, the portable x-ray analyzer can
still provide sucient sensitivity of measurement. The typical application is analysis of
metals in deposits obtained with personal samplers for breathing zone air used by
workers occupationally exposed to polluted air. Samples of air particulates are col-
lected for 8 h by pumping air through a 37-mm-diameter membrane, at a rate of about
2 L=min. These deposits can then by analyzed by the same portable XRF analyzer which
was used for soil screening during remediation eort. Within the last 3 years, the issue of
metals monitoring in stack emissions from industrial incinerators has been the subject of
regulatory action in the United States and Europe. Regulations in the United States are
pending which will limit emissions of toxic metals from incinerators stacks and will
require continuous on-line monitoring for compliance. Of the several attempts at Con-
tinuous Emission Monitoring (CEM) Systems, XRF proved to be a viable and relatively
inexpensive alternative. The proof of principle experiment using XRF was performed by
Piorek et al. in 1995 (Piorek et al., 1995) during the EPA-sponsored eld test in the
EPAs own hazardous waste incinerator in Little Rock, Arkansas. The test showed that
particulate deposits obtained by ltering stack exhaust for 10 min on lter membrane
can be readily analyzed by the portable XRF system with radioisotopes as excitation
sources (Makov et al., 1968). Table 9 lists the capabilities of the portable analyzer for
metals ltered from air on a membrane substrate (Piorek, 1997). As can be seen, the
detection limits for air particulates collected on the lter are on the order of a micro-
gram per cubic meter of air. Further improvement of the performance is possible using
x-ray tubes as excitation sources and integrating the analyzer into an continuous on-line
monitor.
Table 9 Performance of a Si(Li)-Detector-Based Field Portable X-ray Analyzer in Monitoring

Air Particulates in Workplace Air and Industrial Incinerator Exhaust
Detection limit Detection limita PELbin air Detection limit

Element (mg/cm2) (mg/cm3) (mg/cm3) CEMc (mg/cm3)
Cr 0.43 3.0 1000 1.5

Mn 0.45 3.2 50 ND
Fe 0.45 3.2 104 (as Fe2O3) ND
Ni 0.29 2.0 1000 ND
Cu 0.29 2.0 1001000 ND
Zn 0.27 2.0 (15) 103 ND
As 0.16 1.1 10 1.5
Se 0.16 1.1 200 ND
Pb 0.24 1.7 50 3.1
Cd 0.07 0.5 1003000 3.1
Sb 0.06 0.5 500 1.5
Sn 0.05 0.4 2000 ND
a
For one cubic meter of air (gas) pumped through a Millipore SMWP membrane of 9 cm2 area.
b
The OSHA Permissible Exposure Limit in work place air, PEL (as per 29 CFR 1910.1000, 1 Jan. 1977).
c
Hazardous waste combustors, revised standards, proposed rule, 40 CFR Part 60 et al., April 19, 1996. ND not
determined; CEM continuous emission monitor. Source: From Piorek, 1997.

The same technique for analyzing thin-layer samples can be used for measurement of
metallic ions in water, by cycling the water through an ion-exchange membrane. Piorek
and Pasmore (1993) reported the detection limits for transition metals in water at less than
0.1 mg=L if 250 mL of water was cycled seven times through a 37-mm-diameter ion-
exchange membrane, followed by a 200-s analysis with a 0.37-GBq (10 mCi) 109Cd source.
3. Soil Screening for Inorganic Contaminants

On-site analysis of metals in soils, sediments, and mine wastes is required as part of re-
habilitation studies at hazardous waste sites. The distribution of the hazardous metals is
heterogeneous owing to the exigencies of dumping and possible leaching by rainwater.
Many samples must be taken over the surface area and at depths to dene the zones of
metal accumulation and metal depletion. Chappell et al. (1986) and Piorek and Rhodes
(1987) demonstrated that the portable XRF analyzers based on a high-resolution pro-
portional detector and a 3.7-GBq (100 mCi) 244Cm source can be used to determine
concentrations of arsenic, copper, zinc, and lead in soils in the range of approximately
from 10 to 10,000 mg=g, with an accuracy that is adequate for this type of investigation.
Rapid, on-site analyses can be incorporated immediately into a eld investigation pro-
gram, making it possible to change the density of sampling at any spot, depending on the
results of previous analyses. Since then, portable XRF analyzers have been improved to
include high-resolution semiconductor detector probes and extensively used to measure
in situ metals in soil, such as lead, zinc, copper, arsenic, nickel, chromium, and cadmium.
In the majority of reported cases, the correlation between the XRF and the conrmatory
method results [such as Atomic Absorption Spectrometry (AAS) or Inductively-Coupled
Plasma Atomic Emission Spectrometry (ICP-AES)] was very good (correlation coecient
greater than or equal to 0.9) (Piorek, 1994). Cole et al. (1993) report on an extensive lead
study conducted during the summer of 1991 in Leadville, Colorado, where over 3700
samples of soil were analyzed for lead using portable XRF analyzers. The accuracy of the
lead determination by the XRF in that study was estimated at about 8% relative. Another
very important observation from that study is that the accuracy of the determination of
spatial distribution of lead in the soil does not depend so much on the accuracy of the
individual result as on the total (large) number of samples. In other words, raising the
analytical quality of the individual data has very little eect on the total uncertainty;
however, increasing the number of samples will considerably improve the accuracy of the
determination of spatial distribution of lead. This conclusion has been conrmed by other
researchers as well (Raab et al., 1991).
The portable XRF analyzer has been successfully used during remediation eorts at
the cleanup of soil contaminated with chromium (Waligora, 1997). More than 3000
samples were measured in the eld, providing an immediate feedback to an excavating
crew which was working literally on the heels of the eld analytical team. Figure 31
illustrates typical performance parameters of the contemporary portable XRF analyzer
with a Si(Li) detector probe for metals in soil matrix. As it can be seen, the typical de-
tection limits are in the range 50100 mg=kg. The success of portable XRF in soil
screening led to coining of a new term of eld-portable x-ray uorescence (FPXRF),
probably to distinguish this application from the others.
The FPXRF analyzer oers an attractive, in situ alternative to the traditional la-
boratory analysis of contaminated soil. The operator equipped with the portable XRF
analyzer can perform a large number of multielement measurements in situ by placing the
probe directly on the soil surface, thus allowing for the decisions to be made in real time.
Moreover, the measurements can also be performed at any stage of the remediation
Figure 31 Typical detection limits (DLs) for metals in soil obtained with field portable X-ray analyzer equipped with a
Si(Li) detector probe. Conditions: Si(Li) detector, 30 mm2 area; measurement time 200 s; sample matrix: silica sand. K series
excitation with 109Cd and 241Am isotopes. Open rectangles correspond to 1s uncertainty of counting; solid rectangles mark
the DL. The DLs for heavy metals determined via their L series x-rays, such as Pb, Hg, Bi, are numerically similar to those
from Zn to Br. (From Piorek, 1994.)

process to either verify that the cleanup is accomplished or that the work has to continue.
The results obtained with the XRF analyzer will reveal relative variations of contami-
nant(s), their spatial distribution, and pinpoint locations with elevated contamination
levels (so-called hot spots), thus making sampling plans realistic and ecient. This is
particularly important because any contaminated site is likely to have an extremely het-
erogeneous distribution of hazardous chemicals in the soil. For that reason, the sampling
strategies will mandate that many densely distributed samples are taken, in order to ensure
that hot spots are not missed. This type of analysis, which is referred to as screening,
is allowed by the EPA to have uncertainties as large as 50% relative (EPA, 1987). Most
recently, the ocial recognition of the FPXRF as a valid soil characterization method has
materialized in a form of a new EPA Method 6200, which has been published in June of
1997 (EPA, 1997).
4. Analysis of Liquid Hazardous Waste

The analysis of liquid hazardous waste (LHW) is required prior to its treatment in order to
properly set up the treatment process and, also, after the treatment to determine the nal
disposition of the treated waste. Liquid waste is a mixture of solids suspended in a liquid
medium. Solid particles vary considerably in particle size and composition, whereas the
liquid phase is often a mixture of immiscible liquids. The sludge remaining after the
treatment of liquid waste is either transported to a waste dump or, preferably, utilized for
soil amendment in agriculture and forestry because it is often rich in nutrients. However,
depending on the origin of the waste, it may also contain a whole range of heavy metals,
which even at moderately elevated concentrations, are very toxic to plants and animals. In
order to avoid the accumulation of toxic metals in soil, the concentration of these metals in
the original waste, as well as in postprocess sludge, has to be known.
Traditionally, the liquid waste samples are analyzed by a ame or graphite furnace
AAS or ICP-AE. Those methods, while oering low detection limits, are slow and labor
intensive. Additionally, they call for rather involved sample preparation (digestion) and
are relatively expensive. Energy-dispersive x-ray uorescence spectrometry was considered
as an alternative analytical method for liquid waste due to its known features of speed,
multielement character, wide dynamic range, and little to no sample preparation re-
quirement. However, the diversity of form and composition makes LHW an extremely
dicult medium to analyze with XRF as a result of the severe matrix eects present in a
sample of LHW. The severity of matrix eects in liquid hazardous waste precludes the use
of many known calculational models correcting for absorption=enhancement phenomena
because mathematical models are valid only for physically and chemically homogeneous
materials. To overcome these diculties, a novel empirical approach was proposed for
stabilization of the sample matrix by dilution (ASTM, 1997; Piorek et al., 1997), For the
purpose of XRF analysis of liquid hazardous waste, a calcined alumina powder (Al2O3)
was used as a diluent. This powder is characteristic for its highly adsorptive properties
toward liquids. Thus, after adding a small amount of liquid to an aliquot of Al2O3, the
latter instantly absorbs the liquid. After brief mixing and shaking, the originally liquid
sample is converted to a homogeneous powder. The mass ratio of the diluent to sample has
to be maintained constant from sample to sample and should not be smaller than 3:1,
otherwise the sample=diluent mixture will behave more like a slurry than a powder. This
kind of sample matrix stabilization is eective for liquids as well as liquids with suspended
solids. By diluting and mixing, both the liquid as well as the suspended solids are now
suspended in alumina powder, which does not allow waste solids to settle. Another
important function of alumina is that it dominates the matrix of the sample and, therefore,
the composition dierences between the original samples of waste are reduced to easily
manageable levels. For calibration, a set of samples of alumina powder is prepared by
spiking with a known amount of standard solutions. The details of the technique are
described in the ASTM Standard Method D6052-97 (ASTM, 1997). Using a portable
Si(Li)-detector-based probe with a 0.74-GBq (20 mCi) 109Cd source and a 1.11-GBq
(30 mCi) 241Am source, the 200-s measurement time detection limits obtained with this
method for elements ranging from Cr to As were between 35 and 10 mg=kg, respectively.
For heavy elements such as Hg, Pb, Cd, and Sb, detection limits were 12, 8, 4, and
4 mg=kg, respectively.
5. Analysis of Lead in Wall Paint

A prolonged exposure to low levels of lead may lead to serious health problems in young
children, including impairment of the central nervous system, behavioral disorders, and
mental retardation. Paint, dust, soil and, to a lesser extent, food, water, and air are all
potential sources of exposure to lead. After banning the use of leaded gasoline in the U.S.,
lead-based paint is recognized as the principal source of lead in dust and soil. From here it
can easily enter a childs system as the result of hand-to-mouth activity, typical for young
children. These concerns were addressed with federal regulations in the early seventies.
The essence of those regulations is that any applied lead-based paint exhibiting more than
1.0 mg of lead per square centimeter must be removed, as well as any applied to surface
paint that contains more than 0.5% lead by dry weight. In recent years the lead-based
paint danger became the focus of attention in European countries. France, for example,
introduced guidelines for lead levels in paint and followed with enforcement regulations
(Law No. 99-483 of June 9, 1999). It is expected that other countries will follow Frances
example in coming years.
The preferred method for testing applied paint for lead is FPXRF (McKnight et al.,
1989; Piorek et al., 1995). This is because XRF is nondestructive and fast and oers overall
good performance. Additionally, lead x-rays, either K or L series, have high penetrating
power (especially the Ks), and are not interfered with by the other elements which make up
the paint. As the result, the XRF method is quite selective for lead in leaded paint applied
on any substrate. A number of accounts on this subject has been published over the years,
and a number of portable XRF devices was designed for just lead in wall paint mea-
surements. The majority of the instruments used lead K shell x-rays, excited either with
57
Co or 109Cd (the 88-keV g-rays of this isotope), but some have utilized L shell excita-
tion of lead. The latter approach has been reported to be able to measure lead with a
proportional detector and a 2.1-GBq (60 mCi) 244Cm source with a precision of
0.05 mg Pb=cm2. Probably the most successful overall lead in paint analyzer has been
Model LPA-1 from Radiation Monitoring Devices. The self-contained instrument in a
shape of the lightweight pistol uses a 57Co isotope and CdTe detector to determine the lead
concentration in applied paint at a 2s condence level in 5 s measurement time. The
analyzer automatically adjusts the measurement time to reach a preset level of total
measurement uncertainty. The instrument is an example of well thought out ergonomical
design, responding well to the needs of the market. The analyzer can be preset for a
specic, local lead abatement action level and it can generate a hard-copy analytical
report. Another interesting entry in the lead in paint market is the Model XL from the
Niton Corporation (1999). Although a marvel of miniaturization, its shape seems less
conforming to the requirements expected of a hand-held device operated continuously for
several hours. This is also the only commercially available analyzer which uses L shell lead
x-rays for analysis and the ratio of the lead La to Lb lines for determination of the depth at
which leaded paint is present under overcoats of other paint (Shefsky et al., 1997); in those
instances in which leaded paint may be buried under overcoats of paint, the instrument
uses K shell lead lines for measurement, as there are very little aected by top layers of
paint.
I. Analysis of Corrosion Products

An interesting on-line application has recently been reported by Connolly and Millet
(1994) and Connolly and Harvey (1995) for corrosion product monitoring in nuclear
power plant feedwater. By coupling the XRF analyzer probe to a specially designed
sample ow chamber, the authors realized continuous measurement of incremental ac-
cumulation of corrosion products such as iron. The feedwater is circulated through the
sample ow chamber, where it passes through the membrane lter. The solids present in
the water are collected on the lter surface and then measured with an XRF probe. The
measurement is incremental, so that the lter does not have to be removed for analysis
after each sampling cycle. A gas-lled proportional detector and 3.7-GBq (100 mCi) 244Cm
source allow one to routinely achieve the detection limits for iron of 1 ppb, at a 300-s
sampling period followed by 300 s of measurement time. Further work is under way to
improve these performance and to extend the applicability of this method to other ele-
ments and liquid media.
VII. FUTURE OF RADIOISOTOPE-EXCITED XRF ANALYSIS
As we have stated in the Introduction, radioisotope x-ray analysis is mainly useful in

industrial and eld applications. This trend will continue, although the proportion of on-
line installations for process control to number of eld-portable x-ray analyzers will
constantly decrease. First, it will be the result of a more general contemporary trend in the
instrument industry of bringing the analytical method to the site. Second, the number of
applications that can benet from portable XRF analysis is much greater and more di-
versied than the number of installations for process control. Third, radioisotope-based
on-line installations will gradually be displaced by systems based on x-ray tubes. Last but
not least, on-line installations will face erce competition from new analytical technologies
based on lasers, which, in many cases, oer instantaneous results at a high repetition rate.
As a result, in the very near future, radioisotope x-ray analysis may become synonymous
with eld-portable XRF and, therefore, the future of radioisotope X-ray analysis will most
likely depend on the developments in eld-portable XRF.
The next designs of the portable XRF analyzers will feature new, high-resolution-
semiconductor, room-temperature detectors. Most likely these will be improved detectors
based on silicon diodes (p-i-n detector) or composite semiconductors such as ZnCdTe,
CdTe, GaAs, and so forth. A recently introduced x-ray detector (Xash Detector) built on
a silicon chip as a solid-state drift chamber oers count-rate capabilities well into
50,000 cps at an energy resolution still better than 200 eV (Rontec 1997). The portable
XRF analyzer of the future will incorporate a GPS (Global Positioning System) module,
whichif neededwill instantly locate the measurement site on the map andif properly
equippedwill transmit the measurement results via a wireless link to a central data
collection station. An instrument with a GPS chip installed will also be very easy to track
down if misplaced or stolen, a very desirable feature for a radioisotope-containing device.
The FPXRF will travel underground, as an analytical module built into the push-in
probe or in a cone penetrometer. The rst trials were very encouraging (Elam et al., 1997).
Technological progress will also bring us truly small x-ray sources, which will gradually
replace radioisotopes in applications requiring less than 35-keV-energy x-rays (Moxtek
Inc., private information, 1998). We should also expect an increased number of dedicated,
smart XRF analyzers customized to specic applications, such as the already mentioned
measurement of lead in wall paint. New portable instruments will be smaller, lighter, and
smarter than their predecessors. Perhaps the avor of the future direction of develop-
ment of portable, radioisotope excited XRF is best exemplied by Model XL by Niton
Corp. (Fig. 32), a one-piece, miniature XRF analyzer with built-in ADC=MCA, and
weighting only about 1.6 kg (Niton Corp., 1999).
VIII. CONCLUSIONS
X-ray uorescence spectroscopy is perhaps the rst spectroscopic technique to successfully

enter the eld and plant environments. Radioisotope x- and g-ray techniques have been
widely used for analysis in the laboratory, in industrial plants, and in the eld. Because of
their simplicity, they are preferred to x-ray tube analysis techniques in many applications,
particularly for more routine analyses involving a limited range of sample compositions.
The techniques are less sensitive, however, than those based on x-ray tubecrystal spec-
trometer systems and less exible to widely dierent analysis applications. Radioisotope
x- and g-ray techniques have had great impact on industrial and eld applications. Their use
Figure 32 Niton II, XRF Alloy Analyzer based on a silicon p-i-n diode. (Courtesy Niton Corp.)

for the continuous on-line analysis in the coating, mineral, coal, paper, and petroleum in-
dustries has led to better control of the industrial processes. This, in turn, has led to products
that more closely meet specications, with consequently large savings in production costs.
Portable XRF analyzers have been around for about 30 years, and during that
period, their design has been rened and their performance greatly improved. A con-
temporary, high-resolution, portable XRF analyzer brings to the eld site not only an
excellent performance often matching that of the laboratory instrument but also un-
surpassed savings in time and labor, contradicting the popular conviction about the in-
herent inferiority of portable instrumentation. The use of portable instruments in the eld
(e.g., for the sorting of alloys and for detection of hazardous waste materials) has led to a
much more rapid analysis of materials and, hence, to the much wider use of x-ray tech-
niques in eld analysis. Field-portable x-ray uorescence is an example of a well-balanced
compromise among portability, ruggedness, reliability, and analytical performance. There
are not that many analytical techniques that can rival FPXRF in simplicity, speed of
operation, and relaxed requirements of sample preparation. Whenever a fast and frequent
elemental analysis for inorganics is required, there is a place for the FPXRF analyzer.
This applies in particular to scenarios in which a quick verication type of analysis is
needed.
APPENDIX: LIST OF COMPANIES THAT MANUFACTURE RADIOISOTOPE-BASED

X-RAYANALYZERS AND SYSTEMS
AMDL (Australian Mineral Development Laboratories), P.O. Box 114, Eastwood,

SA 5063, Australia
ASOMA Instruments, 11675 Jollyville Road, Austin, TX 78759, USA
BRGM, BP 6009-45060 Orleans, Cedex 02, France
Data Measurement Corporation, P.O. Box 490, Gaithersburg, MD 20877, USA
Detora Analytical, P.O. Box 2747, Alliance, OH 44601-0747, USA
Electrical Engineering and Automation (EMAG), Katowice, Poland
FAG Kugelscher Georg Schafer KG Auf Aktien, Tennenloher Strasse 41,
Erlangen, Germany
Harrison Copper Systems, Inc., AMF Box 22014, Salt Lake City, UT 84122, USA
Harshaw Radiation Detectors, Harshaw=Filtrol Partnership, 6801 Cochran Road,
Solon, OH 44139, USA
Humboldt Wedag, P.O. Box 2729, 4630 Bochum, Germany
Kevex Corporation, P.O. Box 4050, Foster City, CA 94404, USA
Metorex International Oy, P.O. Box 85, SF-02631 Espoo, Finland
Mineral Control Instrumentation Pty. Ltd., P.O. Box 64, Unley, SA 5061, Australia
Mitsubishi Corporation, 6-3, Marunouchi 2-chone, Chiyoda-Ku, Tokyo 100, Japan
Niton Corporation, 900 Middlesex Turnpike, Bldg. 8, Billerica, MA 01821, USA
Outokumpu Oy, PO Box 85, SF-02201, Espoo, Finland
Oxford Instruments, 20 Nueld Way, Abingdon, Oxon OXI4 1TX, UK
Paul Lippke GmbH & Co. KG, Postfach 1760, 5450 Neuwied 1, Germany
Radiation Monitoring Devices, 44 Hunt Street, Watertown, MA 02172, USA
Ramsey Ltd., 385 Enford Rd., Richmond Hill, Ontario, L4C 3G2, Canada
Rigaku Denki, 14-8 Akaoji, Takatsuki-shi, Osaka, Japan
Science Applications Inc., 1257 Tasman Drive, Sunnyvale, CA 94089, USA
Sentrol Systems Ltd., 4401 Steeles Avenue West, North York, Ontario, Canada,
M3N2S4
Sortex Ltd., Pudding Mill Lane, London E15 2PJ, UK
TN Technologies (Texas Nuclear Corporation), 2555 North Interstate Hwy 35,
Round Rock, TX 78689, USA
Tracor X-ray, Inc., 345 East Middleeld Rd., Mountain View, CA 94043, USA
Yokogawa Hokushin Electric Corporation, 9-32 Nakacho 2-chome, Musashino-shi,
Tokyo, 180, Japan
ACKNOWLEDGMENTS
The author thanks the many scientists, organizations, and companies who generously
supplied information used in this chapter and to the following for permission to reprint
gures used in this chapter: Pergamon Press (Figs. 2, 14, 18, 21, 22, and 28); EG&G Ortec
(Fig. 1); The Radiochemical Centre, Amersham (Fig. 4); the International Atomic Energy
Agency (Fig. 7); The Analyst (Fig. 20); Outokumpu Oy (now Metorex Int.) (Figs. 11 and
23); IEEE (Fig. 16); Automatica (Fig. 25); Australian Mineral Development Laboratories
(Fig. 26); The Australasian Institute of Mining and Metallurgy (Fig. 27); and Acta
Polytechnica Scandinavia (Figs. 29 and 30).
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7

Radioisotope-Excited X-ray Analysis

*Previous aliation: Metorex Inc., Princeton, New Jersey.

Copyright 2002 Marcel Dekker, Inc.

Copyright 2002 Marcel Dekker, Inc.

Copyright 2002 Marcel Dekker, Inc.

B. Fluorescent X-ray Intensity

C. Scattered X-ray Intensities

Copyright 2002 Marcel Dekker, Inc.

D. X-ray Fluorescence Analysis

E. X-ray Preferential Absorption Analysis

F. X-ray Scattering Analysis

III. RADIOISOTOPE X-RAY SOURCES AND DETECTORS

Copyright 2002 Marcel Dekker, Inc.

B. X-ray and g-ray Detectors

1. Energy Resolution of the Detector

Copyright 2002 Marcel Dekker, Inc.

2. Energy Resolution of Detector and Minimum Detectable Level

3. Detector Efficiency for X-rays and Detector-Sensitive Area

Energy resolution of detector, FWHM (in eV)

Atomic No. Energy of Dierence in Solid Gas-lled

13 (Al) 1,490 253 117 425 3,000

Copyright 2002 Marcel Dekker, Inc.

Copyright 2002 Marcel Dekker, Inc.

Figure11 X-ray detection efficiencies of Metorex International (formerly Outokumpu Electronics)

Copyright 2002 Marcel Dekker, Inc.

4. Ratio of Full-Energy Peak toTotal Spectrum

5. Comments on the Characteristics of Proportional Detectors

6. Developments in Solid-State Detectors

A. XRF Techniques Based on Solid-State Detectors

Copyright 2002 Marcel Dekker, Inc.

Copyright 2002 Marcel Dekker, Inc.

B. XRF Techniques Based on Proportional Detectors

The relatively modest improvement in energy resolution of the high-resolution

C. XRF Techniques Based on Scintillation Detectors

Copyright 2002 Marcel Dekker, Inc.

Figure 18 Three types of radioisotope XRF assembly based on scintillation detectors.

Copyright 2002 Marcel Dekker, Inc.

Copyright 2002 Marcel Dekker, Inc.

Copyright 2002 Marcel Dekker, Inc.

4. -Ray-Excited X-ray Assemblies

D. X-ray Preferential Absorption Techniques

Copyright 2002 Marcel Dekker, Inc.

F. Count Rates and Calibration

V. FACTORS AFFECTING THE OVERALL ACCURACY OF XRF ANALYSIS

A. Overall Accuracy and Time for Analysis

B. Uncertainties of Sampling and Sample Presentation

1. Uncertainty Due to Sample Heterogeneity

2. Sample Heterogeneity and Detection Limits

C. Choice of Radioisotope X-ray Technique

Application Typical examples

Manufacturera Analyzer type Detector type

Amdel Laboratory Scintillation

Copyright 2002 Marcel Dekker, Inc.

Application Analytical technique, detectorb Manufacturerc

Metal content of XRF/XRA, s and ss, in-stream Amdel

B. Determination of Uranium and Gold in Ore

Table 8 Standard Performance Data for a Typical, Contemporary, Commercially

Alloy group Ti Cr Mn Fe Co Ni Cu Zn Nb/Mo Sn Pb

Copyright 2002 Marcel Dekker, Inc.

C. On-Line Determination of Coating Mass

Another typical coating mass application for XRF instruments is measurement of

D. On-Stream Analysis of Metalliferous Mineral Slurries

4. -Ray-Excited X-ray Assemblies