Chapter 6

Alpha Spectrometry
Nora Vajda
Radiochemical Laboratory, RadAnal Ltd., 1121 Budapest, Hungary

Paul Martin
Australian Radiation Protection and Nuclear Safety Agency, Yallambie VIC 3085, Australia

Chang-Kyu Kim
Korea Institute of Nuclear Safety, Daejeon 305-338, Republic of Korea, Current: Health Physics Unit, Queensland Health Forensic and Scientific
Services, 39 Kessels Road, Coopers Plains, Queensland 4108, Australia

Chapter Outline
I. Introduction 364 1. Preparation of Solid Samples 394
II. Alpha Decay and Alpha-Emitting Nuclides 365 2. Preconcentration of Liquid Samples
III. Detection Systems 368 and Sample Solutions 394
A. Detectors 369 B. Chemical Separation 396
1. Interaction of Alpha Radiation with Detector 1. Separations by Liquideliquid Extraction (LLE) 396
Materials 369 2. Separations by Ion Exchange 399
2. Characterization of Spectroscopic Detectors 371 3. Separations by Extraction Chromatography (EC) 401
3. Gas Ionization Detectors 372 C. Alpha Source Preparation 409
4. Semiconductor Silicon Detectors 373 VI. Determination of Alpha Activity and Recovery 409
5. Scintillation Detectors 375 A. Calibration 410
6. Cryogenic Detectors 379 B. Measurement Procedure 410
B. Electronic Units 379 C. Alpha Spectrum Evaluation 411
IV. Characteristics of the Alpha Spectrum 380 1. Principle of Evaluation 411
A. Peak Shape and Spectrum Analysis 380 2. Nuclide Identification 411
1. Peak Shape and Spectrum Analysis with 3. Peak Area Determination for Nonoverlapping
Si Detectors 380 Peaks 411
2. Peak Shape and Spectrum Analysis 4. Peak Area Determination with Correction for
with Gas Ionization Detectors 386 Overlapping Peaks 411
3. Peak Shape and Spectrum Analysis 5. Calculation of Results 412
with Liquid Scintillation Detectors 387 6. Calculation of the Combined Standard Uncertainty 413
4. Peak Shape with Cryogenic Detectors 387 7. Calculation of the Decision Threshold
B. Counting Efficiency 388 and the Detection Limit 414
C. Background and Contamination in Alpha VII. Quality Control 415
Spectrometry 389 A. Quality Control for Alpha Spectrometers 415
D. Stability of the Alpha Spectrometer 390 B. Validation of the Procedure 415
V. Radiochemical Processing 390 VIII. Conclusions 416
A. Sample Preparation and Pretreatment 394 References 416

Handbook of Radioactivity Analysis. DOI: http://dx.doi.org/10.1016/B978-0-12-384873-4.00006-2 363

Copyright Ó 2012 Elsevier Inc. All rights reserved.
364
I. INTRODUCTION
Alpha spectrometry is a widely applied radioanalytical tech-
nique, primarily due to its high counting efficiency and low
intrinsic background (resulting in a high sensitivity), its versa-
tility in terms of both the range of radionuclides which can be
determined and sample types which can be analyzed, and the
reliability of the technique due to the possibility to use an alpha-
emitting isotope of the element of interest as an internal tracer.
For some special applications, it is possible to carry out
alpha spectrometry using only minimal sample preparation
(Surbeck, 2000; Röttger et al., 2001; Ranebo et al., 2010;
Samuelsson, 2011). However, the short range of alpha particles
through matter means that, in general, separation of the radio-
nuclides of interest from the bulk sample matrix is required.
This involves dissolution of the sample and chemical separation
of the radionuclides prior to source preparation.
In practice, a separate source is normally prepared for each
element for which radioisotopes are to be determined. For each
of these sources, the chemical separation should fulfill three
aims. First, it should remove elements, which would interfere
in the final source preparation step in such a way as to reduce
the recovery of the element of interest. Second, it should
remove elements, which would deposit on the final source,
resulting in a thick source and hence degraded spectral reso-
lution. Third, it should remove other alpha-emitting radionu-
clides which would interfere with the peaks of interest in the
spectrum. A major part of the effort expended in the devel-
opment of alpha spectrometry relates to improvements in these
chemical separation procedures, and in particular minimizing
the time required.
The number of radionuclides that can be reliably determined
using alpha spectrometry is quite large. It includes almost all of
the alpha-emitting radionuclides with half-lives long relative to
the time required for source preparation. Beta-emitting radio-
nuclides can also be determined if they have alpha-emitting
progeny which may be measured on the source following
a suitable ingrowth period. For example, 228Ra may be deter-
mined using its progeny 228Th and 224Ra (Hancock and Martin,
1991), and 227Ac may be determined using 227Th and 223Ra
(Bojanowski et al., 1987).
Another major advantage of alpha spectrometry is its high
sensitivity, with detection limits as low as 1 mBq per sample
being easily achievable. This arises due to several factors. The
first of these is the high yield of the alpha decay process. For
most alpha-emitting radionuclides, there are only a few peaks
within a relatively small energy range, representing a total
intensity of or close to 100% of decays. Second, semiconductor
alpha detectors have a low intrinsic background, being typically
10
5e10
6 counts per second for an uncontaminated detector.
Third, the intrinsic efficiency of the detector system is close to
100% for incident alpha particles. Consequently, the counting
efficiency is dominated by the geometric efficiency, which is
typically about 20e40% for sources placed close to semi-
conductor detectors. A fourth factor is the elimination of
competing radiation by chemical separation, and the last factor
is the low sensitivity of the semiconductor alpha detector to beta
and gamma radiation.
Handbook of Radioactivity Analysis
An outcome of the sensitivity of the technique is the ability
to analyze relatively small sample sizes. For example, for the
determination of uranium- and thorium-series radionuclides in
environmental samples, common sample sizes are of the order
of 1e10 g for soils, sediments, and biological samples, and
0.1e1 L for water samples.
The use of an alpha-emitting isotope as an internal tracer
makes alpha spectrometry a highly reliable analytical tech-
nique, provided no losses occur before the sample and tracer
isotopes have been equilibrated. The internal tracer
compensates not only for losses during the chemical separa-
tions, but also for the counting efficiency of the detection
system. This is because the result is obtained directly from
the ratio of sample to tracer peak areas. Consequently,
a highly accurate knowledge of the counting efficiency is not
required in order to achieve accurate determinations of the
target radionuclides.
A further advantage is that the capital cost for an alpha
spectrometry system, including detector, counting chamber, and
associated electronics, is significantly lower than that for
a number of other systems capable of isotope discrimination.
Counterbalancing this is the requirement for chemical labora-
tory facilities and reagents.
The major disadvantage of alpha spectrometry is that time-
consuming chemical separation procedures are normally
required to remove the bulk matrix, elements which interfere
with recovery of the element of interest, and other alpha
emitters. Only in some special applications (such as the
determination of airborne concentrations of radon progeny) is
alpha spectrometry without chemical separation possible.
Typically, the full chemical digestion, separation, and source
preparation procedure require several steps over several hours.
In recent years, some automated systems have been developed
to reduce the need for operator time in this process (Kim et al.,
2008).
Unlike many other radioanalytical techniques, alpha spec-
trometry is element-based in the sense that each spectrum
consists of the alpha-emitting radionuclides of one element
(plus those alpha-emitting progeny which grow in on the source
in the interval between preparation and counting). This means
that a separate source must be prepared and counted for each
element of interest in the sample. However, it also gives rise to
the advantage that the spectrum is in a sense “predictable.”
Given the element for which the source has been prepared, the
analyst knows which peaks are expected in the spectrum, with
only the relative areas under each peak varying for different
sources. This simplifies spectrum analysis. It also enables an
important quality control check, which is the examination of the
spectrum for peaks which would not be expected for a source of
the given element. The presence of such unexpected peaks may
indicate that the chemical separation was not sufficiently
effective in removing other alpha-emitting radionuclides from
the sample extract.
In some cases, alpha spectrometry has disadvantages in
comparison with other techniques for case-specific reasons. One
important example is the impossibility of distinguishing 239Pu
and 240Pu with conventional alpha spectrometry due to their
overlapping spectra.
Chapter | 6 Alpha Spectrometry
Alpha particle spectrometry has found application in
a number of widely diverse fields, from the analysis of alpha-
emitting radionuclides in nuclear materials of high activity to
environmental samples of low and ultralow activity. An example
of its widespread use in environmental studies is the measure-
ment of 210Po in soil and sediment samples, as an indirect
measure of 210Pb for erosion and sedimentation investigations
(Robbins, 1978). Other examples include measurement of U and
Ra radionuclides to investigate groundwater, surface water, and
seawater processes (Hancock et al., 2000; Porcelli, 2008), and of
210
Po as an atmospheric tracer (Baskaran, 2011).
Alpha spectrometry is commonly used for monitoring of
environmental samples for the impact of nuclear activities.
Examples include actinide determinations on soil samples, and
analysis of water samples downstream of uranium mining
operations for uranium-series radionuclides. The technique is
also used for internal dosimetry for workers, by means of
analysis of biological samples such as urine (Kehagia et al.,
2007; Manickam et al., 2010).
As a result of developments in detector fabrication and
source preparation procedures, as well as progress in the tech-
nology of multichannel analyzers and spectrum evaluation
codes, high-resolution alpha spectrometry became available
from the 1980s. Thus, a precise and sensitive technique was
developed that is suitable for measurement of nuclear data such
as half-life, cross section (Wiltshire, 1984), and emission
probabilities (Bortels and Collaers, 1987). More recently,
cryogenic detectors have dramatically improved the achievable
peak resolution.
Recently, some mass spectrometry techniques, which detect
the radioactive atom itself rather than the emitted radiation,
have shown significant advances in sensitivity for the determi-
nation of long-lived alpha-emitting radionuclides. These
developments have made these techniques rivals to, and in some
applications superior to, alpha spectrometry in terms of sensi-
tivity and/or sample throughput. Nevertheless, the advantages of
alpha spectrometry, especially for shorter-lived radionuclides,
mean that it will remain an important, standard technique for the
foreseeable future.
II. ALPHA DECAY AND ALPHA-EMITTING
NUCLIDES
Alpha decay occurs when a nucleus of helium 42 He2þ called an
“alpha particle” is emitted from a heavy nucleus. After the
decay, the mass number (A) and the atomic number (Z) of the
new nucleus are lower by four and two, respectively:
A
zX / A
4
z
2 Y þ 42 He þ Q (6.1)
During the spontaneous decay, the decay energy Q is
liberated and shared between the reaction products A
4 z
2 Y and
4 He2þ according to the law of conservation of momentum. The
2 tors, the most common being gas ionization, semiconductor,
kinetic energy of the alpha particle (Ea) can be calculated from


1
Ea ¼ Q 1
(6.2)
1 þ mY =ma
365
where Q is the disintegration energy, mY is the mass of the
daughter nuclide Y (also called the recoil atom), and ma is the
mass of the alpha particle (a).
Since the masses of the decay products are significantly
different, the kinetic energy of the alpha particle is almost equal
to the total decay energy Q. The decay energy Q and therefore
the energy of the alpha particle Ea is in the range of 2e8 MeV.
(A more detailed description of alpha decay is given in Chapter I.
section VIII.A.)
Alpha decay is the major decay mode of proton-rich and
high-atomic-number nuclides because in heavy nuclides the
electrostatic repulsive forces increase more rapidly with atomic
number than do the cohesive nuclear forces. Hence, alpha decay
is characteristic for heavy nuclides, predominantly for those
with atomic numbers greater than 83 (i.e., beyond Bi). The
radionuclide of lowest atomic number that emits alpha particles
is 144
60 Nd. There are in total 815 alpha emitters in the Nuclides.net
database (NUDAT 2, 2009) (see in Fig. 6.1).
There are relatively few long-lived alpha-emitting radionu-
clides of relevance in the measurement of environmental and
nuclear samples. A list of the important long-lived alpha-
emitting nuclides and their short-lived progeny is presented in
Table 6.1, together with the basic nuclear properties of half-life,
branching ratio (a emission %), alpha particle energy (Ea), and
emission probability (also called abundance Ia) of the most
intensive alpha lines.
A unique feature of the alpha decay process is the strong
correlation between alpha particle energy and the half-life of the
parent nuclide. It can be clearly seen from Table 6.1 that
isotopes of the highest alpha particle energies have the shortest
half-lives (and therefore highest decay constants). For example,
within the series of 232Th, 230Th, and 228Th, the half-life is
reduced from 1010 years to about 2 years while the alpha
particle energy is increased from 4 MeV to 5.4 MeV. This
illustrates the validity of the law recognized by GeigereNuttall
in 1911, which can be expressed by the following empirical
equation (see Fig. 6.2):
lg l ¼ A þ B lg Ea (6.3)
where l is the decay constant, Ea is the energy of the alpha
particle, and A, B are constants.
Later this process was explained by the quantum mechanical
barrier penetration theory of Gamow (see Chapter 1, Section
VIII.A). Typically, alpha particles have energies in a narrow
range, between 4 MeV and 8 MeV. If the alpha energy is beyond
these values, the half-lives of the nuclides become either too
short for the radionuclides to be easily detected or so long that
they can be regarded as practically stable. Both cases require
special skills and highly sophisticated analytical techniques for
successful measurement.
In alpha spectrometry, alpha particles of different kinetic
energies are “detected” using various types of nuclear detec-
and scintillation detectors. When an alpha particle enters the
detector, it produces (directly or indirectly) charge carriers,
electronecation pairs, electronehole pairs, or electrons,
respectively. The collection of these charge carriers at the
366
FIGURE 6.1 Alpha emitters in the upper right region of the concise chart of the nuclides indicated by gray color. Nuclides are presented by their atomic numbers Z as
a function of neutron number N. (From Magill and Galy, 2005; reprinted by permission of Springer-Verlag Ó 2005)
electrodes gives a current which flows through a resistor
producing a voltage pulse. Those interactions between the
alpha particle and the detector can be utilized in alpha spec-
trometry where the height of the generated pulse is propor-
tional to the kinetic energy of the alpha particle and the pulse
frequency or count rate is proportional to the activity of the
alpha source. Alpha spectra are commonly depicted as the
number of counts collected during a given counting time
against the channel number, where channel number is a linear
function of the pulse height and thus of the energy of the alpha
particle.
A typical alpha decay scheme and the expected energy
spectrum of the alpha particles are shown in Fig. 6.3 and
Fig. 6.4, respectively.
FIGURE 6.2 GeigereNuttall plot: Half-life as a function of atomic number Z
(Loveland et al., 2006). (Reprinted by permission of John Wiley and Sons Ó
2006)
Handbook of Radioactivity Analysis
Alpha decay is characterized by the similarity of the decay
schemes of various radionuclides, which is revealed in the
similarity of the fine structure of the alpha spectra. In the
typical alpha decay process, there are a few possible alpha
particle transitions involving different alpha particle energies
and emission probabilities (see Table 6.1). In the case of
241
Am, four alpha decay processes, and consequently four
types of alpha particles of different energies, can be distin-
guished, although in all processes 237Np is produced. If 237Np
is obtained in an excited state, it will transform spontaneously
to the ground state by the emission of gamma radiation or
conversion electrons.
Direct transformation to the ground state of the daughter
results in the emission of alpha particles of the highest
energy. For almost all even-mass number and for many odd-
mass number alpha-emitting radionuclides, this is the emis-
sion with the highest intensity (with 241Am being an
exception). Thus, a series of alpha particles of slightly
different energies and of increasing abundance with
increasing energy can be usually assigned to a single
radionuclide.
Each alpha particle energy results in an alpha peak in the
spectrum; however, due to the relatively small energy
difference between the peaks they are more or less over-
lapping, resulting in a typical alpha spectrum similar to the
one shown in Fig. 6.4. It is a challenging job to separate the
individual peaks, requiring high-resolution alpha spectrom-
etry (HRAS).
For normal analytical purposes, if the group of alpha peaks
belonging to a single radionuclide is well separated from the
other alpha peak groups in the spectrum, then there is no need to
analyze the individual peaks for nuclide identification and
Chapter | 6 Alpha Spectrometry 367

TABLE 6.1 Basic Decay Data for Alpha-Emitting Radionuclides of Interest (NUDAT 2, 2009)

Nuclide Half-life Ea (keV) Ia (%) Nuclide Half-life Ea (keV) Ia (%)

208 231
Po 2.898 a 5114.9 100 Pa 32760 a 4736.0 8.4
209
Po 102 a 4883 80 4853 1.4
4885 20 4934 3
210
Po 138.376 d 5304.38 100 4951.3 22.8
211
At 7.214 h 5869.5 100 4986 1.4
211
Bi 2.14 m 6278.2 16.23 5013.8 25.4
6622.9 83.77 5028.4 20
212
Bi 60.55 m 5607 1.19 5032 ~2.5
5768 1.78 5058.6 11
232
6050.78 69.91 Th 1.405E10 a 3947.2 21.7
6089.88 27.12 4012.3 78.2
212 232
Po 0.299 us 8784.37 100 U 68.9 a 5263.36 31.55
213
Po 4.2 us 8375.9 100 5320.12 68.15
214 233
Po 164.3 us 7686.82 99.9895 U 1.592E5 a 4729 1.61
215
Po 1.781 ms 7386.2 100 4783.5 13.2
216
Po 0.145 s 6778.3 99.9981 4824.2 84.4
217 234
At 32.3 ms 7066.9 99.9 U 2.455E5 a 4722.4 28.42
218
Po 3.10 m 6002.35 99.9989 4774.6 71.38
220 235
Rn 55.6 s 6288.08 99.886 U 7.038E8 a 4214.7 5.7
221
Fr 4.9 m 6126.3 15.1 4366.1 17
6243.0 1.34 4397.8 55
6341.0 83.4 4414 2.1
222
Rn 3.8235 d 5489.52 99.92 4502 1.7
223
Ra 11.435 d 5433.6 2.27 4556 4.2
5501.6 1.00 4596.4 5.0
235
5539.80 9.2 Np 396.1 d 4925 11.5
5606.73 25.7 5007 24
5716.23 52.6 5025 53
5747.0 9.2 5051 1.8

5871.3 1.0 5108 1.5

224 236
Ra 3.66 d 5448.6 5.06 U 2.342E7 a 4445 25.9
5685.37 94.92 4494 73.8
225 236
Ac 10.0 d 5580 1.2 Pu 2.858 a 5721.00 30.56
5609 1.1 5767.66 69.26
237
5637 4.4 Np 2.144E6 a 4639.4 6.18

5682 1.3 4664.0 3.32

5724 3.1 4766.0 8.3
5732 8.0 4771.0 25.6
5732 1.32 4788.0 47.9
5790.6 8.6 4803.3 1.56

(Continued)
368 Handbook of Radioactivity Analysis

TABLE 6.1 Basic Decay Data for Alpha-Emitting Radionuclides of Interest (NUDAT 2, 2009)dCont’d
Nuclide Half-life Ea (keV) Ia (%) Nuclide Half-life Ea (keV) Ia (%)
5792.5 18.1 4817.3 2.5
238
5830 50.7 U 4.468E9 a 4151 20.9
226
Ra 1600 a 4601 5.55 4198 79.0
238
4784.34 94.45 Pu 87.7 a 5456.3 28.98
226
Ac 29.37 h 5399 100 5499.03 70.91
227 239
Th 18.72 d 5668.0 2.06 Pu 24110 a 5105.5 11.5
5693.0 1.50 5144.3 15.1
5700.8 3.63 5156.59 73.3
240
5708.8 8.3 Pu 6563 a 5123.68 27.1

5713.2 4.89 5168.17 72.8

241
5756.87 20.4 Am 432.2 a 5388.23 1.6
5807.5 1.27 5442.80 13.0
5866.6 2.42 5485.56 84.5
242
5959.7 3.00 Pu 3.733E5 a 4856.2 22.4
5977.72 23.5 4900.5 77.5
242m
6008.8 2.90 Am 141 a 5141.6 5.8

6038.01 24.2 5206.8 89.8

228
Th 1.9116 a 5340.36 27.2 5367.2 1.2
5423.15 5409.3 1.0
229 242
Th 7340 a 4761 1.0 Cm 162.8 d 6069.42 25.0
4797.8 1.5 6112.72 74.0
243
4814.6 9.30 Am 7370 a 5181 1.1

4838 5.0 5233.3 11.0

4845.3 56.2 5275.3 87.4
243
4901.0 10.20 Cm 29.1 a 5686 1.6
4967.5 5.97 5742.1 11.5
4978.5 3.17 5785.2 72.9
5053 6.6 5991.8 5.7
230
Th 7.538Eþ4 a 4620.5 23.4 6010 1.0
4687.0 76.3 6058 4.7
230
U 20.8 d 5817.5 32.0 6066.2 1.5
244
5888.4 67.4 Pu 8.08E7 a 4546 19.4
231
Pa 32760 a 4681 1.5 4589 80.6
244
4713 ~1 Cm 18.10 a 5762.70 23.6

5804.82 76.4

measurement. Rather, each group of peaks is evaluated as a unit,

and the total counts assigned to the appropriate radionuclide.
III. DETECTION SYSTEMS
This approach may be referred to as conventional alpha spec- The core part of an alpha spectrometer is the detector, where the
trometry (AS). interaction of the particles with the matter of the detector takes
Chapter | 6 Alpha Spectrometry
FIGURE 6.3 Decay scheme for 241Am (from Chapter 1, Part VIII.A). The relative abundances of alpha particles and the relevant gamma-ray emissions are
expressed in % (in parenthesis) beside the radiation energy values in MeV. Energy levels of the nuclides are shown as plateaus along the ordinate, and are distributed
along the abscissa, representing the atomic number.
FIGURE 6.4 Simulated alpha spectra of a 241Am source as they appear in
a high-resolution (HRAS e bold black curve) and a low-resolution alpha
spectrum (AS e plain black curve). In the HRAS, the four alpha peaks at 5.389,
5.443, 5.486, and 5.545 MeV can be identified as partially overlapping peaks. In
standard AS the four alpha particles appear in a single broad peak. Spectra were
generated by the AASI simulation software (Siiskonen and Pöllänen, 2004) with
estimated resolutions of Si semiconductor detectors of 14 and 40 keV.
place. The energy of the alpha particle is transformed to
a measurable physical quantity, e.g. electric charge, current, or
voltage. In the process of detection, the charge carriers are
collected and converted to electric pulses.
In spectrometry, pulses are processed in the so-called ‘pulse
mode’ where each interacting particle is detected indepen-
dently. Electric pulse processing units such as preamplifiers
and amplifiers attached to the detector output both amplify and
form (shape) the pulses. Pulses are then digitalized by an
analog-to-digital converter (ADC). From a series of digitalized
369
pulses of different heights at the ADC output, the multichannel
analyzer (MCA) generates a pulse-height spectrum by sorting
the pulses according to their heights and assigning them to
a channel number proportional to the pulse height as illustrated
in Fig. 6.5.
A schematic drawing of an alpha spectrometer is shown in
Fig. 6.6. Alpha spectrometers may contain vacuum chambers
surrounding the detector and the source. Vacuum supply units
usually contain vacuum pumps such as oil rotation pumps,
vacuum gauge, and occasionally a vacuum control system to
adjust the desired pressure.
In spectrometric applications, the basic information of the
radiation (i.e. the type of radiation, the energy of the particles,
and the activity of the source) is conserved in the form of the
shape and height of the electric pulses, and the pulse frequency
or count rate.
The components of the alpha spectrometer are discussed in
more detail in the following.
A. Detectors
1. Interaction of Alpha Radiation with Detector
Materials
Only a few radiation detector types are suitable for the accurate
determination of the energy distribution of alpha particles. Of
these, silicon semiconductor detectors are the most frequently
used at present. Due to instrumental improvements and devel-
opments in spectrum evaluation software, high-resolution alpha
spectrometry using Si detectors became available from the end
of the 1980s.
370
FIGURE 6.5 Transformation of digital pulse data into pulse-height spectrum using a multichannel analyzer (MCA). The left side of the figure shows the pulses
appearing at the detector as a function of time. The right side shows the generated spectrum with the number of pulses as a function of the pulse height.
FIGURE 6.6 Schematic drawing of an alpha spectrometer. H.V. and amp refer
to high-voltage supply unit and amplifier, respectively.
Among gas ionization detectors, ionization chambers and
proportional counters have been used in alpha spectrometry and
a special type of gas detector has been developed for the
determination of pulse-height distribution of alpha particles, the
gridded ionization chamber.
Although scintillation detectors have in general relatively
poor energy resolution, the development of “high-resolution”
alpha-liquid-scintillation spectrometer in combination with
selective chemical procedures offers some advantages in alpha
spectrometry.
The process of detection of alpha particles by various
nuclear detectors is determined by the interactions between the
particle and the detector. The principal characteristics of
the interactions have been described in Chapter I Section VIII.
The most important aspects influencing the detection process in
alpha spectrometry are summarized briefly below.
When alpha particles enter the detector, they immediately
interact with the atomic electrons of the detector material. The
main results of this interaction are excitation and ionization. In
the latter case, electron and positive ion (cation/hole) pairs are
formed. Along its path through the detector the high-energy
alpha particle will create a large number (N) of electronecation
pairs. N can be expressed as
Ea
N ¼
ε between source and detector, and in the detector window.
where Ea is the energy of the alpha particle and ε is the energy
needed to form one electronecation pair.
Since Ea is in the range of a few MeV and ε is e depending
on the type of detector e in the range of 1e100 eV, a single
Handbook of Radioactivity Analysis
alpha particle can produce 10,000e1,000,000 charge carriers
while it loses its energy before it is stopped.
The track of the alpha particles in the detector is almost
straight because the heavy particles are not significantly
deflected by the interacting electrons. The specific energy loss
of the alpha particle, also called the stopping power, is
described by the Bethe formula (see in Chapter I Section XIV).
The alpha particle interaction with the detector is characterized
by a range or distance beyond which no particles penetrate.
This range depends on the energy of the alpha particle and the
type of the detector, i.e., its atomic number and density. As an
example, the range of alpha particles in Si is shown as a function
of alpha energy in Fig. 6.7.
Since alpha energies of radionuclides are not higher than 10
MeV, they are completely absorbed in Si layers of 100-mm
thickness. Thus, Si detectors should not be significantly thicker
if they are used for the measurement of alpha-emitting radio-
nuclides. In the case of gas detectors, the detector thickness
depends on the type and especially on the pressure of the gas in
the detector chamber. Around atmospheric pressure, the range
of 10 MeV alpha particles is about 5e10 cm, and so this is the
desired detector size.
The very short range of alpha radiation enables the design of
detectors, which are able to completely absorb the incident
radiation, without requiring large detector volumes. This fact,
combined with the large number of charge carriers that are
produced, is responsible for the high counting efficiency that is
typical of alpha spectrometry.
However, the limited range of alpha radiation is also
responsible for the major challenge in alpha particle detection,
which is ensuring that alpha particles reach the active volume of
the detector without significant losses. This means reduction or
(6.4) elimination of absorption in the source, any absorbent layers
Absorption and self-absorption in the detection process can be
reduced by ensuring direct contact between the source and the
detector, e.g., by placing the source inside the detector gas
chamber or by dissolving the source in a liquid detector, as in
Chapter | 6 Alpha Spectrometry
103
102
101
E [MeV]
100
ALPHA
10-1
10-2
100 101 102 103 104
Range in Si [μm]
FIGURE 6.7 The range of alpha particles in silicon.
the case of liquid scintillation counting (LSC). In the case of
silicon detectors, absorption can be reduced by the use of
vacuum in the chamber surrounding the detector and the alpha
source. In addition, considerable efforts have been made to
develop radiochemical procedures for the preparation of “infi-
nitely thin” alpha sources that are almost free of self-absorption
(see Section V).
The interaction of alpha radiation with matter is a statistical
process. When monoenergetic alpha particles pass through
matter there is a spread of energies at distances along the beam
path which is called energy straggling. The energy distribution
of an originally monoenergetic beam becomes wider with
penetration depth; however, near the end of the range, the
distribution becomes narrower again due to the reduction of the
beam energy (see Fig. 6.8).
Analogously to energy straggling, the fluctuation in the path
length of the alpha particles due to the statistical nature of the
interactions is known as range straggling.
Energy and range straggling are the basic processes
which are responsible for peak broadening in conventional
alpha spectrometry (see the peaks of 241Am in Fig. 6.4). The
peak shape in alpha spectrometry is affected by many
parameters, including the characteristics of the detector, the
absorbers between the detector, and the source and those of
the source.
The time required to stop alpha particles in the detector is
calculated from its range and average velocity where velocity
(v) is a function of the energy (Ea) and the atomic mass of the
particle (ma):
rffiffiffiffiffiffiffiffi
2Ea
n ¼ (6.5)
ma
Using typical range values, stopping times of alpha parti-
cles are a few picoseconds (10
12 s) in solids and liquids and
371
105
FIGURE 6.8 Schematic drawing of energy straggling of an alpha particle
beam (Knoll, 2010). (Reprinted by permission of John Wiley and Sons Ó 2010)
a few nanoseconds (10
9 s) in gases resulting in the possibility
of very fast detector response.
The operation principles of gas ionization and scintillation
detectors are described in Chapters 3, 7, and 16, and those of
semiconductor detectors are discussed in Chapter 5. The
following sections focus on particular properties of the detectors
used in alpha spectrometry.
2. Characterization of Spectroscopic Detectors
In order to compare various types of detectors the following
parameters are determined:
l energy resolution,
l detection efficiency,
l response time, and
l dead time.
Detector characteristics are not the only important factors that
influence the performance of alpha spectrometers. Other major
contributors to the overall quality of alpha spectra are other
electronic units and the type and quality of the alpha source.
Energy resolution in nuclear spectroscopy is expressed as
the full width at half maximum of the peak (FWHM). In alpha
spectrometry, the energy resolution performance of the detector
is expressed traditionally as the FWHM in keV at the 5486 keV
peak of 241Am.
In alpha spectrometry, peaks are usually not symmetric (not
Gaussian shaped). The asymmetry appears as a low-energy side
tailing that can be better characterized by the full width at one
tenth of the peak maximum (FWTM).
The absolute counting efficiency (εabs) in nuclear spec-
troscopy is defined as the number of pulses recorded over the
number of alpha particles emitted by the source and it equals
U
εabs ¼ 3int (6.6)
4p
372
where εint is the intrinsic efficiency of the detector that is defined
as the number of pulses recorded over the number of quanta
incident on detector, U is the solid angle of the detector seen
from the actual source position, and U/4p is the geometry
factor.
A feature of alpha detectors is that the intrinsic efficiency is
usually 100%. This means that all alpha particles that reach the
active volume of the detector are counted unless the detector
thickness is smaller than the range of alpha radiation in the
detector material. In alpha spectrometry, the determination of
the absolute counting efficiency can be limited to the determi-
nation of the geometry factor, which can be calculated if the
geometry parameters such as source and detector area and
source-to-detector distance in coaxial arrangement are known
exactly (see Section IV.B for more details).
Response time is the time interval between the arrival of the
alpha particle into the detector and the appearance of the
response signal at the detector output. New particles entering
the detector during the response time period are either not
detected or detected together with another pulse causing
a deviating pulse height, i.e., a pileup peak. Dead time is the
minimum length of time that must separate two events in order
that they are recorded as two separate pulses.
In semiconductor alpha spectrometry, response times and
dead times are very short, and so high count rates may be
tolerated without pileup and dead-time corrections. Using gas
ionization detectors, dead times are longer and corrections are
more likely to be necessary. The dead-time (s) corrected count
rate (icor) is calculated from the measured count rate (imeas)
according to the following equation:
imeas
icor ¼ (6.7)
1
imeas s
3. Gas Ionization Detectors
Gas ionization detectors are described in detail in Chapter 3. For
alpha-spectrometric purposes, ionization chambers and
proportional counters can be applied. GeigereMüller counters
are not suitable for measuring the radiation energy because the
electron discharge due to the high gas multiplication envelops
the entire anode wire independently of the original number of
primary electrons produced by the ionizing radiation. Semi-
conductor detectors have replaced gas detectors in many
application fields because they are superior in terms of energy
resolution, response time, ease of operation, and cost. Gas
ionization detectors offer the attractive feature that large alpha
sources can be detected, which is often important in the direct
analysis of some environmental samples without sample
dissolution and chemical separation, such as air samples
(Röttger et al., 2001) or the surface of plate glass (Samuelsson,
2011).
a. Principle of Detection of Alpha Particles
Gas ionization detectors usually consist of a gas-filled cylinder
that serves as a cathode, and an anode wire. The filling gas is
usually a noble gas (Ar or He) or a mixture of gases. Alpha
particles excite and ionize the gas. In the latter process, positive
Handbook of Radioactivity Analysis
gas ions and free electrons are created. The average energy
needed to form an ion pair is 30e40 eV depending on the type of
gas. Therefore, an incident 5 MeV alpha particle creates about
150,000 ion pairs. In an external electric field, electrostatic forces
will move the charges to the electrodes of opposite charge. The
mobility of the free electrons is about 1000 times higher than that
of the positive gas cations. Therefore, typical collection times for
electrons are much shorter (in the range of microseconds)
compared to the millisecond characteristic of cations.
Ionization chambers are operated at low voltage
(100e250 V) while a somewhat higher voltage (300e600 V) is
applied in proportional counters where the accelerated elec-
trons generate new charge carriers in collisions with gas
molecules. This process is called gas multiplication. In
proportional counters, the total number of charge carriers is
proportional to the primary charge carriers generated by the
alpha particle, therefore the pulse height is also proportional to
the particle energy. As a result of gas multiplication (which can
be as high as 106 times), the output pulse is much higher than in
the case of ionization chambers.
For alpha spectrometry, gas ionization detectors are used in
pulse mode. Because of the slow migration of the ions these
detectors are often operated in electron-sensitive mode. By
changing the time constant of the electric circuit the amplitude
of the detected pulse reflects only the drift of the electrons.
However, the amplitude of the pulse becomes sensitive to the
position in the chamber where the alpha particle interaction
takes place. This drawback can be overcome by the use of
gridded ionization chambers.
In the Frisch-grid detector (Fig. 6.9), the ionization
chamber is divided into two parts by the grid, which is main-
tained at an intermediate potential between the original elec-
trodes. Alpha particles enter only the gridecathode
compartment through the use of a collimator. Only the upward
movement of the electrons in the grideanode compartment is
registered by placing the load resistor in the anodeegrid circuit.
When the electrons move from the grid to the anode, the gride
anode voltage begins to drop and the signal voltage begins to
develop across the resistor. The maximum signal voltage (V ¼
n e
/C) is reached when the electrons reach the anode.
The grid is maintained at an intermediate voltage between
the cathode and anode, and therefore the grid becomes almost
transparent for the electrons. Increasing the grid voltage will
cause losses of electrons and the detected count rate will be
reduced (Fig. 6.10).
In the Frisch-grid chamber, a fast and position-independent
pulse is generated by detecting the electron drift separated from
the drift of positive ions.
Gridded ionization chambers have been successfully used
for alpha-spectrometric analysis of large area sources up to 80-
mm radius by Roos and Roos (1999). An absolute counting
efficiency close to 40% was achieved while the energy resolu-
tion was acceptably high (FWHM was about 30 keV).
Major characteristics of gas ionization detectors are as
follows:
l Ionization chambers, preferably gridded chambers, operated
as pulse chambers have been used to obtain alpha spectra.
Chapter | 6 Alpha Spectrometry
FIGURE 6.9 Operational principle of the gridded ionization chamber according to Knoll (2010). Reprinted by permission of John Wiley and Sons Ó 2010. The rise
of the pulse results from the drift of the electrons across the grideanode region d. No signal voltage is generated when electrons move across region y. d and y are the
distances between the grideanode and the interaction positionegrid.
FIGURE 6.10 Change in count rate at different grid to anode and anode to cathode voltages (Roos and Roos, 1999).
l Pulse amplitudes are usually very small because of the lack
of gas amplification; consequently, low-noise preamplifiers
have to be attached to the ionization chambers.
l Energy resolution of the detector is limited by the relatively
high ionization potential (energy needed to create an elec-
tron-ion pair) of the gases. Typical resolutions of 35e40 keV
have been reported.
l Response times are relatively slow, electron collection times
are in the range of ms, and ion collection times are in the
range of ms. In gridded ionization chambers, only the drift of
electrons is detected.
l Absolute counting efficiencies are close to 50% if sources
are placed inside the chamber.
l Gridded ionization chambers are superior to Si detectors
regarding efficiency when large samples (larger than the size
of the Si detector) are measured.
4. Semiconductor Silicon Detectors
Silicon semiconductor detectors are regarded as analogous to
gas ionization as solid-state ionization detectors. The use of
a solid medium has the advantage that the dimensions of the
detector can be kept small while the counting efficiency is as
high as in case of gases. In alpha spectrometry, this means that
373
a 100% intrinsic efficiency can be reached with a Si detector of
100-mm thickness. A major advantage of semiconductors is
their high-energy resolution (only the special-application
cryogenic detectors described below have a higher-energy
resolution). Their drawbacks include the limitations on size and
their high susceptibility to radiation-induced damage resulting
in spectrum degradation.
There are some differences in the pulse generation processes
between gas ionization and semiconductor detectors, which are
as follows:
l The mobilities of the charge carriers are different. In gas
ionization detectors, the mobilities of the electrons are about
1000 times higher than those of the cations, while in semi-
conductor detectors, the mobilities of the electrons are 2e3
times higher than those of the holes.
l The charge collection times are different. The time needed to
collect electronecation pairs is in the range of ms, whereas
that for electronehole pairs is in the range of ms.
l The size of the sensitive volume is dependent on the applied
voltage in semiconductor detectors, while it is constant in
gas ionization detectors.
The properties of semiconductor materials including the
description of the band structure have been discussed in detail in
374
many good monographs (Knoll, 2010; Gilmore, 2008) and are
also described in Chapter 5. Here we focus our discussion on Si
detectors, which are the most frequently used detectors in
routine and also in high-resolution alpha spectrometry.
In Si semiconductor detectors, p-type and n-type Si are
brought together in good contact, and a reverse bias (positive
voltage to the n-type Si) is applied. At the junction of the two Si
layers, an intrinsic layer depleted in any charge carriers is
formed. The reverse-biased pen junction, the so-called pen
diode, is used as an alpha particle detector.
The basic interaction between the ionizing particle and the
detector takes place in the depleted/intrinsic region. When the
alpha particle passes through a semiconductor, electronehole
pairs are created along the track. These charge carriers are
collected by the electric field, with changes in the electric field
being registered as pulses. Pulse amplitudes are small, being in
the range of mA. Since the height of the pulse is proportional to
the energy deposited by the interacting particle, the detector is
suitable for spectrometric measurements.
The average energy expended by the ionizing radiation to
produce one electronehole pair in Si is about 3.6 eV (slightly
higher than the 3.0 eV in Ge). This value is also somewhat
higher than the width of the bandgap in Si (1.12 eV) or the
ionization energy, because the energy imparted by the alpha
particle is not 100% utilized in electronehole pair production.
This value is about an order of magnitude lower than the 30 eV
required to create an electronecation pair in gas ionization
detectors. Therefore, the number of charge carriers is increased
by about 10 times and the statistical fluctuation in number is
reduced, resulting in a better energy resolution as well as in
a better signal-to-noise ratio. The ionization energy depends
slightly on temperature; in Si, it is 3% greater at liquid nitrogen
temperature compared with room temperature.
The electrical resistance of pure Si is high, and therefore the
leakage current across the junction is small. In spectrometric
application, this must not exceed a few nA. This low current is
a major requirement if electric pulses that generate ~mA current
are to be analyzed.
Electrical charges are collected by two ohmic contacts fitted
to the opposite faces of the semiconductor material. The ohmic
contacts are connected to a detection circuit, and an electric
field is applied to collect the charge carriers. Special blocking
electrodes are used where the number of charge carriers is
reduced during application of the electric field in order to reduce
the leakage current of the detector.
According to fabrication technology, silicon semiconductor
detectors are of three different types: the diffused junction detector
(DJD), the surface barrier detector (SBD), and the passivated ion-
implanted detector (PIPSi). Each detector can be regarded as
a reverse-biased compensated detector where n- and p-type Si
crystals are brought into contact and a depleted/intrinsic (i) layer is
formed as the sensitive volume of the detector.
Diffused Junction Detectors. These detectors, belonging to
the first generation of Si diode detectors, are prepared by
diffusion from p-type Si. An n-type impurity, usually P, is
evaporated on one surface of the crystal and is diffused into the
Si crystal to a depth of 0.1e2 mm. A depleted layer is formed
under the surface layer that is relatively thick. The incident
Handbook of Radioactivity Analysis
radiation must pass this “dead layer” before reaching the
sensitive volume. The dead layer causes losses in production of
charge carriers and a reduction in energy resolution.
Surface Barrier Detectors. By etching the surface of an
n-type Si crystal, a p-type layer (oxide) is formed that is coated
by a thin gold layer using vacuum evaporation. SBDs can be
produced starting from a p-type Si that is evaporated by
aluminum to form an n-type contact. Gold or Al serve as electric
contacts and entrance window for the radiation. These detectors
are characterized by a very thin dead layer, resulting in high-
energy resolution and small losses in charge collection. Due to
the very thin entrance window, these detectors are sensitive to
mechanical or chemical impacts and are permeable also for
photons. They can be operated in light-tight chambers that
usually also serve as vacuum chambers.
Passivated Ion-implanted Planar Si (PIPSi) Detectors. At
present, these are the detectors most frequently used for alpha
spectrometry. N-type Si is used as the starting material for
production of PIPSi detectors (PIPS and ULTRA are the
registered trade names of the PIPSi detectors of Canberra and
Ortec). Accelerators of about 10 kV are used to implant B or P
ions as p-type impurities and As as an n-type blocking contact.
PIPSi detectors have the following advantages:
l The implanted Al entrance window is thin and even,
allowing high-energy resolution and small losses in charge
production.
l The implanted Al window is resistant to mechanical effects;
it can be cleaned.
l The leakage current is small.
The flow chart of production of PIPSi detectors is shown in
Fig. 6.11.
Silicon detectors, and especially PIPSi detectors, find
widespread application in standard alpha spectrometry. Since
the 1980s considerable efforts have gone into improving the
detection systems and developing high-resolution alpha spec-
trometry which allows the determination of nuclides that emit
alpha particles of similar energies.
High-resolution alpha spectrometry (HRAS) is not based
on a new detection principle, and does not require a new type of
instrumentation, but all possible efforts are expended to
improve the energy resolution. PIPSi detectors of thin window
and small size (20e50 mm2) are used. The alpha sources are
prepared with special care, typically with vacuum sublimation
or electrodeposition to obtain an almost infinitely thin and even
sample layer after radiochemical processing. The source-to-
detector distance is kept high (several times the diameter of the
detector) to have a small solid angle of measurement (<1% of
4p sr), and so absolute counting efficiencies are typically less
than 1% (typically 0.1 to 0.2%). Because of the low counting
efficiency, a source strength of a few tens of Bq or more are
a requisite. A high vacuum and high stability of the electronic
equipment are assured by special technical tools. Temperature
control and source collimation might be necessary. Conversion
electrons are sometimes deflected by magnetic deflectors to
avoid alpha-electron coincidences. The typical energy resolu-
tion of such a system is less than 10 keV, significantly less than
the typical values of 30e80 keV for standard alpha
Chapter | 6 Alpha Spectrometry
n - Si
SiO2
B
As
p+
n+
Al
Al
FIGURE 6.11 Steps in PIPSi detector fabrication. (Amoudry and Burger, 1984, reprinted by permission of Elsevier Ltd. Ó 1984)
spectrometry. Due to the low counting efficiency, HRAS cannot
be used for the analysis of low-activity samples such as envi-
ronmental samples, but it can be applied in combination with
a spectrum deconvolution code for the analysis of high-activity
samples. HRAS is especially suitable for the analysis of isotope
pairs of similar energies such as 239Pu and 240Pu, or 243Cm and
244
Cm, which are spectroscopically separated.
Major characteristics of Si semiconductor detectors are as
follows:
l Surface barrier and preferably passivated implanted planar
Si detectors are used to obtain alpha spectra.
l Pulse amplitudes are usually very small (in the range of
a few mA) but well detectable after amplification.
l The typical leakage current of a PIPSi detector is in the range
of nA.
l Energy resolution of the detector is high due to the low
ionization energy needed to create an electronehole pair.
Typical resolution of the detector is 10e20 keV depending
on detector performance and size.
l Charge collection times for electronehole pairs are fast, in
the range of ms. There is a relatively small difference
between the collection times of electrons and holes (a factor
of 2e3).
375
n-type Si crystal
passivation by surface oxidation
removal of oxide layer
from the entrance window
ion implantation using accelerator,
doping with B p-type impurity,
doping with As n-type impurity at
rear side to form blocking contact
heat treatment at 600oC,
fast cooling, removal of the
non adhering layer
evaporation of Al
excess Al removal on front side
Al electric contact at rear side
l Absolute counting efficiencies are close to 50% if sources
are placed close to the detector inside the chamber.
l Si detectors usually have low background resulting in a high
counting sensitivity.
Semiconductor Si detectors have proved to have more advan-
tages than gas ionization detectors and have replaced them in
most applications.
5. Scintillation Detectors
Detection of ionizing radiation by scintillation detectors is based
on the emission of light as a result of the interaction of the
radiation with the detector material (called a scintillator) fol-
lowed by collection of light and its conversion into electrical
pulses using photomultiplier tubes or photodiodes. Scintillation
detection is one of the oldest techniques in the measurement of
radioactivity having had widespread application for the detection
of alpha, beta, and gamma radiation in the past. At present, most
of the applications are related to gross counting of alpha, beta,
and gamma radiation due to the typically high counting effi-
ciency and the low cost of the instrumentation while radiation
spectroscopy is limited by the insufficient energy resolution of
the scintillators to allow the identification of the radionuclides in
376
an isotope mixture. Scintillation gamma spectrometry was
a basic tool until about the 1980s, but it was gradually replaced
by semiconductor spectrometry of much better energy resolution.
The operation mechanisms and application fields of liquid
scintillation detectors are described in Chapters 7 and 9 and
those of solid scintillators are summarized in Chapter 16.
Here, we are summarizing the principles of operation and
showing only the alpha-spectrometric application, the so-
called high-resolution alpha-liquid-scintillation spectrometry
(a-LSC).
Scintillation detectors include solid and liquid scintillators
as well as inorganic and organic scintillators. For all these
different types, the basic process used for detection is fluores-
cence which is the prompt emission of visible radiation (light).
Good scintillator materials are characterized by the following:
1. high scintillation efficiency in converting the kinetic energy
of the particle to light;
2. linearity of conversion which means that the light yield is
proportional to the deposited energy, thus allowing spec-
trometric analysis;
3. good optical properties including transparency to the
emitted light to allow efficient light collection;
4. fast response time with prompt light emission; and
5. high density or high atomic number e this is required only
for the detection of gamma radiation.
Inorganic alkali halide crystals, such as NaI(Tl) and CsI(Tl),
usually meet the requirements of (1), (2), (3), and (5), but are
usually slow in response time. Organic scintillators such as solid
plastics and liquid scintillators are usually faster but the light
yield is lower and the requirements of high density and atomic
number are not fulfilled.
The main parts of a scintillation detector are the scintillator,
which converts the radiation energy to visible light photons, and
the photoelectron-multiplier (PM) tube containing the photo-
cathode, the multistage electron-multiplying section made of
a series of electron-multiplying dinodes and an anode for
collection of the amplified charge situated in a glass vacuum
envelope. Photocathodes are responsible for converting the
energy of the photons into electrons. If the light appears as
a pulse, the photoelectrons produced will also form a pulse of
similar time duration. The number of electrons emitted by the
cathode is multiplied on the dinodes where the multiplication
factor can be as high as 106e108 depending on the applied
voltage. The electric pulse at the anode of the PM tube can be
directly counted without further amplification by a simple
counter, a single or a multichannel analyzer. Typical tubes have
fast response times. When they are illuminated by a short light
pulse, an electron pulse will be produced at the anode with a time
width of a few nanoseconds after a delay time of 20e50 ns.
The sensitivity of the scintillation detector consisting of
a scintillator and a PM tube to radiation can be calculated by the
following assumptions: The blue light emitted by the scintillator
has a wavelength (l) of about 400 nm. According to Planck’s
equation, the energy of the photon is therefore about 3 eV.
Taking into account that the conversion efficiency of the scin-
tillator is 5e20%, then the number of photons generated by
Handbook of Radioactivity Analysis
a particle of 1 MeV energy is about 15000e60000. The effi-
ciency of the photocathode to convert photons into electrons is
typically 10%. Therefore, the expected number of electrons at
the output of the photocathode is 1500e6000. Altogether, about
200e700 eV energy is required to produce a photoelectron. The
corresponding “ionization energy” of gas ionization and semi-
conductor detectors is one and two orders of magnitude lower,
respectively. This difference is the basic reason for the poor
energy resolution of scintillators compared to gas ionization and
especially to semiconductor detectors.
The mechanism of scintillation in inorganic and organic
scintillators is different.
Mechanism of scintillation in inorganic crystals with
activators. Inorganic scintillators are insulators characterized by
a band structure where the lower band (the valence band)
represents the electrons that are bound to lattice sites of the
crystals and the upper band (the conduction band) represents the
electrons that can migrate throughout the crystal. The gap (the
forbidden band) between the two bands is wide (above 5 eV). If
energy is deposited in the crystal by radiation, electrons in the
valence band can be elevated to the conduction band leaving
a hole behind. The addition of small amounts of impurity, called
an activator, to the pure crystal will create an intermediate energy
level within the gap (a luminescence center) through which the
excited electron can de-excite back to the valence band while
emitting a visible photon with a reduced energy. This photon will
serve as the basis of scintillation detection. De-excitation
processes are typically fast with a half-life of about 100 ns.
Besides the luminescence centers, impurities in the crystal
can create electron traps. De-excitation of the electrons from the
electron traps does not result in visible light emission or the
light emission is delayed causing an “afterglow” appearing in an
increased background during the measurement.
Detection of alpha particles by solid scintillators. Among
the great variety of inorganic scintillators (e.g., NaI(Tl), Cs(Tl),
CsI(Na), CaF2(Eu), LiI(Eu), and bismuth germinate), ZnS(Ag)
is the one that has been exclusively used for the detection of
alpha particles. It has a high radiation conversion efficiency of
about 20%. The maximum wavelength of the emitted photons is
450 nm, close to the maximum sensitivity of the photocathode.
The principal decay constant is 0.2 ms. Its major drawback is
that it is crystallized as polycrystalline powder, which is not
adequate for spectrometric measurements. Usually a thin layer
of 20‒30 mg/cm2 thickness is mounted on a glass surface.
A thicker layer of ZnS loses transparency.
Mechanism of scintillation in organic crystals, liquids,
and gases. In organic scintillators, excitation and de-excitation
processes take place in single molecules independent of their
physical state, i.e., solid, liquid, or gaseous state, in marked
contrast to inorganic scintillators. Scintillation arises from
transitions of electrons between the energy levels of the organic
molecule.
The energy spacing between the ground and the excited
levels is 3e4 eV for many organic scintillators. In both states,
there are several vibrational energy levels where the energy
spacing is much smaller (about 0.15 eV) that these levels can
also be occupied. The molecules at room temperature and in the
absence of radiation occupy the ground state. When radiation
Chapter | 6 Alpha Spectrometry
passes the scintillator the deposited energy excites the molecule,
and this is followed by fast (ps) de-excitation. De-excitation to
the ground level does not result in light emission. Fluorescent
light is emitted in those de-excitation processes where the
excited molecule goes back to one of the vibrational levels of
the ground state. In organic scintillators, delayed light emission
(phosphorescence) is also often observed.
In mixtures of organic molecules, the excitation energy
undergoes substantial transfer from one molecule to another.
This energy transfer plays an important role in liquid scintilla-
tors where often a high concentration of nonscintillating solvent
is mixed with a small concentration of an efficient scintillator.
The primary energy transfer takes place in the solvent and the
excitation energy is finally emitted as photons by the scintillator
molecule. Scintillation cocktails often contain a third organic
molecule called a wavelength shifter that can change the
wavelength of the emission spectrum so that it is better fitted to
the absorption maximum of the photocathode. Scintillator
molecules usually contain aromatic rings of carbohydrates, but
oxygen and nitrogen atoms can be included in the aromatic ring
structure.
Detection of alpha particles by LSC. Liquid scintillators are
frequently used for the detection of alpha particles. Commercial
liquid scintillation counters (LSCs) developed for the detection
of low-energy beta particles can be used to measure alpha
particles without self-absorption losses, giving 100% absolute
counting efficiency. This advantage is counterbalanced by the
limited resolution of the scintillators. A typical energy resolution
using commercial LS system is about 20e25%; so alpha spec-
trometry is difficult or almost impossible to achieve.
Detection of low-level alpha radiation by a commercial LSC
is difficult because the scintillation yield of the alpha particles is
lower by about a factor of 10 than that of beta particles. There-
fore, the spectra of the alpha radiation of 4e6 MeV appear in the
same region as the spectra of beta particles of 400e600 keV.
Furthermore, the response of organic scintillators to alpha or
beta radiation is not completely linear; deviation from linearity
is found at low energies. The explanation of this behavior was
given by Birks (1964). In organic scintillators such as LSC, only
a small fraction of the kinetic energy of the alpha particles is
converted to light and the remainder is dissipated in the matter
as heat and lattice vibrations. The high ionization density along
the track of the alpha particle causes damages to the organic
molecules that leads to quenching (absorption) of the fluores-
cence light created in the interaction. It is expected that the light
output (dL/dx) is proportional to the specific energy loss of the
particle (dE/dx) if there is no quenching:
dL dE
¼ S (6.8)
dx dx
where S is the normal scintillation efficiency.
The Birks’ formula expresses the deviation from the normal
scintillation due to quenching:
dE
dL S
¼ dx (6.9)
dx dE
1 þ kB
dx
377
where kB is treated as an adjustable parameter to fit experi-
mental data for a given organic scintillator.
The reduced scintillation efficiency is a special feature of
the interaction of heavy charged particles with organic scintil-
lators, and makes alpha spectrometry using commercial LSC
very difficult.
To avoid the interference of alpha and beta LS spectra, a new
technique of pulse-shape discrimination (PSD) has been
introduced. In organic scintillators, fluorescent light is produced
in a very rapid “prompt” process as well as in a slower process
corresponding to delayed fluorescence. The response times of
the processes are in ns and 100-ns ranges, respectively, as shown
by the shape of the pulses depicted as pulse intensity versus time
in Fig. 6.12. The slow scintillation component is higher for
particles of high specific energy loss (dE/dx) such as alpha
particles and heavy charged particles. Based on the differences
in the pulse shapes it is possible to separate pulses due to alpha
particles from those originating from beta or gamma radiations.
Using special electronic circuits for PSD, alpha and beta spectra
are constructed from a single LS spectrum. Using this tech-
nique, which is available in modern LS counters, the problems
of overlapping alpha and beta spectra due to reduced scintilla-
tion efficiency can be eliminated.
Alpha spectrometry by high-resolution a-LSC. A so-called
high-resolution alpha-LSC characterized by an FWHM of
200e400 keV for alpha particles in the energy range of 4e7
MeV has been developed for the measurement of alpha spectra
of separated radioelements such as uranium and thorium.
A small volume of extracted sample mixed with an organic
scintillator is detected by a single PM tube in a special geometry
shown in Fig. 6.13.
The differences in fluorescent yields of alpha and beta
particles cause troublesome background interference from beta
and gamma radiations in the alpha counting. With the selection
of an appropriate scintillator, alpha-produced pulses are about
30 ns longer than beta-produced pulses. Based on this
FIGURE 6.12 Typical pulse shapes in LS spectrometry. Tailing refers to
delayed fluorescence. The contribution of the slow component to the pulse is
higher for alpha particles than beta particles.
378
FIGURE 6.13 Schematic drawing of the sample, reflector, and photomultiplier
tube arrangement for alpha-LSC. (McKlveen and McDowell, 1984, reprinted by
permission of Elsevier Ltd. Ó 1984)
difference, beta-produced pulses are electronically rejected by
a PSD. The system is called photoneelectron-rejecting alpha-
liquid-scintillation (PERALS) spectrometer. The use of PSD is
responsible for rejection of the pulses originating from inter-
fering gamma rays and conversion electrons, which are emitted
by many of the alpha-decaying nuclides (see Table 6.1).
The improved energy resolution of the PERALS system is
a consequence of
l the small sample size,
l the efficient geometric arrangement,
l the rejection of electrons and photons by the use of PSD,
l the use of aqueous immiscible scintillator and organic
extractant, and
l the removal of dissolved O2 by purging the sample with
Ar gas.
Eliminating the presence of water and dissolved O2 helps
reduce quench effects that result in highly variable light
production and, as a consequence, poor resolution in conven-
tional LSC. In the PERALS spectrometer e differing from the
commercial LSC instruments dedicated for tritium and 14C
measurement e a single PM tube is applied. In order to analyze
alpha-emitting nuclides with the relatively low-resolution
PERALS spectrometer, selective chemical separations have to
be performed. For this purpose, a great variety of special
extractive scintillators have been developed that serve as solvent
extractants and liquid scintillators at the same time. A list of the
available extractive scintillators is given in Chapters 7 and 9.
Recently, an alpha spectrum evaluation code has been devel-
oped to deconvolute PERALS spectra that will be discussed in
Section IV.A.3 (Aupiais, 2004).
The major characteristics of scintillation detectors used for
determination of alpha particles are as follows:
l Among the great number of activated inorganic scintillators,
ZnS(Ag) has been used to detect alpha particles. Liquid
scintillation detectors are also used to detect alpha particles.
Handbook of Radioactivity Analysis
High-resolution alpha-LSC is applied for alpha-spectrometric
measurements.
l Pulse amplitudes are usually directly measurable because
amplification is performed by the dinode system of the PM
tubes.
l Scintillators are characterized by their light yield or scin-
tillation efficiency, which is usually higher in the case of
inorganic than organic scintillators. The total light yield
of inorganic scintillators is about 10000e50000 photons/
MeV.
l The wavelength of the light emitted by organic and inorganic
scintillators is in the range of 400e450 nm and 300e550 nm,
respectively. This is coupled to the photocathode that has
highest sensitivity in the range of 300e600 nm.
l The light yield of organic scintillators is about an order of
magnitude lower for alpha particles than for electrons due to
quenching caused by radiation-damaged organic molecules.
l Energy resolution of the scintillation detector is poor due to
the high energy (a few hundreds of eV) needed to produce
a photoelectron. Typical energy resolution of a NaI(Tl)
detector for gamma radiation is about 8e10%. The energy
resolution of a commercial LSC for alpha particles is
20e25%.
l Responses of scintillation detectors are usually fast, in the ns
range for organic scintillators and somewhat slower in case
of inorganic scintillators (in the nsems range). The rise and
fall of the light output can be characterized by a full width
half maximum (FWHM) of the light versus time profile,
called response time FWHM, analogously to the FWHM of
the counts versus energy distribution. The very good time
resolution of the scintillators is preserved in pulse processing
by PM tubes.
l Absolute counting efficiencies of solid scintillators depend
on the counting geometry and the type of radiation to be
detected. The counting efficiency of LSC for high-energy
beta and alpha particles is 100%; for low-energy beta
particles, such as for 3H the efficiency is 30
40%.
l Scintillation counters generally have high background,
increasing the detection limit compared to measurements
with gas ionization and semiconductor detectors. The most
significant source of noise is the spontaneous emission of
thermionic electrons by the photocathode. (Various sources
of background and the techniques of background reduction
are discussed in detail in Section IV.C.)
l The performance of LSC is strongly dependent on quench-
ing (see Chapter 7) which causes losses in the light output of
the scintillator either by hindering the light production
(chemical quenching) or by absorbing the produced light
(color quenching).
Although semiconductor Si detectors proved to have
advantages over scintillation detectors in spectrometric
measurements, liquid scintillators are used in various fields
including gross alpha/beta counting and absolute activity
determination due to high counting efficiency; recently, the
high-resolution alpha spectrometry (PERALS) has been
successfully used for fast spectrometric determination of
some alpha emitters.
Chapter | 6 Alpha Spectrometry
6. Cryogenic Detectors
In recent years, a measurement technique has been developed
which is based on the thermal detection of alpha particles using
very sensitive detectors, called bolometers. The bolometer is
a calorimeter operated at very low temperature, typically below
100 mK. The bolometer has two major parts, an absorber where
the energy of the single alpha particle results in a temperature
rise and a thermal sensor (thermometer) to measure it. At this
very low temperature, the heat capacity of the absorber, which
can be a dielectric, a metal, or a semiconductor material,
becomes so small that the temperature rise due to the interaction
of a single alpha particle becomes detectable.
In the interaction of alpha particles with matter, energy is
transferred to electrons by inelastic collisions that induce ioni-
zation and excitation. The energy is distributed between the
production of charge carriers (in semiconductor materials
electronehole pairs) and phonons (lattice vibrations and heat).
In bolometers, the energy of the phonons is detected. If the
electronehole pairs recombine in the bolometer within the time
resolution of the system, their energy is also transferred to
phonons that are also detected.
Bolometers have the great advantage that theoretically better
energy resolution can be achieved than in the case of Si
detectors. Juillard (1999) calculated that the FWHM in a Ge or
Si bolometer is in the order of 1 keV for alpha particles of
5-MeV energy. Leblanc et al. (2006) reported a 4-keV FWHM
for an alpha spectrum measured with a composite cop-
peregermanium bolometer and an external electrodeposited
238
Pu source. The detector response was in the range of
10
8e10
7 V/keV, the pulse rise and decay times were about
1 and 5 ms, respectively. Fig. 6.14 shows the schematic drawing
of the CueGe bolometer used for the measurements.
After further development and optimization, bolometers will
probably find application in metrology where extremely high-
FIGURE 6.14 Bolometer B300 developed by Leblanc et al. (2006) (reprinted
by permission of Elsevier Ltd. Ó 2006). A Cu absorber disk (1) is thermally
coupled to a Ge heat diffusing volume (2,3) coupled to a large thermometer (4).
Pure Ge pillars (5) assure a rigid support and the thermal link to the thermal bath
(7). The detector frame is fixed on the cold plate of the refrigerator. The
bolometer was tested in a 20 mK dilution refrigerator, placed in a Faraday cage
and decoupled from ground vibrations.
379
resolution alpha spectrometry is required for the accurate
determination of nuclear data (see also Chapter 16 for a detailed
treatment of bolometers).
B. Electronic Units
The basic alpha-spectrometric measurement system consists of
a detector, electronics to process the signals, a power supply
unit, a chamber (a light-tight chamber in the case of a light-
sensitive Si detector and a gastight chamber in the case of a gas
ionization detector) surrounding the detector, a vacuum system
to reduce the chamber gas pressure, and absorption of alpha
radiation, and a software package to analyze the spectra. The
signal processing electronics usually contains the preamplifier,
the main amplifier, the analogedigital converter, and the
multichannel analyzer, as illustrated previously in Fig. 6.6.
In semiconductor detectors, the preamplifier is usually
a charge-sensitive amplifier, while in scintillation detectors it is
the photomultiplier tube (PMT). The various types of pream-
plifiers are described in detail in Chapter 16.
The roles of the main amplifier are (i) to further amplify the
signal and (ii) to shape the signal from the discharge curve to
a signal in pulse shape. In the main amplifier, only the first part
with the increase of the discharge curve is used in order to speed
up the signal processing significantly.
The analogedigital converter (ADC) determines the height
of the pulse signal supplied from the main amplifier. This
pulse height is then converted to a number of channels by the
multichannel analyzer (MCA). The MCA counts the number
of events per channel, and generates the pulse-height
spectrum.
With the advent of personal computers (PCs) at the begin-
ning of the 1980s a powerful system of standardized processor,
large computing and storage power, and a large variety of
interfaces became available for spectrometric purposes. At
present, there are two types of PC-based MCA systems, PC
plug-in cards and NIM modules under PC control. Spectrum
data are stored either in PCs or in stand-alone storage modules.
In both cases, setup and control of the MCA is accomplished via
a computer program, and spectrum evaluation software is
usually also installed in PCs.
With the increasing development of complex digital elec-
tronics, the so-called digital amplifiers for spectroscopy were
developed that are not only amplifiers but also analyzers.
These systems digitize the signals from the preamplifier
directly and then process them digitally. The great advantage
of the digital amplifier is the large signal throughput. As
a result, extremely high count rates can be processed almost
without interference.
The high voltage supply is adapted to the type of detector
and provides a very clean and stable signal. Noise of the high-
voltage power supply has a detrimental effect on the spectra
resulting in degraded energy resolution or deviations in the
amplification of the signals, e.g. in the case of scintillation
detectors.
A detailed description of the electronic units is given in
Chapter 5 on gamma spectrometry and in several good mono-
graphs (Knoll, 2010).
380 Handbook of Radioactivity Analysis

of 6.8 mg/cm2. By increasing the source thickness to a few

IV. CHARACTERISTICS OF THE ALPHA mg/cm2, the self-absorption of alpha radiation is increased;
SPECTRUM peaks become wider causing poor energy resolution and the
A. Peak Shape and Spectrum Analysis low-energy tailing increases.
Energy resolution (FWHM). Alpha peaks are character-
The major characteristics of the alpha-particle spectra depend ized in routine analytical practice by the FWHM value, which
on the type and quality of the detector and the electronic units, can be easily determined from the spectrum as the peak width in
the geometric arrangement, and the quality of the alpha source. keV at the half of the peak height. The FWHM values of alpha
The operating principles and the major characteristics of the peaks are usually larger than the specified values for the
various types of detectors have been discussed above. Energy detector. While typical FWHM values of PIPSi detectors are
resolution, pulse shape, response times, and counting efficien- 17e19 keV and 30e37 keV for detectors of 300 and 1200 mm2
cies are basically determined by the detector; other factors will active area, respectively, those of alpha spectra in routine
contribute to the overall performance but cannot overcome analytical work are in the range of 30e80 keV very much
limitations of the detector. A thick alpha source, a thick depending on the source quality. FWHM values of high-
absorber layer between the source and the detector, or an uneven resolution alpha spectrometry are between 10 and 20 keV when
detector window will negatively affect the energy resolution, detector resolution is close to 10 keV.
while electric noise in the signal processing will increase the The statistical fluctuation in the number of the electrone
background. In the present section, the various factors influ- hole pairs produced in the detector determines the theoretically
encing the alpha spectra are discussed first based on the example achievable energy resolution of an alpha spectrometer. The
of semiconductor Si alpha spectrometry, followed by a brief number of electronehole pairs varies due to the presence of
discussion of other detector types. impurities, to crystal defects that can trap the charge carriers,
and due to possible recombination and to various secondary
processes (e.g., crystal damage and lattice vibration). A
1. Peak Shape and Spectrum Analysis significant part of the energy deposited in the detector does not
with Si Detectors create electronehole pairs but appears as heat and vibrations
a. Peak Shape (phonons). According to theoretical calculations, the limit of the
energy resolution in Si detectors (when processes taking place
Typical alpha spectra of various resolutions and shapes taken by
outside the detector such as absorption and self-absorption are
a PIPSi detector are shown in Fig. 6.15. The sources contain
neglected) is about 7e10 keV (Steinbauer et al., 1994; Amou-
various amounts of natural U and so have various thicknesses.
dry, 1990). This is not far from the measured FWHM values that
They were prepared after chemical processing, and coprecipi-
can be obtained by HRAS.
tation with lanthanide fluoride; measurements were performed
A measured FWHM in standard alpha spectrometry depends
using a PIPSi detector (Pöllänen et al., 2005).
on many other parameters of the detection system, the
Fig. 6.15 shows the effect of self-absorption on peak
geometric arrangement of the source and the detector, and the
shape. The curve of highest resolution is a typical thin alpha
properties of the alpha source itself. Each process causes peak
source obtained from a routine sample preparation procedure
broadening. The final FWHM can be calculated from the indi-
similarly to the curve in Fig. 6.4. This source has a thickness
vidual contributions as
FWHM2 ¼ FWHM2d þ FWHM2s þ FWHM2a (6.10)
238
U 234 where d, s, and a refer to detector, source, and absorber effects,
U
respectively.
2.3 mg/cm2
Number of counts (logarithmic scale)

PIPS
Si
detector
0.90 mg/cm2
window

c
b
0.38 mg/cm2 235
U a d
e
vacuum or air
6.8 μg/cm2

1 2 3 4 5
Energy (MeV)

FIGURE 6.15 Alpha spectra of samples composed of natural U with different

source thicknesses. The peaks on the left and right correspond to 238U and 234U source
(Pöllänen et al., 2005, reprinted by permission of Elsevier Ltd. Ó 2005). Spectra
source support plate
are shifted along the vertical axis to show the differences in peak width (reso-
lution) and tailing. FIGURE 6.16 Paths of alpha particles (a to e) in the sourceedetector system.
Chapter | 6 Alpha Spectrometry 381

FIGURE 6.17 Simulated alpha spectra of a mixed source containing equal activities of 238U and 234U when absorber thickness (0 mm, 5 mm, and 20 mm) is changed
(absorber is a plastic foil of 0.5 g cm
3 density). Detector FWHM and source thickness, assumed to be 14 keV and 0.4 mm (6.8 mg/cm2), not influencing the spectrum
shape significantly. Spectra were generated by the AASI simulation software (Siiskonen and Pöllänen, 2004).

The effect of the geometric arrangement on the energy
resolution is illustrated in Fig. 6.16.
Alpha particles emitted by the radionuclides embedded in
the source material can have different paths before entering the
Si detector. They can deposit energy in the source (such as
particles b and c). All particles (aee) will deposit energy in the
air gap between the source and the detector and in the detector
window. The first process represents self-absorption and the
latter ones represent absorption. The role of air absorption can
be neglectable if high vacuum is present in the detector
chamber, but very often it is desirable to attain a limited air
pressure to protect the detector from recoil particles (see below).
Altogether, the contributions of absorption in the source (“self-
absorption”), in the detector window, and in any other absorbent
to the total absorption are different. Each process causes
reduction of the total energy deposited in the Si detector and
each process results in a range and energy straggling of the
monoenergetic alpha particles. The lengths of the arrows in
the Si material represent the paths of the alpha particles and the
energy deposited by each particle in the active volume of the
detector. Variation in these individual energy depositions results
in peak broadening.
Absorption and self-absorption have different effects on the
alpha spectrum. If only absorption has a significant contribution
to energy losses (thin source but thick absorber), then the
spectrum is shifted to lower energies because all alpha particles
lose part of their energy in interactions outside the detector. It
also causes peak broadening due to the variation in energy loss
outside of the detector due to varied angles of incidence, and to
the reduction in number of charge carriers produced in the
detector. If only self-absorption has a significant contribution to
energy losses (as in the case of thick sources), then the peak is
broadened but the spectrum is not shifted. This is because
particles originating from the surface layer of the source can
reach the detector without loss of energy due to self-absorption.
The effect of absorption and self-absorption on the alpha spectra
is shown in Figs 6.17 and 6.18, respectively.
Absorption and self-absorption depend on the composition,
density, homogeneity, and surface roughness of the absorber
and source. In the AASI (advanced alpha-spectrometric

FIGURE 6.18 Simulated alpha spectra of a mixed source containing equal activities of 238U and 234U with varying source thickness (0.4 mm, 20 mm, and 40 mm
with relevant source surface densities of 6.4; 320; and 640 mg/cm2). Detector FWHM and absorber thickness assumed to be 14 keV and 0 mm (0 mg/cm2), not
influencing the spectrum shape significantly. Spectra were generated by the AASI simulation software (Siiskonen and Pöllänen, 2004).
382
simulation, 2011), a Monte Carlo simulation code, all these
parameters can be adjusted.
The resolution of alpha detectors is dependent on the
detector size. The reason is that large detectors cannot be
prepared with a completely even thickness of the window and
without surface inhomogeneity. Inhomogeneity and surface
roughness in the source, the detector, or even the absorber will
result in increased FWHM values.
The peak resolution in alpha spectrometry depends on the
measuring geometry, i.e., in the relative positions of the source
and the detector. When the source is placed parallel to and in
line with the detector, peak broadening is observed when the
source is moved toward the detector. This phenomenon can be
easily interpreted by the increased angle under which the alpha
particles can reach the detector, resulting in an increased path in
the detector window and a reduction of energy deposited in the
effective volume of the detector (see Fig. 6.16). This effect of
source-to-detector distance on FWHM is especially significant
in case of thick detector windows (e.g., in the case of diffused
junction detectors).
Alpha spectra measured with Si detectors are characterized
not only by the FWHM values but also by the asymmetric peak
shape. Peaks usually have a Gaussian shape on the high-energy
side and a low-energy tailing as shown in the Figs 6.15, 6.17 and
6.18. Some isotopes (e.g., 241Am and 243Am) have a small high-
energy tailing as illustrated in Fig. 6.4.
Individual alpha lines of a single radionuclide referring to
the fine structure of the alpha decay usually have slightly
different energies; therefore, they are not separated as individual
alpha peaks even in high-resolution alpha spectrum but are more
or less overlapping with each other (see Fig. 6.4). If the reso-
lution is poor, the lines apparently appear in a single wide
asymmetric peak of poor resolution or a peak with inflection
points at the positions of the nonresolved smaller peaks.
Due to the complexity of the processes resulting in peak
tailing, the FWHM parameter is not enough to describe the peak
shape, unlike other spectrometries such as gamma spectrometry
and LSC. In a simplified case, the full width at tenth maximum
(FWTM) parameter is used together with FWHM but in more
detailed studies the whole peak shape has to be described by
peak fitting algorithms. Systematic studies have in recent years
revealed the physical processes responsible for the asymmetric
shape of alpha peaks.
High-energy tailing originates from pulses that are detected
as the sum (coincidence) of the alpha pulses and the pulses due
to conversion electrons (or to a lesser extent to low-energy
gamma radiation) emitted by the same radionuclide if the pulses
are detected within the resolution time of the detector. For
example, 241Am emits alpha particles of 4 different energies and
gamma radiation of 4 different energies. Instead of gamma
emission, the nuclide can be stabilized by the emission of
conversion electrons of discrete energies. These electrons of
low energy are detected with high efficiency by the Si detector.
Thus, pulses on the high-energy side of the alpha particle
originate basically from the true coincidences of alpha particles
and conversion electrons. Alpha-electron and alpha-photon
coincidences in high-resolution alpha spectrometry have been
studied in detail by Siiskonen and Pöllänen (2006).
Handbook of Radioactivity Analysis
The origin of peak broadening and low-energy tailing is
a complex process which can be observed in all types of alpha
spectra produced by Si detectors including low- and high-
resolution spectra and spectra of isotopes emitting either
a single alpha particle or different alpha particles with or
without the emission of gamma photons.
Alpha peaks have an asymmetric shape with low-energy
tailing in both high- and low-resolution alpha spectrometry, but
the physical phenomena responsible for this shape are different.
In HRAS where absorption and self-absorption are reduced to
a minimum, the physical processes have been studied in detail by
several authors (Steinbauer et al. 1994; L’Hoir, 1984). Peak
broadening originates from energy-straggling processes that
include absorption of alpha particles (e.g., in the dead layer/the
window of the Si detector) and the electronic noise (e.g., in the
detector and the amplifier) which cannot be eliminated. This
peak broadening can be described by a Gaussian function. The
low-energy tailing arises from the processes where the deposited
energy of the alpha particles in the Si detector does not result in
the production of electronehole pairs. Such processes are
collisions of the alpha particles with the Si nuclei and further
interactions of the knocked-on Si ions in the crystal. Stopping of
these ions (such as by recoil, heat, and phonon generation) results
in pulse-height defect (PHD) that can appear as tailing in the
spectrum. Low-energy tailing can be described by exponential
functions.
In low-resolution alpha spectrometry, these fundamental
processes are overshadowed by other types of interaction of
alpha particles usually taking place outside the detector. Low-
energy tailing and peak broadening are explained by absorp-
tion and self-absorption of the alpha particles, such as
l absorption in gases in the vacuum chamber,
l absorption in the detector window, and
l self-absorption in thick sources.
Absorption results in peak shifting, peak broadening, and peak
tailing. In the case of self-absorption, there is no peak shifting
(as measured at the upper limit of the peak), but there is peak
broadening and increased tailing, as discussed above (see Figs
6.17 and 6.18). Ideally, sources should be infinitely thin to avoid
self-absorption. Significant peak deterioration for uranium
sources was observed above a source density of 100 mg/cm2 by
Martin and Hancock (2004a), although the significance will
depend upon the homogeneity of the sources and on the energy
difference for the lines of interest.
The processes influencing alpha peak shape in the case of
thick sources have been investigated by Monte Carlo simula-
tion (Ziegler et al. 1996; Pöllänen et al., 2007). Pöllänen found,
that in thick sources, the peak-shape distortion is influenced by
source thickness, source density, source shape inhomogenei-
ties, and by the elemental composition of the source (see Figs
6.15, 6.17 and 6.18). The AASI software uses Monte Carlo
simulations to generate alpha spectra of thick alpha sources. It
was shown by Pöllänen et al. (2005) how the properties of the
alpha source (such as inhomogeneities) affect the peak shape,
especially the tailing. Simulated and measured spectra agreed
well when source inhomogeneities were also taken into
account.
Chapter | 6 Alpha Spectrometry 383

   
b. Peak Fitting Functions A u
m s2 1 u s
f ðuÞ ¼ A,pu ðuÞ ¼ exp þ 2 erfc pffiffiffi þ
Various mathematical models have been proposed to describe 2s s 2s 2 s s
the shape of monoenergetic alpha peaks, and are used for fitting (6.15)
the alpha peaks in spectrum evaluation codes. The fitting
procedure involves This fitting function obtained from a Gaussian and one expo-
nential function can describe the asymmetric peak shape rela-
l the selection of the peak-shape model which depends on tively well. It has two shape parameters s and s and two
a number of parameters, parameters characterizing the peak area A and the peak position
l selection of the optimization criteria for fitting the model to m. For a measured spectrum composed of several peaks, the sum
the measured data, and of fitting functions F(u) is calculated by the addition of the
l the choice of the numerical optimization procedure. individual f(u) functions.
As a result of fitting, measured data are compared with calcu- However, it was found that the fitting function (6.15) does
lated values, the goodness of fit is described and usually peak not describe well the tailing (especially long tailing). There-
areas and peak positions are calculated together with their fore, instead of one exponential, two or three exponential
uncertainties. functions or occasionally two exponentials and a constant were
To describe the asymmetry of the alpha peaks, modified included in the fitting functions. It was found useful first to
Gaussian functions were used from the end of the 1960s, but subtract the constant, then use the following fitting function
these functions failed to describe the peak tailing (Garcı́a- F(u) that comprises a Gaussian function to describe the peak
Toraño et al. 1999). Later, the use of a combination of Gaussian region and two exponential functions to describe the tailing as
and exponential functions was proposed. The analytical convolution of two exponential of a steeper and a less steep
function consisting of a Gaussian and a one-sided exponential functions. The explicit form of the fitting function is as
function was first proposed by L’Hoir (1975) and it has been follows:
used for the analysis of alpha peaks in HRAS by several authors " !
Xm
Ai 1
h u
mi s2
(Watzig and Westmeier, 1978; Bortels and Collaers, 1987; FðuÞ ¼ exp þ 2
Bortels et al., 1995; Martin-Sanchez et al., 1996). i¼1
2 s1 s1 2s1
Bortels and Collaers (1987) used a Gaussian and one or two 
 !
1 u
mi s h u
mi s2
exponential functions. In certain cases, a step function had to be erfc pffiffiffi þ þ exp þ 2
subtracted from the spectrum before data processing. In the 2 s s1 s2 s2 2s2
peak-shape model, two random variables (x, y) are considered 
#
1 u
mi s
where x has a normalized Gaussian probability-density function erfc pffiffiffi þ
2 s s2
px(x) with s resolution,
(6.16)


1 x2
px ðxÞ ¼ pffiffiffiffiffiffi exp
2 (6.11) This fitting function consisting of one Gaussian and two expo-
s 2p 2s
nential functions has four shape parameters, i.e., s, s1, s2, and h,
which are the same for all peaks and two parameters, i.e., Ai
and y has a normalized left-sided exponential with parameter s: (peak area) and mi (peak position), that are specific for each
1  y peak.
py ðyÞ ¼ exp Hð
yÞ (6.12) The peak fitting model involved in a spectrum evaluation
s s
software was used successfully for the deconvolution of spectra
where H(
y) is the left-sided unit-step function where H(x) ¼ 1 acquired by HRAS. The method allows even the identification
for
N < x < 0, otherwise H(x) ¼ 0. of the strongly overlapping peaks of 239Pu and 240Pu, and it is
The random variable u ¼ x þ y (the energy variable) is adequate for the determination of exact emission probabilities
characterized by a joint probability-density function pu(u): of alpha-emitting nuclides. The major drawbacks of the method
are that
Z0
pu ðuÞ ¼ py ðyÞpx ðu
yÞdy (6.13) l relatively high source activities (sometimes 10 Bq) are
required even with very long counting times to have

N
acceptable statistics while the energy resolution is kept also
The normalized function after integration is excellent (in alpha spectrometry, the requirement toward

    high resolution are contradicting the requirements toward
1 u s2 1 u s high efficiency) and
pu ðuÞ ¼ exp þ 2 erfc pffiffiffi þ (6.14)
2s s 2s 2 s s l many fitting parameters are used, which makes the fitting
more accurate but the numerical optimization becomes more
in which erfc is the complementary error function. Taking into
complicated.
account the actual peak area A that is different from unity and
the position of the peak center m in the Gaussian function, one Other models to fit the alpha spectra have been developed by
obtains the expression of the fitting function f(u) for a single Koskelo et al. (1996), Garcı́a-Toraño (1997, 2003), and Lozano
alpha peak: et al. (2000). As an example, the results of deconvolution of the
384 Handbook of Radioactivity Analysis

-5
100000

Iteration# 0 Chi-sq1.1
10000

Counts per Channel 1000

100

10

1
1028 1060 1092 1124 1156 1188
Channel Number
FIGURE 6.19 Graphical presentation of a deconvolution of the multiplet containing the alpha lines of 239Pu and 240Pu by HRAS. Fitting was by the ALPACA code.
Single lines represent the fitted peaks and the sum spectrum, the histogram represents the measured points. The goodness of the fit is shown by plotting the residuals in
the upper curve. (Garcı´a-Toraño, 2006, reprinted by permission of Elsevier Ltd. Ó 2006)

spectrum of 239Pu and 240Pu using the ALPACA code developed
at the Spanish institute CIEMAT (Garcı́a-Toraño, 2006) are
shown in Fig. 6.19. The spectrum consists of the five badly
overlapping peaks at energies in the following order: 5105 keV
(239Pu line), 5124 keV (240Pu line), 5144 keV (239Pu line), 5157
keV (239Pu line), and 5168 keV (240Pu line). These isotopes are
known as the ones that cannot be determined by routine alpha
spectrometry, because the five lines lie within a very narrow
energy range of 65 keV. (Routinely used alpha spectrometers
require about 200-keV peak-to-peak separation to avoid peak
overlapping.) Nonetheless, the determination can be done by
high-resolution alpha spectrometry (HRAS) using a spectrum
deconvolution software.
Bortels et al. (1995) extended the method for the analysis of
value was about 2% when equally large peaks having a separa-
tion of about one FWHM were analyzed (Fig. 6.20).
For relatively low-statistics alpha spectra from measure-
ments at a relatively high solid angle, 239Pu/240Pu activity ratios
in the range of 1.4 down to 0.1 could be determined in the above
example.
In low-activity samples, several other functions have been
used to describe the low-energy side peak tailing while the peak
239
Pu
Counts per Channel

alpha spectra of low statistics. These sources usually have

a finite source thickness, a source diameter of a few centimeters,
and the detector diameter is increased (>100 mm2) while
10
the source-to-detector distance is reduced increasing the solid
angle e all factors resulting in a reduced energy resolution. It
was shown that the fitting functions developed for infinitely thin
sources with high resolution (<10 keV) cannot be used directly
for sources of lower resolution (>10 keV).
It was shown that in low-statistics alpha spectra, there is 1
insufficient information on the spectrum tailing to use the fitting
function in eqn (6.16); therefore, the simpler model using 650 700 750
a single exponential function (6.15) was used for spectrum Channel Number
deconvolution. Furthermore, it was found that the peak decon- 4
Residuals
Relative

volution is successful only if single isotope spectra are used as

constraints when spectra of mixed sources are evaluated. In Pu
analysis, pure 239Pu standard was used as single isotope source.
The use of statistical weights in the fitting of low-activity
samples has been proposed by Garcı́a-Toraño (1994).
Bortels et al. (1995) fitted triplets or quadruplets in the
common region to the nuclide 239Pu and 240Pu depending on the
actual resolution. Besides the activities, the activity ratio of
239
Pu/240Pu could be calculated. The deviation from the target
0
-4
FIGURE 6.20 Fitted spectrum and residuals (relative deviation of measured
and fitted values) of a mixed 239Pu and 240Pu source prepared by drop deposition
(Bortels et al., 1995, reprinted by permission of Elsevier Ltd. Ó 1995). Peak
FWHM is 12.4 keV. Source activity was 17.5 Bq and the activity ratio of
239
Pu/240Pu was 0.67. Spectra were measured with a 300 mm2 PIPS detector in
a solid angle of about 13% of 4p sr. Quadruplets were used in the fits. (The peaks
not labeled in the figure belong to 240Pu.).
Chapter | 6 Alpha Spectrometry
FIGURE 6.21 Alpha peak fitting by a Gaussian and a modified Gaussian
function according to LaMont et al. (1998). (Reprinted by permission of
Springer-Verlag Ó 1998)
center and the high-energy side of the peak have been usually
described by Gaussian function. Fitting models developed by
LaMont et al. (1998), Vintro et al. (1996), and Mitchell et al.
(1998) are much simpler than the models developed for HRAS.
LaMont et al. (1998) also used a modified Gaussian function
to model the tailing (see Fig. 6.21). The Gaussian portion of the
peak is fitted by eqn (6.17) when x > c
t:
ðx
cÞ2
f ðxÞ ¼ h$e
w2 (6.17)
The modified Gaussian portion of the peak tailing is fitted by
eqn (6.18) when x  c
t:
tð2x
2cþtÞ2
f ðxÞ ¼ h$e
w2 (6.18)
where x is the energy variable at which to compute f(x), h is the
peak height, c is the center of the peak, t is the distance below c
where shape deviates from Gaussian, and w ¼ FWHM$0.60056.
The method was used for the determination of 239Pu/240Pu
activity ratios using a commercially available alpha spectrom-
eter with an ULTRA detector of 50 mm2 area. Sources were
prepared by electrodeposition. Sourceedetector distance was
1.8 cm and the resulting resolution was 16 keV FWHM. Peak
heights and centroid energies were constrained. An acceptable
agreement was found between calculated 239Pu and 240Pu
activities and the target values.
MicroSAMPO, a commercially available software origi-
nally developed for gamma spectrometry (Aarnio et al., 1987),
was used to fit the alpha peaks of low-activity samples by Vintro
et al. (1996) and Mitchell et al. (1998). The fitting model is
a modified Gaussian with left- and right-handed exponential
tails. The fitting function does not take into account the long-
range tailing; but it still was used successfully for deconvolution
385
of 239Pu and 240Pu, as well as 243Cm and 244Cm peaks. The latter
issue is especially important, because the relatively short-lived
Cm isotopes cannot be analyzed by mass spectrometric tech-
niques. In order to perform spectrum deconvolution of these
nuclides in environmental samples, a relatively good energy
resolution is required. In the case of analysis of Cm nuclides, the
FWHM value was 13e15 keV, a PIPS detector of 100 mm2 was
used, the source-to-detector distance was 15 mm, and the
sources of about 10-mBq activity were counted for an extremely
long time (5  106 s).
The recently released WinALPHA code, which is freely
available from the Physics Section of the IAEA (Capote Noy
et al. 2004), uses the following analytical model (Garcı́a-
Toraño, 2003). To describe the peak, a pure Gaussian is used
above the peak center and a 2nd Gaussian with a wider resolu-
tion (s) is used below the peak maximum:
2

ðx
cÞ
2
f ðxÞ ¼ A$e
2s
l;r (6.19)
where f(x) is the value for the channel x, A is the peak amplitude,
c is the channel number at peak maximum, and sl,r is the
resolution on the left or right side of the peak describing the
asymmetry.
The low-energy tailing is described by the following
equation:

 
x
c 0:5
f ðxÞ ¼ B exp
C (6.20)
sd
where B and C are parameters that are obtained from the shape
parameter n as follows:
expð
n2 =2Þ
B ¼ A (6.21)
expð
2n2 Þ
C ¼ 2n3=2 (6.22)
Thus, the set of shape parameters (n, sl, and sr) are constant within
one spectrum and a fitting function containing relatively few
parameters has been obtained. The accurate description of the
tailing outside the vicinity of the peak center is not possible.
c. Alpha Spectrum Evaluation Codes
In the alpha spectrum evaluation process, defined analytical
functions containing several shape parameters are fitted to the
measured spectrum data. To solve the nonlinear fitting problem
initial parameter values have to be provided, then optimization
procedures are used to solve the nonlinear least-squares fitting
problem by one of the methods such as the NewtoneRaphson,
the LevenbergeMarquart, or the Simplex method. The good-
ness of fitting can be characterized by various techniques, e.g.,
calculating the goodness of fitting (R2), the chi-square value
(c2), and/or the fitting residuals. A summary of the mathemat-
ical procedures for least squares fitting is given by Garcı́a-
Toraño (1999, 2006).
As a result of fitting, the unknown parameters of the algo-
rithm are determined. Using the fitted function with the known
parameters, spectra can be deconvoluted into the individual
peaks that contribute to the final measured spectrum. The
386
convoluted spectrum is the simple sum of the individual
reconstructed spectra of the given nuclide.
Computerized spectrum evaluation programs can be used
for the analysis of overlapping peaks of one or more nuclides or
also for the analysis of complicated spectra containing several
radionuclides. At present, there are several software in use
which allow the fitting of alpha spectra with different levels of
complexity, from simple peak integration to nonlinear fitting
algorithms.
An intercomparison exercise of four commercially available
alpha software programs was carried out under the auspices of
the IAEA in 1997 (Blaauw et al., 1999; IAEA, 1999; Garcı́a-
Toraño et al., 1999). All of these programs are general-purpose,
commercial codes not dedicated for the analysis of high-reso-
lution alpha spectra. AlphaVision (EG&G Ortec, USA) uses
a Gaussian function with one low-energy exponential function
that is fitted to the peaks with the Simplex method. The code can
be operated in peak search and fit as well as library search and fit
mode. The code is operated in selected regions in peak search
mode. The Alps code (Westmeier GmbH, GE) is based on the
fitting of a Gaussian with one- or two-folded exponentials with
a linear least-squares algorithm in three passes. By the alpha
analysis software of Genie 2000 (Canberra Industries Inc.,
USA) the line shape model is a modified Gaussian function (see
eqns 6.17 and 6.18) and peak areas can be determined either by
summation of singlets or by nonlinear least-squares fitting of
singlets and multiplets using a modified Marquardt algorithm for
fast convergence. Peak search is performed either using a library-
driven routine or by the Generalised Second Differential Method.
In Winner Alpha code (Eurisys Mesures, FR), peak areas are
determined either by summation of singlets or by nonlinear least-
squares fitting of singlets or multiplets using a modified Mar-
quardt algorithm for fast convergence. Peak search is performed
either using a library-driven routine or by the Generalised Second
Differential Method. Comparison was done in terms of deter-
mination of peak area, peak position, deconvolution capabilities,
uncertainty calculation, nuclide identification in case of large and
small peaks, and doublets. All programs had difficulties with the
analysis of small peaks. It was clear that the results left room for
improvement, e.g., in uncertainty calculation.
Hurtado et al. (2008) made a comparison of the Genie 2000
and the WinALPHA codes. Both codes are general-purpose
codes using a relatively small number of fitting parameters. The
WinAlpha code uses the line-shape algorithm described in eqns
6.19
6.22 and it performs a nonlinear fit of the spectra with the
LevenbergeMarquardt optimization method. WinALPHA has
two modes of operation, library-driven and automatic peak
search modes. The basic properties of the Genie 2000 code are
described in the previous section. Codes were compared in
terms of accuracy and precision in the analyses of environ-
mental samples. Both codes provide correct peak areas and peak
search results. WinALPHA performs a full uncertainty calcu-
lation and a better peak deconvolution than Genie 2000.
The WinALPHA program was successfully used for the
determination of the 240Pu/239Pu activity ratio in samples from
a reprocessing plant and a heavy water reactor by Srinivasan
et al. (2005) and Aggarwal and Alamelu (2007), respectively.
Electrodeposited Pu sources were measured with Si detectors of
Handbook of Radioactivity Analysis
25 mm2 by HRAS. (The FWHM value was 15 keV in the latter
case.) Good agreement was found between measured and tar-
geted activity ratios.
Examples of other alpha spectrum evaluation codes are
ALFAS by Babelovswsky and Bortels (1993), ALPACA by
Garcı́a-Toraño (1994), FITBOR by Martin-Sanchez et al.
(1996), and Sigma-Plot by Jandel Scientific Inc. (1998).
While many spectrum evaluation codes have been developed
for the analysis of high and ultra-high-resolution alpha spectra
of thin alpha sources, less attention has been paid to the analysis
of thick sources. As discussed above, peak resolution and the
peak shape for thick sources are basically determined by self-
absorption. The ADAM (Advanced Deconvolution of Alpha
Multiplets) code is a general-purpose program for alpha spec-
trometry using Si detectors. The peak shape model in ADAM is
convolution of a Gaussian distribution (characterized by
FWHM) with low-energy side exponential tail. Up to three
exponential functions characterized by the slopes of the expo-
nentials 1/l, 1/m, and 1/n (in keV) and their area ratios R1 and
R2 are possible. The software can also take into account the
coincidences between alpha particles and electrons or low-
energy photons. The computer program known as AASI
(Siiskonen and Pöllänen 2006) provides coincidence informa-
tion for ADAM to be included in the fitting. Using the ADAM
software, the 239Pu/240Pu multiplet in chemically processed
samples could be successfully deconvoluted. The method gave
acceptably good results for the 239Pu/240Pu activity ratio using
Si detectors as large as 1200 mm2 (FWHM 21 keV) (Pöllänen
et al., 2011). There are tests in progress to use the code for the
analysis of sources of poor resolution and low statistics, such as
unprocessed environmental samples (air filters, evaporated
liquids, swipes, and smooth surfaces).
2. Peak Shape and Spectrum Analysis
with Gas Ionization Detectors
Properties of alpha spectra obtained by gridded ionization
chambers are not basically different from the spectra taken by
PIPSi detectors.
Fig. 6.22 shows an example of the asymmetric peak shape
with low-energy tailing that is similar to those of the peaks
Counts 230
Th
450
400
350
300
238 Pu
250
200
239-240 Pu
150
100
238
U
234U
50
0
3500 3750 4000 4250 4500 4750 5000 5250 5500 5750 6000
Energy keV
FIGURE 6.22 Alpha spectrum of a mixed source measured by a gridded
ionization chamber (CEA, 2009).
Chapter | 6 Alpha Spectrometry 387

Counts
1800 226
Ra 4,78 MeV
1600

1400 222
Rn 5,49 MeV
1200 218
Po 6,00 MeV
1000
214
800 Resolution 230 keV
Po 7,69 MeV
600

400
Resolution 465 keV

200

0 50 100 150 200 250 300 350 400 450 500

Channel Number

FIGURE 6.23 Alpha spectrum of 226Ra and progeny measured by a PERALS spectrometer (CEA, 2009).

obtained by semiconductor alpha spectrometry. Typical resolu- Counts

tions are somewhat poorer than in the case of PIPSi detectors, the 232
Th
FWHM is not smaller than 30 keV. Spectra obtained by gridded
ionization chambers can be evaluated by the same method as for 8.0x101
low-resolution alpha spectra using PIPSi detectors. 228
Th
6.0x101
α
3. Peak Shape and Spectrum Analysis 230Th
with Liquid Scintillation Detectors 4.0x101

α + IC L shell
Peak shapes in LS spectrometry are different from those
2.0x101
measured with gas ionization and semiconductor detectors. α + IC M shell
A typical alpha spectrum of 226Ra and progeny measured with
PERALS spectrometer is shown in Fig. 6.23. 0.0

The peaks in the spectrum are symmetric, and can be

modeled by a Gaussian function. The main reason for the
symmetric shape is the lack of absorption and self-absorption in
LSC where samples are mixed with the scintillation cocktail.
(Absorption and self-absorption are the major reasons for peak
broadening and low-energy tailing when “thick” sources are
measured with semiconductor detectors.)
LS spectra are characterized by relatively poor resolution
even in case of the so-called high-resolution alpha-LSC using
the PERALS spectrometer. The FWHM is typically a few
hundred keV (see in Fig. 6.24) and the variation of the resolu-
tion as a function of energy is more pronounced than in semi-
conductor alpha spectrometry. This resolution does not allow
the detection of the individual alpha lines belonging to many
alpha-emitting isotopes. For example, in the figure above the
alpha radiations of 226Ra at 4.601 MeV and 4.783 MeV appear in
a single common peak and cannot be resolved. The Rn and Po
isotopes shown in the same spectrum are monoenergetic.
Alpha peaks in LS spectra may also have tailing but this
appears on the high-energy side of the peaks as shown in Fig. 6.24.
This high-energy tailing can be observed in the case of those
nuclides that emit several alpha particles of different energies
and the daughter nuclides de-excite to the ground state by
internal conversion or the emission of gamma radiation. Internal
conversion produces electrons that cause scintillation in the
cocktail. Since the scintillation efficiency of electrons is about
10 times higher than those of alpha particles (Section III.A.5),
a sum peak resulting from the true coincidence of the alpha
4000 5000 6000 7000 8000
Energy keV
FIGURE 6.24 High-resolution alpha-LSC (PERALS) spectrum of an extrac-
ted Th source showing spectrum deconvolution (green curves). In the case of
228
Th, the calculated positions of the a peak, and the pileup peaks originating
from the coincidences of the a peak and the conversion electrons, are indicated
with red lines (CEA, 2009).
particle and conversion electron will appear at a higher energy
than the alpha peak itself. This phenomenon was taken into
account to better describe the alpha peak shape in LSC by
Aupiais (2004) and the spectra successfully deconvoluted by
fitting several Gaussian functions to both the direct alpha peaks
and the pileup peaks of alpha particles and conversion electrons
as shown in Fig. 6.24. The method was successfully used for the
determination of U and Th nuclides in water by alpha-LSC.
4. Peak Shape with Cryogenic Detectors
The energy resolution of the alpha spectrum using bolometers is
extremely high. Measured FWHM values below 5 keV have
been reported (Leblanc et al., 2006). The alpha spectrum of
a 241Am source is shown in Fig. 6.25.
The superior resolution of alpha spectra using bolometers
compared to that of Si detectors is explained by differences in
the nature of the interaction of the alpha particle with the
detector. In the case of Si detectors, alpha particles have to pass
the detector window (the electric contact), whereas there is no
detector window in bolometers. Inside the Si detector there is
388 Handbook of Radioactivity Analysis

FIGURE 6.25 Alpha spectrum of an external sputtered 241Am source measured with the bolometer B306 (Leblanc et al., 2006, reprinted by permission of Elsevier
Ltd. Ó 2004). Time of measurement was 12 h. The individual peaks at 5443 and 5486 keV are completely separated.

a relatively large statistical fluctuation in the number of In the case of a point source placed a distance of H in front of
generated and detected electronehole pairs due to the presence an alpha detector of radius RD, the following equation can be
of impurities, crystal defects that can trap the charge carriers, used to calculate the absolute counting efficiency:
due to possible recombination and to secondary processes (e.g.,
0 1
crystal damage and lattice vibration). All of these intrinsic
processes as well as the instability of the electronic units 1B H C
εabs ¼ @1
qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiA (6.23)
contribute to degradation in the energy resolution (see eqn 2 H 2 þ 4R2 D
6.10). Thermal detectors are less sensitive to the fluctuations in
the number of electronehole pairs, because the total energy of The solid angle (the absolute counting efficiency) of various
the phonons (heat and lattice vibrations) is detected. If elec- source and detector arrangements can be calculated by Monte
tronehole pairs recombine within the time constant of the Carlo simulations; the results of calculations are given in tables.
bolometer, they will be also detected as phonons. However, as in Gascon and Munoz (2003) developed two theoretical formulas
the case of Si detectors, energy losses due to secondary emis- to calculate the efficiency of extended sources where RS is the
sion processes cannot be avoided in bolometers. radius of the source and D is given in Fig. 6.26. The simplified
According to the calculations of Amoudry (1990) and geometry formula obtained by an approximation with an infinite
Steinbauer et al. 1994), the theoretical contribution of the basic series is given below:
processes of detection to the energy resolution of Si detectors is  
10.5 and 7.4 keV, respectively, and Juillard (1999) obtained 1 R2D 3 R2S R2D H
εabs ¼

FWHM less than 3 keV for Si and Cu bolometers. 2 DðD þ HÞ 16 D5
(6.24)
 
B. Counting Efficiency 5 R4S R2D H 3
þ H 2
R2D
32 D9 4
In radiochemical determinations, radioactive tracers are added to
the unknown sample, and the activity of the sample is determined
from the relative number of counts in the analyte and tracer
peaks. In this case, a knowledge of the absolute counting effi-
ciency is not necessary to calculate the results (see below).
However, it is needed to determine the chemical recovery, which
is an important quality control check. In addition, in cases where
the tracer is determined by a separate measurement, the counting
efficiency must be known. An example of the latter case is the use
of 133Ba as a tracer for Ra determination, where the 133Ba is
measured using gamma spectrometry.
Since the intrinsic counting efficiency of the Si semi- Source
conductor detectors is 100%, determination of the counting
efficiency can be performed by calculating the solid angle
presented by the radioactive source to the detector (see in
Section III.A.2), provided the activity on the source is evenly FIGURE 6.26 Geometrical arrangement of the alpha source and the detector
distributed. A schematic drawing of the sourceedetector used for calculation of the counting efficiency according to Gascon and Munoz
geometrical arrangement is shown in Fig. 6.26. (2003).
Chapter | 6 Alpha Spectrometry
The calculated efficiencies were compared with each other and
with experimentally determined values, and a good agreement
was found. Therefore, the use of the above simplified formula
can be recommended. Efficiencies are often determined by
measurements when standard alpha sources of known activity
concentration and the same geometry (same size of the active
source area, same distance from detector) are available.
Efficiencies are often calculated by Monte Carlo simulations
if the sizes of the source and the detector window and the exact
geometric arrangement are known. The AASI simulation soft-
ware available through the Internet (Siiskonen and Pöllänen,
2004) can calculate the efficiency. Calculated efficiencies as
a function of sourceedetector distance, source diameter, and
detector diameter are given in Fig. 6.27.
FIGURE 6.27 Counting efficiencies as a function of (a) sourceedetector
distance (H); (b) source diameter (VS); and (c) detector diameter (VD). Effi-
ciencies were calculated by the AASI code according to Siiskonen and Pöllänen
(2004).
389
Typical counting efficiencies for a small source (RS < RD),
close (5
10 mm) to a Si detector of 300
600 mm2 are about
20
40%. The efficiency decreases significantly as the sourcee
detector distance is increased. If the source radius becomes
larger than that of the detector, there is a drop in the efficiency.
Calculated efficiencies can only be used for a sourcee
detector system if absorption and self-absorption are not high
(i.e., not resulting in counting losses), and if the activity on the
source is reasonably homogeneously distributed. Counting
efficiencies can also be affected (increased) by back scattering
of the alpha particles from the sample holder.
C. Background and Contamination
in Alpha Spectrometry
Semiconductor alpha spectrometers usually have a low back-
ground, originating mainly from electric noise of the instru-
ment. Since alpha pulses have a high energy and electric noise is
usually in the low-energy region, they can be easily discrimi-
nated (i.e., separated by pulse height). The typical background
of a new spectrometer in the region of a single alpha-emitting
isotope can be as low as 1 count per a couple of days
(10
5e10
6 cps). This low background is responsible for the
extremely high sensitivity of alpha spectrometry. Detection
limits as low as 1 mBq per sample are easily achievable,
provided contamination of the detector, the detection chamber,
and the sample source are avoided.
Contamination of the detector can take place when parti-
cles from sources are sputtered or splashed onto the detector or
the chamber surface. This can happen when sources do not
adhere strongly to the source support. The vacuum can help
remove loosely bound particles from the source. This type of
contamination can usually be removed by careful cleaning of
the detector (PIPSi detectors are washable) or the chamber
walls.
Recoil contamination takes place if recoil causes products
of alpha decay to sputter from the source onto the chamber walls
or (in the worst case) the surface of the detector. If the recoil
atoms or their short-lived progeny are themselves alpha emit-
ters, this will raise the background. Recoil atoms, like other
accelerated or implanted particles, adhere strongly to the
surfaces and are almost impossible to remove. For example,
when measuring natural Th, the alpha-emitting 224Ra as the
decay/recoil product of 228Th can contaminate the detector.
Since 224Ra has several short-lived progeny they can all accu-
mulate in the detector window creating a background that
contains the following alpha peaks: 224Ra, 220Rn, 216Po, 212Bi,
and 212Po. This contamination will “decay” by the half-life of
224
Ra (3.7 days). A typical 228Th spectrum is shown in Fig. 6.28.
After measurement of the Th source, the background spectrum
may contain all these radionuclides except 228Th.
Three techniques have been used to avoid recoil contami-
nation in alpha spectrometry:
l operating the spectrometer with an air barrier,
l covering the source with a thin even foil (Van der Wijk et al.,
1987; Vainblat et al., 2004), and
390
228
FIGURE 6.28 Alpha spectrum of a Th source with ingrown progeny (from Mietelski (2011).
l applying a voltage between the source and the detector
where the source is negatively biased by a few volts (Sill and
Olson, 1970).
The idea behind the first two protective measures is that
a properly selected absorber can stop the recoil particles of high
mass and low kinetic energy while alpha particles of low mass
and high kinetic energy pass through the absorber. An absorber
layer of about 12 mg/cm2 thickness can reduce the recoil
contamination by a factor of 1000. Nonetheless, using any type
of absorber between the source and detector will increase
energy straggling and reduce the energy resolution. It will also
slightly shift the spectrum to a lower-energy region. Applying
a negative bias to the source can retain the positively charged
recoil atoms on the source, although a small chamber pressure
(at least 12 mg/cm2) is still required to prevent recoiling atoms
from reaching the detector before they are attracted back to the
source (Sill and Olson, 1970).
Alpha spectrometers have to be protected from contamina-
tion due to oil vapors that can be released into the vacuum
system if rotary vacuum pumps are applied to evacuate the
alpha chamber. Oil contamination is a real danger if the vacuum
pump fails, as oil particles can backstream due to the prevailing
vacuum. To avoid oil contamination, a vacuum trap or filter can
be installed between the pump and the chamber.
D. Stability of the Alpha Spectrometer
System stability is very important in alpha spectrometry when
long measurements of low-activity samples lasting for several
days are performed.
Long-term stability is affected by environmental condi-
tions with special respect to the detector junction. Surface
barrier detectors fail when the encapsulation of the detector is
damaged. The junction of the PIPSi detector is implanted in the
Si matrix assuring higher intrinsic stability.
Alpha detectors are sensitive to temperature changes. The
leakage current of a Si diode doubles for every 5.5e7.5  C
change. The current change results in a change of the detector
Handbook of Radioactivity Analysis
voltage, which can affect the overall gain of the preamplifier
and cause a spectrum shift.
V. RADIOCHEMICAL PROCESSING
In order to obtain high-energy resolution, “good quality” alpha
sources have to be prepared. Prerequisites for good-quality
sources are that the deposit be thin and homogeneous with
a smooth flat surface. Since the range of alpha radiation from
the alpha-emitting radionuclides is less than 100 mm in typical
condensed phases, the source thickness is desirably much less
than this value. Taking into account that the source diameter
should not exceed that of the detector, alpha sources should
contain less than 10 mg/cm2 material or less than 50-mg
material on a source of 2.5-cm diameter.
To meet this requirement,
l samples are prepared and pretreated by mechanical and
physicochemical operations,
l chemical separations are performed to separate the analyte
from the matrix components and any interferences of the
sample, and
l thin sources are prepared for alpha spectrometry.
The steps involved in radiochemical analysis by alpha-emitting
nuclides are shown in Fig. 6.29.
Sample preparation and pretreatment cover all operations
that are performed before the chemical separation of the ana-
lyte, e.g., drying, homogenization, sieving, destruction of the
sample, and preconcentration of the analyte. A short discussion
of the methods is given in Section V.A.
Radiochemical processing includes, besides sample prepa-
ration and preconcentration, the chemical separation of
elements using various separation techniques, the most common
being precipitation, coprecipitation, distillation, ion exchange,
solvent extraction (also called liquideliquid extraction) and
extraction chromatography (also called solid-phase extraction),
and the source preparation.
In the case of environmental samples, several grams of
matrix material are usually removed to obtain thin alpha
Chapter | 6 Alpha Spectrometry 391

Sample collection Tracers are those radionuclides that are added to the sample
and preparation in order to quantify the chemical recovery. Either they are not
present in the sample or the activity added to the sample is much
larger than the amount present in the sample. Tracers are
Addition of tracer assumed to behave in the same way as the radionuclide(s) to be
determined. Tracers are typically, but not exclusively, the
isotopes of the same element as the analyte nuclides. A few
Sample dissolution examples of frequently used tracers are listed in Table 6.2. The
best tracers are relatively long-lived alpha-emitting isotopes that
emit alpha radiation of different energy from the analyte
Chemical separation nuclides.
Carriers are stable elements showing similar chemical
properties to the analyte(s). Unfortunately, many of the alpha-
Deposition onto emitting nuclides do not have stable isotopes, but sometimes
counting disc stable elements belonging to the same group of the periodic
table can be used as carriers. For example, stable Ba is often
used as a carrier for Ra. The mass of the stable carrier before
Count in an
alpha spectrometer and after separation can be determined by various analytical
techniques such as gravimetry, atomic absorption spectrometry
(AAS), optical emission spectrometry (OES), or mass spec-
Calculation of trometry (MS).
tracer recovery As the final step of radiochemical processing, alpha sources
& sample activity are prepared. The most frequently used techniques are elec-
FIGURE 6.29 Steps involved in radiochemical analysis by alpha spectrom- trodeposition and micro-coprecipitation. Occasionally, drop
etry. (Martin and Hancock, 2004b, reprinted by permission of Supervising deposition methods (evaporation) are also used with or without
Scientist Division Ó 2004) the addition of surface-active agent. The first two techniques
have been described in detail in the ASTM Standard Practices
C1284-10 and C1163-08, respectively. An overview of alpha
source preparation methods is given in Section V.C.
Chemical separations are discussed using as examples the
sources. It is not always necessary to separate all of the alpha- most important alpha-emitting radioelements/radionuclides
emitting radionuclides from the element to be determined, but including artificial (Pu, Np, Am, and Cm) and naturally
there are several nuclide couples whose peaks cannot be occurring (U, Th, Ra, and Po) radionuclides in environmental
resolved by means of standard alpha spectrometry. Examples of radioactivity measurements in Section V.B. Alpha spectrometry
well-known interferences are the following: 238Pu and 241Am;
237
Np, 230Th, and 234U; and 239Pu and 209Po. If the radioele-
ments such as Pu and Am, or Np, Th and U, or Pu and Po,
respectively, are chemically separated the interference issue can
be overcome and the originally interfering nuclides can be TABLE 6.2 Frequently Used Tracers and Analytes
determined in separate alpha sources. If interferences of the in Alpha Spectrometry
radioisotopes of the same element occur, such as in case of Analytes Tracers Decay mode of tracer
239
Pu and 240Pu, or 243Cm and 244Cm, chemical separations will 239,240 238 242 236
Pu, Pu Pu, Pu Alpha
not solve the problem. In some cases, the ingrowth of short-
237 239
lived alpha-emitting progeny on the source can be used (e.g. in Np Np Beta, gamma
the case of 223Ra and 224Ra). However, in general, high-reso- 241
Am, 243
Cm, 243
Am Alpha
244
lution alpha spectrometry or other analytical techniques such as Cm, 242Cm
mass spectrometry have to be introduced in such cases. 238
U, 235
U, 234U 232
U, 233U Alpha
Whenever chemical separations are performed, losses of the 232
analytes can appear almost unexpectedly in different parts of the Th, 230Th, 228Th 229
Th Alpha
226
procedure. For example, losses may occur during sample Ra, 224Ra, 223Ra, 225
Ra Beta (alpha-emitting progeny)
228
destruction due to volatility or sample splashing. They may also Ra(beta)
occur during separations due to absorption on the walls of the 226
Ra, 224Ra 133
Ba Beta, gamma
beakers or on the surfaces of undissolved residues: this is 210 208 209
Po Po, Po Alpha
because typically trace or ultratrace amounts of the analytes are
227 225
processed. To process such small amounts, special methods are Ac Ac Alpha (alpha-emitting progeny)
used to minimize losses and to determine the chemical 243
Am, and 133
Ba are nonisotopic tracers for the determination of Cm
recovery based on the application of radioactive tracers or and Ra nuclides.
chemical carriers.
392 Handbook of Radioactivity Analysis

is a routinely used measurement method for the determination

of radionuclides of these elements. TABLE 6.3 List of Standards and Procedures for the
In order to reveal the principle of the radiochemical Separation and/or Determination of Th, U, Np, Pu, Am,
processes, the basic chemical properties of actinides (Th, U, Cm, Po, and Ra Radionuclides by Alpha Spectrometry
Np, Pu, Am, and Cm) and Po and Ra relevant for the chemical Standard Title
separations are briefly summarized below. Several monographs
ISO 18589-4 (2007) Measurement of Radioactivity in the
and review papers have been published about the radiochem-
Environment. Soil. Part 4. Measurement of
ical processing of samples to determine Th (Hyde, 1960), U Pu Isotopes by a-Spectrometry
(Roberts et al. 1986), Np (Burney and Harbour, 1974), Pu
ISO 11483 (2005) Nuclear fuel technology e Preparation of
(Coleman, 1965; Cleveland, 1970; Hoffman, 2001), Am and
plutonium sources and determination of
Cm (Penneman and Keenan, 1960; Warwick et al., 1996), Po 238
Pu/239Pu isotope ratio by alpha
(Matthews et al., 2007; Henricsson et al., 2011), and Ra spectrometry
(IAEA, 2010a) using both old and new separation procedures,
ASTM C1001-05 Standard Test Method for Radiochemical
and good books and book chapters are also available that deal Determination of Plutonium in Soil by
with groups of these radioelements (Bagnall, 1957, 1966; Katz Alpha Spectroscopy
et al., 1986; Wolf, 2006; Nash et al., 2006; Hou and Roos,
ASTM D3865-09 Standard Test Method for Pu in Water
2007; Vajda and Kim, 2011; Lehto and Hou, 2011). A list of
recently published standards and procedures is given in ASTM C1205-07 The Radiochemical Determination of
Americium-241 in Soil by Alpha
Table 6.3.
Spectrometry
Th, U, Np, and Pu are the 2nd, 4th, 5th, and 6th members of
the actinide group, respectively. In aqueous solutions they ASTM C1475-05 Standard Guide for the Determination of
237
Np in Soil
exist in the þ3, þ4, þ5, and þ6 oxidation states, respectively,
with the exception of Th which has only one stable form in ASTM D3972-09 Standard Test Method for Isotopic
solution, Th(IV). The most stable forms of U, Np, and Pu are Uranium in Water by Radiochemistry
U(VI), Np(V), and Pu(IV), respectively. In alkaline solutions ASTM D6239-09 Standard Test Method for Uranium in
U(VII) and Np(VII) are also stable. Because the standard Drinking Water by High-Resolution
electrode potentials of the various Pu and Np species in acidic Alpha-Liquid-Scintillation Spectrometry
solutions are only slightly different, the various forms can ASTM C1284-10 Standard Practice for Electrodeposition of
coexist in solutions. Since the oxidation states of U, Np, and the Actinides for Alpha Spectrometry
Pu can be changed by the addition of oxidizing or reducing ASTM C1163-08 Standard Practice for Mounting Actinides
agents, the separation processes can be controlled. According for Alpha Spectrometry using Neodymium
to the actinide theory of Choppin et al. (1997), differences Fluoride
among the various oxidation states of a single actinide are ASTM D3084-05 Standard Practice for Alpha-Particle
greater than those of different actinides in the same oxidation Spectrometry of Water
state.
ASTM C1561-10 Standard Guide for the Determination of
The formation of complex ions in aqueous solutions with Plutonium and Neptunium in Uranium
inorganic ions or organic compounds is an important feature of Hexafluoride and U-rich Matrix by Alpha
the chemistry of the actinides. The relative complex-forming Spectrometry
tendency of actinide (An) species is the following: IAEA/AQ/11 (2009) A Procedure for the Rapid Determination
þ of Pu Isotopes and Am-241 in Soil and
An4þ ðIVÞ> An3þ ðIIIÞzAnðVIÞO2þ
2 > AnðVÞO2 Sediment Samples by Alpha Spectrometry

The stability series of the inorganic complexes of tri-, tetra-, and
hexavalent actinides are the same:
OH
> carbonate> oxalate> F
zacetate
>




4 > NO3 zCl > ClO4
SO2

There are small differences among the stability constants of the
different actinides in the same oxidation state.
Oxidation state adjustment and complex-forming conditions
have been discussed in many papers, and the conditions of
oxidationereduction reactions as well as stability constants of
a great number of complexes have been measured. The
formation of the given species is influenced by many parameters
(composition of the sample, the presence of oxidative/reductive
agents, amount and stability of the reagents, kinetics of the
process, etc.), and it is an especially challenging job if several
actinides are present in the same solution.
IAEA/AQ/12 (2009) A Procedure for the Determination of
Po-210 in Water Samples by Alpha
Spectrometry
Since tetravalent actinides have the highest complexing
power, the adjustment of this valence state has formed the
crucial part of many separation procedures. To keep Th, U, Np,
and Pu in tetravalent oxidation state in the same solution is
impossible, thus oxidation state adjustment is a kind of
compromise among various possibilities.
Np(IV) is easily formed by the addition of various reducing
agents, e.g., ferrous ions, iodide ions, to hydrochloric or dilute
nitric acid solutions. Strong reducing agents generating Fe2þ in
situ by the reduction of Fe3þ, e.g., hydrazine and
Chapter | 6 Alpha Spectrometry
hydroxylamine, are adequate for the adjustment of Np(IV) and
U(IV) oxidation states. These agents reduce Pu to Pu(III).
Trivalent Pu can be oxidized back to tetravalent species by
various oxidizing agents. To stabilize the Pu(IV) state without
further oxidizing it to Pu(V) or Pu(VI) only, a few moderately
strong oxidizing agents can be used, e.g., NaNO2 can be added
to nitric acid solutions to oxidize Fe2þ and consequently Pu to
Pu(IV) or H2O2 can be added to hydrochloric acid solutions
while Np still remains tetravalent and U is oxidized back to
U(VI). NaNO2 and H2O2 are much less effective if Pu in higher
oxidation states has to be reduced to the tetravalent form.
Besides tetravalent species, hexavalent ones can often
form strong complexes. Hexavalent states of Pu, Np, and U
can be obtained using strong oxidizing agents, e.g., HBrO3,
KMnO4, and K2S2O8. Redox conditions of actinides have
been studied by many authors and several reviews are also
available.
Am and Cm are the 7th and 8th members of the actinide
group. In aqueous solutions, Am can exist in the þ3, þ4, þ5,
and þ6 oxidation states. Although Am(III) can be oxidized
theoretically to Am(IV), that form exists only in basic solu-
tions in the presence of strong complexing agents such as
phosphates; however, the species is unstable and will be
reduced back to the tervalent state easily. Although Am can be
oxidized in aqueous solutions to penta- and hexavalent states
with a strong oxidizing agent, e.g., Ag-catalyzed K2S2O8
þ
forming oxo cations Am(VI)O2þ 2 and Am (V)O2 , the most
stable form is the tervalent one (Osváth et al. 2009). Curium
has only exclusively tervalent species in aqueous solutions.
The relative complex-forming tendency of Am species
depending on the charge density is the same as those of other
actinides:
þ states for Po; however, þ4 is the most stable state in solution
2 wAm ðIIIÞ> Am ðVÞ O2
Am ðVIÞ O2þ 3þ
The lack of the tetravalent Am and Cm species of the highest
complex forming power and the chemical similarity of Am to
Cm, as well as to the lanthanides, badly influence the separation
possibilities. This is the main reason why Am and Cm chemistry
is still the most challenging part of actinide analysis.
The stability series of the inorganic complexes of Am(III)
and Cm(III) are the same as those of other actinides:
OH
; CO2

2
2




3 > F ; HPO4 ; SO4 > Cl ; NO3 > ClO4
Thiocianate (SCN) complexes of Am and Cm do not have
high stability, but because of their relatively high separation
factors toward lanthanides, they play an important role in Am
and Cm purification.
Ra: Within group 2, Ca, Sr, Ba, and Ra form a series of
closely related elements. All are highly electropositive metals
existing in the þ2 oxidation state in solution. The chemical
properties of these elements vary in a reasonably systematic
manner down the group. For example, all form insoluble
sulfates, with the solubility product following the series
CaSO4 > SrSO4 > BaSO4 > RaSO4. When Ra is coprecipitated
with other group 2 sulfates, or with PbSO4 , the insolubility of
RaSO4 causes Ra to be enriched in the sulfate lattice relative to
the primary precipitate cation (Langmir and Riese, 1985).
393
The similarity in their chemical properties means that Ca, Sr,
and, especially, Ba are very effective carriers for Ra. It also
means that separation of Ra from the other group 2 elements is
the primary challenge for high-resolution alpha spectrometry of
Ra. For samples with a high Ca content, such as bone, separa-
tion of Ra from the bulk Ca may present difficulties (Yamamoto
et al., 1991). However, for most samples it is the separation of
Ra from Ba which is the main problem, due to their very similar
chemistries.
There are two basic approaches to the difficulty of separa-
tion of Ra and Ba. One of these is to separate the group 2
elements from the bulk matrix, and then to carry out a final
RaeBa separation. This can result in a high-resolution source
but is time consuming. The alternative approach is to copreci-
pitate Ra with BaSO4 following the bulk matrix separation, and
to filter this precipitate for use as the alpha source (e.g., Sill,
1987b). The precipitation and filtration steps are relatively fast,
and high recoveries can be expected. However, the poorer peak
resolution will generally preclude the use of 225Ra as a tracer.
It may also preclude the determination of 223Ra and 224Ra,
although the use of microprecipitation techniques may allow
this (Nour et al., 2004). In addition, the tracer commonly used,
133
Ba, is not an isotope of Ra, and so there is the potential for
differences in recoveries between tracer and analyte.
Po: The chemistry of the group 16 elements (O, S, Se, Te,
and Po) varies in a more-or-less regular manner down the series.
Due to increased atomic radius, electronegativities decrease
down the group and the elements exhibit increasing metallic
character. Hence, while O, S and Se are nonmetals and form
covalent bonds, Te shows some metallic character and cationic
properties, while Po is essentially a metallic element. There is
evidence for the formation of e2, þ2, þ4, and þ6 oxidation
(Figgins, 1961).
The S to Po members of group 16 have d orbitals available
for use in bonding, and hexacoordinate compounds are most
common for Te and Po. Complexes of the form PoXe 5 or
PoX5(H2O)
are formed in dilute halide solution, while PoX
2 6
is formed in more concentrated acid solutions (X ¼ Cl, Br, or I)
(Bagnall, 1983). In the absence of more strongly complexing
organic agents, halide complexes can be extracted into some
organic solvents.
One important feature of Po is its volatility. This varies with
chemical form (Mabuchi, 1963). Po has been shown to be partly
volatilized from some samples above 100  C (Martin and Blan-
chard, 1969). Polonium halides have been reported to be volatile
above 150  C, but this may depend upon the conditions as only
minimal losses were reported by Svetlik et al. (2010) at 350  C for
deposits dried from HCl solution. Po volatility is important for
potential losses during sample preparation, digestion, and chem-
ical separation. It also means that Po can migrate from the alpha
source in the counting chamber and contaminate the detector. This
latter problem seems to be reduced by a period of exposure to air
before counting (Bagnall, 1957, 1966).
Po spontaneously autodeposits onto the surfaces of several
metals including Ag, Cu, and Ni from dilute acid solution. Auto-
deposition onto metal disks (usually Ag) is the most common
source preparation technique for Po due to its simplicity and the
394
fact that it results in separation from other metal ions including
other alpha emitters (Smith and Hamilton, 1984; Matthews et al.,
2007). This being the case, the preceding chemical separation
techniques required are generally less extensive than for other
alpha emitters. Some published methods rely only on autodepo-
sition for separation, and for simpler sample matrices this may be
sufficient. However, the presence of interfering elements, espe-
cially Fe, can result in lowered recoveries and spectral degrada-
tion. Consequently, for general applicability a separation step is
recommended (Lin and Wu, 2009).
A. Sample Preparation and Pretreatment
The objectives of sample preparation and pretreatment are to
obtain a solution that:
l is homogenous, free of any insoluble residues that would
interfere during the subsequent chemical processing and
could retain the analyte,
l is free of any organic material that could form complexes
with the analyte or the reagents resulting in poor recovery,
l is of relatively small volume in order to achieve significant
volume reduction for large-volume liquid samples, and
l contains the analyte preconcentrated usually due to semi-
selective group separation.
1. Preparation of Solid Samples
For soil, sediment, and minerals, sample preparation and
pretreatment usually mean drying in an oven, homogenizing
and sieving (optional), and removal of organic material by
ashing, followed by wet chemical destruction.
a. Sample Ashing
In the case of actinide determination, samples are usually ashed
at 450e600  C for a couple of hours or days. Elevated
temperatures are not desirable because of the formation of
refractory particles. In the case of volatile elements such as Po,
dry ashing should be replaced by wet ashing.
b. Sample Dissolution
For sample dissolution, several methods have been used
including acid leaching with mineral acids (most frequently
with 8 M HNO3 in the case of actinide determination or aqua
regia) and complete destruction by a mixture of mineral acids
typically including nitric, hydrochloric and hydrofluoric acids,
and hydrogen peroxide. Kenna (2009) studied the leachability
of Pu and Np from sediment samples by applying a series of
extractants. If hydrofluoric acid is used to volatilize silica as
SiF4, then boric acid is added afterwards to the final solubili-
zation in order to complex any fluorides. Wet acid decompo-
sition can be carried out in open systems such as in Teflon
beakers on a hot plate, or in closed systems such as in
a microwave oven or pressure bombs. The higher the pressure
and the temperature, the faster is the chemical reaction.
Significantly higher temperatures than the boiling points of
the aqueous systems can be attained by fusion with a variety of
Handbook of Radioactivity Analysis
salts, thus speeding up the destruction process. Several good
monographs and papers have been published about sample
decomposition methods (Bock, 1979; Sill and Sill, 1995; Chiu
et al., 1984; Claisse, 1995) that can be applied to the analysis of
actinides. Fusion is a very effective way of rapid and complete
sample decomposition, but large amounts of salts often together
with impurities are transferred to the sample solution, which
may create problems in the course of subsequent chemical
separations. The other disadvantages of fusion are that usually
only relatively small samples can be treated, and that it is
inappropriate for Po determinations due to the large losses that
occur at the high fusion temperatures. NaOH, Li borate, and
mixed carbonateeborate have been used for fusion in actinide
chemistry. Sill et al. (1979) and Sill (1980) proposed a very
efficient potassium fluoride/pyrosulfate fusion to treat refrac-
tory material.
Several standards about sample decomposition are available.
This standard is withdrawn. Standard ASTM D1971-95
describes hot plate and convection-oven digestion of water and
solid samples with nitric and hydrochloric acids, standard
ASTM D430912 is about microwave digestion with hydro-
chloric and nitric acids for determination of metals and
groundwater, and the US EPA Method 3052 (1996) discusses
microwave-heated, closed-vessel decomposition of ashes, bio-
logical tissues, oils, oil-contaminated soils, sediments, sludges,
and soils.
In the case of biological samples, complete destruction is
preferred and carried out usually by the combination of dry and
wet chemical ashing. Because of the lack of silicates and
refractory components the use of HF can be omitted. Micro-
wave digestion is a preferred way of decomposition of smaller
samples. An efficient way of decomposition of organic mate-
rials is the Fenton’s reaction using hydrogen peroxide and Fe2þ
catalyst.
2. Preconcentration of Liquid Samples
and Sample Solutions
a. Preconcentration of Actinides
Preconcentration of actinides by coprecipitation is a frequently
used method for large volumes of water samples as well as for
sample solutions obtained after destruction of solid samples.
A well-selected coprecipitant concentrates the analyte in a small
volume, removes most of the cationic and anionic interferences
and helps increase the decontamination factor (DF) for the
whole radiochemical procedure.
Bismuth phosphate (BiPO4) was the first precipitate applied
in large-scale processing of Pu; BiPO4 carries Pu(III) and
Pu(IV) and was used to separate Pu from U and fission products
in both technology and analyses (Kimura, 1990). The copreci-
pitation of Am with BiPO4 was studied by Mathew et al. (1981),
who found that below 0.3 M acid concentration Am is carried
with the precipitate.
The most frequently used carriers of actinides are the
following: ferric and ferrous hydroxides, lanthanide fluorides
and hydroxides, alkaline earth oxalates, phosphates and fluo-
rides, some other phosphates and oxalates, barium sulfate, and
Chapter | 6 Alpha Spectrometry
manganese dioxide. The coprecipitation behavior of actinides is
discussed in detail in the compilation of Katz et al. (1986).
Hydroxide precipitates, e.g., ferrous and ferric hydroxides,
lanthanide hydroxides, and calcium phosphate, and calcium/
magnesium carbonates are formed in neutral or basic solutions.
Hydroxide, phosphate, and carbonate precipitates are usually
easily dissolved with acids. Ferric hydroxide is known to
coprecipitate actinides in all oxidation states, but sometimes
recoveries are low, which is why ferrous hydroxide as
a reducing agent is preferred. Coprecipitations taking place in
acidic media (e.g. fluorides) are usually more selective than
those formed in basic solutions (e.g. hydroxides).
Calcium fluoride and especially lanthanide fluorides of low
solubility form precipitates in 4e5 M HF solution. Fluoride
precipitates can be dissolved as borate complexes, and carry
only tri- and tetravalent actinides. The separation of actinides by
coprecipitations usually takes advantage of the oxidation and
reduction cycles.
Barium sulfate carries only tri- and tetravalent actinides. It
can be dissolved either with EDTA or with HClO4. The use of
EDTA is beneficial if samples have Ca, Mg, and Al content that
forms strong complexes and can be separated from actinides
during a succeeding lanthanide hydroxide precipitation. Sill and
Willis (1966) developed a method for the separation of Np from
Ce, Ba, and La based on its coprecipitation with barium sulfate
under strict oxidation state control. The oxidation state of Np is
adjusted with H2O2 to Np(IV), which is coprecipitated with
barium sulfate from a sulfuric acid solution containing potas-
sium sulfate. Then Np is oxidized with chromic acid to Np(VI)
and separated from fission products that cannot be oxidized and
form precipitate with a next barium sulfate. The Np alpha
source is also prepared by coprecipitation with microcrystals of
barium sulfate. Sill and Willis (1966) adopted this method for
the simultaneous determination of Np, Pu, and U based on
a series of barium sulfate coprecipitations. Coprecipitation of
Th with BaSO4 may be enhanced by the addition of Kþ to the
solution (Burk and Wiles, 1983), or alternatively prevented by
the use of a La3þ holdback carrier (deJong and Wiles, 1984).
Moore (1963) developed a procedure that was later
improved by Sill (1984) for the simple separation of Am from
many elements including actinides and lanthanides. Americium
was oxidized to its hexavalent state with ammonium peroxy-
disulfate in a dilute nitric acid solution. The nonoxidizable
lanthanides and actinides were than precipitated as fluorides and
filtered off. The Am was then reduced and coprecipitated with
LaF3. In the improved method of Sill, the nonoxidized rare
earths were coprecipitated with BaSO4 or NdF3 while oxidized
Am(VI) was kept in solution. After reduction with H2O2,
Am(III) was coprecipitated with a small amount of NdF3
allowing direct detection of the alpha source (discussed subse-
quently in source preparation). By this method, Am can be
separated also from the nonoxidized Cm isotopes.
MnO2 precipitated from KMnO4 and MnCl2 at pH 8e9 is
used for the preconcentration of Am, Pu, and Np from seawater
samples at the IAEA’s Marine Environmental Laboratory
(LaRosa et al, 2005). MnO2 is dissolved with HNO3eH2O2.
The pH dependence of the precipitation of metal oxalates
was studied by Yamato (1982), who found that calcium oxalate
395
formed at pH  1.5 carries Am almost quantitatively. Oxalate
precipitates are easily decomposed by ashing or wet chemical
oxidation.
The following precipitates have been recently used to
preconcentrate actinides from various samples: ferric
hydroxide, ferrous hydroxide, calcium oxalate, ferric
hydroxide and calcium oxalate, calcium phosphate, calcium
fluoride, lanthanum fluoride, manganese dioxide, manganese
dioxide and ferric hydroxide. For the concentration of actinides
from large volume of water or solutions of biological origin,
special extraction chromatographic materials of extremely high
distribution coefficients have also been developed and applied,
e.g., TEVA, TRU, DIPHONIX, and DIPEX resins (see in detail
in the next section). Smith et al. (1998) developed a method for
the preconcentration of Am and Pu from wastewaters using
a synthetic water-soluble metal binding, i.e., phosphonic acid
polymer that was removed from the waste by ultrafiltration.
Chemical yields over 90% have been achieved.
b. Preconcentration of Po and Ra
Coprecipitation with iron hydroxide (Narita et al., 1989; Jia
et al., 2001; Zikovsky, 2002) or MnO2 (Carvalho, 1997; Peck
and Smith, 2000; Martin and Hancock, 2004b; Bojanowski
et al., 2005) has been commonly used for preconcentration of Po
and Ra, particularly from bulk water samples. Coprecipitation
with Ca3(PO4)2 has also been used for Ra and Pb (Nonova et al.,
2009). Coprecipitation with MnO2 is very commonly used for
processing seawater and other saline waters (e.g., Towler et al.,
1996; Grabowski and Bem, 2010). Direct adsorption from water
samples of Ra onto MnO2-coated disks for alpha spectrometry
has also been used (Eikenberg et al., 2004).
Iron tends to interfere with subsequent chemical separation
and autodeposition of Po. Consequently, for Po determinations
following coprecipitation with iron hydroxide, an Fe removal
step, such as solvent extraction with di-isopropyl ether, may be
required.
Coprecipitation with PbSO4 is commonly used for pre-
concentration of Ra and separation from the bulk matrix (Sill,
1987b; Kehagia et al., 2007). Radioisotopes of Pb and Ra have
also been coprecipitated with Pb(NO3)2, with U and Th
remaining in solution (Lozano et al., 2010).
Coprecipitation with BaSO4 is also commonly used for
preconcentration and separation of Ra, often as an extra step
after coprecipitation with PbSO4. Yamamoto et al. (1989) used
coprecipitation with barium chromate, and performed a subse-
quent Ra/Ba separation. Commercial salts of Ba may contain
traces of Ra, and so the reagent used should be pretested, and
the amount used minimized. The use of a Ba salt coprecipitation
usually means that a Ra/Ba separation will not be carried out,
although it may be possible to do so if only small amounts of Ba
are present. Alternatively, liquid scintillation spectrometry may
be performed.
For Po preconcentration, coprecipitation with cobalte
ammonium pyrrolidine dithiocarbamate (Co-APDC) chelate
has been used (Gascó et al., 2002; Wildgust et al., 1998). Po(IV)
also coprecipitates with BiPO4 at low pH (Hölgye, 2007).
396
B. Chemical Separation
Actinides are amenable to a variety of chemical separation
procedures including precipitation/coprecipitation (see above),
liquideliquid extraction, ion-exchange chromatography,
extraction chromatography, and the combination of two or more
of these methods.
1. Separations by Liquideliquid Extraction (LLE)
Three types of extractants can be distinguished:
1. Neutral extractants that form neutral (ion association)
complexes with the actinide ions involving the counterions,
very often nitrates or chlorides and the organic molecule
forming chemical bonding via electron donor atoms of the
organic molecules (oxygen, phosphoryloxygen, sulfur, and
nitrogen).
2. Amine extractants where positively charged organic amines
form complexes with anions via Coulomb forces, and anions
in the complexes can be replaced by anionic actinide
complexes in a manner analogous to anion exchange; amine
extractants are long-chain alkyl or aryl quaternary amines or
primary, secondary, tertiary amines that form organic
cations with acidic hydrogen.
3. Acidic extractants that form chelate complexes with the
actinide cations replacing the Hþ in the organic compound.
Groups 1. and 2. can be regarded together simply as ion
association complexes. Ion association complexes have the
advantage of being applied in acidic media. In general,
distribution coefficients are increased when acid concen-
tration increases. On the contrary, chelates are used in media
of low acidity because Hþ ions are competitors of the
cations for the binding sites.
a. Chemical Separation of Actinides by LLE
Many of the LLE procedures for actinides have been developed
for the large-scale separation of U and Pu for the nuclear
industry. Procedures for the separation of minor actinides (Np,
Am, and Cm) are under investigation. Solvent extraction offers
usually moderate selectivity, but the extraction efficiency can be
increased by performing the process in a continuous techno-
logical system.
Traditional extractants. Originally, the LLE of Pu and U
was accomplished with a wide range of organic acids, ketones,
esters, alcohols, and ether; the most well known being tri-butyl
phosphate (TBP) used in the PUREX process. Both Pu and U
nitrate complexes have acceptable high (but still relatively low)
distribution coefficients for technological purposes. Neptunium
follows Pu in the extraction processes whenever the oxidation
states are the same but adjustment often fails. The nitrate
complexes are even less retained by TBP (Nash et al. 2006).
Methyl-i-butyl ketone (MIBK) and TBP were used for
analytical purposes for the determination of Pu in the fifties and
sixties. At present, TBP is used in a mixture with carba-
moylmethyl-phosphine oxide (CMPO) for extraction chroma-
tography (discussed subsequently).
Handbook of Radioactivity Analysis
While tetra- and hexavalent actinides are readily extracted
by organic acids, ketones, esters, alcohols, and ethers, neither of
these organic compounds nor tri-butyl phosphate can extract the
trivalent Am. Trivalent Am3þ cations do not form stable ion
association complexes with simple monofunctional organic
compounds; they can be complexed with bifunctional
compounds, do not have the affinity to form anions, but can be
extracted/retained by chelates.
Chelate extractants. Among the ketones, tenoyl-tri-fluor
acetone (TTA) has quite significant analytical applications. It is
a diketone with a sulfur-containing aromatic ring and a fluorine-
substituted methyl group that exists mainly in enol form, thus
acting as a chelate. TTA has been used for analytical purposes to
separate Pu from various samples in the past and recently for the
separation and purification of Pu in combination with anion
exchangers from marine sediment samples and extremely
high DFs were achieved while Pu recovery was 56%. (Donard
et al., 2007).
TTA proved to be one of the most selective reagents for the
separation of Np(IV) when Pu is kept in trivalent Pu(III)
oxidation state. TTA was used as early as 1947 by Magnusson
(Coleman, 1965). Neptunium was reduced, then retained from
1 M HNO3 or HCl on about 0.5 M TTA in xylene, and finally
stripped with 8e10 M HNO3. TTA has also been used for
speciation studies where “TTA extractable” species are regar-
ded as tetravalent ones (Wolf, 2006).
The trivalent Am and Cm cations can form stable chelates
with TTA, but only at relatively high pH. Sekine et al. (1987)
used 0.5 M TTA in xylene to purify Am from a solution at
pH  4.
1-Phenyl-3-methyl-4-benzoyl-5-pyrazolone (PMBP) is
a N-containing ketone that also forms chelates in the enol form
and has gained application in Am separations. It extracts several
elements from more acidic media than TTA. Distribution
coefficients for Am and the separation factor of lanthanides are
slightly higher than in TTA. Jia et al. (1997) extracted Am from
a 0.1 M HNO3 solution into a mixture of 0.05 M PMBP and
0.025 M t-octylphosphine oxide (TOPO) in cyclohexane.
Americium was back-extracted with 5 M HNO3. Jia et al.
(1998) used PMBP/TOPO extraction to purify Am before
preparation of alpha sources. Am was extracted from a DTPA/
lactic acid solution directly into 0.05 M PMBP þ 0.025 M
TOPO in cyclohexane. Extraction maximum (about 90%) was
in the pH range 1e2.
Bis-2-etylhexyl-phosphoric acid (HDEHP) as a chelate
shows selectivity for cations of higher charges against those of
lower charges, thus HDEHP is a frequently used extractant in
Am, Cm separations, and is a good choice for the separation of
tetravalent actinides.
The distribution coefficients (D) for Am in HDEHP solution
strongly depend on the acidity of the aqueous phase, e.g., lg(D) ¼
1 for Am extraction by 0.5 M HDEHP in i-octane if the HNO3
concentration is 0.1, and lg(D) ¼ 4 in 0.01 M HNO3 solution
(Myasoedov et al., 1974). The separation of trivalent actinides
from lanthanides is only possible if strong complexants, e.g., lactic
acid, DTPA, are added to the aqueous phase. HDEHP has been
used for the separation of Am together with Cm and the lantha-
nides. It was observed that Fe severely interferes with the
Chapter | 6 Alpha Spectrometry
extraction. Bernabee et al. (1980) extracted Am from 72% HClO4
solution into 15% HDEHP in n-heptane. Americium was back-
extracted with 4 M HNO3. Holm et al. (1979) extracted Am from
0.01e0.001 M HNO3, and back-extracted it with 4 M HCl.
In the standard test method ASTM C1205-07 for “The
Radiochemical Determination of Americium-241 in Soil by
Alpha Spectrometry” 241Am is determined in soil samples up to
10 g. The soil is completely dissolved by the use of pyrosulfate
fusion. After the initial separation on barium sulfate, Am
together with other actinides and lanthanides is extracted from
concentrated HClO4 solution with 15% HDEHP in n-heptane
and back-extracted with 5 M HNO3. Americium is separated
from other trivalent actinides and lanthanides by oxidation of
Am and precipitation of the interferences with LaF3. The
standard test method is based on the procedure developed by
Sill and Willis (1966).
In the procedure of Jia et al. (1998), Am was extracted from
0.1 M HNO3 on a supported KF-HDEHP column, followed by
its stripping with 6 M HNO3. Am was separated from lantha-
nides on a 2nd KF-HDEHP column using 0.07 M DTPA e 1 M
lactic acid solution. The average chemical yield for the whole
procedure including Pu and Sr removal and purification of
the Am fraction with PMBP/TOPO extraction (see above)
was 58%.
Ramebäck and Skillberg (1998) extracted Pu and Np after
oxidation with bromate as Pu(IV), Pu(VI), and Np(VI) together
with U, Am, and Cm from 0.1 M HNO3 solution using HDEHP,
then stripped Am and Cm with 5 M HNO3, followed by the
back-extraction of Np with 1 M HNO3/hydroxylamine and
Pu(III) with 3 M HCl/TiCl3. Chemical recoveries for Pu, Np,
and Am were high, 91%, 82%, and 97%, respectively.
In the recently issued standard test method ASTM D6239-09,
uranium is separated from drinking water with an extractive
scintillator that contains HDEHP as extractant. Uranium is
extracted from a 0.01 M DTPA solution at pH 2.5 and 3.0 while
extraction of undesired ions is masked by forming strong DTPA
complexes. Uranium isotopes are determined by high-resolution
alpha-liquid-scintillation spectrometry.
Ion association complexes. Later attention of scientists
was turned to other organophosphorous compounds than
phosphates including phosphonates, phosphinates, and phos-
phine oxides which showed higher selectivities for many
actinides from acidic media. Besides TBP, tri-octyl-phosphine
oxide (TOPO) is the most well-known representative of the
neutral organophosphorous compounds. Pimpl and Higgy
(2000), Ayranov et al. (2005), and Lujaniene and Sapolaite
(2005) used TOPO as solvent extractant for preconcentration
of Pu and Am from acidic leach solutions. By reducing the
acidity, TOPO can also extract trivalent actinides. Pu together
with Th, U was extracted from 4 Me6 M HNO3 to TOPO in
cyclohexane. Then, the acidity was reduced, the pH of the
solution was adjusted to 1 and Am was also extracted with
TOPO, and back-extracted with 2 M HNO3. Kalmykov et al.
(2004) extracted Pu and Np together from 5 M HCl with
TOPO, selectively back-extracted Pu as Pu(III) with 1 M HCl
and ascorbic acid. Np(IV) remaining in the organic phase was
irradiated after evaporation in order to determine 237Np by
neutron activation analysis (NAA).
397
Dibutyl-N,N-diethylcarbamylphosphonate (DDCP) as
a bifunctional organophosphorous compound is one of the first
representatives of a new group of extractants, that was applied
in acidic solutions. DDCP has been used to extract Am (and
Cm) from 12 M HNO3 by Ballestra and Fukai (1983). Lantha-
nides followed Am in the procedure. Americium was back-
extracted into 2 M HNO3. Significant improvement was
recorded in the Am recovery (69e79%) for the overall proce-
dure including coprecipitations, anion-exchange separations,
and source preparation compared to the procedure using
HDEHP. DDCP extraction became the basis of the method for
Am determination in seawater at the IAEA’s Marine Environ-
mental Laboratory (1989). Actinides were preconcentrated by
coprecipitation with MnO2 and ferric hydroxide; Pu, Np, and Th
were separated by anion-exchange chromatography; Am was
coprecipitated with Ca oxalate, and passed through an anion and
a cation exchanger. Americium was extracted with DDCP.
Finally, Amelanthanide separation was performed on an anion-
exchange resin column. Later DDCP was replaced by a new and
more effective bifunctional organophosphorous extractant, the
CMPO.
CMPO is octyl(phenyl)-N,N-di-i-butylcarbamoyl-methyl-
phosphine oxide, a neutral organophosphorous extractant used
in conjunction with t-butyl phosphate as a process solvent
(Horwitz et al. 1986). The attractive feature of the process is that
it allows the extraction of Am and its separation from tetra- and
hexavalent actinides by using different strip solutions. The
pitfall of the procedure is that Am is not separated from Cm and
lanthanides. The distribution ratios of tri-, tetra-, and hexavalent
actinides and nonactinide elements, the mechanism of extrac-
tion, were determined in nitric and hydrochloric acids by Hor-
witz et al. (1987). In the analytical practice, the extraction
chromatographic version of the CMPO/TBP extractant called
TRU resin has had widespread use (discussed below in the
section on EC).
The higher oxidation states of Am (preferably the complex-
forming hexavalent state) are not stable in the presence of
organic materials.
Amine extractants. Tertiary amines act as strong base anion
exchangers and strongly retain the nitrate or chloride complexes
of tetravalent Pu and Np, e.g., [Pu(NO3)6]2e and [Pu(Cl)6]2e
formed in concentrated acidic solutions. Tri-octyl amine
(TOA) is the most frequently used liquid amine extractant.
Alamine 336 also called tri-capryl amine is a mixture of n-octyl
and n-decyl amines. The use of amine extractants for Pu anal-
ysis has a long tradition and TOA still has a widespread
analytical application, especially as supported liquid extractant
(see later under extraction chromatography). Jia et al. (1998)
separated Pu as Pu(IV) from the leachate of soil samples by
extraction with TOA and achieved a Pu recovery of 85%. In the
experiment, TOA was fixed to microthene particles. Sill and
Willis (1966) used Aliquat 336 to extract Np(IV) from envi-
ronmental samples. Vance et al. (1998) used amine extraction
from 0.25 M H2SO4 to separate U from Np. Neptunium was not
extracted and could be detected directly from the aqueous phase
using ICP-MS.
Chen et al. (2001a) developed a method for the determina-
tion of 237Np in soil and sediment samples up to 10 g and
398
seawater up to 100 L using both alpha spectrometry and ICP-
MS. Neptunium separation consists of a preconcentration with
mixed Fe oxides precipitated in the presence of K2S2O5
reducing agent, extraction with TOA from 8
10 M HCl,
repeated coprecipitation with Fe(OH)2, and purification of
Np(IV) by anion exchange from 8 M HNO3. An overall
recovery of 74
93% was achieved while DFs for U, Th, and Pu
were also high (>104). The method was extended for the
simultaneous determination of 239,240Pu, 241Am, 237Np, 234U,
238
U, 228Th, 230Th, 232Th, 99Tc, and 210Pbe210Po in environ-
mental materials (Chen et al., 2001b).
Trivalent actinides are not well retained by amine extrac-
tants from acidic solutions. Amine extractants as well as anion
exchangers have found another application field in americium
chemistry; they have been used for the separation of trivalent
actinides from lanthanides.
Separation of Am from lanthanides. For the separation of
trivalent actinides from lanthanides, new extraction systems
containing a soft donor atom (N, S, and Cl) have been proposed
based on the experience that actinides form slightly stronger
complexes with ligands containing soft donor atoms than
lanthanides. The soft donor atom may be present as free ion
(SCNe or Cle) or in a water-soluble complexant or in a lipo-
philic organic extractant. This idea formed the basis of the
separations from the early 1940s. Solvent extraction, ion
exchange, and extraction chromatographic techniques fit
prominently in these processes.
The extractability of tervalent actinides is increased by
adding special complexants or high amounts of salts to the
aqueous phase. In technology, i.e., in the TALSPEAK process,
DTPA containing the soft donor N atom and lactic acid were
added to the aqueous solution to form stronger complexes with
Am than with lanthanides, thus allowing their separation using
HDEHP (see above). The procedure of Jia et al. (1998) is based
on the same principle.
SCNe complexant containing the soft donor S and N atoms
can help increase the separation factor between Am, Cm, and
lanthanides. Moore (1964) first applied quaternary amines to
lanthanide/actinide group separations examining the system
Aliquat 336/xylene/H2SO4eNH4SCN.
Quaternary amines (0.6 M Alamine 336 in diethylbenzene)
are used to selectively extract Am from 11 M LiCl in 0.2 M HCl
solution while lanthanides remain in the raffinate. The actinides
are subsequently back-extracted with 5 M HCl. The separation
factor between Am and Eu was 108 (Nash et al. 2006).
Research for the development of new extraction systems to
achieve better extractability of Am and higher separation factors
for americiumelanthanide separations has been continued.
Many new candidate molecules for the selective extraction of
actinides especially minor actinides, e.g., bistriazinylpyridine
(BTP), thiophosphinic acid derivatives as CYANEX-301, cobalt
dicarbollide, crown ethers, and calixarenes, have been studied
but have not been applied to analytical applications so far. In the
analytical practice, anion-exchange resins or EC materials are
favored to solvent extraction.
Comparative evaluation of LLEs. Acid dependence of the
distribution coefficients for all elements including actinides was
determined by many authors and data were compiled in the form
Handbook of Radioactivity Analysis
of periodic tables. An example of such a data collection was
published as the Table of Chromatographers (Lederer, 1992).
Among the extractants discussed above, the distribution coeffi-
cients (D) for tetravalent actinides such as Pu(IV) are increasing
in the following order: TBP/7 M HNO3 < TTA/0.5 M
HNO3 < TOPO/1 M HNO3 < TOA/4 M HNO3 < HDEHP/1 M
HNO3 starting from ~20 for the TBP and ending at ~2000 for the
HDEHP system (Myasoedov et al. 1974). The retention sequence
of the various extractants is the same for other tetravalent species
such as Np(IV) and Th. Bigger differences in D values exist for
different oxidation states. The distribution coefficients (D) for
trivalent actinides (Am and Cm) are increasing in the following
order: TTA/ pH  4 < PMBP/0.1 M HNO3 < TOPO/0.1 M
HNO3 < HDEHP/0.1 M HNO3 < DDCP/12 M HNO3 < CMPO-
TBP/2 M HNO3 starting from ~1 for the TTA and ending at ~100
for the CMPO system (Myasoedov et al. 1974). For the hexavalent
U(VI) species, the following order of D has been reported: TTA/
1 M HNO3 < TBP/4 M HNO3 < TOA/4 M HNO3 < HDEHP/
8 M HNO3 < TOPO/1 M HNO3 with the highest value of 800 in
the latter case (Myasoedov et al. 1974). In the case of ion associ-
ation complexes, D values can be increased by the addition of
salting-out agents.
Although in many analytical applications LLE has been
replaced by more efficient chromatographic techniques, solvent
extraction is most appropriately applied to measurements by
liquid scintillation (LS). Extractive scintillators containing
solvent extractants discussed above and scintillation cocktails
have been developed for the PERALS alpha-liquid-scintillation
spectrometers (Ensor, 1998; PERALS homepage). In the
ETRACÒ procedure Pu is extracted by a high-molecular-weight
tertiary amine converted to nitrate form. The ALPHAEX system
based on HDEHP extractant can be applied for the separation of
Am. Uranium can also be extracted with HDEHP containing
extractive scintillator (see above). Dazhu et al. (1991) used the
extractive scintillator containing TOPO extractant in
PPOenaphthaleneetoluene scintillator cocktail for the rapid
determination of U, Pu, Am, and Cm in the nuclear fuel cycle
and in environmental samples. A detailed list of extractive
scintillators is found in Chapters 7 and 9 of this book.
New extractants. New extractants of high distribution
coefficient for trivalent actinides and lanthanides (Nash et al.
2006) are under investigations. Malonamides are the non-
phosphorous-containing alternatives of CMPO. Diglycolamides,
i.e. N,N,N’,N’-tetradecyl-3-oxapentanediamide (TODGA) and
N,N,N’,N’-tetradecyl-3-oxapentanediamide (TDDGA), were
found to have extremely high distribution coefficients for Am
nitrate complexes from concentrated nitric acid solutions. At
present, these extractants exhibit the greatest affinity for triva-
lent actinides. Alkyl-di-thio-phosphine acids, crown ethers, and
calixarene compounds are also under investigation.
b. Chemical Separation of Po by LLE
Po can be extracted into tri-butyl phosphate from strong HCl
solutions (Figgins, 1961). Other organic agents forming
complexes include EDTA and diethyldithiocarbamate (DDTC).
When complexed with DDTC, Po can be extracted into chlo-
rinated hydrocarbons such as chloroform from HCl solution
Chapter | 6 Alpha Spectrometry
over a wide range of acid strengths. This is useful for separation
of Po from Pb and Bi, as Po is extracted from HCl solutions of
higher acid concentration than either Bi or Pb (Smithson et al.,
1979; Wai and Lo, 1982; Kim et al., 2009). Po-210 can be
effectively separated from lead samples using a DDTCetoluene
extraction with EDTA and citrate as masking agents for the Pb
ions (Uesugi et al., 2010).
Other extractants reported in the literature include tri-octyl-
phosphine oxide (TOPO) in toluene (Jia et al., 2004), di-n-octyl
sulfide (Johansson and Skarnemark, 2001), tri-isooctylamine
(TIOA) in xylene solution (Chen et al., 2001c), APDC in MIBK
(Shannon and Orren, 1970), “Aliquot 336” (Ibrahim and
Whicker, 1987), and trilaurylamine (TLA) into xylenes
(Roseberry and Scott, 1985).
2. Separations by Ion Exchange
The most frequently used cation-exchanger resins are the
strongly acidic sulfonated resins containing
SO
3 groups. Less
acidic phosphorylated and carboxylated resins are also avail-
able. The positively charged counterions can be replaced by any
other cations. The ion-exchange affinity of the cations increases
with increasing charge and decreasing hydrated ion radius. All
þ
actinide species, i.e., An4þ, An3þ, AnO2þ 2 , and AnO2 , espe-
cially the tetra- and trivalent species, are retained well (high D)
at low acidities and they are removed from the resin by
concentrated acids, but no special selectivity against other
cations was observed. Ion exchangers are typically used in the
form of chromatographic columns assuring much better sepa-
ration than batch techniques.
Cation exchangers have been used for the preconcentration
of actinides from high-volume dilute acidic solutions. Fjeld
et al. (2005) used a cation resin column for the preconcentration
of actinides from groundwater and liquid radioactive wastes.
Cation exchangers have also been used for the chromatographic
separation of actinides in ion chromatographs (IC) either alone
or together with anion exchangers as mixed-bed resins. IC
separation fits well to the purposes of separation of actinides
prior to ICP-MS, but is less adequate for alpha spectrometry
due to small sample masses. Pu(III) and Am(III) were
successfully separated on a cation-exchange column TCC-II by
Jernström (2006) using different complex-forming eluents and
detecting the sources by alpha spectrometry. Samples were
loaded from dilute HCl solution, Pu was stripped with dipico-
linic acid, and Am eluted with oxalic acid. Jernström (2006)
also used mixed-bed ion-exchanger CSA5-CGA5 column for IC
of Pu and Am.
Separation of Am from lanthanides using cation exchangers.
Trivalent Am3þ cations are usually retained well (high D) at low
acidities. Several other elements coadsorb with Am including
lanthanides. As the concentration of HCl increases, the distri-
bution coefficient for Am declines, whereas those for lantha-
nides is smaller, which is revealed by increasing separation
factors.
One of the oldest techniques for the separation of Am
from lanthanides is based on cation-exchange chromatography
using complexing agents, e.g., hydroxycarboxylic acids.
Ammonium citrate and ammonium lactate have been used; a-
399
hydroxy-i-butyric acid (a-HIBA) proved to be the most
effective eluent for the selective separation of Am. Choppin
and Silva (1956) separated Am from the lanthanides on
a jacketed (temperature-controlled) cation-exchange column
using a-HIBA. Aminopolyacetic acids (e.g., EDTA and
DTPA) have also been used as eluents. The disadvantages of
their use are the low solubility and the slow establishment of
the equilibrium.
Ageyev et al. (2005b) separated Am and Cm from lantha-
nides by cation-exchange chromatography with gradient elution
using 0.16e0.4 M a-HIBA after removal of Pu with anion
exchange. Yields of Pu and Am were in the ranges of 60e80%
and 50e70%, respectively, when 100e200 g of environmental
samples exposed to the emissions from the Chernobyl accident
were analyzed. A similar technique has been used for the
purification of the Am fraction by Berlioz et al. (2005).
In anion exchangers, the functional groups are various
amines. Strong basic anion exchangers with substituted
quaternary amines strongly retain tetra- and hexavalent acti-
nides from concentrated nitric and hydrochloric acid solutions.
The selectivity of the anion resin for actinides is high, because
only a few other cations (e.g., Fe in HCl) are able to form strong
anionic complexes in acids. For example, the distribution
coefficient (D) for Pu(IV) is as high as 104. Fig. 6.29 shows the
distribution coefficient (D) for various elements in nitric and
hydrochloric acids.
Uranium and thorium. Thorium can be strongly retained on
an anion resin from 8 M HNO3 while U as U(VI) is better
retained from 9 M HCl with an acceptable high distribution
coefficient (D). Uranium can be easily separated from Th with
anion resins, but U and Th cannot be retained well from the
same solution. These properties have been utilized in the
analysis of uranium isotopes in water, urine, and soil samples
according to the ASTM standard test methods D3972-09,
C1473-11, and C1000-11, respectively. Uranium is retained on
a strongly basic anion exchanger from 8 Me9 M HCl solution
after sample destruction and preconcentration with ferrous
hydroxide precipitate. Uranium can be stripped from the
column with 0.1 Me1 M HCl. In case of soil samples, Fe is
removed from the load solution before separation by extraction
of the chloride complexes with di-i-propylether.
Plutonium. A convenient way to separate Pu selectively
from other ions is to load tetravalent Pu(IV) from 8 M HNO3
on an anion resin, remove the possible interferences, primarily
Th, by washing the column with 9 M HCl because this does
not form chloride complexes. Plutonium can be stripped as
Pu(III) with 9 M HCl using a reducing agent, e.g., iodide. This
is the procedure that became the basis of many methods.
Because of the high selectivity of the resin for Pu(IV), very
often a single chromatographic separation provides sufficient
purity for the analysis. Basically the same procedure was
already used in the sixties (Coleman, 1965), and has been used
by many authors recently (Moreno et al., 1997; Qu et al.,
1998; Pilviö, 1998; Michel et al., 2008; Komosa and Chibowski,
2002; Solatie, 2002; Hrnecek et al., 2002; Vioque et al., 2002;
Berlioz et al., 2005; LaRosa et al., 2005, Ageyev et al., 2005a;
Giardina et al., 2006; Lee et al., 2000; Jakopic et al., 2007; and
Michel et al., 2008).
400
The standard procedures for Pu analysis by a-spectrometry
are usually also based on anion-exchange separation. According
to the ASTM C1001-05 standard (Standard Test Method for
Radiochemical Determination of Plutonium in Soil by Alpha
Spectroscopy), 10e50 g of soil are destructed with a mixture of
nitric, hydrofluoric, and hydrochloric acids. Pu is isolated by
anion exchange, followed by alpha source preparation.
According to the standard ASTM D3865-09 “Test Method for
Pu in Water”, Pu is coprecipitated with iron as ferric hydroxide,
the coprecipitated Pu is dissolved, and the solution is adjusted to
8 M in HNO3 for anion-exchange separation, then the alpha
source is prepared. The recommended procedures of the Inter-
national Atomic Energy Agency described in the Technical
Report Series 295 from 1989 and in the most recent publication
from 2012 (IAEA, 2012) are also based on the separation of Pu
by anion-exchange chromatography. The latest ISO standard,
ISO 18589-4 and BS 07/30047016 DC (Apr 2007) on
“Measurement of Radioactivity in the Environment. Soil. Part 4.
Measurement of Pu Isotopes by a-Spectrometry” recommends
the optional use of HDEHP extraction, strong basic anion resin
chromatography, and extraction chromatography using TRU
resin (see later) for Pu determination.
Many examples exist on the use of anion-exchange resins for
Pu separation from HCl solution. Samples containing Pu(IV)
are loaded from 9 M HCl on the column and after washing Pu is
stripped using a reducing agent. This procedure has the disad-
vantage that the anionic ferric chloride complex is also retained
by the anion resin. Similar procedures were used from the
sixties up to the present. Lee et al. (2008) studied the oxidation
states of Pu in HCl solutions and carried out Pu separation from
9 M HCl solution in the presence of NaNO2. Pu was stripped
with 0.36 M HCl þ 0.01 M HF, and the Pu recovery as
a mixture of Pu(IV) and Pu(VI) was >75%.
Neptunium. Anion resins, both from nitric and hydrochloric
acid solutions, are used for the selective separation of Np. In
reducing media, when Np is turned to the tetravalent form and
Pu is reduced to trivalent state, the separation of Np from Pu is
easily accomplished. This is the most common method of
selective 237Np separation. Np was retained as Np(IV) together
with Th on anion resin from 8 M HNO3 in reducing media in the
procedures of Niese and Niese (1985) and Germian and Pinte
(1990). According to the procedures of Koyoma et al. (1998),
Michel et al. (1999), Moreno et al. (1997), and LaRosa et al.
(2005), Np(IV), Pu(IV), and Th were retained also from 8 M
HNO3 followed by the selective stripping of the actinides. The
tetravalent oxidation states were adjusted by applying reduc-
tion/oxidation cycles with or without addition of NaNO2 or
H2O2. Np(IV) and Pu(IV) together with U can be retained on
anion resin from 9 to 10 M HCl load solution. Then Pu is
stripped selectively with 9e10 M HCl/0.1 M NH4I followed by
stripping of Np with more dilute 1e4 M HCl. In the procedure
of Rosner et al. (1993) fractionation of Np between the wash
and the Np strip solutions was observed. Sumiya et al. (1994)
and recently Joe et al. (2007) successfully used similar proce-
dures. To achieve higher DFs the anion-exchange procedures
are sometimes repeated (Beasley et al., 1998) or additional
purification steps using TTA, TEVA, and TOPO extraction (see
later) are included. Anion-exchange resin has been used to
Handbook of Radioactivity Analysis
separate Np from U from 4 M acetic acid solution when Np is
released while U is retained (Winkel et al., 1971).
If Np and Pu are to be detected in the same fraction, they can
be loaded as tetravalent species and stripped also together (Kim
et al., 1992; Qiao et al., 2011).
Americium. Am(III) does not form strong complexes with
nitrate or chloride ions and is not well retained on anion resins.
In concentrated HCl solutions (>11 M) there is an increase in
the retention of Am on anion exchangers while lanthanides are
adsorbed less. However, the difference is not as high as in the
case of cation exchangers. Thus, the separation of Am from
lanthanides is less successful under these conditions.
Separation of Am from lanthanides using anion exchangers.
The presence of alcohol in the media enhances the anion
exchange of Am especially in nitric and sulfuric acids. Guseva
et al. (1976) measured distribution coefficients as high as 5000
from 0.5 M HNO3 in 95% methanol. Lighter lanthanides also
have high distribution coefficients while heavy lanthanides do
not. In an HCl-methanol system, the anionic complexes of Am
together with the heavy lanthanides are well retained by the
resin, while light lanthanides are less retained. Both the HNO3 e
methanol and the HCl e methanol systems, and preferably, the
combination of the two systems can be used for Amelanthanide
separation. A mixture of 0.5e1.0 M HNO3 and 90e96%
methanol was reported as the load and wash solutions by many
authors (Holm and Fukai, 1976; Ballestra and Fukai, 1983, etc.)
followed by stripping of the best retained Am with a mixture of
0.5e1.5 M HNO3 and 70e86% methanol (Jernström, 2006) or
simply with HCl (Livens and Singleton, 1989) or HNO3 (Bains
and Warwick, 1993). Methanol has been replaced with ethanol
with similarly good results.
Kraus et al. (1955) found that many elements have higher
distribution coefficients in LiCl solutions than in HCl. The
sorption of Am on anion exchangers increases with increase in
LiCl concentration, whereas the sorption of lanthanides varies
only slightly favoring Amelanthanide separation. The separa-
tion is further improved if alcohol is added to the LiCl solution,
e.g., a good separation was achieved with 8 M LiCl and 40%
methanol on Dowex 1x8 anion-exchange resin by Guseva et al.
(1976).
The group separation of trivalent actinides and lanthanides
can be carried out with concentrated (>8 M) NH4SCN solution
as eluent (Surls and Choppin, 1957). Lanthanides are less
strongly retained on an anion column in the SCN form than Am.
Am can be stripped with 4 M HCl. Bojanowski et al. (2005) and
Lovett et al. (1990) applied this method successfully for the
analysis of marine environmental samples.
Guseva and Tikhomirova (1968) showed that the best
separation can be achieved with 1e2 M NH4SCN solution
containing 50e70% methanol, ethanol, or propanol. This
procedure became the basis of many methods where
Amelanthanide separation was necessary. Holm et al. (1979)
used this procedure for the final purification of the Am fraction
from large amounts of environmental samples (200 L seawater,
100 g sediment, and 500 g biological material) after the removal
of the interfering components. The final residue containing Am
and lanthanides was dissolved in a few milliliters of 1 M
HNO3e93% methanol and was loaded on an anion-exchange
Chapter | 6 Alpha Spectrometry
resin column. The column was washed with dilute
HCleNH4SCNemethanol solution to remove lanthanides, and
Am together with Cm was stripped using 1.5 M HCle80%
methanol. The overall chemical recovery varied between 40%
and 80%. A similar procedure was followed by Yamato (1982)
to determine Pu and Am from 50 g of soil. In the final purifi-
cation of Am, 1 M HNO3e93% methanol, 0.1 M HCle0.5 M
NH4SCNe80% methanol, and 1.5 M HCle86% methanol
solutions were used as load, wash, and strip solutions, respec-
tively; 75e92% chemical recoveries for Am were reported for
the whole combined procedure.
The procedure has been successfully applied by many
laboratories for Amelanthanide separation. It is the recom-
mended procedure in the laboratories of the IAEA, in both
Monaco and Seibersdorf (LaRosa et al., 1989, 2005). It has been
used by Jakopic et al. (2007) for the analysis of environmental
samples.
Polonium. Ion-exchange resins are less commonly used
nowadays for Po separations than methods based on LLE or
extraction chromatography. Polonium is strongly adsorbed onto
anion-exchange resin across a wide range of acid concentra-
tions. Although this can be used for effective separation, the
approach requires large elution volumes (Reischmann et al.,
1984; Skwarzec et al., 2001). Cation-exchange resins have been
used to adsorb Po from dilute acid solutions, with elution by
7 M HCl (Reischmann et al., 1984).
Radium. Strong basic anion-exchange resins do not retain
the group 2 elements (Fig. 6.30) but may be used to remove
other alpha emitters, major cations, and/or anions, such as
sulfate (Gleason, 1980) or chromate (Yamamoto et al., 1989).
Hence, the use of anion-exchange resins may be preparatory to
a final cleanup step for Ra.
Cation-exchange resins may be used for preconcentration of
Ra and separation from the bulk matrix for sample digests or
aqueous samples. The digest is taken up in dilute HCl or HNO3
for loading onto the resin, and washed with dilute acid before
eluting Ra with higher concentrations of these acids (e.g., Volpe
et al., 1991; Lawrie et al., 2000; Crespo, 2000). However, to
effectively separate Ra from Ba and Sr on a cation-exchange
resin it is generally necessary to use complexing agents.
Gleason (1980) developed a separation method using
cyclohexane-diaminetetraacetic acid (CyDTA) which has been
a basis for several methods reported since then (Yamamoto
et al., 1989; Rodriguez-Alvarez and Sanchez, 1995; and Jia
et al., 2006). Hancock and Martin (1991) used EDTA and
ammonium acetate on 50WX12 cation-exchange resin before
washing and elution of Ra. Volpe et al. (1991) also used EDTA
solution with cation-exchange resin columns.
3. Separations by Extraction Chromatography (EC)
In EC, also called solid-state extraction and reversed-phase
partition chromatography, liquid extractants are adsorbed
onto the surface of inert solid support material. The theory
of EC was described already more than 30 years ago in
the book of Braun and Gherseni (1975). EC has the
following advantages compared to solvent extraction and ion
exchange (IE):
401
l the extraction process takes place in the thin surface layer
allowing good contact of the reagents and fast exchange
kinetics compared to ion exchangers,
l as a result of the chromatographic technique more effective
separation is achieved than in batch technique in which LLE
is performed,
l less reagents and chemicals are used than in IE or LLC,
l less hazardous waste is produced, and
l the whole process is more economic.
Attempts have been made to replace solvent extraction by
extraction chromatography from the end of the 1960s.
a. EC of Actinides
The chelating extractant, HDEHP, showing high distribution
coefficient for Am from dilute acid solutions has been
prepared as a solid EC material on various supports to serve as
stationary phase. HDEHP was prepared on hydrophobic
support by Horwitz and Bloomquist (1975). Jia et al. (1997)
used microporous polythene support. The 0.01 M HNO3 load
solution containing Am was passed through the column,
washed with 0.1 M HNO3, and Am was stripped with 0.07 M
DTPAe1 M lactic acid. Pu and Po were separated before using
supported TOA columns. Jia et al. (1998) determined Pu, Sr,
and Am in a sequential separation procedure. First Pu and Sr
were separated by EC, after which Am was concentrated on an
HDEHP column. Americium was eluted with a 0.07 M
DTPAe1 M lactic acid solution to separate it from lantha-
nides. The Am fraction was purified by an extraction with
PMBP/TOPO. The chemical recovery for Am was 58%, and
the source was free from Fe, Po, and lanthanide contamina-
tion. Desideri et al. (2002) determined actinides in depleted
uranium. After EC separation of the actinides using supported
TOA columns, the Am fraction was cleaned using a supported
HDEHP column (pH 2.4). Arginelli et al. (2005) prepared
HDEHP on polythene support and loaded the pretreated urine
sample from dilute acidic solution (pH 2) on the column, Am
was stripped with 4 M HCl. Supported HDEHP has become
commercially available as Ln resin produced by Eichrom Co.
McAlister and Horwitz (2007) characterized the Ln resin
by measuring the capacity factors k’ of various elements
(see Fig. 6.31).
Gleisberg and Köhler (2002) separated Np from uranyl
nitrate solution using Ln resin column. Np and Pu species
were retained from 10 M HCl load while U entered into the
effluent.
Meanwhile the interest for Am separation by HDEHP has
declined due to the development of more efficient extraction
chromatographic materials (see TRU resin later).
Supported TOPO on Microthene (microporous poly-
ethylene) and TOA on Icorene (microporous polyethylene)
were prepared by Jia et al. (1998) from the seventies.
Supported TOPO on Kieselgur was used by Afsar and
Schüttelkopt (1988). Americium was loaded onto the column
from 0.1 M HNO3, washed with 0.1 M HNO3, and stripped with
8 M HNO3.
Delle Site et al. (1973) separated actinides from urine
samples on Microthene-supported TOPO loaded from 4e6 M
402
FIGURE 6.30 Distribution coefficient (D) for various elements of the periodic chart on a strong basic anion-exchange resin in (a) nitric and (b) hydrochloric acids.
(Lederer, 1992, reprinted by permission of John Wiley and Sons Ó 1992).
HNO3. Actinides were stripped consecutively with 0.3 M H2SO4
(Th), 6 M HCl
0.2 M HF (Pa), 1 M HF (U), 6 M HCl þ Cl2
(Np), and 6 M HCl þ 0.1 M HI (Pu). Americium was separated
on a Microthene-supported HDEHP column. Acceptable high
recoveries (>70%) were obtained with the exception of Am even
in the presence of DTPA complexing agent.
EC using supported TOPO was successfully applied for Pu
determination by Cozzella et al. (2002).
Handbook of Radioactivity Analysis
Supported liquid anion exchangers were used for the
separation of Np from environmental samples in the procedure
of Yan-Qin et al. (2001). Neptunium was retained on a Teflon-
coated TOA from 2 M HNO3 and stripped with hot 0.02 M
oxalic acid/0.16 M HNO3. High recovery (>80%) and high DF
against U (>104) were obtained. In the most recent work of
Desideri et al. (2011), Am, Cm, Pu, Np, and U were separated
from small volumes of water samples and determined by alpha
Chapter | 6 Alpha Spectrometry
FIGURE 6.31 Uptake of various elements by Ln resin from HNO3 solutions.
(McAlister and Horwitz, 2007, reprinted with permission of Eichrom Technol-
ogies LLC Ó 2012)
spectrometry. Samples were loaded onto macroporous PE-
supported TOA from 9 M HCl solution and Am, Pu, Np, and U
were sequentially stripped. Recoveries higher than 74% were
reported for each actinide.
Horwitz et al. (1966) reported a method that can separate
Am from Cm on a supported (hydrophobic diatomaceous earth)
Aliquat 336 column using 8 M LiNO3
0.01 M HNO3 for
loading and 3.5 M LiNO3
0.01 M HNO3 solution to separate
Am from Cm. More than 99% of Am and Cm were recovered in
a radiochemically pure state (<0.1% impurity). The method
was also applied to separate mg quantities of Am and Cm
(Horwitz et al., 1967).
Giardina et al. (2006) used Microthene-supported TOPO,
Icorene-supported TOA, anion-exchange resin, and TRU resin
(see later) for the separation of Pu from urine samples followed by
alpha-spectrometric determination. Methods were compared with
the standard procedure based on anion-exchange chromatography.
All methods gave good Pu recoveries (>80%) and DFs were
acceptably high for naturally occurring radionuclides. Smaller
DFs were obtained by TRU resin (discussed subsequently).
From the nineties, a new family of EC materials has been
developed for the separation of actinides by Horwitz and
colleagues at Argonne National Laboratory, USA, and later
these materials became commercially available from EiChrom
Co. and Triskem SAS. The EC materials have been carefully
403
characterized by measuring the physical and chemical prop-
erties, distribution coefficients, extraction kinetics, elution
behavior, and by developing separation procedures for special
purposes. If a single resin is not capable of the separation of
all the desired radionuclides because of limited selectivity, the
use of tandem column arrangements is recommended, in
which the effluent of one column serves as the load solution
for the subsequent one. Because kinetics of the extraction is
fast, the columns can be operated at higher flow rates than
gravity flow; for this purpose, vacuum boxes have been
proposed.
TEVA resin (Horwitz et al., 1995) dedicated to the sepa-
ration of TEtraVAlent actinides is a supported quaternary
amine-based (Aliquat 336) liquid anion exchanger where the
support material is Amberchrom CG-71ms. TEVA as an analog
of strong basic anion exchangers is expected to be an excellent
chromatographic material for the retention of Pu(IV) and
Np(IV). The resin capacity factors (k’) that are directly
proportional to the distribution coefficients for Pu(IV) and
Np(IV) in 6 M HNO3 are 3  104 and 4  103, respectively, and
are superior to other actinides. This is the reason why the TEVA
resin has received widespread application in Pu and Np analysis
since the first report of Horwitz in 1995 (see in Fig. 6.32).
Uranium and thorium: Capacity factors for Th and U(VI) on
TEVA resin from HNO3 solutions as shown in Fig. 6.32 are
relatively low, and the selectivity for U and Th in concentrated
HCl solutions is limited.
Plutonium: Varga et al. (2007c) used TEVA resin for the
separation of Pu from environmental samples of 1e5 g after
a CaF2 coprecipitation. NaNO2 was used to adjust the oxidation
state of Pu(IV). The sample was loaded in 3 M HNO3, eluted
with 6 M HCl, and Pu was stripped with 0.1 M HNO3/0.1 M HF.
The Pu recovery for the whole procedure including alpha source
preparation was 72e93% and the DF for U was >105, which
was also sufficient for ICP-MS measurement. Chamizo et al.
(2008) determined Pu in environmental samples without pre-
concentration using TEVA chromatography. Pu(IV) was loaded
on the column in 3 M HNO3/Al(NO3)3, followed by washing
with 6 M HCl and stripping with 0.5 M HCl. Recovery of Pu
(>60%) and DF for U(>100) was somewhat poorer than in the
previous method, probably due to the lack of a selective pre-
concentration. Several authors used TEVA successfully for the
separation of Pu for ICP-MS measurements (see the review of
Kim et al., 2004). The standard procedures for the determina-
tion of actinides in water (ACW13VBS, ACW16, and ACW17)
developed by EiChrom Technologies, Inc (available from www.
eichrom.com) are based on the use of different column sets
where Pu is separated by TEVA extraction chromatography.
Neptunium: For the individual determination of 237Np,
samples are usually loaded on TEVA column from 2 M to 3 M
HNO3 after reduction of Np to Np(IV) while Pu is in the non-
retainable Pu(III) oxidation state. Neptunium can be stripped
with dilute HNO3eHF mixture. High Np yields were obtained
in the procedures of Anton et al. (2006), Ayranov et al. (2005),
and Maxwell and Jones (1998) analyzing soil, sediment, and
nuclear materials, respectively.
If Np and Pu are to be determined together, the sample has to
be loaded on TEVA after adjusting the Np(IV) and Pu(IV)
404
FIGURE 6.32 Capacity factors k’ of various actinides on TEVA resin from HNO3 and HCl solutions. (www.eichrom.com, reprinted with permission of Eichrom
Technologies LLC Ó 2012)
oxidation states (see earlier). Kenna (2002, 2009) obtained high
yields for both elements analyzing sediment samples, while Np
recoveries varied between 19% and 54% in the procedure of
LaRosa et al. (2008). In the rapid separation procedure for the
determination of 237Np and Pu isotopes in large soil samples,
Maxwell et al. (2011b) also found that Np recoveries were
reduced when the matrix content increased (sample masses
were higher than 30 g). Plutonium recoveries were high (>82%)
and independent of matrix effect. In the standard procedure for
the determination of Th and Np in water (ACW08) developed
by EiChrom Technologies (1995), quantitative recoveries have
been attained using the simple TEVA procedure.
The standard procedure for the determination of 237Np in
soil (ASTM C1475-05) is based on the use of TEVA column.
The Np(IV) oxidation state is adjusted using ferrous sulfamate
and NaNO2. Sample is loaded from 2.5 M HNO3/0.5 M
Al(NO3)3 and Np is stripped with 0.02 M HNO3/0.02 M HF.
Americium: Am(III) is only slightly retained on TEVA resin
from nitric or hydrochloric acid solutions. The maximum of the
distribution coefficient is 0.1. However, TEVA resin, analog to
anion-exchange resins, can be used for the separation of Am from
lanthanides, which was performed by loading the sample in a 2 M
NH4SCNe0.1 M formic acid solution followed by the elution of
Handbook of Radioactivity Analysis
lanthanides with 1 M NH4SCNe0.1 M HCOOH and stripping
Am (together with Cm) with 0.25e2 M HCl (Horwitz et al.,
1995). Good separation was achieved. A pitfall in the procedure
is the same as in the case of the classical Amelanthanide sepa-
ration using anion exchanger, i.e., it is difficult to dissolve larger
sample amounts in a small volume of load solution. The method
is applied after the separation of Am from most of the sample
components. The same method was applied by Berne (1995) in
the standard procedure of the Environmental Measurement
Laboratory (EML), USA, for the determination of Am in soil
after leaching the actinides, removal of Pu and Th with anion-
exchange resin, concentrating Am from the effluent with Ca
oxalate coprecipitation, and separating Am from most of the
interferences on a TRU column (see later). The procedure was
applied for the purification of the Am fraction by Michel et al.
(2008) and Maxwell and Jones (2008). Jernström (2006) sepa-
rated Pu(III) and Am(III) on TEVA resin, whereby plutonium
was adsorbed quantitatively (98.5e99.1%) by the resin when
loaded and washed with a mixture of 2 M ammonium thiocya-
nate in 0.1 M formic acid. Quantitative elution of Pu(III) from the
resin was achieved with 0.25 M HCl. Sorption of Am(III) on
TEVA resin was quantitative in the same mixture, and americium
was eluted from the resin with 0.25 M HCl.
Chapter | 6 Alpha Spectrometry
UTEVA resin (Horwitz, 1992) is a dipentyl-pentyl phos-
phonate impregnated Amberlite XAD-7 EC material that was
designed to separate U and TEtraVAlent actinides. Because the
resin contains a phosphonate compound, actinides are retained
at higher distribution coefficients than on phosphates, e.g., TBP.
The k’ capacity factor for Pu(IV), Np(IV), U(VI), and Th(IV) is
about 103, 4  102, 4  102, and 2  102, respectively, in 8 M
HNO3, which assures acceptable retention and easy removal of
the tetra- and also the hexavalent actinides (see the capacity
factors of actinides on UTEVA from HNO3 and HCl solutions in
Fig. 6.33).
Apostolidis et al. (1998) developed a procedure for the
determination of Pu and U from reprocessing solution using
a single UTEVA column. The oxidation state of Pu was
adjusted with H2O2 and the sample in 4 M HNO3 was loaded
on the column and Pu was subsequently eluted with dilute
HNO3 containing hydroxylamine and ascorbic acid as reducing
agents. Finally, U was stripped with bioxalate solution. A high
recovery (>95%) was achieved for Pu with a DF for U of
about 104.
Pu and Np were determined by UTEVA EC in a combined
procedure with the analysis of Th and U from environmental
and nuclear waste samples by Vajda et al. (2003) after pre-
concentration of the actinides in reduced form with ferrous
hydroxide. The sample solution was loaded in 8 M HNO3, that
contained ferric nitrate as salting-out agent. Pu was stripped
FIGURE 6.33 Capacity factors k’ of various actinides on UTEVA resin from HNO3 and HCl solutions. (www.eichrom.com, reprinted with permission of Eichrom
Technologies LLC Ó 2012)
405
with 9 M HCl/0.1 M NH4I as Pu(III), Th and Np were stripped
together with 4 M HCl, and U was eluted finally with dilute
acid. Pu recoveries varied in the range of 69e92% and the DF
was high enough to obtain Pu alpha sources without interfer-
ences. Osváth et al. (2009, 2010) improved the procedure by
using a strong oxidizing agent to form Np(VI) and Pu(VI), that
are retained by the resin together with U; they purified the
NpeTh strip solution by EC separation on a 2nd UTEVA
column from 9 M HCl solution. In the modified procedure, Pu
and Np recoveries were 65e82% and 66e93%, respectively,
and the Np source could be analyzed by ICP-MS while Pu and U
sources were measured by alpha spectrometry.
Guerin et al. (2010) determined the k’ values of Np(VI) on
various EC materials including TEVA, UTEVA, TRU, and DGA
from HNO3 and HCl solutions. The Np oxidation state was
adjusted with KBrO3, KMnO4, K2S2O8, Ag2O, and O3. A
simple method using two UTEVA columns was used to detect
Np in soil and sediment samples. Np recovery was 70%.
In the rapid procedure of Ohtsuka et al. (2006), UTEVA is
used in an ion chromatograph directly connected to ICP-MS.
The authors claim that the complete analysis of an environ-
mental sample (1 g) including destruction by fusion is per-
formed within 60 minutes.
TRU resin (Horwitz et al., 1993 and Berne, 1995) is
a chromatographic material comprised of a tri-n-butyl phos-
phate (TBP) solution of the bifunctional organophosphorous
406
extractant octyl(phenyl)-N,N-di(iso-butyl)-carbamoyl-methyl-
phosphine oxide (CMPO) adsorbed on an inert polymeric
substrate (Amberlite XAD-7). It was designed to separate all
TransUranium nuclides including trivalent Am and Cm besides
the tetra- and hexavalent species. Extremely high capacity
factors were measured on TRU resin in concentrated nitric acid
solutions, k’ is higher than 105, 5  104, 104, and 103 for Pu(IV),
Np(IV), Th, and U(VI), respectively, at HNO3 concentrations
above 1 M, and for Am the k’ is about 100. Unfortunately, Fe3þ
present in the sample is also retained and competes for actinide
bonding sites, especially for those occupied by the less strongly
retained Am (Cm). Reduction of Fe to Fe2þ helps reduce the
interference. The capacity factors of actinides on TRU from
HNO3 and HCl solutions are shown in Fig. 6.34.
TRU resin has recently become a popular tool for the
separation of Am; however, it can be used also for the retention
of other actinides either for preconcentration or also for
analytical separations. It seems to be an ideal material for the
simultaneous separation of all actinides. TRU resin replaced
almost exclusively all the methods used for concentration of Am
in the past, i.e., chelating extractants and cation exchangers.
Recently, several new molecules have been synthesized and
have proven to be superior to TRU material regarding the
distribution coefficient for Am or even separation factors, but
the development of analytical procedures has a time lag and
applications are scarce, yet. Due to the moderately high distri-
bution coefficient for Am on TRU and the various interferences
from trivalent ions, e.g., Fe and lanthanides and from matrix
components, the separation procedures cannot avoid adequate
preconcentration of Am.
FIGURE 6.34 Capacity factors k’ of various actinides on TRU resin from HNO3 and HCl solutions. (www.eichrom.com, reprinted with permission of Eichrom
Technologies LLC Ó 2012)
Handbook of Radioactivity Analysis
Berne (1995) determined Am, Pu, and U in air filter and
water samples. The sample was loaded in 8 M HNO3/NaNO2.
Am was eluted with 0.025 M HNO3, and Pu and U together with
bioxalate. Because of cross-contaminations, it was recom-
mended to separate Pu first on an anion-exchange resin and use
the TRU resin for the purification of Am, only. This procedure
was followed by many laboratories later, including the Envi-
ronmental Measurements Laboratory, at the IAEA Laboratories
at Seibersdorf and Monaco (Moreno et al., 1997, 1998; IAEA,
2012; LaRosa et al., 1989, 2001, 2005).
Horwitz et al. (1993) recommended a procedure for the
sequential separation of actinides using a single TRU column.
Actinides were loaded in 2 M HNO3 after reduction when Pu was
present as Pu(III). Am was eluted with 4 M HCl, Pu was eluted
with 4 M HCl/0.1 M hydroquinone, followed by stripping of Th,
Np, and U with 1.5 M HCl, 1 M HCl/0.03 M oxalic acid, and
0.1 M ammonium bioxalate, respectively. This procedure was
slightly modified and applied for the rapid determination of Am,
Pu, Th, and U in small environmental samples (1 g) by Vajda
et al. (2009). After LiBO2 fusion and CaF2 coprecipitation, the
oxidation state was adjusted with NaNO2 turning Pu to Pu(IV).
The sample was loaded in 2 M HNO2. Am was stripped with 4 M
HCl. Pu was eluted after fast on-column reduction with 4 M HCl/
0.1 M TiCl3. High recoveries were obtained for both Am (96%)
and Pu (85%), and no traces of contamination were detected in
the Am and Pu alpha sources. The behavior of Np on TRU resin
was also tested; however, a good separation from U was not
attained. A sequential separation procedure for the determination
of the actinides in power plant effluents was developed by Spry
et al. (2000). In the 3 M HNO3 load solution Pu was present as
Chapter | 6 Alpha Spectrometry
Pu(III), and it was oxidized after retention on-column with
NaNO2. Am was stripped as above, Th was eluted with 4 M HCl/
0.01 M HF, and Pu with 0.1 M bioxalate. Am and Pu recoveries
were acceptably high (52 and 56%, respectively). The robust
procedure for the determination of plutonium and americium in
seawater developed by Sidhu (2003) is based on MnO2/Fe(OH)3
preconcentration of the actinides and their separation using
a TRU column. Pu as trivalent ion was loaded together with other
actinides from 3 M HNO3, and it was stripped after Am with 4 M
HCl/0.02 M TiCl3. High recoveries were achieved for both
nuclides (Pu: 78%, Am: 85%). Similar procedures were applied
by Olahova et al. (2005) and Gogorova and Matel (2007).
In the ASTM standard guide C1561-10 for the determination
of Pu and Np in uranium hexafluoride and U-rich matrix, two
TRU columns are used. U is separated by retention on the 1st
column from a 0.1 M oxalic acide2 M HNO3 solution, then
other actinides are retained on the 2nd column from 3 M HNO3.
Americium, Th, and Pu are selectively stripped with 4 M HCl,
1.5 M HCl, and 1 M HCle0.1 M oxalic acid, respectively.
Separations using UTEVAeTRU tandem resin columns:
Several multistage EC methods were proposed for the simul-
taneous separation of actinides, but the one which became the
most frequently used is based on the tandem column set of
UTEVAeTRU. Thakkar (2001, 2002) described the detailed
procedure in 2001 as the rapid sequential separation of U, Th,
Pu, and Am. Actinides were preconcentrated with calcium
phosphate (pH ¼ 9), then dissolved in 3 M HNO3/1 M
Al(NO3)3. Pu was reduced to Pu(III) with ferrous sulfamate and
ascorbic acid. The sample was loaded on the tandem column
where UTEVA was the 1st column and TRU was the 2nd. After
loading and washing, the columns were separated. Th and U
were removed from the UTEVA column eluting them subse-
quently with 5 M HCl/0.05 M oxalic acid, respectively. On the
TRU column, Pu was oxidized to Pu(IV) with 2 M HNO3/0.1 M
NaNO2, then Am and Pu were stripped after each other with
4 M HCl and 0.1 M ammonium bioxalate, respectively. This
procedure resulted in high recoveries for Pu (>80%) and Am
(>72%) as well as for U (>79%), and also relatively high DFs
(in the Pu fraction DF for U > 104). This simple and fast
procedure was frequently used with minor changes in different
laboratories (LaRosa et al., 2001; Varga et al., 2007a, 2007b;
Jakopic et al., 2007; and Mellado et al. 2001).
DIPEX resin (Horwitz et al., 1997), also called ACTI-
NIDE resin, is a neutral, bifunctional organophosphorous
extractant, consisting of bis(2-ethylhexyl)meth-
anediphosphonic acid supported on an inert polymeric
substrate. It has extraordinary affinity for actinides from dilute
acids. The capacity factor for Pu(IV) and Np(IV) from 0.1 M
HCl solution is about 2  107 and 107, respectively, and the
same for Am, the traditionally least extractable actinide is even
one order of magnitude higher (2  108). Actinides together
with the extractant can be recovered from the resin by alcohol
stripping and wet oxidation. These properties can be exploited
in the preconcentration of actinides from large-volume samples
or complex matrices. The direct analytical application of the
resin may be limited by the incomplete removal of the acti-
nides from the resin. Burnett et al. (1997) used DIPEX resin
for the preconcentration of actinides from soil solutions and
407
large-volume water samples. Actinides from soil samples after
NaOH fusion, dissolution, and ferrous hydroxide scavenge
were concentrated on a DIPEX column. Isopropanol was used
to solubilize the extractant that retained the actinides followed
by the oxidation of the organic component. Basic calcium
phosphate was used to scavenge the actinides repeatedly, and
the final separation was performed on a UTEVAeTRU tandem
column setup as described below. Recoveries of Pu, Am, and U
varied in a wide range (31e91%, 22e99%, and 60e85%,
respectively). ACTINIDE resin was used for the preconcen-
tration of Pu and Am from human tissue followed by the
separation of Pu with anion-exchange resin by Qu et al. (1998).
The overall recovery for Pu was high (>80%) assuring the
adequacy of the preconcentration, as well.
DIPHONIX resin (Chiarizia et al. 1997) can be regarded as
the chelating ion-exchange resin analog of the DIPEX extrac-
tion chromatographic material. It contains geminally substituted
diphosphonic acid groups chemically bound to a styrenic-based
polymer matrix. It also contains strongly hydrophilic sulfonic
acid groups in the same polymer network. Also, extremely high
capacity factors were observed for the retention of all actinides,
close to those of DIPEX from dilute acid, but several transition
metals (e.g., Cr, Ni, Cu, and Zn) are also retained. The removal
of the actinides is more problematic due to the massive resin
structure. Strong complexing agents can remove the actinides
that have to be decomposed or the resin itself has to be
destroyed. Analytical procedures have been proposed by the
authors, but because of the difficulties in removing the actinides
from the resin they have not been applied in practice. Ros-
skopfova and Holkova (2005) reported the use of DIPHONIX
resin for the preconcentration of actinides from large soil
samples followed by their separation using different eluents,
i.e., Am was stripped with 6 M HNO3 and Pu with 4 M HCl/
0.015 M TiCl3. Recoveries for Am were high (70, 78%) but
varied for Pu (37, 93%).
DGA resin (Horwitz et al., 2005) consists of N,N,N’,N’-
tetraoctyldiglycolamide adsorbed onto Amberchrom CG-71
resin. Like the DIPEX resin, DGA retains Am strongly; in
concentrated HNO3 solutions (>1 M) the capacity factor of Am
is higher than 104. High capacity factors were found also for Pu
(>103) at high HNO3 concentrations, but they were not
significantly smaller at low acidities. DGA resin can be used
advantageously for the separation and purification of Am
without losses from various matrices, e.g., soil and water.
The capacity factors of actinides on DGA resin are shown in
Fig. 6.35.
Maxwell and Culligan (2006) and Maxwell and Jones
(2008) developed a very promising rapid method for the
determination of actinides in large soil samples up to 200 g.
Samples are fused with NaOH and actinides are preconcentrated
with Ce(OH)3 and CeF3 coprecipitation. Stacked TEVAe-
TRUeDGA cartridges are loaded with 8 M HNO3. TEVA
serves for separation of Th and Pu(IV), while Am (and Cm) are
separated with the TRUeDGA multistage column. Americium
originally retained on TRU was eluted with 4 M HCl and
transferred to the DGA column. Americium was stripped from
DGA with dilute (0.25 M) HCl solution. Am and Pu recoveries
for the whole procedure were high, varying between 76 and
408
FIGURE 6.35 Capacity factors k’ of various actinides on DGA resin from HNO3 and HCl solutions. (www.eichrom.com, reprinted with permission of Eichrom
Technologies LLC Ó 2012)
98% and 61 and 92%, respectively. The method was adopted for
the analysis of water samples (Maxwell, 2006) up to 1 L and
extended for the determination of Sr radionuclides using Sr
resin. The procedure combined the advantages offered by the
rapid and effective destruction with NaOH fusion, the selective
preconcentration of actinides with Ce(OH)3 and CeF3, and the
EC separation using highly specific resins, i.e., TEVA for Pu
and TRUeDGA for Am.
Recently, Maxwell et al. (2011a) developed a rapid simpli-
fied method for the determination of Pu and Np in water
samples using a stacked column set of TEVA and DGA resins.
In the combined procedure, Pu(IV) and Np(IV) were retained on
a TEVA column first, then Pu was reduced and retained as
Pu(III) on the DGA column together with U. From the DGA, U
was eluted with 0.1 M HNO3 and Pu(III) was stripped with
0.02 M HCl/0.005 M HF/0.0005 M Ti3þ. High recoveries and
DFs for U (higher than 106 and 104 in case of Pu and Np,
respectively) were reported. The resulting source quality met
the requirements of both alpha spectrometry and ICP-MS.
b. EC of Radium and Polonium
Sr Resin is an extraction chromatography material particularly
useful for separation of group 2 elements, with an especially
high affinity for Sr. In nitric acid solutions, uptake of Ra is lower
than Pb, Sr, and Ba, but higher than Ca. Radium and Ba uptake
are highest at approximately 2e3 M HNO3, while Sr uptake
increases monotonically with HNO3 concentration. Lawrie et al.
(2000) used 3 M HNO3 on Sr Spec resin as a final cleanup step
to separate Ra and Ba prior to alpha spectrometry. Although the
main reported applications to date have been for separations
preparatory to mass spectrometry (e.g., Yokoyama and Naka-
mura, 2004), the material shows promise for expanding the
application to alpha spectrometry for Ra isotope analysis.
Handbook of Radioactivity Analysis
Vajda et al., (1997) developed a method for the separation of
Po using Sr Spec resin. The digest is loaded on the column in
2 M HCl. Bismuth and several other matrix components
including Fe are eluted with the 2 M HCl wash while Po and Pb
are retained. Po may then be eluted with 6 M HNO3, and Pb
subsequently eluted with 6 M HCl. The column may be reused 1
or 2 times after the first extraction (Vre
cek et al., 2004; Kim
et al., 2009).
3MÔ EmporeÔ Radium Rad Disks are a filter-like
membrane on which a Ra ion selective crown ether is
embedded. They are especially useful for preconcentration and
separation of Ra from water samples and other aqueous solu-
tions. The disks are commonly analyzed using gamma spec-
trometry, as little further sample preparation is required.
However, the Ra may be eluted (for example, with alkaline
EDTA) and a source for alpha spectrometry prepared


(Durecová, 1997; Purkl and Eisenhauer, 2003).
c. Combined Procedures
Combined procedures are often used for chemical separations of
a single element in order to have high decontamination factors
for one element or for the simultaneous determination of several
elements. It is a rare case when an element can be separated
adequately for alpha spectrometry by a single procedure.
There is a huge variety of combined procedures that cannot
be discussed in the frame of this chapter (see the reviews,
books referred to at the beginning of this section). The following
combinations have been reported recently (Vajda and
Kim, 2011):
anion-ion exchange resineanion-ion exchange resin,
anion-ion exchange resineTEVA resin,
anion-ion exchange resineUTEVA resin,
anion-ion exchange resineTRU resineTEVA resin,
Chapter | 6 Alpha Spectrometry
anion-ion exchange resinecation ion exchange resin,
LLE with TOPOeUTEVAeTRU,
LLE with TOPOeTRUeTEVA,
LLE with TOPOeTEVAeTRUeTEVA,
LLE with TOPOeHDEHP,
UTEVAeTRU,
TEVAeTRU,
TEVAeUTEVA,
TEVAe DGA,
TEVAeUTEVAeTRU,
TEVAeTRUeUTEVA, and
TEVAeTRUeDGA.
C. Alpha Source Preparation
Following chemical separation from the sample matrix, the
analytes must be prepared as a thin, flat, uniform source suitable
for alpha-spectrometric analysis. The basic characteristics of
a high-quality source are that the alpha particles lose only
a small and consistent amount of energy while exiting the
source (minimizing energy straggling), the geometry of the
source-detector arrangement results in a high counting effi-
ciency, this efficiency is consistent between sources, the deposit
is robust, the deposited activity is relatively homogeneous
across the deposit, and the source is easy to handle and store.
There are three main methods of source preparation: evap-
oration, coprecipitation with a microcrystalline precipitate, and
electrodeposition. In the ASTM standard D3084e05 on
”Standard Practice for Alpha-Particle Spectrometry of Water”
all three methods are described.
The evaporation technique involves depositing the solution
onto a stainless-steel or platinum disk, and evaporating the
solution in such a way that a uniformly covered surface is
obtained. This method is quick and ensures a very high
recovery. A difficulty is ensuring that the source deposit
is uniform and, for that purpose, a wetting or spreading agent
is usually used (Lally and Glover, 1984). A further disadvan-
tage is that deposits do not always adhere tenaciously to the
substrate.
Micro-coprecipitation of actinides on a rare-earth fluoride,
often NdF3, followed by filtration on a smooth surface
membrane filter of small pore size (0.1
0.2 mm) produces
a good-quality alpha source (ASTM Test Method C1163, Sill,
1987a). For Ra, the most commonly used coprecipitation
method for source preparation is with BaSO4 as described by
Sill (1987b). Coprecipitation and filtration are more rapid than
electrodeposition; however, a disadvantage is that the resulting
filter is flexible and may require adhesion to a backing to
prevent curling.
In electrodeposition, metallic radionuclides are electro-
chemically plated with high yield from an electrolyte solution
onto a metal cathode surface. Most commonly, a polished
stainless-steel cathode planchet is used, although a metal-coated
plastic film may be used for specialized applications, such as
coincident photon and alpha spectrometry (Johnston et al.,
1991). The anode is typically Pt wire or gauze. The anode is
often rotated to stir the solution, although bubbling by gas
409
formed at the anode may provide sufficient mixing. A variety of
electrolytes has been used to close the electric circuit, including
sulfate, oxalate, and acetate buffers.
In most cases, metallic elements are deposited with high
yield in a relatively nonselective manner, with the exception of
group 1 and 2 elements. For the widely used method of
Hallstadius (1984), deposition yields were reported to be
between 90 and 99% for Cm, Am, Pu, Np, U, Th, Pb, and Po,
and <1% for Ra.
An aqueous/alcohol electrolyte solution (e.g., 1 mL 0.1 M
HNO3 and 9 mL propanol) may be used to electrodeposit Ra
(Smith and Mercer, 1970; Hancock and Martin, 1991). Alter-
natively, Ra may be deposited from an aqueous solution of
ammonium acetate and nitric acid, or ammonium oxalate and
HCl, usually with the addition of a small amount of Pt in
solution (Roman, 1984; Orlandini et al., 1991; Hamilton et al.,
1994).
Electrodeposition is often performed at a constant current
density (0.5e1 A/cm2) and low voltage (<10 V) for about half
an hour to two hours. A standard procedure for electroplating
actinides from a solution of ammonium sulfate was published in
2000 and reapproved in 2010 (ASTM C1284-00). For alpha-
spectrometric purposes, the last two procedures are routinely
used.
Polonium spontaneously autodeposits onto the surfaces of
several metals including Ag, Cu, and Ni from dilute acid
solution. Autodeposition onto metal disks (usually Ag) is the
most common source preparation technique for Po due to its
simplicity and the fact that it results in separation from other
metal ions including other alpha emitters (Smith and Hamilton,
1984 and Matthews et al., 2007). Electrodeposition can also be
used for Po source preparation (Uesugi et al., 2010).
Ultra-thin Am, Cm, and Th sources may be prepared by the
adsorption of insoluble compounds onto a substrate (Wyllie and
Lowenthal, 1984; Martin and Hancock, 2004b). The alpha peak
resolution for these sources is very high. However, the recov-
eries obtained are relatively low and, although useful for the
preparation of high-quality test sources, the technique has not
been used for routine analysis.
Whichever method is used for source preparation, perfect
homogeneity of the deposited activity across the source cannot
be expected. With careful design of the deposition system,
a reasonably even and consistent deposit can be attained
(Klemen
ci
c and Benedik, 2010). Nevertheless, on a small scale
it can be expected that the activity and source thickness will
show some “graininess,” which will mean that the effect of the
deposit on peak resolution will be greater than that expected
purely from the deposited mass per unit area (Martin and
Hancock, 2004a).
VI. DETERMINATION OF ALPHA ACTIVITY
AND RECOVERY
In order to determine alpha-emitting radionuclides by alpha
spectrometry the following procedure is performed: alpha
sources are prepared by radiochemical separation, the
alpha spectrometer is calibrated, sample, background, and
410
blank sources are counted with the alpha spectrometer for
adequate counting times, the spectra are analyzed (i.e., peaks
are identified and peak areas are calculated), and the activities
of the identified nuclides are calculated. In the present chapter,
the major steps of alpha activity determination are discussed
using examples from standard semiconductor alpha spec-
trometry. The same method can be used in the case of gas
ionization detectors without significant changes. High-resolu-
tion alpha and high-resolution LS spectra are usually evalu-
ated by computer codes that have been briefly discussed
above.
A. Calibration
Calibration of the instrument comprises energy, resolution, and
efficiency calibration that may be established from the same
source, most likely a calibration source (CS) containing known
quantities of at least two radionuclides emitting alpha radiation.
The CS should have activities such that instrumental dead time
resulting in lost counts can be avoided. The limitation of
approximately 100 Bq is a typical value. The CS is placed in the
detector chamber at a distance from the source that is larger than
the detector diameter to reduce the geometric effect on FWHM
value, then the counting chamber is evacuated, and the system
bias is adjusted to the factory given value. The source is counted
during a measurement period that produces a relatively low
counting uncertainty. A typical alpha spectrum of a CS is shown
in Fig. 6.36.
Energy calibration is carried out by plotting the known
energies (E) of the peaks belonging to highest alpha abundance
against the peak location channel numbers (ch) referring to the
peak center position. Usually a straight line is fitted to the
points as
E ¼ b þ m$ch (6.25)
where m is the slope and b is the intercept of the line. Because
the energy response of the detector is reasonably linear, the
measurement of two points is sufficient for routine analytical
FIGURE 6.36 Alpha spectrum of a commercially available calibration source
containing 239Pu, 241Am and 244Cm. The source was prepared by vacuum
evaporation and counted with a PIPSi detector with 300 mm2 surface area at
a distance of 5 cm from the detector.
Handbook of Radioactivity Analysis
purposes. However, modern spectrometry software packages
perform calculations based on the measurement of several peaks
and may include cubic or quadratic terms to account for minor
nonlinearity.
Calibration of the energy resolution is performed by
measuring the peak width at channels corresponding to the half
of the maximum counts and expressing the width in energy units
(see Fig. 6.36). The stability of FWHM values is an important
indicator of good system performance.
In principle, efficiency calibration can be performed
according to the following equation from the measurement of
the same CS, if the calibration standard is measured in the same
geometry as the sample source:
rCS
rBG
ε ¼ (6.26)
ACS $Ia $D
where ε is the counting efficiency, rCS is the gross count rate of
the calibration source [cps], rBG is the background count rate
[cps], ACS is the activity of the calibration source at the refer-
ence date [Bq], Ia is the alpha abundance, and
D ¼ e
lCS $tCS
is the decay factor for the calibration source from the reference
date to the measurement date, where lCS is the decay constant of
the calibration source [s
1] and tCS is the time from the refer-
ence date of the calibration source to the measurement date [s].
The law of uncertainty propagation for a single measure-
ment according to the above equation or preferably the standard
deviation of multiple measurements can be used to express the
standard uncertainty of ε.
In practice, calibration sources rarely have the same geom-
etry as those for the sources prepared from the sample for anal-
ysis. Therefore, calibration sources of the required geometry
have to be prepared from standard solutions. These sources are
used to determine the counting efficiency as described above.
The efficiency of a solid-state alpha spectrometry detector is
not a function of energy over the typical energy range of emitted
alpha particles due to the high stopping power of alpha particles in
Si. Therefore, the average of the efficiencies of multiple alpha
peaks can be calculated to obtain a more accurate efficiency value.
When a sample source is analyzed with an alpha-emitting
tracer as an internal standard, the efficiency does not affect the
result of analysis because the count rates of the analytes are
directly related to the count rate of the tracer. Therefore, an
exact knowledge of the efficiency is only necessary to calculate
the chemical recovery. However, when a sample source is
analyzed without an alpha-emitting tracer then the efficiency is
used to calculate the activity of the analyte.
The standard practice of calibration of alpha spectrometers
is described in ASTM D7282-06 standard.
B. Measurement Procedure
Sample sources are placed in the vacuum chamber. The selec-
tion of the distance of the source from the detector is always
a kind of optimization between efficiency and resolution, and it
depends very much on the source activity. The chamber is
Chapter | 6 Alpha Spectrometry
pumped until a vacuum of about 15 mbar is achieved if it is
desirable to protect the detector from the recoil contamination
or of about 0.01 mbar if high resolution is of major concern.
Then the detector voltage is set to the value recommended by
the detector manufacturer. Counting times are selected
according to the activity of the source and the required counting
uncertainty. Low-activity environmental samples are typically
counted for several days.
C. Alpha Spectrum Evaluation
1. Principle of Evaluation
The activity of the analyte is determined from the known
activity of the tracer that was added to the sample and the ratio
of the peak areas belonging to the analyte and the tracer. The
method is called isotope dilution alpha spectrometry, and has
the advantage that the calculated activity is inherently corrected
for chemical losses, because losses of the analyte are taken to be
equal to those of the tracer. This is a very realistic assumption
whenever the tracer and the analyte are isotopes of the same
chemical element in the same chemical form but the procedure
should be used with care if this is not the case.
2. Nuclide Identification
In isotope dilution alpha spectrometry, chemical separation is
designed to favor one element or a group of elements. There-
fore, only a limited number of isotopes are expected in the alpha
source, and identification of the nuclides simply means
comparing the peak energy in the spectrum with the alpha
energies of the expected nuclides and possible contaminants
that could be present due to failure of separation. For example,
after chemical separation of Pu from an environmental sample
one can expect the peaks of 238Pu, the common peak of 239Pu
and 240Pu, and the peak of the tracer 242Pu or 236Pu (Fig. 6.37).
A very important quality control procedure in alpha spec-
trometry involves checking the spectrum for the presence of
alpha peaks from elements other than the one of interest. This
may be due to the failure of the chemical procedure to achieve
high separation efficiency due to matrix effects, or the presence
in the sample of a relatively high activity of the contaminating
radionuclide. As examples, possible interferences in the Pu
spectrum are Th isotopes if anion-exchange separation of Pu is
ROI
Counts
Pu-242
ROI
Pu-239, 240
ROI
Pu-238
Channel number
FIGURE 6.37 Setting regions of interest of equal width for the evaluation of
the well-separated peaks of Pu nuclides.
411
performed from nitric acid solution or traces of U isotopes in the
Pu source if anion-exchange separation of Pu has been per-
formed from hydrochloric acid solution.
3. Peak Area Determination for Nonoverlapping
Peaks
The counts in the peak corresponding to the analyte are inte-
grated, and the counts of the tracer nuclide in the channel region
of the same width are also integrated. Blank samples are also
processed and analyzed to determine the background contri-
bution to the counts in the regions of interest (ROIs).
4. Peak Area Determination with Correction
for Overlapping Peaks
Due to the asymmetric character and significant low-energy
tailing of alpha peaks, the low-energy peaks are sitting on the
tails of all the peaks of higher energies. This tailing has to be
corrected for, and this correction is especially important if the
peaks are close to each other or if the count rate in the higher
energy peak is much greater than that in the lower energy peak.
In Fig. 6.38, partially overlapping peaks of 239,240Pu and
238
Pu are shown according to the ISO 11483:2005 standard. The
exact activity ratio of 238Pu/239,240Pu can be determined after
tailing correction. There are two standardized methods for the
determination of peak area of overlapping peaks, the so-called
geometric progression decrease (GPD) method and the expo-
nential decrease (ED) method that have been described in detail
in the standard.
The basic idea in the GPD method is that the counts in the
tail of a peak decrease in geometric progression. It is assumed
that the shapes of the different peaks in the same spectrum are
the same; therefore, in the flat portion of tail, peak tailing
contributions are proportional to the corresponding peak areas,
and the tails are the sum of all single peaks of higher energies.
According to Fig. 6.38, four regions of interest (A, B, C, and
D) of equal channel numbers are selected. The high-energy end
of ROI A is selected as the center energy of the 2nd peak plus the
half of its FWHM. The low-energy end of ROI A is fixed so that
the region is not extending into the region of the 1st peak. The
high-energy end of ROI B is selected similarly to ROI A as
the center energy of the 1st peak plus the half of its FWHM. The
width of ROI B is the same as that of ROI A. ROI C and ROI D
are selected so that the difference between the two neighboring
peaks as well as the width of each ROI are the same. The
constant ROI width is selected so that the ROIs should not
extend to the regions of any other peaks. The sum of the counts
in ROIs A, B, C, and D are calculated and called as a, b, c, and d,
respectively. The corrected ratio of the peak areas (Rcor) is
calculated according to the geometric progression decrease as
follows:
a a
Rcor ¼ ¼ ac (6.27)
bcorrected b

ad
bþ
c
Thus, the values of a and the tailing corrected bcorrected are
obtained for the calculation of the exact activity or activity
412
FIGURE 6.38 Tailing correction for partially overlapping peaks according to standard ISO 11483: 2005.
concentration. The complicated uncertainty calculation is
described in the ISO standard.
The basic idea in the ED method is that the decrease of
counts in the tailing region can be described by an exponential
function. The ROIs A and B are selected as described above. An
exponential function is fitted to the points in the region between
ROI A and ROI B:
0
Yi ¼ A0 $eB $Xi (6.28)
where Yi and Xi are the number of counts and the number of
channels belonging to the measured spectrum data point, and A0
and B0 are the fitted parameters of the exponential function.
Then the area under the assumed tailing curve in ROI B is
calculated as the sum of counts SYi using the parameters of the
fitted curve. The corrected area of the 1st peak is obtained as
b
SYi and the corrected ratio of the peak areas (Rcor) is
calculated as
a CT $n
Rcor ¼ P (6.29)
b
SYi
i in:ROI B
The uncertainty calculation of the corrected peak area is given
in the ISO standard.
Both methods of tailing correction have limitations in
applications: Spectra of relatively high-energy resolution, and
high counts are required, as well as the peaks have to be relatively
well separated so that the regions can be selected without inter-
ferences from other peaks. Both methods have been successfully
used for the accurate determination of 238Pu/239,240Pu isotope
ratios in nuclear fuel samples by alpha spectrometry.
Corrected peak areas can be determined by the spectrum
evaluation codes that have been described in Section A.1.3.
5. Calculation of Results
The calculation of results comprises calculation of the massic
activity of the radionuclide and its standard uncertainty.
Handbook of Radioactivity Analysis
The latter can be occasionally replaced by the calculation of the
standard deviation of repeated measurements. Additionally,
chemical recoveries and decision thresholds as well as detection
limits should be calculated.
The ratio of the net counts of the peaks belonging to the
tracer and the analyte (n/nT) is used to calculate the activity
concentration of the analyte in the sample on the date of
chemical separation (a1) taking into account the activity
concentration of the tracer solution (CT), the masses of the
sample (ms) and the tracer solution (mT) used, and the decay of
the tracer between its calibration date and counting ( fT). The
decay of the analyte between separation and counting is
neglected when the nuclides are long-lived. The method of
calculation of the results has been described by Kanisch
(2004).
The massic activity of the analyte (a1, Bq kg
1, dry) at the
separation time can be calculated by the following formula:
a1 ¼ (6.30)
$mT $fT
ms $nT
where the decay correction factor is calculated as follows:
fT ¼ expð
lT $tT Þ
where lT is the decay constant of the tracer [years
1] and tT is
the time interval between the reference date of the tracer and the
separation time [years].
Finally, the massic activity of the analyte in the sample is
calculated back to the date of sample collection (a0):
a0 ¼ a1 expðlA t1 Þ (6.32)
where lA is the decay constant of the analyte [years
1] and t1 is
the time interval between the sampling date and the separation
time [year].
The detection efficiency (ε) is not needed directly for the
calculation of the activity concentration in isotope dilution
alpha spectrometry. However, it allows one to calculate the
Chapter | 6 Alpha Spectrometry 413

chemical recovery (R) from the activity of the tracer added and n r
uðrÞ2 ¼ 2
¼ (6.36)
the net counts in the corresponding peak: tm tm
nT Thus, the uncertainty of count rates for analyte and analogously
R ¼ $expðlT $tT Þ (6.33)
CT $mT $ε$tm for tracer in alpha spectra can be calculated according to the
The detection efficiency is determined from the activity of following equation:
a calibration source and the net count rate measured in the same ng rg
uðrg Þ2 ¼ ¼ (6.37)
geometry as the sample (see Eq. 6.26). 2
tm tm
Calculation of the activities of all analyte isotopes (e.g., ngT rgT
238
Pu and 239,240Pu) are performed in the same way replacing uðrgT Þ2 ¼ 2
¼ (6.38)
tm tm
the relevant analyte data in the equation and using the same
tracer data (e.g., 242Pu). In the case of background,
pffiffiffi the number of counts are usually
small and the uðnÞ ¼ n equation is not valid; therefore,
background uncertainties are calculated from the average and
standard deviation of several long-time background measure-
6. Calculation of the Combined Standard
ments according to
Uncertainty P
r0i
Activities in the source and massic activities of the analytes in i
the sample are determined according to eqn (6.30). r0 ¼ (6.39)
nb
Calculation of the combined standard uncertainty can be
performed according to the ISO Guide to the Expression of where r0 is the average of nb measurements, each resulting in r0i
Uncertainty in Measurement (1995), or according to the IAEA background count rate,
(2004) publication on Quantifying Uncertainty in Nuclear P
Analytical Measurements. First, the individual uncertainties of ðr0i
r0 Þ2
the input parameters are calculated or estimated, then the uðr0 Þ ¼ i (6.40)
nb
1
uncertainty of the activity concentration u(a0) is calculated
according to the law of uncertainty propagation. where u(r0) is the standard deviation of the nb repeated back-
ground measurements.
The average value for r0T and the standard deviation u(r0T)
a. Individual Uncertainty Components are derived similarly.
Uncertainty in weighing of sample mass. The uncertainty 1. The uncertainties for decay correction factor, u( fT) can be
associated with the mass of sample is estimated using the data calculated as follows:
from the calibration certificate of the analytical balance and the
manufacturer’s recommendations on the uncertainty estimation uð fT Þ ¼ fT $tT $uðlT Þ (6.41)
of the balance. If it is assumed that the balance with 0.1 mg of
uncertainty is used for weighing the sample and the linearity where uncertainties of the decay constants are obtained from
distribution is assumed to show a rectangular distribution, the nuclear tables.
standard uncertainty in weighing of the sample mass can be The uncertainty of measuring time is neglected: u(t)¼0.
calculated by the following formula:
b. Combined Uncertainty
0:1
pffiffiffi ¼ 0:058 mg (6.34) Combined uncertainty in the determination of the massic
3
activity of the analyte (a1) is calculated according to the general
The contribution for the linearity has to be accounted for twice, formula:
once for the tare and once for the gross mass (tare þ sample), vffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
u
2
leading to an uncertainty u(ms) of uX vai
qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi uða1 Þ ¼ t uðxi Þ2 (6.42)
vx i
uðms Þ ¼ 2  ð0:058Þ2 ¼ 0:082 mg (6.35) i

Uncertainty in the mass of the tracer solution is calculated where xi are the individual parameters of the result a1. In the
similarly. basic eqn (6.30), net counts are replaced by net count rates
Uncertainty of the activity concentration of the tracer expressed as the difference of gross and background count rates
solution. The uncertainty of the certified concentration of the in order to take into account that counting times of sample and
tracer solution on a calibration, u(CT), is provided by the background are usually different. The basic equation for the
producer. calculation of the result is therefore
Uncertainty of net count rates of analyte and tracer.
Since CT $ðrg
r0 Þ
pffiffiffi n a1 ¼ $mT $fT (6.43)
uðnÞ ¼ n, and r ¼ , therefore ms $ðrgT
r0T Þ
tm
414 Handbook of Radioactivity Analysis

and a1 is dependent on the parameters a1 ¼ f (rg, r0, rT, r0T, CT, separation time u(a1) by differentiating eqn (6.32). Each partial
ms, mT, fT). Thus, partial derivatives of a1 are calculated for each derivative can be calculated as follows:
parameter as follows: va0 a0
¼ (6.55)
va1 a1 va1 a1
¼ (6.44)
vrg ðrg
r0 Þ va0
¼ a0 t1 (6.56)
va1 a1 vlA
¼
(6.45)
vr0 ðrg
r0 Þ Therefore, the combined relative uncertainty of the massic
activity of the analyte [Bq kg
1, dry] on the sampling date
va1 a1
¼
(6.46) (m(a0)) can be calculated by the following formula:
vrgT ðrgT
r0T Þ



va1 uða0 Þ 2 uða1 Þ 2 2
¼

a1
(6.47) ¼ þ t1 $uðlA Þ2 (6.57)
vr0T ðrgT
r0T Þ a0 a1

va1 a1 Calculation of the relative uncertainty of the chemical recovery

¼
(6.48) is made based on eqn (6.33) that can be expressed with count
vCT CT
rates instead of counts:
va1 a1
¼
(6.49)
vms ms rgT
r0T
R ¼ $expðlT $tT Þ (6.58)
va1 a1 CT $mT $ε
¼
(6.50)
vmT mT urel ðRcal Þ2 ¼ urel ðrT Þ2 þ urel ðCT Þ2 þ urel ðεÞ2 þ urel ðmp Þ2
va1 a1 þ urel ð fT Þ2
¼
(6.51)
vfT fT
(6.59)
where va1 va1 ngT n0T rgT r0T
¼
tT a1 and ¼ 0 (6.52) Since uðrT Þ2 ¼ 2 þ 2 ¼ þ (6.60)
vlT vtT tm t0 tm t0
The uncertainty of the analyte concentration on the separation
and urel ð fT Þ2 ¼ tT2 $uðlT Þ2 (6.61)
time u(a1) can be calculated as follows:

2
2 the following equation is obtained:
a 1 a 1


uða1 Þ2 ¼ $uðrg Þ2 þ
$uðr0 Þ2 rgT r0T 1
rg
r0 rg
r0 2
urel ðRcal Þ ¼ þ $ þ urel ðCT Þ2

2
2 tm t0 rgT
r0T
a1 a1
þ $uðrgT Þ2 þ $uðr0T Þ2 þ urel ðεÞ2 þ urel ðmp Þ2 þ tT2 uðlT Þ2 (6.62)
rgT
r0T rgT
r0T

2

2 Similarly, the relative uncertainty of the counting efficiency is
a1 a1 a1
þ $uðCT Þ2 þ
$uðms Þ2 þ $uðmT Þ2 calculated from eqn (6.26):
CT ms mT
2 2

2
þ ð
tT a1 Þ $uðlT Þ rCS rBG 1
urel ðεÞ2 ¼ þ $ þurel ðACS Þ2 þ urel ðIÞ2
(6.53) tCS t BG r CS
r BG
2
and u(rg) and u(rgT) can be replaced by eqns (6.37) and þ t 2
CS uðl CS Þ
(6.38) to get the final expression for the measurement (6.63)
uncertainty: where the indexes CS and BG refer to the calibration source and

2
2 the background in the peak of the calibration source, ACS is the
2 a1 rg a1 known activity of the calibration source, and I is its alpha decay
uða1 Þ ¼ $ þ
$uðr0 Þ2
rg
r0 tm rg
r0 probability/abundance, tCS is the time elapsed from source

2
2 calibration to measurement, and lCS is the decay constant of the
a1 rgT a1
þ $ þ $uðr0T Þ2 calibration source.
rgT
r0T tm rgT
r0T

2

a1 a1 2
þ $uðCT Þ2 þ
$uðms Þ2 7. Calculation of the Decision Threshold
CT ms

2 and the Detection Limit
a1
þ $uðmT Þ2 þ ð
tT1 a1 Þ2 $uðlT Þ2 a. Decision Threshold
mT
In accordance with ISO 11929 (2010), the decision threshold,
(6.54)
a*, is obtained from the following equation:
Combined uncertainty in the determination of the analyte on the
sampling date, u(a0), can be derived from the uncertainty on the a ¼ k1
a uð0Þ (6.64)
Chapter | 6 Alpha Spectrometry
where k1
a ¼ 1.65 is often chosen as default, and u(0) can be
calculated from eqns (6.54) and (6.57) by substituting the value
of r0 background instead of rg, the measured value of the ana-
lyte. The decision threshold is obtained as activity concentration
expressed in Bq kg
1.
b. Detection Limit
In accordance with ISO 11929 (2010), the detection limit, a#, is
calculated by iteration according to the following equation:
a# ¼ k1
a uð0Þ þ k1
b uða# Þ (6.65)
Assuming a ¼ b then k1
a ¼ k1
b ¼ k. The detection limit is
obtained as activity concentration expressed in Bq kg
1.
VII. QUALITY CONTROL
General requirements for the competence of testing and cali-
bration laboratories are summarized in the ISO/IEC 17025
(2005) standard. Here, we discuss specific issues of QC of alpha
spectrometers and validation of alpha-spectrometric methods.
A. Quality Control for Alpha Spectrometers
Instrument performance is regularly monitored by counting
check sources. The same alpha source containing at least two
alpha-emitting radionuclides can be used to check the energy,
the FWHM and the efficiency calibration of the detector/alpha
spectrometer. The check source is counted under fixed condi-
tions similar to those used for samples. The parameters char-
acterizing the stability of the system are the peak location, the
FWHM, and the counting efficiency of a selected radionuclide
present in the check source. The measured values are plotted in
a control chart as a function of counting date/time. Average
values and established control limits are also plotted in each
control chart. The 2s and 3s deviations from the mean values
are regarded as warning and control levels. When measured
values are out of the warning-level range, the instrument has to
be checked or repaired, and it may be that the detector has to be
replaced. If the measured values are out of the control limit
range, measurements are suspended until the spectrometer has
been repaired. The frequency of control measurements is
regulated in the Quality Manual of the laboratory but it is
desirable to perform QC measurements before each series of
analysis. Additionally, background measurements are per-
formed on a regular basis to check detector contamination.
As an example, the efficiency control chart of an alpha
spectrometer is shown in Fig. 6.39 together with the average
value of the measurements and the warning and control levels
that were established by the first seven data points.
B. Validation of the Procedure
Methods that have been developed at the laboratory, which are
nonstandard methods or amplifications and modifications of
standard methods, have to be validated to demonstrate that they
fit the purposes of application. According to the ISO/IEC 17025
(2005) standard, the techniques used for the determination of
415
Efficiency calibration of alpha spectrometer with
PIPS detector A-300-19-AM
0.009
0.008
Efficiency
0.007
0.006
1997/03/11 1999/12/06 2002/09/01 2005/05/28
Date
FIGURE 6.39 Control chart of an alpha spectrometer showing the efficiency
data and their uncertainty (1s) as well as the average values, warning levels
(2s deviation from the average), and control levels (3s deviation from the
average).
the performance of a method are one of, or a combination of, the
following:
1. calibration using reference standards or reference materials,
2. comparison of results achieved with other methods,
3. interlaboratory comparisons (intercomparison exercises or
proficiency tests),
4. systematic assessment of the factors influencing the result,
and
5. assessment of the uncertainty of the result based on scientific
understanding of the theoretical principles of the method
and practical experience.
Whenever standards and reference materials with known
concentrations of the analytes are available, it is recommended
that measurements be carried out using these materials. Refer-
ence materials are provided for a great variety of alpha-emitting
nuclides by the IAEA, IRMM, and NIST, among others. Results
obtained by alpha spectrometry can often be compared with
those obtained by other techniques such as mass spectrometry,
gamma spectrometry, and liquid scintillation counting.
Recently, an increasing number of interlaboratory comparisons
have been organized by national and international institutes, and
network laboratories (e.g. IAEA, 2010b).
Although systematic assessment of the factors influencing
the result (point 4 above), and evaluation of the uncertainty
components (point 5) are extremely important, method valida-
tion should not be based exclusively on one of these validation
techniques. It is desirable to apply e whenever it is possible e
the combination of the validation techniques (points 1e3). For
example, the recommended procedure of the IAEA for the
simultaneous determination of Pu and Am nuclides in envi-
ronmental samples was validated by preparing the uncertainty
budget, by the measurement of 6 different reference materials
by the proposed procedure, and by an interlaboratory compar-
ison with two participating expert laboratories. In the course of
the validation procedure, the performance parameters of the
method including accuracy, uncertainty, detection limit, range
of results, selectivity, linearity, repeatability and reproducibility,
and robustness against external influences or cross-sensitivity
against interferences have to be assessed (IAEA, 2012).
416
VIII. CONCLUSIONS
In recent years, the position of alpha spectrometry as the tech-
nique of choice when reliable isotopic analysis of very low-
activity levels is required has been challenged somewhat by
improvements in other radioanalytical techniques, especially
mass spectrometry. This is particularly the case for very long-
lived radionuclides such as 238U and 235U. However, for shorter-
lived alpha emitters such as 210Po, the sensitivity of alpha
spectrometry remains unchallenged due to a combination of low
background and high detection efficiency.
The need for sample digestion and lengthy chemical sepa-
rations remains the main drawback for standard alpha spec-
trometry analysis. The use of microwave digestion and the
development of methods for fusion of solid samples or copre-
cipitation from water are increasingly common approaches for
sample preparation and digestion. The development of methods
utilizing extraction chromatography is a major step forward for
chemical separation, particularly for actinides. Some progress
has also been made in automated chemical separations.
With increasing requirements on laboratories for traceability
of results and for accreditation, the existence of standard,
validated methods and of proficiency tests is becoming more
important. Several methods have been published by ASTM,
IAEA, and ISO, partially fulfilling this need. However, the large
matrix of analytes and sample types which can be analyzed by
alpha spectrometry means that a complete and up-to-date set of
such methods is unlikely to materialize, and laboratories will
continue to develop methods based on their specific needs.
A wide variety of proficiency tests and reference materials
would also be desirable for a similar reason.
The use of spectrum deconvolution software in conjunction
with high- and medium-resolution alpha spectrometry is
a promising tool to analyze overlapping peaks and alpha sources
of “poor quality.” Developments in spectrum evaluation can
help replace or at least simplify chemical sample processing and
the analysis of those nuclides whose spectra could not be
evaluated with conventional alpha spectrometry.
Despite the challenges, conventional alpha spectrometry
remains important as a workhorse for many standard applica-
tions, as an essential tool in a number of important specialist
applications, and as a reliable and high-sensitivity technique for
research and other investigative work.
TERMS AND DEFINITIONS, SYMBOLS
AND ABBREVIATIONS
CT the certified concentration of the tracer on the reference date [Bq g
1]
mT the mass of the tracer taken [g]
ms the mass of sample [L]
R the chemical recovery of the analyte
fT the correction factor for the decay of the tracer during elapsed time
[days] between the reference date of tracer and the beginning of the
measurement
lT the decay constant of the tracer [years
1]
lA the decay constant of the analyte [years
1]
tT the time interval between the reference date of the tracer and the
separation time [years]
Handbook of Radioactivity Analysis
a0 the activity concentration of the analyte on the sampling date [Bq kg
1]
a1 the activity concentration of the analyte at the separation time [Bq kg
1]
a* decision threshold [Bq kg
1]
a# detection limit [Bq kg
1]
t1 the time interval between the sampling date and the separation time
[year]
n and nT net counts in ROIs (region of interest) of analyte and tracer
[counts], respectively,
ng and ngT gross counts in ROIs (region of interest) of analyte and tracer
[counts], respectively,
n0, and n0T blank or background counts in ROIs (region of interest) of
analyte and tracer [counts], respectively,
r and rT net count rates in ROIs (regions of interest) of analyte and tracer
[counts], respectively,
rg and rgT gross count rates in ROIs (regions of interest) of analyte and
tracer [counts], respectively,
r0, and r0T blank or background count rates in ROIs (regions of interest) of
analyte and tracer [counts], respectively,
tm the sample counting time (sec)
t0 the counting time of blank (sec)
u(fT) the uncertainty of correction factor for decay of the tracer during
elapsed time [years] between the reference date of tracer and the
separation time
uc(a0) combined uncertainty of the activity concentration of the analyte on
sampling date [Bq kg
1]
u(lA) the uncertainty of the decay constant of the analyte [year
1]
u(CT) the uncertainty of the certified concentration of the tracer solution
according to the calibration [Bq g
1]
u(n), u(nT) the uncertainty of the net counts in the ROIs of the analyte and
the tracer, respectively
u(mT) the uncertainty of mass of the tracer [g]
u(ms) the uncertainty of mass of sample [kg]
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