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Page 1 of 49 Analytical Methods
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DOI: 10.1039/C6AY00920D
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3 1 Alpha-particle spectrometry for the determination of alpha emitting
4
5 2 isotopes in nuclear, environmental and biological samples: Past, Present
6 3 and Future
7
8 4 Suresh Kumar Aggarwal
9
10 5 Fuel Chemistry Division, Bhabha Atomic Research Centre, Trombay, Mumbai 400 085,
11
India
Analytical Methods Accepted Manuscript

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Published on 27 May 2016. Downloaded by University of Cambridge on 13/06/2016 16:07:43.
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13 7 Present Address: 1006, Sunflower, Neelkanth Gardens, Govandi-E, Mumbai 400 088, India
14 8 Email: skaggr2002@gmail.com
15
9
16
17 10
18 11 ABSTRACT
19
20 12
21 13 Alpha spectrometry (AS) is an important and useful radiometric analytical technique for the
22 14 qualitative identification and quantitative determination of α-emitting radionuclides in
23
24 15 environmental, biological and nuclear technology related samples. Isotope dilution alpha
25 16 spectrometry (IDAS), using a suitable tracer (spike), along with a suitable method of alpha
26 17 spectrum evaluation to account for the tail contribution due to energy degradation, provides
27
18 accurate data on the concentration because this approach eliminates uncertainties in chemical
28
29 19 yield in the elaborate sample preparation and purification steps. Non-isotopic tracers (N-
30 20 IDAS) can also be used for simultaneous determination of actinide isotopes. High resolution
31 21 alpha spectrometry with deconvolution algorithms can now resolve close lying α-energies of
32
33
22 radionuclide pairs e.g. (239Pu, 240Pu; 233U, 234U; 238Pu, 241Am etc.). Nuclear decay data on the
34 23 emission probabilities of different α-energies emitted by an α-emitter, and half-lives are being
35 24 constantly improved by detailed critical studies at various international laboratories. Nuclear
36 25 technology depends strongly on alpha spectrometry for precise and accurate data on 232U,
37 236
38 26 Pu, 238Pu and 241Am in different fuel samples. Alpha spectrometry is poised to play an
39 27 important role in the future decommissioning of aged reactors and nuclear waste disposal
40 28 programs, to determine long-lived radioactive nuclides. Fast and better source preparation
41
29 methods are in great demand to minimize the time to provide data on various nuclear forensic
42
43 30 samples and in emergency contamination situations. Semiconductor passivated and
44 31 implanted planar silicon (PIPS) detectors with active surface areas that range from 20 mm2 to
45 32 about 2000 mm2 are used for high and low-activity samples, respectively. Exotic detectors
46
47 33 based on cryogenic micro-calorimetry, magnetic calorimetry, and Q-value spectroscopy
48 34 (using super-conducting transition edge sensor) capable of giving energy resolution of 1-3
49 35 keV at 5.5 MeV are being developed. Enriched isotopes of actinides and reference materials
50
36 of known activity ratios are required by researchers world-wide. This review discusses recent
51
52 37 advances that have taken place in the last decade in the important metrological radiometric
53 38 technique of alpha spectrometry.
54 39
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40 Keywords: Alpha spectrometry, silicon detector, source preparation, spectrum evaluation,
57 41 emission probability, half-life, radionuclide, tracer, nuclear spectroscopy.
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3 42 1. Introduction
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5
6 43 Alpha-particle spectrometry (AS) is an important analytical technique for the
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8 44 determination of trans-actinium and other α-particle emitting radionuclides, with high
9
10 45 sensitivity in the nuclear, environmental and biological samples.1-8 This radiometric
11

12 46 technique is based on the characteristic α-particle energy of each α-emitting radionuclide, and
13
14
47 thus can be used for the qualitative and quantitative analysis of different α-emitting
15
16
17 48 radioactive isotopes of an element. Unique features of AS compared to other radiometric
18
19 49 techniques like γ-ray spectrometry are very low background, and no variation in the detector
20
21 50 efficiency with energy (4 MeV to 9 MeV) because of the short range of α-particles. This
22
23 51 independence of efficiency with energy (i.e., intrinsic efficiency of one) allows the accurate
24
25
26 52 determination of alpha activity ratios without the need of a standard for efficiency calibration.
27
28 53 Additionally, the instrumentation is relatively less expensive compared to other techniques
29
30 54 like mass spectrometry, e.g. thermal ionization mass spectrometry (TIMS), inductively
31
32 55 coupled plasma source mass spectrometry (ICPMS), etc. However, as will be discussed
33
34
56 below, AS depends upon radiochemical separation, the preparation of a thin, weightless and
35
36
37 57 uniform source on a suitable backing material, and requires a suitable algorithm to account
38
39 58 for the tail contribution at low energy peaks due to energy degradation of the high energy
40
41 59 peaks. Additionally, there is a problem of contamination of the semi-conductor detector with
42
43 60 the recoil nuclides (particularly in the case of 232
U, 233
U, and their daughter products). Also
44
45
46 61 the coincidence of α-particles with conversion electrons and photons must be minimized for
47
48 62 accurate determination of α-particle emission probabilities (Pα) of an α-emitter and for
49
50 63 activity ratio determination.
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52 64 The accurate detection of α-particle energies is a valuable analytical tool in the
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54
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65 discovery of heavier actinide elements. Characterization of a few atoms of a new actinide
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3 66 element is usually done by following the decay systematic with α-particle energies of the
4
5 67 daughters produced.
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68 A number of reviews have been published at various times by researchers about
8
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10 69 source preparation, de-convolution algorithms, and applications of α-spectrometry9-16.
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However, there is no review available that deals with all these topics. The present review is
12 70
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14 71 written with the objective to summarize the role of AS in nuclear, environmental and
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16 72 biological sciences. The limitations and hurdles faced by researchers with AS for various
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19 73 applications are highlighted. Additionally, the latest developments which have taken place in
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21 74 the last decade in AS detectors, de-convolution algorithms and analytical methodology, at
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23 75 various laboratories, are also discussed.
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25 76
26
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28 77 2. Principle and Instrumentation
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30 78 Alpha spectrometry involves the qualitative detection and quantitative determination
31
32 79 of peak areas of α-energy peaks in the recorded α-spectrum. Table 1 gives a list of the various
33
34
80 α-emitting radionuclides that are of interest in various samples. Instrumentation for α-
35
36
37 81 spectrometry is relatively simple, and generally consists of a semi-conductor silicon detector
38
39 82 (surface barrier or ion-implanted), a charge-sensitive pre-amplifier, a linear amplifier, and a
40
41 83 multi-channel analyser (MCA) or a personal computer (PC) with a suitable interface card for
42
43 84 data acquisition and processing. The source deposited with α-emitter is placed at the bottom,
44
45
46 85 with detector mounted at the top end. Both the source and the detector are mounted in a
47
48 86 vacuum chamber which is evacuated to a pressure of 10-2 to 10-3 torr with a rotary pump. A
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50 87 voltage of about 100 V (+ve or –ve that depends upon the detector type) is generally applied
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52 88 to the detector from a stable power supply. The source to detector distance should be at least
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89 equal to or more than two times the diameter of the detector to get an optimum system
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57 90 resolution. For the environmental samples, the source is kept very close to the detector to
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3 91 achieve high efficiency so as to reduce the α-spectrum recording time, and to minimize the
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5 92 random uncertainty due to counting statistics. These aspects are discussed in detail below.
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7
93 2.1. α-Source preparation methods
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9
10 94 The preparation of a good quality α-source which should be thin, weightless, uniform,
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and homogenous on a suitable flat and smooth substrate is one of the most important pre-
12 95
13
14 96 requisites to obtain a good quality α-spectrum with high resolution, and a small low energy
15
16 97 tail contribution. The smooth surface is essential so that the alpha particles do not lose energy
17
18
19 98 due to crevices or roughness of the backing surface. Different substrates, e.g. electro-
20
21 99 polished stainless steel (SS), platinum (Pt), tantalum (Ta), nickel (Ni), aluminium (Al), etc.
22
23 100 can be employed. Amongst these, electro-polished SS with mirror finish is used routinely
24
25 101 because it is cheap and is easily available. Ta is used in the case of HCl solutions, and Pt is
26
27
102 generally preferred when a high resolution is required. The yield of source preparation
28
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30 103 method should be high to minimize the loss/wastage of the radioactive actinide element,
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32 104 particularly in the case of enriched isotopes used to prepare sources for determination of
33
34 105 emission probabilities, and for various nuclear physics experiments. Additionally, the method
35
36 106 should not lead to preferential deposition of an actinide element from a mixture of actinides.
37
38
39 107 Different methods of α-source preparation include (i) electrodeposition (ED) in aqueous or
40
41 108 organic medium, (ii) vacuum sublimation, (iii) drop-deposition DD (also referred to as direct
42
43 109 evaporation or stippling) with or without a spreading agent like tetra ethylene glycol (TEG),
44
45 110 and, (iv) precipitation. Other methods used are self-deposition or auto-deposition (for
46
47
111 polonium), and electro-spraying. A number of reviews and several reports are available in
48
49
50 112 literature about the various source preparation methodologies17-36 .
51
52 113 Amongst the various source preparation methods mentioned above, DD from aqueous
53
54 114 solution (e.g., HNO3) is the simplest and the easiest method but gives a poor resolution, and a
55
56 115 large low energy tail contribution. DD method is generally used for qualitative and semi-
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3 116 quantitative analysis of the α-emitting nuclides. The use of a spreading agent e.g., TEG is
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5 117 recommended in DD to improve the source uniformity and quality of the α-spectrum, but
6
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118 evaporation of the solution along with the spreading agent, under a heat lamp (e.g. an infra-
8
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10 119 red lamp) takes a few hours to dry-up 26-29. The DD method is the only choice when working
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with two or more actinide elements present in a mixture e.g., in the case of non-isotopic
12 120
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14 121 dilution alpha spectrometry (N-IDAS)37,38. One serious limitation of the DD method is that it
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16 122 leads to non-uniform source because of clumping around individual particles or accumulation
17
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19 123 of the solid at the periphery. This non-uniform distribution was observed in studies with N-
20
21 124 IDAS based on the use of 233U as a non-isotopic tracer for the simultaneous determination of
22
23 125 Pu, Am and Cm. However, Pu sources prepared by extraction of Pu(IV) into thenoyl
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25 126 trifluoroacetone (TTA) in benzene, and direct transfer of the organic solution containing Pu-
26
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127 TTA complex onto the disk was shown to give good quality sources comparable to those
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30 128 obtained by electrodeposition35.
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32 129 Vacuum sublimation approach produces the best quality sources, which is a must for
33
34 130 the nuclear data measurements e.g., the emission probabilities of various α-energies of an
35
36 131 isotope. However, the method requires an elaborate set-up, and gives poor deposition yield.
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39 132 This vacuum sublimation method has been used to prepare excellent quality sources of pure
40
41 133 enriched radioactive isotopes for nuclear data measurements. Recently, the method was
42
235
43 134 employed to prepare highly enriched U (> 99.9%) targets (areal density 600 µg.cm-2) by
44
45 135 vacuum sublimation of UF4 from a resistance heated Ta crucible on Al backing, required for
46
47
136 neutron fluence measurements in nuclear reactors39.
48
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50 137 Electrodeposition from aqueous (e.g., dil. HNO3 ) or organic medium (e.g., isopropyl
51
52 138 alcohol) is commonly used for the assay of actinides in samples from different stages of the
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54 139 nuclear fuel cycle, as well as for the environmental and biological samples. Actinides are
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56 140 deposited as hydrated oxides in aqueous medium in contrast to molecular plating in the
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3 141 organic medium. ED is vulnerable to co-deposition of other elements e.g., Fe and is,
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5 142 therefore, generally preceded by separation and purification of the actinide element with
6
7
143 solvent extraction, ion exchange or extraction chromatography to obtain the actinide element
8
9
10 144 in pure chemical and radiochemical form. The details of the ED methods are given in various
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reviews. ED requires detailed investigations to optimize the different parameters e.g., volume
12 145
13
14 146 of solution in the cell, current density, voltage, distance between the cathode and anode,
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16 147 shape of the anode, etc. to obtain a high deposition yield, and thin uniform deposit. Also,
17
18
19 148 selection a suitable aqueous medium is mandatory for this purpose. Various electrolytes, e.g.
20
21 149 (NH4)2SO4, NH4NO3, NH4Cl, (NH4)2C2O4, ammonium formate, and their mixtures have been
22
23 150 used by researchers for ED of different actinides, at sub-µg to milligram levels32-34. An
24
25 151 evaluation of electrodeposition procedure with a current of 500 mA, and different electrolytes
26
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152 (e.g. ammonium chloride, ammonium sulphate, sulphuric acid and ammonium oxalate) for U,
28
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30 153 Pu and Am showed ammonium oxalate to be the best among these from the point of view of
31
32 154 deposition yield, temperature rise, and attack on the stainless steel disk30. Table 2 summarizes
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34 155 some of the electrodeposition procedures used.
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36 156 Co-precipitation with NdF3, CeF326 is quite popular for the assay of actinides, present
37
38
39 157 at mBq.L-1 amounts, in the biological and environmental samples. This method is generally
40
41 158 preceded by separation and purification of the actinide element with extraction
42
43 159 chromatography16, and is time-consuming.
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45 160 Thick sources are required, in the case of U, because of long half-lives of the naturally
46
47
161 occurring U isotopes, for nuclear physics, and other nuclear data measurements experiments.
48
49
50 162 In such cases, the adherence and homogeneous distribution of the deposit must be checked
51
52 163 and ensured. Several researchers have reported these investigations 32,33. A detailed study was
53
54 164 recently performed on the preparation of thick U targets (1.5 mg/cm2) by electrodeposition,
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56 165 employing SS and Al as the backing material in aqueous [5.7 % (NH4)2C2O4 in 0.3 M HCl],
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3 166 and organic media [(CH3)2CHOH isopropanol]32. The sources were heated to 100oC after
4
5 167 washing and drying to obtain good adherence of the U deposit. Quality of the sources was
6
7 109
168 checked by α-autoradiography, Cd radioisotope excited energy dispersive X-ray
8
9
10 169 fluorescence (EDXRF), scanning electron microscopy (SEM), and low energy tail in alpha
11

spectrometry. Homogeneous uniform distribution and cracks were observed in all the
12 170
13
14 171 sources. Platinum anode was partly dissolved, observed by Pt on the alpha source, by ED in
15
16 172 the ammonium oxalate medium on SS backing. The best sources were obtained with
17
18
19 173 ammonium oxalate on SS (1.5 mg.cm-2), and isopropyl alcohol on Al (0.6 mg.cm-2).
20
21 174 Adsorption of Ra onto MnO2 coated disks was used for pre-concentration of Ra from
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23 175 water samples, followed by source preparation40. The disks (35 mm diameter) were prepared
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25 176 on a polyvinyl polymer based substrate washed with ethanol, HCl, and isopropyl alcohol, and
26
27
177 immersing the substrate with stirring in a KMnO4 solution at 70oC for two hours. The MnO2
28
29
30 178 coated disks were washed with distilled water, dried in air, and dipped in the Ra containing
31
32 179 solution for Ra adsorption. A pH of 7.5 was maintained for the solution, and quantitative
33
34 180 adsorption of Ra was obtained in 24 hr from water samples. The disks were washed with
35
36 181 water, dried at room temperature and used for alpha spectrometric analysis. Resolution of 23
37
38
39 182 keV (FWHM) at 4.82 MeV, with a detector of 1200 mm2 , was obtained in these studies.
40
41 183 There is a need to develop rapid methods of good quality source preparation for
42
43 184 nuclear forensic, and in emergency contamination situations. A number of studies were
44
45 185 performed in the recent years to combine the separation, purification, and source preparation
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47
186 steps, and at the same time, meet the requirement of rapid analysis. Recently, spin-casting of
48
49
50 187 solutions of various complexes onto glass substrates was employed to prepare thin films.41
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52 188 The Kläui-type tripodal oxygen donor ligand, i.e. ethyl-substituted complex
53
54 189 Na[Cp*Co(P(O)(OEt)2)3] with cyclopentadienyl dialkylphosphito-cobalt framework, in 2mM
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56 190 toluene was observed to bind 80 to 88% of dissolved Pu under equilibrium conditions. The
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3 191 film (10 nm thick) of the complex was cast by spinning at 800 rpm for 10 s first, and then at
4
5 242
192 3600 rpm for 30 s. Pu spike (70 mBq) was added to the dissolved soil sample
6
7
193 (contaminated Rocky Flats soil, NIST SRM 4353A), and purification of Pu was done with
8
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10 194 LaF3 co-precipitation followed by anion exchange separation. Pu(IV) solution in 0.1 M
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HNO3 was added onto the film, and was allowed to equilibrate for 30 min. A resolution of 33
12 195
13
14 196 keV (FWHM) was achieved with 300 mm2 Si detector, and distance of 5 mm between the
15
16 197 sample and the detector. The results obtained on the determination of Pu (16±0.7) mBq.g-1 in
17
18
19 198 the environmental soil sample agreed with the certified value (16.8±1.8) mBq.g-1. A nuclear
20
21 199 glass debris sample was also tried successfully for Pu determination with this method.
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23 200 Studies were reported for the preparation of polymer ligand film (PLF) for Pu
24
25 201 determination by incorporation of di(2-ethylhexyl) phosphoric acid (HDEHP) ligand into
26
27
202 polystyrene film with ligand to polymer ratio of 1:5 for optimum recovery and spectrum
28
29
30 203 resolution42 . The PLFs were characterized by scanning electron microscopy for surface
31
32 204 defect, and alpha auto-radiography for Pu distribution. Hot spots were observed in the film
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34 205 with Pu concentrated along the edges and in the centre. This non-uniform distribution would
35
36 206 lead to errors in the determination, due to self-absorption effects or changes in the efficiency
37
38
39 207 calibration, in the absence of tracer or spike. The addition of a tracer for the actinide element
40
41 208 of interest would, however, eliminate uncertainties due to these artefacts.
42
43
44 209 A thin phosphate–sulfate bifunctional polymer layer anchored on the surface of
45
46 210 microporous poly(ethersulfone) (PES) membrane (0.1 to 0.2 µm pore size) by UV induced
47
48 211 surface grafting was developed for the determination of Pu in nuclear fuel samples43,44. The
49
50
51
212 polymerizing mixture consisting of a saturated solution of pure HEMP (phosphoric acid 2-
52
53 213 hydroxyethyl methacrylate ester) and AMPS (2-acrylamido-2-methyl-1-propane sulphonic
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55 214 acid) in 1:1 mol proportion was dissolved in water, homogenized with ultrasonication, and
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57 215 was poured onto unprotected surface (glossy). This surface was immediately subjected to
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3 216 photo-irradiation with 365 nm UV light in a photo-reactor for 15 min. The tape from
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5 217 membrane pieces was removed, washed thoroughly with methanol and water to remove
6
7
218 ungrafted monomers, dried under vacuum, and hydrated with deionized water. The optimum
8
9
10 219 thickness, physical and chemical structures of the bifunctional layer were studied with
11

secondary ionization mass spectrometry (SIMS), SEM, and SEM–EDS (energy-dispersive
12 220
13
14 221 spectroscopy). The optimized membrane was used for the pre-concentration of Pu(IV) from
15
16 222 aqueous solutions (3–4 M HNO3), followed by direct alpha spectrometric analysis of the
17
18
19 223 membrane. A recovery efficiency of (86±3%) was obtained for Pu(IV). Experiments
20
21 224 conducted with single actinide element indicated no significant sorption of Am(III) (about
22
23 225 7%), but appreciable sorption of U(VI) (78±3%). The quality of α-spectra recorded were
24
25 226 comparable (FWHM of 18-23 keV at 5.50 MeV) to those from drop deposited sources
26
27
227 (FWHM of 17-20 keV at 5.50 MeV) with 450 mm2 PIPS detector. The relatively large low-
28
29 238
30 228 energy tail contribution of about 5% per unit Pu/(239Pu+240Pu) α-activity ratio was
31
32 229 corrected for by the G.P. method, and the Pu concentration values obtained by mem-IDAS
33
34 230 (membrane based-IDAS) were in good agreement with the conventional approach of IDAS
35
36 231 and IDMS.
37
38
39 232 An exotic approach based on the use of an inductively coupled plasma source mass
40 241
41 233 spectrometer (ICPMS) was recently adopted to prepare Am sources for high resolution
42
43 234 alpha spectrometry36. The secondary electron multiplier detector in the quadrupole based
44
45 235 ICPMS was replaced with a block having a stainless steel disc mounted for collection of the
46
47
236 isotope. ICPMS can be used to prepare isotopic pure sources because it reduces the other
48
49
50 237 adjacent α-emitting isotopes by mass separation in the analyser of the mass spectrometer, and
51
52 238 the implant process leads to an atomic scale coating to produce a thin and homogeneous
53
54 239 source.
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3 240 To improve the source quality for the determination of radioactive impurities in high
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5 240
241 purity Pu, a drop of diluted Ludox colloidal silica as seeding agent mixed with diluted
6
7
242 Tween20 as wetting agent was deposited in the centre of the disk, and was air dried prior to
8
9
10 243 the radioactive solution deposition. The sources were dried using hot nitrogen jets to
11

accelerate the evaporation and minimize the growth of large crystals. The sources were
12 244
13
14 245 covered by a thin VYNS foil, immediately after drying to avoid the loss of radioactive
15
16 246 material.45
17
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247
19
20
248 2.2. Detectors for α-spectrometry
21
22
23 249 Magnetic spectrographs were used in the past to determine the emission probabilities
24
25 250 of different α-particles. However, these systems had the drawback of poor transmission, and
26
27 251 thus required long spectra-recording times. Gridded ionization chambers with energy
28
29 252 resolution of about 30 keV (FWHM) at 5.5 MeV were more commonly used for α-
30
31
32
253 spectrometry in the past. Presently, silicon surface-barrier (SSB) and passivated implanted
33
34 254 planar silicon (PIPS) detectors are commonly employed for α-spectrometry. PIPS detectors
35
36 255 are quite popular these days because of their smaller leakage currents, and thin dead layers
37
38 256 which help to improve the detector resolution46. Detectors with sensitive area of 20 mm2 to
39
40
257 more than 2000 mm2 are available (Table 3), and can be selected based on the experimental
41
42
43 258 requirements. For traditional-high resolution alpha spectrometry (T-HRAS) work, small area
44
45 259 detectors are preferred in contrast to the environmental samples that necessitate the use of
46
47 260 large area detectors because of high efficiency requirement. These PIPS detectors have a very
48
49 261 low background (< 0.1 mBq) in the energy region of interest (4 to 9 MeV), and unlike the γ-
50
51
52
262 spectrometry systems, the detector efficiency does not vary with energy in this energy region.
53
54 263 Energy calibration of the system can be done with an α-source emitting α-particles with two
55
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56 264 distinct energies. A combined source of Gd (T1/2= 74.6 yr, Eα=3.182 MeV, 100%) and
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3 265 Cm, with an energy range of about 3 MeV, was prepared by electrodeposition for
4
5 266 calibrating α-specrometry system over a period of 50 years with no difficulties that arise from
6
7
267 recoil build-up or source degradation.47
8
9
10 268 Contamination of these semi-conductor detectors by recoil nuclei is one of the
11

common problems, particularly in cases when the daughter nuclide is also an α-emitter (e.g.
12 269
13
228
14 270 Th, 229Th, 232U, 233U, etc.). This contamination arises, because the emission of an α-particle
15
16 271 with 5 MeV energy results in recoil of the residual nucleus with a recoil energy of about
17
18
19 272 100 keV. This recoil energy is sufficient for the daughter atoms to get separated from the
20
21 273 source, and attach to the detector and walls of the vacuum chamber. This recoil
22
23 274 contamination can be mitigated either with control of the source-detector chamber pressure48,
24
25 275 or by introduction of a film between the source and the detector40 . It was shown49 that this
26
27
276 recoil contamination can be reduced by a factor of 1000 by raising the air pressure to 12
28
29
30 277 µg.cm-2 in the vacuum chamber, and with the application of a negative voltage (-6V) to the
31
32 278 source plate to collect the positively charged daughter nuclei stopped by air. The use of a
33
34 279 stopper foil is attractive for α-spectrometry systems not equipped with air-recoil suppression
35
36 280 system. The procedure to use a stopper foil degrades the resolution that depends upon the
37
38
39 281 thickness of the foil. However, the source can be kept quite close to the detector, and this
40
41 282 short distance between the source and the detector is an advantage in terms of higher
42
43 283 efficiency, particularly for environmental samples. Coating with a thin film of Mylar of 0.25
44
45 284 mg.cm-2 (metalized film made of polyester or polycarbonate coated with aluminium) was
46
47
285 shown to alleviate the contamination problem with recoil nuclei, and also in the case of 210Po,
48
49
50 286 with no significant change in FWHM of the alpha spectra50. Disposable thin collodion
51
52 287 (cellulose nitrate) films were used as catchers to stop the recoil contamination of the
53
54 288 detector51, for sources prepared by electrodeposition as well as by co-precipitation. Thin
55
56 289 formvar film (polyvinyl formaldehyde) was used as a stopper foil in the determination of
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3 290 Ra in water samples by α-spectrometry40. Because of the shift in the pulse height of the
4
5 291 spectrum from a source coated or covered with a foil, the energy calibration must be done
6
7
292 with the standard source of the same type.
8
9
10 293 One of the problems in recording α-spectra with PIPS detectors is the true
11

coincidences between the α-particles and conversion electrons/X-rays from the gamma
12 294
13
14 295 transition depopulating the levels fed by the α-decay52. This coincidence effect is totally
15
16 296 absent in a magnetic spectrograph due to a very low magnetic rigidity (1000 times less) of
17
18
19 297 conversion electrons of keV energy compared to that of α-particles of MeV energy. This
20
21 298 coincidence summing effect in PIPS detectors must be minimized for accurate determination
22
23 299 of emission probabilities of α-particles of various nuclides. This is because the summing
24
25 300 effect leads to increased tail-effect which distorts the spectrum enhancing the summing-in
26
27
301 and summing-out effects. For example, in an α-spectrum with the two main α-energies α0 and
28
29
30 302 α1 (energy of α0 > energy of α1), and a conversion electron CE of energy CEe, the coincident
31
32 303 summing of Eα1 and CEe will lift the tail of Eα0.. This summing effect will, therefore, reduce
33
34 304 the true counts of Eα1 under its own peak. One of the ways to mitigate this effect is to
35
36 305 increase the distance between the source and the detector and thus reduce the solid angle.
37
38
39 306 However, this is not possible always, particularly in the environmental samples where the
40
41 307 source must be kept close to the detector to reduce the uncertainty from counting statistics.
42
43 308 Another way to account for the coincidence summing effect is with the use of a magnetic
44
45 309 field to deflect away the electrons.53,54 A magnetic field of about 0.2T was used with a
46
47
310 distance of 16 mm between the poles. In addition, to reduce the scattered electrons from
48
49
50 311 entering the detector, a collimator that consisted of three tantalum diaphragms (0.1 mm thick
51
52 312 with 9 mm diameter opening), was kept in the magnetic field at a position coaxial with the
53
54 313 source and detector.
55
56
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2
3 314 Two permanent magnets (nickel-coated Nd2Fe14B magnets with maximum field
4
5 315 strength of 460 mT), mounted in parallel were used to create a quasi-uniform magnetic field,
6
7
316 and the distance between the two magnets was larger than the diameter of the source. It was
8
9
10 317 shown that 93% of the conversion electrons with energies upto 85 keV were rejected with
11
magnets separated by 36 mm54. This approach was found to be superior to previous method

12 318
13
14 319 of repeated measurements at different distances followed by extrapolation to infinite distance.
15
16
17 320 A massive bolometer (760 g of TeO2 as energy absorber) was shown to give an
18
19 321 average energy resolution of (4.2±0.3) keV (FWHM) for 5.407 MeV α-particles from 210
Po,
20
21
22 322 in an underground nuclear physics experiment at Gran Sasso Underground Laboratory in
23
24 323 Italy55. A resolution of 5.5 keV (FWHM) at 5.5 MeV was reported with a bolometer (high purity
25
26 324 Cu on Ge) operated at 20 mK.56
27
28
29 325 A cryogenic micro-calorimeter based α-spectrometry system, operated at 140 mK,
30
31 326 with an energy resolution of 1.06±0.04 keV (FWHM) at 5.3 MeV was developed to resolve
32
33 239 240 238 241
327 close-lying α-particle energies of Pu, Pu and Pu, Am57. The system consists of a
34
35
36 328 thermometer which is a superconducting transition-edge sensor (TES) made of a thin-film
37
38 329 bilayer of Mo and Cu; an absorber (bulk superconducting Sn with low heat capacity) to
39
40 330 convert α-particle kinetic energy into thermal excitations, and a thermal weak link between
41
42 331 them and a temperature bath.
43
44
45 332 Detection of 5.5 MeV α-particles with a Au:Er (0.3% Er) magnetic calorimeter was
46
47
48 333 reported.58 The device is based on measurement of change in the magnetic moment, with a
49
50 334 superconducting quantum interference device (SQUID), because of change in temperature
51
52 335 caused by the absorption of particle energy. A cryogenic detector composed of a meander-
53
54 336 type metallic magnetic calorimeter (MMC) that uses a paramagnetic material (gold doped
55
56
337 with erbium, Au:Er) as a temperature sensor, and a gold-foil absorber was developed for high
57
58
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2
3 338 resolution α-spectrometry (HRAS). An energy resolution of 3.2 keV (FWHM) at 5.50 MeV
4
5 339 was achieved at a temperature of 40 mK with this detector59. Recently, Q-value spectroscopy
6
7
340 with a super-conducting TES with an attached gold foil to absorb the radiation, drop
8
9
10 341 evaporated sources on gold foil, and mechanical kneading of the absorber (radioactive
11
deposit) was shown to give a resolution of 1 keV (FWHM) at 5.5 MeV60. 240
Pu/239Pu atom

12 342
13
14 343 ratios determined by the Q-value spectroscopy agreed well with those obtained with thermal
15
16 344 ionization mass spectrometry (TIMS). However, these are highly specialized systems, and
17
18
19 345 have not been used for routine α-spectrometry measurements.
20
21 346
22
23 347 3. α-Spectrum Evaluation
24
25
26 348 The response of a silicon detector to alpha particle energy deposition is not Gaussian
27
28 349 because a part of the energy is lost to nuclear collisions which do not create electron-hole
29
30 350 pairs. This leads to a low energy tail on the alpha peak. The extent of peak tailing will depend
31
32 351 on a number of factors including active area (size) of the detector, energy difference between
33
34
352 the peaks, activity ratio of high energy to low energy peak, source to detector distance (SDD),
35
36
37 353 detector collimation, source and detector chamber pressure, peak analysis window size, and
38
39 354 source deposit thickness48. It is advisable to use a logarithmic vertical scale in plots of α-
40
41 355 spectra to show small peaks and the low-energy tail. This low energy tail contribution can
42
43 356 generally be described by an exponential function. In some cases (e.g. 241
Am, 212Po, 213Po), a
44
45
46 357 high energy tail is also seen and this tail is due to summing/coincidence of α-particles and
47
48 358 conversions electrons/photons/β- particles61. Several inter-laboratory, inter-comparison
49
50 359 experiments were also conducted in the past to examine the alpha-spectra evaluation
51
52 360 procedures.62-66
53
54
55
361 The α-spectrum evaluation can be divided into three different topics i.e., (i)
56
57 362 calculation of peak areas to determine α-activity ratios of different α-emitting nuclides e.g.,
58
59
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2
238
3 363 Pu/(239Pu+240Pu), 243Am/241Am, 234U/238U etc., referred to as simple alpha spectrometry (S-
4
5 364 AS) in this manuscript, (ii) traditional high resolution alpha spectrometry (T-HRAS) to
6
7
365 resolve close lying α-energy peaks e.g., 239Pu and 240Pu, 233U and 234U, 238Pu and 241Am, etc.,
8
9
10 366 and (iii) ultra high resolution alpha spectrometry (U-HRAS) to determine the emission
11
240 241

probabilities of various α-particle energies of a single radioactive nuclide e.g., Pu, Am,
12 367
13
14 238 67-79
368 U, etc. A number of computer algorithms have been developed in the past , and the
15
16 369 choice of a particular algorithm is governed by the application of the data and the counting
17
18
19 370 statistics of the alpha spectra. For example, in the case of environmental and biological
20
21 371 samples, with α-spectra of low (poor) statistics, deconvolution of peaks is not needed
22
23 372 because an accurate determination of peak areas is of paramount importance.
24
25 373 The peak areas are calculated with regions of interest (ROIs) option in the software,
26
27
374 and by application of a suitable α-spectrum evaluation procedure either (i) to account for the
28
29
30 375 tail contribution at low energy peak due to energy degradation of high energy peak, or (ii) to
31
32 376 deconvolute partly resolved or unresolved α-energy peaks with a suitable algorithm. The first
33
34 377 option is used when quantitative determination of an α-emitting radionuclide is required with
35
36 378 or without the use of a tracer. Simple and easy to adopt procedures (e.g., geometric
37
38
39 379 progression (G.P.) decrease of the tail) are available for this purpose80. The second option of
40
41 380 deconvolution for high resolution alpha spectrometry (HRAS) or for Pα determination
42
43 381 requires relatively complex and sophisticated software for accurate analysis. A number of
44
45 382 researchers have developed and used various computer programs to fulfil this objective67-79.
46
47
383 Many of these involve peak shape parameter and a Gaussian fitting for the α-peak in addition
48
49
50 384 to 2 or 3 exponential functions for the low energy tail.
51
52 385 The S-AS does not need deconvolution of the α-energy groups, but requires
53
54 386 accounting of the low-energy tail from the energy degradation of high energy peak in the α-
55
56 387 spectrum. Two inter-laboratory, inter-comparison experiments ASET-7462 and AS-7663 were
57
58
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2
3 388 organized by Karlsruhe Centre, Germany in 1974 and 1976, respectively, for the evaluation
4
238
5 389 and determination of Pu/(239Pu+240Pu) α-activity ratios. In our laboratory at Trombay,
6
7
390 India, a simple approach based on the geometric progression (G.P.) decrease of the counts in
8
9
10 391 the far tail of the spectrum was shown to provide precision and accuracy of 0.5%, with silicon
11
238
Pu/(239Pu+240Pu) alpha activity ratios for

surface barrier detector, in the determination of
12 392
13
238
14 393 the determination of Pu, and Pu concentration with IDAS80,81. Synthetic mixtures with
15
16 394 known α-activity ratios (range 0.1 to 10) were used to evaluate the precision and accuracy
17
18
19 395 achievable with the G.P. method80. The success of this α-spectrum evaluation method led to
20 238
21 396 the development of IDAS with Pu spike, and R-IDAS (reverse-isotope dilution alpha
22
239
23 397 spectrometry) with Pu spike, for the determination of Pu concentration in Pu samples of
24
25 398 low and high burn-up, respectively81. This G.P. method of α-spectrum evaluation is very
26
27
399 simple, and it involves the selection of four regions in the α-spectrum and the total peak areas
28
29
30 400 in these regions by using region-of-interest (ROI) facility. This program was also employed
31
32 401 in the Safeguards Analytical Laboratory (SAL) of IAEA at Seibersdorf, Vienna in the
33
34 402 determination of 238Pu/(239Pu+240Pu) α-activity ratios. The IDAS and R-IDAS methodologies
35
36 403 are useful alternatives to those laboratories which do not have access to expensive mass
37
38 242
39 404 spectrometers, and Pu tracer used for isotope dilution mass spectrometry (IDMS). The
40
41 405 methodology was also used for mixtures of other actinide elements/isotopes, including the
42
233
43 406 development of non-isotopic dilution alpha spectrometry (N-IDAS). U has been
44
45 407 demonstrated as a useful tracer for N-IDAS for the determination of Pu, Am and Cm
46
47
408 isotopes, with drop-deposited sources37,38. The problem of non-homogeneity in the activity
48
49
50 409 distribution in N-IDAS, observed by the measurement of α-activity ratios from the centre and
51
52 410 periphery of the deposit, was mitigated with the use of a large area (450 mm2) PIPS detector.
53
54 411 An iterative Monte Carlo simulation with spectral fitting (AASIFIT) was shown to be useful
55
56
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2
3 412 to determine activity ratios from strongly overlapping asymmetric peaks of environmental
4
5 413 samples such as non-processed aerosol filters.79
6
7
414 T-HRAS involves the deconvolution of close-lying α-particle energies of one or more
8
9 239 240 241 238 233 234 243 244
10 415 radioactive isotopes e.g. Pu and Pu, Am and Pu, U and U, Cm and Cm.
11

Several computer algorithms were developed and published to resolve these close-lying α-
12 416
13
14 417 particle energy groups. Most of these involve fitting the high energy side of the peak to a
15
16 418 Gaussian function, and one or more exponential functions (weighted or otherwise) for the tail
17
18
19 419 portion. Quadratic tail functions and non-linear least squares fits were also used for the tail
20
21 420 function. An intercomparsion of the four commercially available softwares i.e., Alphavision,
22
23 421 ALPS, Genie-2000, and WinnerAlpha was organized in 1997 by IAEA by giving the various
24
241
25 422 reference α-spectra from sources of natural U, Pu isotope mixture, Am+243Am and
26
27 226
423 Ra+daughters, to the four participating laboratories (Austria, Netherlands, Spain and
28
29
30 424 U.K.). The results published64-66 showed that three of the four software are able to resolve
31
32 425 different alpha energy peaks. A need to further improve the software was expressed at that
33
34 426 time. The program WinALPHA76 which was made available by IAEA to all the international
35
36 427 laboratories world-wide, is quite popular these days and has been used to determine the
37
38
39 428 activity ratios of various close-lying α-emitting isotopes.
40
41 429 The U-HRAS demands a sophisticated computer algorithm, to determine accurately
42
43 430 the α-emission probabilities of different α-energies in any radionuclide. A number of
44
45 431 advanced programs are available in literature for this purpose, and these can also be used for
46
47
432 T-HRAS. ALFA software has been used quite successfully by a number of researchers until
48
49
50 433 recently70. A code “Colegram” was developed to analyse low statistics spectra, and did not
51
52 434 require any nuclear data library.74 The other programs include ADAM82 (Advanced
53
54 435 deconvolution of alpha multiplets), ALPACA (with low energy region reproduced by a
55
56 436 hyperbolic function), ALFITex code78, etc. Recently, a line model with up to 10 left-handed
57
58
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2
3 437 and 4 right-handed exponentials, with an option to reduce the number of exponential
4
5 438 functions, was demonstrated77 to be useful to determine alpha emission probabilities, to
6
7
439 determine alpha activity ratios, and to deconvolute the alpha peaks, even in thick sources.
8
9
10
440 Five different α-spectra evaluation methods were compared61 to determine
11

12 241
13 441 Am/243Am ratios from low-statistics spectra recorded from sources prepared by
14
15 442 electrodeposition (< 1 Bq/source) as well as by coprecipitation with NdF3 (activity < 4
16
241
17 443 Bq/source). Four gravimetrically prepared mixtures with Am/243Am α-activity ratios of
18
19 444 0.549, 1.008, 2.062 and 9.413 were used in these studies. The films (thickness 4 µg/cm2 to 12
20
21
22 445 µg/cm2) made from a mixture of collodion and iso-amylacetate were inserted between the
23
24 446 source and the detector to attenuate the α-particles. The detailed studies showed that the
25
241
26 447 degree of peak deformation and tailing govern the accuracy of the Am/243Am ratios
27
28 448 calculated by various algorithms.
29
30
449
31
32
33
34 450 4. Tracers in Alpha Spectrometry
35
36 451 Tracers are used in α-spectrometry as chemical yield monitors in the purification and
37
38 452 separation procedures used, to determine electrodeposition yield, and in isotope dilution
39
40
41 453 alpha spectrometry (IDAS) for concentration determination of various radionuclides. The
42
43 454 tracers are very important in quantitative analyses which involve elaborate separation and
44
45 455 purification procedures (e.g. in complex environmental and biological samples). Table 4
46
47 456 presents various tracers used for different actinides. An excellent discussion on the choice of
48
49
457 tracers for the determination of α-emitting actinide isotopes in marine samples is given by
50
51
52 458 Harvey and Lovett83. There are several criteria which need be satisfied in the selection of a
53
54 459 tracer, also known as a spike. The tracer should have the same chemical behaviour as the
55
56 460 radionuclide of interest. It is essential to ensure complete equilibration between the tracer and
57
58
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2
3 461 the determinant. The tracer should have a long half-life to eliminate frequent calibration or
4
5 462 purification from the progenies, and the α-energy of the tracer should preferably be lower
6
7
463 than that of the determinant so that over-spiking in unknown samples or with samples of very
8
9
10 464 low concentration of α-emitting isotope, does not introduce tail contribution due to energy
11

degradation at the peaks of determinant. At times, the selection of the tracer will also depend
12 465
13
14 466 upon its availability and the cost. Ideal tracers are rarely available for different radioactive
15
16 467 isotopes. As an example, 232
U is a commonly used tracer for the determination of naturally
17
18
19 468 occurring isotopes (234U, 235
U and 238
U) and also to determine 236
U in reactor-produced U.
20 228 230 232 228
21 469 Th is used as a tracer for the determination of Th and Th. In samples where Th is
22
229
23 470 also to be determined, alternative tracer Th is employed. For determination of Pu in
24
25 238 239 240
471 environmental samples, different nuclides of interest are Pu, Pu and Pu. The two
26
27 236 242
472 tracers used are Pu and Pu, with the latter offering the advantage of long half-life and
28
29 241 242 244 243
30 473 low α-energy. For Am and Cm, Cm determination, Am is popularly used as a
31
32 474 chemical yield monitor. Sometimes, due to the non-availability of ideal tracers (e.g. in the
33
34 475 case of Pu), 238Pu is also used as a tracer. However, this would not allow the determination of
35
36 476
238
Pu in the given sample from the same source, and an independent recording of the α-
37
38 238
39 477 spectrum from unspiked sample is required. Pu was demonstrated as a useful spike81 for
40
41 478 the determination of Pu concentration in dissolver solution of irradiated fuel of low burn-up
42
238
43 479 with Pu/(239Pu+240Pu) α-activity ratio of less than 0.1. For Pu samples with
44
238
45 480 Pu/(239Pu+240Pu) α-activity ratios higher than 0.1 as in the case of high burn-up samples,
46
47 239 233
481 Pu was demonstrated as a useful spike. Non-isotopic tracer (e.g. U in NIDAS) was also
48
49
50 482 used for the simultaneous determination of Pu, Am and Cm37. This necessitates the source
51
52 483 preparation by drop-deposition to eliminate the preferential deposition of any of the nuclides
53
54 484 in electrodeposition. In such cases, it is essential to ensure uniform distribution of various α-
55
56
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3 485 emitters on the source, or use a large area detector with a diameter more than the source
4
5 486 diameter.
6
7
487 An attempt was reported in literature84 to determine 238
Pu, 239
Pu, 240
Pu and 242
Pu
8
9
10 488 isotopes in gravimetrically prepared mixtures that contained 20 Bq of each of 238Pu and 242Pu,
11
239 240

with varying amounts of Pu and Pu. Pu was purified with extraction chromatography
12 489
13
14 490 using TEVA resin, and electrodeposited source were prepared on polished stainless steel
15
16 491 disks. The spectra were recorded at SDD of 9 mm and 48.5 mm ADAM (for peak shape) and
17
18
19 492 AASI (Advanced alpha spectrometric simulation for efficiency) programs were used for
20
21 493 spectra evaluation. The activities obtained for SDD of 9 mm and 48.5 mm were slightly
22
23 494 above and below, respectively, of the expected values. It was shown that the methodology
24
25 495 without tracers can be adopted successfully on non-processed samples (e.g. in the field
26
27
496 samples for nuclear forensics).
28
29
30 497
31
32 498 5. Applications of Alpha Spectrometry
33
34
35 499 5.1 Environmental Samples
36
37 500 AS is important for the determination of all anthropologically introduced α-
38
39 501 emitters in the environment85-89 (e.g., soil, vegetation, water, etc.) due to mining and
40
41
42
502 exploration, nuclear electricity production, nuclear fuel reprocessing, handling and storage of
43
44 503 nuclear wastes, unfortunate nuclear reactor accidents like Chernobyl (Russia) and Fukushima
45
46 504 (Japan), atmospheric weapon tests, and accident of satellite with nuclear power source of
47
48 238
505 Pu. As an example, determination of Ra in environmental samples (e.g. water) is important
49
50
506 in geographical regions with high concentrations of U and Th in soils and geological
51
52
53 507 deposits85-88. Additionally, because of the high solubility of Ra, it can be introduced into the
54
55 508 marine environment by phosphate industries, production water needed for extraction of
56
57 509 oil/gas, primary steel and iron industries, and ceramic industries90.
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2
3 510 Studies were reported91 for the effect of detector size (450 mm2 and 600 mm2), source
4
5 511 to detector distance (5 to 30 mm), activity (5.84 Bq to 2775 Bq), vaccum in the source and
6
7
512 the detector chamber (0.0098% to 3% of atmospheric pressure) with continuous pumping or
8
9
10 513 chamber hold mode (with pump electrically switched off) on the resolution, efficiency, tail
11

contribution, etc. for the analysis of environmental samples with alpha spectrometry. It was
12 514
13
14 515 observed that the pressure in the chamber is one of the important parameters in the
15
16 516 environmental samples because the samples must be counted for a number of days in view of
17
18
19 517 the low activity on the α-source. The results obtained in an IAEA inter-comparison
20
21 518 experiment for the determination of 239Pu, 238Pu, 234U and 238U in spinach powder, with 236Pu
22
232
23 519 and U as tracers showed that there was no significant difference in the data obtained for
24
25 234 238
520 U and U, from low and medium activity samples, when the pressure in the chamber
26
27
521 varied form 6.7 Pa (pump on) to 2700 Pa (hold mode). Recently, a honeycomb collimator
28
29
30 522 was developed to perform high resolution α-spectrometry at ambient pressure, particularly to
31
32 523 detect contamination within a short time92. It was shown that contamination of 1 Bq/cm2 at
33
34 524 any smooth and flat surface can be detected within 10s, with longer time needed for
35
36 525 radionuclide identification. A prototype hand-held instrument ADONIS (advanced on-site
37
38
39 526 investigation using alpha spectrometry) using CAM2000AM detector with an active diameter
40
41 527 of 50 mm, with an aluminium coated mylar sheet (3.5 µm thick) between the source and the
42
226
43 528 detector, was demonstrated for the test runs. Electrodeposited Ra sourced were used to
44
226 222 210
45 529 evaluate the effect on energy resolution of Ra, Rn and Po peaks93. The energy
46
47
530 resolution values obtained for 222Rn were significantly poorer than those for 226Ra and 210Po,
48
49
50 531 with similar data on 210Po better than that on 226Ra. These observations were explained based
51
52 532 on the distribution of the radionuclides in the sources and the effect of Rn diffusion.
53
54
55 533 Bergamini et al. determined3 226
Ra in water samples employing 225
Ra (from 229
Th
56
57 534 standard) as a chemical yield monitor, which was measured via its alpha emitting daughter
58
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2
217
3 535 At (7.07 MeV). Three stages of separation were carried out for Ra purification. The
4
5 536 separation consisted of extraction chromatography with Ln resinTM (Eichrom Industries Inc.,
6
7
537 USA) for removal of Ac, Dowex 50W X 8 cation exchange resin to remove Th, and
8
9
10 538 electrodeposition of purified Ra from 0.17M ammonium oxalate in nitric acid medium (pH
11

2.6) at a constant current of 800 mA for 90 min. Stainless steel disks were used as the
12 539
13
14 540 substrate for source preparation. The results obtained on certified PNI water samples with
15
16 541 226
Ra concentrations in the range of 50 to 147 Bq.L-1 agreed well within the experimental
17
18
19 542 uncertainties. The time of complete analysis was shortened to 3 days compared to 20-38 days
20
21 543 required in the previously reported methods.
22
234
23 544 Alpha spectrometry is commonly used to determine U/238U ratios and U
24
94,95 234
25 545 concentrations in surface and deep ground natural waters . The U/238U α-activity ratio
26
27
546 in natural uranium is 1, in accordance with the secular equilibrium between the two isotopes.
28
29
30 547 However, large deviations in the activity ratio (0.5 to 40 in the surface water, 1.14 in the sea
31
32 548 water), and significant differences in the dissolved U concentrations (0.01 to 5 µg.L-1 in
33
34 549 surface waters, 0.1 to 50 µg.L-1 with values up to 10,000 µg.L-1 in ground water, and 3.3
35
36 550 µg.L-1 in sea water) were observed because of U-series disequilibrium. These variations are
37
38
39 551 attributed to differences in the redox atmosphere (mainly reducing conditions) as well as the
40
41 552 dissolution of recoil nuclide 234U. These data were used for many applications e.g., to classify
42
43 553 aquifers (augmenting, steady state, decaying/remobilization), to understand the sources and
44
45 554 mixing proportions of aquifer water, to resolve hydro-geological problems96, for ore
46
47 234
555 prospecting, earthquake prediction, and radiometric dating. Studies on the U/238U α-
48
49
50 556 activity ratios and the U-content were reported in groundwater samples from the deep
51
52 557 Complexe Terminal (activity ratios 1.7 to 2.5 with U concentrations 1.35 to 2.4 µg.L-1) and
53
54 558 Continental Intercalaire (activity ratios 3.2 to 15.4 with U concentrations 0.006 to 0.57µg.L-1)
55
56
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2
3 559 aquifers of southern Tunisia because this groundwater resource lies under the entire expanse
4
5 560 of the Sahara.
6
7
8 561 An interlaboratory experiment was conducted in 2007/2008 for the determination of
9
10 234
562 U/238U α-activity ratios in three different mineral water samples, and the reference values
11

12
13 563 were obtained by considering the data obtained at two laboratories viz., Institute for
14
15 564 Reference Materials and Measurements (IRMM, Belgium) and Bundesamt für Strahlenschutz
16
17 565 (BfS, Germany)97. The researchers at BfS used UTEVA extraction resin for pre-concentration
18
19 566 of U, and electrodeposition on SS disks for source preparation. At IRMM, U was first
20
21
22 567 preconcentrated with Fe(OH)3 at pH 9 to 10 employing ammonia solution. This step was
23
24 568 followed by UTEVA column for U separation, and micro-coprecipitation with CeF3 was used
25
26 569 for source preparation26 . Twelve samples of 1.5 L, and 10 samples of 3L mineral water were
27
28 570 employed, and 232U tracer calibrated by defined solid angle geometry was used as a chemical
29
30
571 yield monitor98. The α-spectrum from each source was recorded for 4 days with a 450 mm2
31
32
33 572 PIPS detector at each laboratory. The mean activity values of 234U in one of the samples were
34
35 573 (45.0 ± 1.8) mBq.L-1 and (44.7 ± 1.6) mBq.L-1 for 1.5 L and 3 L samples, respectively, while
36
238
37 574 the corresponding U activities were (22.3 ± 1.0) mBq.L-1 and (22.0 ± 1.0) mBq.L-1. The
38
39 575 reference values arrived at were (43.8 ± 1.6) mBq.L-1 and (21.7 ± 1.0) mBq.L-1, for 234U and
40
41 238
42 576 U, respectively. All the uncertainties given are one standard deviation. The statistical
43
44 577 analysis by analysis of variance (ANOVA) of the data showed inhomogeneity among the
45
234
46 578 different samples, and the U/238U activity ratios significantly higher than unity showed the
47
48 579 presence of disequilibrium effect.
49
50
51
580 Pu (Bq.kg-1) was determined in bilberry samples collected from region close to
52
53 581 Chernobyl reactor site (in an international intercomparison evaluation experiment conducted
54
242
55 582 by IRMM, Belgium). The samples were spiked with proficiency test sample and with Pu
56
57 583 tracer for isotope dilution alpha spectrometry. Pu was separated from Th, U, Np, Am with
58
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2
3 584 two extraction chromatography columns of U-TEVA and TRU Eichrom resins.99
4
5 585 Electrodeposited sources with 450 mm2 PIPS detector were used for the determination.
6
7
586 Results obtained were consistent with the reference values for three different bilberry
8
9
10 587 samples.
11

Acid leaching and fusion dissolution techniques were compared to determine U
12 588
13
14 589 (Bq.kg-1) in soil samples with α-spectrometry on electrodeposited sources and isotope
15
16 590 dilution alpha spectrometry with 232
U as a spike. The final results obtained on two IAEA
17
18
19 591 proficiency test samples and one IAEA reference material (IAEA-375) showed the fusion
20
21 592 dissolution technique (mixture of Na2CO3, K2CO3 and H3BO3 ; 1:1:1) to be superior to acid
22
23 593 leaching.100
24
25
26 594 5.2 Biological Samples
27
28
29 595 AS is also useful for the determination of actinides in biological samples in the case
30
31 596 of accidental exposure of the occupational workers. The monitoring of Ra concentration
32
33 597 levels is required because Ra is an alkaline earth element, and can get accumulated in bones
34
35 598 with time through ingestion and consumption of agricultural products/live stock leading to
36
37
38
599 the formation of bone-tumors.
39
40 600 Thorium isotopes (228Th, 230Th and 232Th) were determined in human tissue (lung and
41
42 601 lymph nodes) using 229Th as a tracer.101 The tissue samples were subjected to dry as well as
43
44 602 wet-ashing digestion procedure. Thorium was purified with anion exchange procedure, and
45
46
603 electrodeposited sources were prepared on 99.7% pure Vanadium planchets. Large area PIPS
47
48
49 604 detector (450 mm2), with a distance of 0.5 mm between the source and the detector, was used
50
51 605 to achieve high counting efficiency (20%). Detection limits (Bq) of 6 x 10-4, 2.8 x 10-4, 2.8 x
52
53 606 10-4 were obtained for 228
Th, 230
Th and 232
Th, respectively. Detection limit of pre-
54
55 607 concentration neutron activation analysis (PCNAA) was found to be better by a factor of 50
56
57 232
58
608 for Th determination. However, PCNAA depends upon the availability of reactor for
59
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2
3 609 irradiation and also separation of Th from biological matrix to avoid the activation of
4
5 610 elements present in the tissue sample.
6
7
611 Uranium isotopes (234U, 235 and 238U) were determined in urine samples using 25 mBq
8
9 232
10 612 of U as a tracer. Uranium was co-precipitated with calcium phosphate, the precipitate was
11

digested with HNO3+H2O2 mixture, and uranium was purified by extraction chromatography
12 613
13
14 614 with Eichrom UTEVA resin.4 Electrodeposited sources on stainless steel disks, 450 mm2
15
16 615 detector, and one week of α-spectrum recording time was followed. The method was
17
18
19 616 developed to obtain a minimum detectable concentration (MDC) of 2 mBq/day in 24 hr-urine
20
21 617 sample. An MDC value of 0.6 mBq/day was obtained
22
239
23 618 Alpha spectrometry was used for the determination of Pu (added externally) in
24
25 242
619 urine samples of volunteers. Pu was used as a tracer and Pu in the urine samples was pre-
26
27
620 concentrated by evaporation/micro-precipitation. The samples were digested in a microwave
28
29
30 621 oven, and Pu was purified with anion-exchange extraction chromatography. The results (at pg
31
32 622 levels) were comparable with those obtained with high resolution-inductively coupled plasma
33
34 623 mass spectrometry (HR-ICPMS) and accelerator mass spectrometry (AMS).102 However,
35
36 624 minimum detectable activity was superior with HR-ICPMS (23 fg) and AMS (0.44 fg)
37
38
39 625 compared to that with alpha spectrometry (50 fg). Alpha spectrometry offers the advantages
40
41 626 that sample is available after recording the spectrum, and repetition can be done, if required.
42
43 627
44
45
46 628 5.3 Nuclear Fuel Samples
47
48 232
629 AS is highly useful to determine relatively short-lived isotopes, e.g. U (T1/2 =
49
50 238
630 70.6 ±1.1 yr), Pu (T1/2 = 87.74 ± 0.03 yr) in fuel materials103-106, because of their low
51
52
53 631 abundances (< 1%), high alpha specific activity, and ubiquitous isobaric interferences from
54
232
55 632 Th and 238U, respectively, in their determination with elemental mass spectrometry.
56
57
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2
241
3 633 AS is routinely used for the determination of Am in Pu-bearing fuel materials for
4
5 241
634 their chemical quality assurance, because of the specification limit of 0.25 wt% of Am in
6
7
635 Pu107-109. The technique is also commonly employed for the determination of 238Pu in Pu, and
8
9 232 233 232
10 636 U in U produced by the reactor irradiation of uranium and Th, respectively. Data on
11
amount of 232U are important to calculate the shielding required for future handling of 233U in

12 637
13
14 638 fuel fabrication, because of the hard γ-ray (2.6 MeV) from 208Tl present in the decay chain of
15
16 639 232
U. Determination of 232
U in 233
U is important because the abundance of 232
U can reveal
17
18 233
19 640 information about the irradiation history of production of U, and also evaluate the
20
21 641 suitability of the material for nuclear explosives104. Accurate data on 232
U and 238
Pu are also
22
23 642 required to develop computer codes to calculate theoretically the build-up of these isotopes
24
25 643 during reactor irradiation. Isotope dilution alpha spectrometry (IDAS)81 provides a viable
26
27
644 alternative to isotope dilution mass spectrometry (IDMS) for the determination of Pu
28
29
30 645 concentration in irradiated fuels, in the event of non-availability of commonly used enriched
31
242
32 646 Pu as a spike in IDMS, and also to those laboratories not having access to expensive mass
33
34 647 spectrometers. AS, either alone, or in conjunction with mass spectrometry can be used for the
35
36 648 precise and accurate determination of α-decay half-lives of various trans-actinium
37
38
39 649 isotopes110,111. Data on the build-up of Am and Cm isotopes (241Am, 243
Am, 242
Cm, 244
Cm,
40
41 650 etc.) required for computer code development are also provided by AS. Alpha spectrometry
42
43 651 can also be used to develop separation and purification procedures (solvent extraction, ion
44
45 652 exchange, extraction chromatography, etc.) for a mixture of actinides, and determine the
46
47
653 decontamination factors of various actinides in these procedures.
48
49 232
50 654 U was determined in 233U by AS, preceded by the purification of U with solid phase
51
52 655 extraction using UTEVA resin (diamyl amylphosphonate, DAAP)103. The purification
53
54 656 involved loading the sample in 3M HNO3 onto the resin column, washing with 10 mL of 3M
55
56 657 HNO3 and elution of U with 5 mL of 0.01% HEDPA (hydroxyethylidene diphosphonic
57
58
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2
3 658 acid). The purified U sample was digested with concentrated HNO3 and 30% H2O2. The
4
5 659 residue was dissolved in 5 mL of 15% Na2SO4, 2.5 mL of 5% NaHSO4 and 2 mL of water.
6
7
660 Electrodeposited source on stainless steel planchet was prepared in (NH4)2C2O4 medium (1
8
9
10 661 mL of 20 g.L-1). The alpha spectra were recorded for about 50 hours. The 232
U/233U ratios
11
obtained were (3.06 ± 0.14) x 10-6 and (1.12 ± 0.02) x 10-6 in the IRMM-040a and an

12 662
13
14 663 unknown sample, respectively, and were in good agreement with the results of gamma-ray
15
16 664 spectrometry within experimental uncertainties.
17
18 229
19 665 Alpha-activity ratio of Th/228Th was determined by measuring the gross α-activity
20 217 213
21 666 and the α-activity ratios of their daughters (viz., At and Po which are the daughters of
22
229 212 228
23 667 Th, Po which is a daughter of Th) with α-spectrometry112. Alpha spectrometry is
24
25 238 241 232 233
668 routinely used to determine Pu and Am in Pu-bearing fuel materials, and U in U
26
27
669 produced by thermal neutron irradiation of 232Th in a nuclear reactor.
28
29 238
30 670 Pu/(239Pu+240Pu) α-activity ratios determined with α-spectrometry in Pu samples
31
32 671 obtained from different reactors were used to develop useful isotope correlations113-116 with
33
34 672 other Pu isotope ratios determined by thermal ionization mass spectrometry (TIMS). These
35
36 673 isotope correlations are important to determine the origin of Pu, type of reactor, etc. for
37
38
39 674 nuclear forensic applications.
40 210
41 675 For the determination of Pb (Bq/kg) in refined Pb used as a low-background
42
210 210
43 676 gamma ray shielding material, Po (progeny of Pb) was determined by α-spectrometry
44
45 677 with 209Po as a tracer to monitor the chemical yield in separation117. Spontaneous deposition
46
47
678 of Po onto Ag disks, preceded by separation with Sr-spec resin (Eichrom Industries, USA)
48
49
50 679 was employed for source preparation.
51
52 680
53
54 681 6. High Resolution Alpha Spectrometry (HRAS)
55
56
57
58
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2
3 682 Table 5 gives a list of the radionuclides with close-lying α-energies, that need to be
4
5 683 resolved with HRAS. HRAS with commercially available Genie software was used to resolve
6
7 233
684 and determine U/234U activity ratios in synthetic and water samples118. It was noted that
8
9
10 685 deconvolution based on three peaks instead of four multiplets resulted in better accuracy of
11

the data. The results were compared with those obtained by accelerator mass spectrometry
12 686
13
14 687 (AMS).
15
16 688 HRAS with spectral deconvolution on electroplated sources, with 100 mm2 PIPS
17
18 243 244
19 689 detector, was used to resolve α-energies of Cm and Cm isotopes with an aim to
20 242
21 690 determine accurately the Cm/244Cm amount ratio119. This was necessary to correct for the
22
23 691 interference of α-energy of 243Cm at that of 242
Cm. The technique was also used to determine
24
243
25 692 Cm/244Cm ratio in samples of seabed sediment collected near the Sellafield outfall, riverine
26
27
693 sediment close to Mayak reprocessing plant, and soil and lichen from within the Chernobyl
28
29 243
30 694 exclusion zone. The Cm/244Cm ratio near Sellafield was determined to be < 2%, and 6-
31
32 695 8% near Mayak and Chernobyl.
33
34 696 High resolution alpha spectrometry (HRAS) with a suitable de-convolution algorithm
35
36 697 can be used to resolve close lying α-energy emitters, e.g. 240
Pu/239Pu which is an important
37
38
39 698 parameter indicating the source of Pu contamination82,120-123. This is because the 240
Pu/239Pu
40
41 699 atom ratio depends upon many factors including the burn-up of the irradiated fuel, type of
42
43 700 reactor, etc., and its value in the atmospheric fall out has been experimentally determined at
44
240
45 701 several laboratories. HRAS on electrodeposited sources was used to determine Pu/239Pu
46
47
702 isotope amount ratios in Pu samples, and using WinALPHA for deconvolution of the α-
48
49
50 703 spectrum. The results obtained were compared with those from TIMS, and the data agreed
51
52 704 within 1% by the two analytical techniques122,123. Uranium isotopes in irradiated thorium
53
54 705 dioxide sample were also determined with the WinALPHA deconvolution algorithm124.
55
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2
3 706 Another software ADAM along with AASI was also used to resolve 240Pu and 239Pu peaks in
4
5 707 α-spectrometry on a variety of samples with widely varying activity ratios82.
6
7
8 708 7. Decay Data of Radionuclides
9
10 709 7.1 Emission Probabilities
11

12 710 The need to determine accurate decay data of various actinide radionuclides was
13
14
711 identified by IAEA125,126. The scientists from CIEMAT, Madrid, Spain and IRMM (formerly
15
16
17 712 CBNM), Geel, Belgium have been continuing an excellent collaboration and cooperation for
18
19 713 more than two decades, and have produced the best data on the α-particle emission
20
21 714 probabilities of several important radio-nuclides127-139. For the accurate determination of α-
22
23 715 particle emission probabilities of different α-emitters, sources prepared by vacuum
24
25
26 716 sublimation from a tungsten filament, of isotopically pure nuclides (99.9% or better) and high
27
28 717 radiochemical purity, on quartz disks of optical surface quality and stainless steel disks were
29
236
30 718 used. To prevent the recoil contamination of the detector (e.g. in case of Pu), the sources
31
32 719 covered with VYNS film (without touching the source) were used. Magnetic field (about 0.1
33
34
720 T) was used to deflect away the conversion electrons, and thus reduce the conversion-electron
35
36
37 721 and alpha particle summing-in and summing-out effects. PIPS detectors of 20 mm2 to 50
38
39 722 mm2 active areas were used to obtain the best possible resolution. Thin and extremely high-
40
41 723 isotopic purity sources produced by means of an electromagnetic isotope separator at
42
43 724 Argonne National Laboratory, USA that involved deposition of 200 eV ions from the
44
45 246 250
46 725 decelerated beam onto thin Al foils were used for studies on Cm and Cf.134 Extensive
47
48 726 studies were required for long-term measurements (3 years) of alpha spectra on the
49
50 727 electrodeposited sources of 238U (activity of 1 Bq), limiting the source thickness to 26 µg.cm-
51
52 728 2
, and with 150 mm2 PIPS detector (to optimize the resolution and counting statistics) for α-
53
54
55
729 emission probabilities.140 In these studies, electro-deposition was preferred to vacuum
56
57 730 evaporation because of the higher yield of the former, and three different methods of electro-
58
59
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2
3 731 deposition were evaluated to obtain a homogeneous source21. Additionally, it was shown
4
5 732 conclusively that magnet system is superior to mathematical correction approach to
6
7
733 circumvent the α-particle and conversion electron coincidence effect. Alpha-particle emission
8
9
10 734 probabilities of a number of radionuclides have been determined over the last decade131-139.
11

7.2 Half-lives
12 735
13
14 736 Αlpha spectrometry is an important radionuclide metrology technique for the
15
16 737 determination of α-decay half-lives of α-emitters. For example, direct parent decay method
17
18 242
19 738 was used to determine the α-decay half-life of Cm. To eliminate the uncertainties in
20 242
21 739 absolute determination of the α-activity, activity ratio of Cm/244Cm was measured
22
23 740 periodically to obtain an accurate value of the half-life of 242Cm110 . Daughter growth method
24
25 741 was employed to determine the β- decay half-life of 241
Pu by determining the ingrowth of
26
27 241
742 Am with α-spectrometry. Synthetic mixtures were prepared to obtain 100% increase in the
28
29 241
30 743 Am/242Pu and 241
Am/(239Pu+240Pu) α-activity ratios in 30 days141. Isotope dilution α-
31
243 241
32 744 spectrometry with Am as a spike was also used to determine the ingrowth of Am142 .
33
34 745 Αlpha spectrometry along with thermal ionization mass spectrometry was employed in the
35
36 746 relative activity method to determine precise and accurate data on the half-lives of a number
37
38 232 242 243 244
39 747 of trans-actinium isotopes (e.g. U, Pu, Am, Pu)143-146. A double dilution
40
41 748 methodology was developed to maintain the isotope amount ratio as well as the α-activity
42
43 749 ratio close to unity to minimize the uncertainties in experimental determination of isotope
44
45 750 amount ratios and α-activity ratios147. The half-life ratio of 238
U/235U was determined with
46
47 235
751 high resolution α-spectrometry on three different U enriched materials148. The method
48
49 234
50 752 involved the measurement of U/235U activity ratio by α-spectrometry, and the data on
51
234
52 753 U/238U half-lives ratio from literature.
53
54 754 8. Challenges in alpha spectrometry
55
56
57
58
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2
3 755 Presently, there are many challenges to be solved in alpha spectrometry. High
4
5 756 resolution alpha spectrometry to resolve the close lying alpha-particle energy emitters, e.g.
6
7 239
757 Pu and 240Pu demands the commercial availability of economically viable rugged detectors
8
9
10 758 with resolutions of 1-2 keV (FWHM) at 5.5 MeV. Reference materials for different α-activity
11
ratios, e.g. 234U/238U, 238Pu/(239Pu+240Pu), 241Am/243Am, etc. are non-existent so far, and these

12 759
13
14 760 are urgently needed to develop and validate different low energy tail contribution correction
15
16 761 algorithms. Enriched isotopes, e.g. 232U, 236Pu, 238Pu, 242Pu, 243Am, 248Cm of various actinide
17
18
19 762 elements to be used as spikes or tracers for chemical recovery, and in IDAS experiments need
20
21 763 to be commercially available to nuclear researchers at various international laboratories.
22
23 764 Though a large number of computer programs for alpha spectra evaluation have been
24
25 765 developed and published by various researchers, still an internationally recognized user-
26
27
766 friendly software to evaluate low statistics and high statistics alpha spectra with the option to
28
29
30 767 include different shape parameters is required. A method for simultaneous quantitative
31
32 768 electrodeposition from a mixture of actinides is of great interest. Films with complexing
33
34 769 agents which can be used to separate and pre-concentrate the radionuclides, and can also be
35
36 770 used for alpha spectra recording will be useful for rapid analysis in the emergency situations
37
38 41-44, 149,150
39 771 . Development of green solvents and novel methodologies like cloud point
40
41 772 extraction which reduce the amounts of radioactive waste are urgently warranted151. Intensive
42
43 773 research is going on at various laboratories to satisfy these urgent requirements. Inductively
44
45 774 coupled plasma sources used in solution based ICPMS can be investigated to prepare thin,
46
47
775 homogeneous and quantitative sources. Though, the approach would mark under-utilization
48
49
50 776 of ICPMS technology, but a large number of quadrupole based ICPMS systems, replaced by
51
52 777 magnetic sector based ICPMS instruments, will become available in future, and can be
53
54 778 employed for source preparation. There is a need to organize and conduct international, inter-
55
56 779 laboratory comparison and evaluation experiments for the determination of different alpha-
57
58
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2
3 780 emitting isotopes in environmental and biological samples. This is of great importance
4
5 781 considering the renewed interest in nuclear energy, and for nuclear forensics in the present
6
7
782 world-scenario. Accurate experimental data on minor actinides (Am, Np and Cm), and for U
8
9
10 783 and Pu in irradiated fuels will be useful to develop and validate theoretical computer codes in
11

various new reactor concepts (proposed generation IV nuclear reactors). The development of
12 784
13
14 785 low temperature micro-calorimeter based α-spectrometry system may provide a useful
15
16 786 analytical tool, in future, for routine HRAS work with actinides. All the above developments
17
18
19 787 will be highly useful to improve the accuracy of nuclear data, e.g. half-lives, emission
20
21 788 probabilities etc. The decommissioning of aged nuclear power reactors world-wide, and the
22
23 789 migration studies of actinides into the environment of nuclear waste-repositories would
24
25 790 require determination of long-lived radionuclides in variety of samples, and this would also
26
27
791 involve α-spectrometry for the analysis of various samples. It is of utmost importance to
28
29
30 792 motivate the young generation to learn and perform the interesting studies with actinides, to
31
32 793 ensure the future availability of human resources for safe handling of radioactive isotopes.
33
34 794 The author hopes that the challenges and the excitements mentioned here would encourage
35
36 795 the present and future generation of science students to venture into nuclear and radio-
37
38
39 796 analytical chemistry. Researchers with specialized interest in Chemistry, Physics, Statistics,
40
41 797 Mathematical modelling, and Instrumentation will be a great asset for new developments in
42
43 798 the ultra-sensitive analytical techniques e.g. alpha-particle spectrometry, mass spectrometry
44
45 799 etc.
46
47
48 800 9. Acknowledgements
49
50 801 The author is grateful to the authorities at Bhabha Atomic Research Centre (BARC),
51
52 802 Mumbai of the Department of Atomic Energy (DAE), India, where he worked for more than
53
54
55
803 4 decades in various aspects of radio-analytical chemistry of actinides employing alpha
56
57 804 spectrometry and mass spectrometry. Sincere thanks are due to my mentors Dr H.C.Jain and
58
59
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2
3 805 late Dr M.V. Ramaniah (my Ph.D. guide) for encouraging me to develop a method to correct
4
5 806 for the low energy tail contribution in alpha spectrometry, and to validate isotope dilution
6
7
807 alpha spectrometry for Pu concentration determination in irradiated fuels, using indigenous
8
9 238
10 808 Pu spike prepared by Dr K. Raghuraman, Sh. A.V. Jadav and Sh. C.K.Sivaramakrishnan. I
11

record my sincere thanks and deep appreciation to colleagues from erstwhile Radiochemistry
12 809
13
14 810 Division, and now at Fuel Chemistry Division of BARC. Dr P.M.Shah, Mr A.R.Parab, Mr
15
16 811 V.L.Sant, Mr S.N.Acharya, Mr A.I.Almaula, Dr S.A.Chitambar, Mr R.K.Duggal, Dr (Ms)
17
18
19 812 Radhika Rao, Dr G.Chourasiya, Mr P.A.Ramasubramanian, Mr C.P.Singh, Mr A.S.Rawat,
20
21 813 Mr G.K.Prasad, and late Mr V.D.Kavimandan were involved at various stages of the
22
23 814 experimental work during the development of alpha spectrometry for various applications.
24
25 815 Contributions of Dr (Ms) D.Alamelu, Dr (Ms) N.N.Mirashi, Dr (Ms) Sumana Paul, and Dr
26
27
816 Arnab Sarkar in alpha spectrometry for 238Pu and 241Am determination in fuel materials, for
28
29
30 817 high resolution alpha spectrometry, and for developing Pu-isotopic composition based
31
32 818 isotope correlations are gratefully acknowledged. Thanks are to the two anonymous
33
34 819 reviewers for their constructive suggestions to improve the review.
35
36 820
37
38
39 821 10. References
40 822
41 823 1. U. Wenzl, and D.Herz, Alpha-spectrometry in nuclear fuel analysis, J. Radioanal.
42
43 824 Chem., 1974, 21, 473-483.
44 825 2. R.Wellum and R.Molinet, The determination of 232U and 236Pu in solutions of
45 826 irradiated reactor fuel by alpha-spectrometry, Nucl. Instrum. Meth. Phys. Res., 1984,
46
827 223, 523-527.
47
48 828 3. G. Bergamini, M. H. T. Taddei, M.M.L. Rosa, M. T. Ferreira, L.T.V. Cheberle, S.
49 829 M. C. dos Santos, N. A. Mariano and E. C. T. Ramos, Determination of 226Ra in
50 830 drinking water samples by alpha spectrometry, J. Radioanal. Nucl. Chem., 2016, 307,
51
52 831 829-834.
53 832 4. E. Manickam, S. Sdraulig, and R.A.Tinker, Method design and validation for the
54 833 determination of uranium levels in human urine using high resolution alpha
55
834 spectrometry, J. Environ. Radioact., 2008, 99, 491–501.
56
57
58
59
60
View Article Online
DOI: 10.1039/C6AY00920D
1
2
3 835 5. R. Bojanowski, Z. Radecki, and K. Burns, Determination of radium and uranium
4 836 isotopes in natural waters by sorption on hydrous manganese dioxide followed by
5
6 837 alpha-spectrometry, J. Radioanal. Nucl. Chem., 2005, 264, 437-443.
7 838 6. J. Eikenberg, A. Tricca, G. Vezzu, S. Bajo, M. Ruethi, and H. Surbeck,
8 839 Determination of 228Ra, 226Ra and 224Ra in natural water via adsorption on MnO2-
9 840 coated discs, J. Environ. Radioactivity, 2001, 54, 109-131.
10
11 841 7. S. F. Boulyga, C. Testa, D. Desideri, and J. S. Becker, Optimisation and application

of ICP-MS and alpha-spectrometry for determination of isotopic ratios of depleted
12 842
13 843 uranium and plutonium in samples collected in Kosovo, J. Anal. At. Spectrom., 2001,
14
15
844 16, 1283–1289.
16 845 8. ALMERA proficiency test on the determination of radionuclides in spinach, soil and
17 846 water (IAEA-CU-2007-04), IAEA/AQ/3, IAEA, 2009.
18 847 9. H.C.Jain and S.K.Aggarwal, Role of alpha spectrometry in nuclear technology, In
19
20 848 "Artificial Radioactivity", Ed. K.N.Rao and H.J.Arnikar, Tata McGraw-Hill, New
21 849 Delhi, India, 1985, p. 263.
22 850 10. E. Garcia-Torano, Current status of alpha-particle spectrometry, Appl. Radiat. Isot.,
23
851 2006, 64, 1273–1280.
24
25 852 11. N. Vajda and C.K.Kim, Determination of Pu isotopes by alpha spectrometry: a
26 853 review of analytical methodology, J. Radioanal. Nucl. Chem., 2010, 283, 203–223.
27 854 12. N. Vajda, Up-to-date radiochemical methods for the determination of long-lived
28
29 855 radionuclides in the environment, J. Anal. Sci. Technol., 2011, 2, A108-A114.
30 856 13. N. Vajda and C.K. Kim, Determination of transuranium isotopes (Pu, Np, Am) by
31 857 radiometric techniques: a review of analytical methodology, Anal. Chem., 2011, 83,
32 858 4688-4719.
33
34 859 14. N. Vajda, P. Martin, and C.K. Kim, Alpha spectrometry, in Handbook of
35 860 Radioactivity Analysis, Chapter 6, 2012, 363-422, (Ed.) M.F. L'Annunziata,
36 861 Academic Press, DOI: http://dx.doi.org/10.1016/B978-0-12-384873-4.00006-2.
37
38
862 15. P. DeRegge and R. Boden, Review of chemical separation techniques applicable to
39 863 alpha spectrometric measurements, Nucl. Instrum. Meth. Phys. Res., 1984, 223, 181-
40 864 187.
41 865 16. E. P. Horwitz, R. Chiarizia, M. L. Dietz, and H. Diamond, Separation and
42
43 866 preconcentration of actinides from acidic media by extraction chromatography, Anal.
44 867 Chim. Acta, 1993, 281, 361–372.
45 868 17. N.A. Talvitie, Electrodeposition of actinides for alpha spectrometric determination,
46
869 Anal. Chem., 1972, 44, 280–283.
47
48 870 18. A.E. Lally, and K.M. Glover, Source preparation in alpha spectrometry, Nucl.
49 871 Instrum. Meth. Phys. Res., 1984, 223, 259-265.
50 872 19. S.K.Aggarwal, G.Chourasiya, R.K.Duggal, C.P.Singh, A.S.Rawat, and H.C.Jain, A
51
52 873 comparative study of different methods of preparation of sources for alpha
53 874 spectrometry of plutonium, Nucl. Instr. Methods Phys. Res., 1985, A238, 463-468.
54 875 20. M.T. Crespo, A review of electrodeposition methods for the preparation of alpha-
55
876 radiation sources, Appl. Radiat. Isot., 2012, 70, 210-215.
56
57
58
59
60
View Article Online
DOI: 10.1039/C6AY00920D
1
2
3 877 21. V. Jobbagy, M.T.Crespo, R.V.Ammel, M. Marouli, A. Moens, S. Pomme, and E.
4 878 Garcia-Torano, Preparation of high-resolution 238U α-sources by electrodeposition: a
5
6 879 comprehensive study, J. Radioanal. Nucl. Chem., 2013, 298, 345–352.
7 880 22. L. Hallstadius, A method for the electrodeposition of actinides, Nucl. Instrum.
8 881 Methods Phys. Res., 1984, 223, 266-267.
9 882 23. V. Tsoupko-Sitnikov, F. Dayras, J. de Sanoit, and D. Filossofov, Application of
10
11 883 rotating disk electrode technique for the preparation of Np, Pu and Am α-sources,

Appl. Radiat. Isot., 2000, 52, 357-364.
12 884
13 885 24. J. Janda, P. Sladek, and D. Sas, Electrodeposition of selected alpha-emitting
14
15
886 radionuclides from oxalate-ammonium sulfate electrolyte and measured by means of
16 887 solid-state alpha spectrometry, J. Radioanal. Nucl. Chem., 2010, 286, 687–691.
17 888 25. R.Van Ammel, S.Eykens, R.Eykens, and S.Pomme, Preparation of drop-deposited
18 889 quantitative uranium sources with low self-absorption, Nucl. Instr. Meth. Phys. Res.
19
20 890 A, 2011 (October).
21 891 26. C.W. Sill, and R.L. Williams, Preparation of actinides for alpha spectrometry without
22 892 electrodeposition, Anal. Chem., 1981, 53, 415–421.
23
893 27. M. Miguel, A. Dellesite, S. Deron, W. Raab and H. Swietly, Preparation of drop
24
25 894 deposited plutonium sources on porcelain support : results and limitations of alpha
26 895 spectrometric analyses, Nucl. Instrum. Meth. Phys. Res., 1984, 223, 270-275.
27 896 28. S.K.Aggarwal, G.Chourasiya, R.K.Duggal, C.P.Singh, A.S.Rawat and H.C.Jain,
28
29 897 Determination of plutonium concentration by isotope dilution alpha
30 898 spectrometry without purification from 241Am and a bulk of other impurities, Fres.
31 899 Z. Anal. Chem., 1986, 323, 148-152.
32 900 29. S.K.Aggarwal, G.Chourasiya, R.K.Duggal, R.Rao, P.A.Ramasubramanian, and H.C.
33
34 901 Jain, Reverse isotope dilution alpha spectrometry using 239Pu spike for determining
35 902 plutonium concentration in high burn-up fuel samples without purification from
36 241
903 Am and a bulk of other impurities, J. Radioanal. Nucl. Chem., Letters, 1987, 119, 1-
37
38
904 12.
39 905 30. J.S. Oh, P. E. Warwick, I.W. Croudace, and S.-H. Lee, Evaluation of three
40 906 electrodeposition procedures for uranium, plutonium and americium, Appl. Radiat.
41 907 Isot., 2014, 87, 233-237.
42
43 908 31. O.A.Dumitru, R.Cs.Begy, D.C.Nita, L.D.Bobos, and C.Cosma, Uranium
44 909 electrodepostion for alpha spectrometric source preparation, J. Radioanal. Nucl.
45 910 Chem., 2013, 298, 1335-1339.
46
911 32. L. Benedik, G. Sibbens, A. Moens, R. Eykens, M. Nečemer, S.D. Škapin, and
47
48 912 P.Kumpa, Preparation of thick uranium layers on aluminium and stainless steel
49 913 backings, Appl. Radiat. Isot., 2014, 87, 238-241.
50 914 33. N. N. Mirashi, J. N. Mathur, S. Prakash, and M.V. Ramaniah, Studies on the
51
52 915 electrodeposition of uranium on aluminium, Appl. Radiat. Isot., 1986, 37, 358–359.
53 916 34. N.N.Mirashi and S.K.Aggarwal, Studies for the simultaneous quantitative
54 917 electrodeposition of plutonium and americium for alpha-spectrometry, J. Radioanal.
55
918 Nucl. Chem., 2009, 279, 777-781.
56
57 919 35. G.Chourasiya, S.K.Aggarwal, R.K.Duggal, C.P.Singh, A.S.Rawat and H.C.Jain,
58 920 Determination of plutonium concentration by isotope dilution alpha spectrometry
59
60
View Article Online
DOI: 10.1039/C6AY00920D
1
2
3 921 using TTA extraction and drop deposited sources, Radiochim. Acta, 1984, 36, 187-
4 922 190.
5
6 923 36. M. P. Dion, M. Liezers, O.T. Farmer III, B.W. Miller, S. Morley, C. Barinaga, and
7 924 G. Eiden, Improving alpha spectrometry energy resolution by ion implantation with
8 925 ICP-MS, J. Radioanal. Nucl. Chem., 2015, 303, 877-884.
9
926 37. S.K. Aggarwal, R.K. Duggal, R. Rao, P.A. Ramasubramanian, and H.C. Jain,
10
11 927 Precision and accuracy in the determination of plutonium-239/uranium-233,

12 928 americium-241/uranium-233 and curium-244/uranium-233 alpha activity ratios

13 929 byalpha spectrometry, J. Radioanal. Nucl. Chem., 1986, 106, 295-307.
14
15
930 38. S.K. Aggarwal, R.K. Duggal, R. Rao, P.A. Ramasubramanian, and H.C. Jain,
16 931 Investigations for the determination of plutonium concentration employing non-
17 932 isotopic diluents in alpha spectrometry (NIDAS), Radiochim. Acta, 1987, 41, 23-29.
18 933 39. J. Heyse, M. Anastasiou, R. Eykens, A. Moens, A. Plompen, P. Schillebeeckx, G.
19
20 934 Sibbens, D. Vanleeuw, and R. Wynants, Characterization of 235U targets for the
21 935 development of a secondary neutron fluence standard, J. Radioanal. Nucl. Chem.,
22 936 2014, 299, 1055-1059.
23
937 40. O. A. Rusu, R. C. Begy, L. D. Bobos, S. Dreve, and C. Cosma, Determination of
24
25 938 long-lived radionuclides in water by alpha spectrometry, AES Bioflux, 2011, 3, 148-
26 939 155.
27 940 41. S. K. Hanson, A. H. Mueller, and W. J. Oldham, Jr., Kläui ligand thin films for rapid
28
29 941 plutonium analysis by alpha spectrometry, Anal. Chem., 2014, 86, 1153-1159.
30 942 42. J. H. Rim, E. R. Gonzales, C. E. Armenta, K. Unlu, and D. S. Peterson, Developing
31 943 and evaluating di(2-ethylhexyl) orthophosphoric acid (HDEHP) based polymer
32
944 ligand film (PLF) for plutonium extraction, J. Radioanal. Nucl. Chem., 2013, 296,
33
34 945 1099-1103.
35 946 43. S. Paul, A. K. Pandey, Pranaw Kumar, S. Kaity, and S.K. Aggarwal, Tailored
36 947 bifunctional polymer for plutonium monitoring, Anal. Chem., 2014, 86, 6254−6261.
37
38
948 44. S. Paul, A.K. Pandey, R.V. Shah, and S.K. Aggarwal, Chemically selective polymer
39 949 substrate based direct isotope dilution alpha spectrometry of Pu, Anal. Chim. Acta,
40 950 2015, 878, 54-62.
41 951 45. G. Sibbens, T. Altzitzoglou, L. Benedik, S.Pomme´, and R. VanAmmel, α-particle
42
43 952 and γ-ray spectrometry of a plutonium solution for impurity determination, Appl.
44 953 Radiat. Isot., 2008, 66, 813–818.
45 954 46. S.K.Aggarwal, R.K.Duggal, P.M.Shah, R.Rao and H.C.Jain, Experimental evaluation
46
47
955 of the characteristic features of passivated ion implanted and surface barrier detectors
48 956 for alpha spectrometry of plutonium, J. Radioanal. Nucl. Chem. – Articles, 1988,
49 957 120, 29-39.
50 958 47. A.F. Novgorodov, N.A. Korolev, and F. Roesch, A combined 148Gd/244Cm source for
51
52 959 energy calibration of α-spectrometers, Appl. Radiat. Isot., 2006, 64, 540-542.
53 960 48. P. Martin, and G.J. Hancock, Peak resolution and tailing in alpha-particle
54 961 spectrometry for environmental samples, Appl. Radiat. Isot., 2004, 61, 161-165.
55
962 49. C.W. Sill, and D.G. Olson, Sources and prevention of recoil contamination of solid-
56
57 963 state alpha detectors, Anal. Chem., 1970, 42, 1596–1607.
58
59
60
View Article Online
DOI: 10.1039/C6AY00920D
1
2
3 964 50. N. Vainblat, O. Pelled, U. German, G. Haquin, A. Tshuva, and Z.B. Alfassi,
4 965 Determination of parameters relevant to alpha spectrometry when employing source
5
6 966 coating, Appl. Radiat. Isot., 2004, 61, 307-311.
7 967 51. K. G. W. Inn, E. Hall, J. T. Woodward IV, B. Stewart, R. Pollanen, L. Selvig, S.
8 968 Turner, I. Outola, S. Nour, H. Kurosaki, J. LaRosa, M. Schultz, Z. Lin, Z. Yu, and C.
9 969 McMahon, Use of thin collodion films to prevent recoil-ion contamination of alpha-
10
11 970 spectrometry detectors, J. Radioanal. Nucl. Chem., 2008, 276, 385–390.

52. S. Pommé, Typical uncertainties in alpha-particle spectrometry, Metrologia, 2015,
12 971
13 972 52, S146–S155.
14
15
973 53. G. Bortels, D. Mouchel, R. Eykens, E. Garcia-Toraño, M.L. Aceña, R.A.P. Wiltshire,
16 974 M. King, A.J. Fudge, and P. Burger, P., Alpha-particle emission probabilities in the
17 975 decay of 237Np, Nucl. Instrum. Methods Phys. Res., 1990, A295, 199-206.
18 976 54. J. Paepen, A. Dirican, M. Marouli, S. Pomme, V. Van Ammel, and H. Stroh, A
19
20 977 magnet system for the suppression of conversion electrons in alpha spectrometry
21 978 Appl. Radiat. Isot., 2014, 87, 320–324.
22 979 55. A. Alessandrello, C. Broferio, O. Cremonesi, E. Fiorini, A. Giuliani, A. Nucciotti, M.
23
980 Pavan, S. Pirro, G. Pessina, S. Parmeggiano, E. Previtali, M. Vanzini, L. Zanotti, E.
24
25 981 Coccia, V. Fafone, C. Bucci, and A. Rotilio, A massive thermal detector for alpha
26 982 and gamma spectroscopy, Nucl. Instr. Meth. Phys. Res., 2000, A 440, 397-402.
27 983 56. E. Leblanc, N. Coron, J. Leblanc, P. de Marcillac, J. Bouchard, and J. Plagnard,
28
29 984 High-energy resolution alpha spectrometry using cryogenic detectors, Appl. Radiat.
30 985 Isot., 2006, 64, 1281–1286.
31 986 57. R.D. Horansky, J.N. Ullom, J.A. Beall, G.C. Hilton, K.D. Irwin, D.E. Dry, P.E.
32 987 Hastings, S.P. Lamont, C.R. Rudy, and M.W. Rabin, Superconducting calorimetric
33
34 988 alpha particle sensors for nuclear non-proliferation applications, Appl. Phys. Lett.,
35 989 2008, 93, 123504-123506.
36 990 58. K. Sato, T. Ishikawa, Y. Ishisaki, T. Ohashi, T. Oshimai, and N. Y. Yamasakii,
37
38
991 Detection of 5.5 MeV α-particles with a magnetic calorimeter, Japanese J. Appl.
39 992 Phys., 2004, 43, 6477-6478.
40 993 59. W.S. Yoon, Y.S. Jang, G.B. Kim, K.J. Kim, M.S. Kim, J.S. Lee, K.B. Lee, M.K. Lee,
41 994 S.J. Lee, H.J. Lee, Y.N. Yuryev, and Y.H. Kim, High energy resolution cryogenic
42
43 995 alpha spectrometers using magnetic calorimeters, J. Low Temp. Phys., 2012, 167,
44 996 280-285.
45 997 60. A.S. Hoover, E.M. Bond, M. P. Croce, T. G. Holesinger, G. J. Kunde, M.W. Rabin,
46
998 L.E. Wolfsberg, D.A. Bennett, J.P. Hays-Wehle, D. R. Schmidt, D. Swetz, and J.
47
48 999 N.Ullom, Measurement of the 240Pu/239Pu mass ratio using a transition-edge-sensor
49 1000 microcalorimeter for total decay energy spectroscopy, Anal. Chem., 2015, 87,
50 1001 3996−4000.
51
52 1002 61. Z. Lin, A. Berne, B. Cummings, J. J. Filliben, and K.G.W. Inn, Competence of alpha
53 1003 spectrometry analysis algorithms used to resolve the 241Am and 243Am alpha peak
54 1004 overlap, Appl. Radiat. Isot., 2002, 56, 57-63.
55
1005
56
57 1006
58 1007
59
60
View Article Online
DOI: 10.1039/C6AY00920D
1
2
3 1008 62. W. Beyrich and A. Cricchio, The ASET-74 Intercomparison experiment on the
4 1009 evaluation of alpha spectra of plutonium, Report KfK 2265/EUR 5208e, 1976.
5
6 1010 63. G. Bortels, J. Broothaerts, P. DeBievre, M. Gallet, W.Wolters, K.M. Glover, M.
7 1011 King, R.A.P. Wiltshire, E.L. Garner, L.E. Machlan, and I.L. Barnes, The AS-76
8 1012 interlaboratory experiment on the alpha spectrometric determination of Pu,
9 1013 Kernforschungzentrum Karlsruhe, Report KfK 2862/EUR 6402e, 1979.
10
11 1014 64. International Atomic Energy Agency (IAEA), Vienna, Austria, Intercomparison of

alpha particle spectrometry software packages, IAEA-TECDOC-1104 (1999).
12 1015
13 1016 65. M. Blaauw, E. Garcıa-Torano, S. Woods, and S. Fazinic, The 1997 IAEA
14
15
1017 Intercomparison of commercially available PC based software for alpha-particle
16 1018 spectrometry, Nucl. Instrum. Methods Phys. Res., 1999, A428, 317–329.
17 1019 66. E. Garcıa-Torano, M.T. Crespo, S. Woods, M. Blaauw, and S. Fazinic, The 1997
18 1020 IAEA test spectra for alpha particle spectrometry, Nucl. Instrum. Methods Phys. Res.,
19
20 1021 1999, A428, 330-335.
21 1022 67. W. Watzig and W.Westmeier, ALFUN: a program for the evaluation of complex
22 1023 alpha-spectra, Nucl. Instrum. Methods, 1978, 153, 517-524.
23
1024 68. E. García-Toraño, and M.L. Aceña, NOLIN: nonlinear analysis of complex alpha
24
25 1025 spectra, Nucl. Instrum. Methods Phys. Res., 1981, 185, 261-269.
26 1026 69. G. Bortels and P.Collaers, Analytical function for fitting peaks in alpha-particle
27 1027 spectra from Si detectors, Appl. Radiat. Isot., 1987, 38, 831-837.
28
29 1028 70. T. Babeliowsky and G. Bortels, ALFA: a program for accurate analysis of complex
30 1029 alpha-particle spectra on a PC, Appl. Radiat. Isot., 1993, 44, 1349-1358.
31 1030 71. E. García-Toraño, Analytical line shape for fitting alpha-particle spectra taken with
32 1031 silicon detectors. In: Proceedings of the International Symposium on advances in
33
34 1032 alpha-, beta- and gamma-ray spectrometry, 18–20 September 1996, St. Petersburg,
35 1033 pp. 17, 1997.
36 1034 72. J.C. Lozano, and F. Fernandez. Application of singular value decomposition to the
37
38
1035 analysis of alpha-particle spectra, Nucl. Instrum Methods, 1998, A 413, 233–238.
39 1036 73. J.C. Lozano, S. Madruga, and F. Fernandez, A function using cubic splines for the
40 1037 analysis of alpha-particle spectra from silicon detectors, Nucl. Instr. Methods, 2000,
41 1038 A 449, 356–365.
42
43 1039 74. F. Dayras, Analysis of 239Pu, 244Cm and 243Am alpha spectra using the unfolding code
44 1040 Colegram without prior use of a nuclear data library, Nucl. Instr. Methods Phys. Res.,
45 1041 2002, A 490, 492–504.
46
1042 75. E. García-Toraño, A model shape for the analysis of alpha-particle spectra, Nucl.
47
48 1043 Instrum. Methods Phys. Res., 2003, A 498, 289-291.
49 1044 76. R.C.Noy, E. García-Torano, E. Mainegra, and E. Lopez, The WinALPHA code for
50 1045 the analysis of alpha-particle spectra, Nucl. Instrum. Methods Phys. Res., 2004,
51
52 1046 A525, 522-528.
53 1047 77. S. Pomme and B. C. Marroyo, Improved peak shape fitting in alpha spectra, Appl.
54 1048 Radiat. Isot., 2015, 96, 148-153.
55
1049 78. B. C. Marroyo, A. M. Sanchez, and M. J. Vargas, ALFITeX: a new code for the
56
57 1050 deconvolution of complex alpha-particle spectra, J. Radioanal. Nucl. Chem., 2013,
58 1051 296, 1247-1252.
59
60
View Article Online
DOI: 10.1039/C6AY00920D
1
2
3 1052 79. T. Siiskonen and R. Pollanen, New approach to alpha spectrum analysis : iterative
4 1053 Monte Carlo simulations and fittings, Progress in Nucl. Sci. Technol., 2011, 2, 437-
5
6 1054 441.
7 1055 80. S.K.Aggarwal, S.A.Chitambar, V.D.Kavimandan, A.I.Almaula, P.M.Shah,
8 1056 A.R.Parab, V.L.Sant, H.C.Jain and M.V.Ramaniah, Precision and accuracy
9 1057 determination of 238Pu/(239Pu+240Pu) alpha activity ratio by alpha spectrometry,
10
11 1058 Radiochim. Acta, 1980, 27, 1- 7.

81. M.V.Ramaniah, H.C.Jain, S.K.Aggarwal, S.A.Chitambar, V.D.Kavimandan, A.I.
12 1059
13 1060 Almaula, P.M.Shah, A.R.Parab and V.L.Sant, Isotope dilution alpha
14
15
1061 spectrometry for the determination of plutonium concentration in irradiated fuel
16 1062 dissolver solution: IDAS and R-IDAS, Nucl.Technol., 1980, 49,121-128.
17 1063 82. R. P̈ollanen, T. Siiskonen, S. Ihantola, H. Toivonen, A. Pelikan, K. Inn, J. La Rosa,
18 1064 and B.J. Bene, Determination of 239Pu/240Pu isotopic ratio by high-resolution alpha-
19
20 1065 particle spectrometry using the ADAM program, Appl. Radiat. Isot., 2012, 70, 733-
21 1066 739.
22 1067 83. B. R. Harvey and M. B. Lovett, Use of yield tracers for the determination of alpha-
23
1068 emitting actinides in the marine environment, Nucl. Instrum. Meth. Phys. Res., 1984,
24
25 1069 223, 224-234.
26 1070 84. R. Pollanen, T. Siiskonen, S. Ihantola, H. Toivonen, A. Pelikan, K. Inn, J. LaRosa,
27 1071 and B. Bene, Activity determination without tracers in high resolution alpha-particle
28
29 1072 spectrometry, J. Radioanal. Nucl. Chem., 2011, 290, 551–555.
30 1073 85. G.J. Hancock and P. Martin, Determination of Ra in environmental samples by α-
31 1074 particle spectrometry, Appl. Radiat. Isot., 1991, 42, 63–69
32 1075 86. M.T. Crespo, On the determination of 226Ra in environmental and geological samples
33
34 1076 by α-spectrometry using 225Ra as yield tracer, Appl. Radiat. Isot., 2000, 53, 109–114
35 1077 87. G. Jia, G. Torri, P. Innocenzi, R. Ocone, A. Di Lullo, Determination of radium
36 1078 isotopes in mineral and environmental water samples by alpha-spectrometry, J.
37
38
1079 Radioanal. Nucl. Chem., 2006, 267, 505–514.
39 1080 88. M. M. L. Rosa, V. A. Maihara, M. T. Ferreira, L. T. V. Cheberle, G. Bergamini, R.
40 1081 L. Bonifa´cio, M. H. T. Taddei, A comparative study of 226Ra determination using
41 1082 total counting and alpha spectrometry in environmental water samples, J. Radioanal.
42
43 1083 Nucl. Chem., 2016, 307, 817-820.
44 1084 89. S. L. Maxwell, B. K. Culligan, and J. B. Hutchison, Rapid fusion method for
45 1085 determination of plutonium isotopes in large rice samples, J. Radioanal. Nucl.
46
1086 Chem., 2013, 298, 1367–1374.
47
48 1087 90. United Nations: Sources and effects of ionizing radiation. United Nations Scientific
49 1088 Committee on the Effects of Atomic Radiation (UNSCEAR). United Nations, New
50 1089 York, 2000.
51
52 1090 91. D.D. Rao, V. Sudheendran, and P.K. Sarkar, Optimization of parameters of alpha
53 1091 spectrometry with silicon detector for low level measurements of actinides in
54 1092 environmental samples, Appl. Radiat. Isot., 2012, 70, 1519-1525.
55
1093 92. R. Pollanen, K. Perajarvi, T. Siiskonen, J. Turunen, High-resolution alpha
56
57 1094 spectrometry at ambient air pressure: towards new applications, Nucl. Instr. Meth.
58 1095 Phys. Res., 2012, A 694, 173–178.
59
60
View Article Online
DOI: 10.1039/C6AY00920D
1
2
3 1096 93. M.J.Vargas, Study of the energy resolution in alpha-particle spectra from
4 1097 electrodeposited radium sources, J. Radioanal. Nucl. Chem., 2001, 250, 445–448.
5
6 1098 94. J.K. Osmond, and J.B. Cowart, The theory and uses of natural uranium isotopic
7 1099 variations in hydrology, At. Energy Rev., 1976, 14, 621-769.
8 1100 95. S.K.Aggarwal and P.M.Shah, A comparative study of 234U/238U alpha activity ratios
9 1101 by alpha spectrometry and calculated from mass spectrometric data, J. Radioanal.
10
11 1102 Nucl. Chem., 1998, 230, 265-270.

96. N. Chkir and K. Zouari, Uranium isotopic disequilibrium for groundwater
12 1103
13 1104 classification: first results on complexe terminal and continental intercalaire aquifers
14
15
1105 in Southern Tunisia, Environ. Geol., 2007, 53, 677-685.
16 1106 97. Y. Spasova, L. Benedik, M. Vasile, M. Beyermann, U. Wätjen, and S. Pommé, 234U
17 1107 and 238U in mineral water: Reference value and uncertainty evaluation in the frame of
18 1108 an inter-laboratory comparison, J. Radioanal. Nucl. Chem., 2009, 281, 113-117.
19
20 1109 98. G. Sibbens, S. Pomme´, and T. Altzitzoglou, Standardisation of low activity actinide
21 1110 solutions by alpha-particle counting at a defined solid angle, Appl. Radiat. Isot.,
22 1111 2004, 61, 405–408.
23
1112 99. M. Seferinoğlu, N. Aslan, A. Kurt, P. E. Erden, and H. Mert, Determination of
24
25 1113 plutonium isotopes in bilberry using liquid scintillation spectrometry and alpha-
26 1114 particle spectrometry, Appl. Radiat. Isot., 2014, 87, 81-86.
27 1115 100.A. Diricann and M.Sahin, Comparison of acid leaching and fusion techniques to
28
29 1116 determine uranium in soil samples by alpha spectrometry, Appl. Radiat. Isot., 2016,
30 1117 109, 189-192.
31 1118 101.S.E. Glover, R.H. Filby, and S.B. Clark, Determination of isotopic thorium in
32 1119 biological samples by combined alpha spectrometry and neutron activation analysis,
33
34 1120 J. Radioanal. Nucl. Chem., 1998, 234, 201-208.
35 1121 102.H. H.-Mendoza, E. Chamizo, A. Delgado, M. G.-Leon, and A. Yllera, Comparison
36 1122 of methods and application of alpha spectrometry and mass spectrometry techniques
37
38
1123 for 239Pu determination in biological samples, J. Anal. At. Spectrom., 2011, 26, 1509-
39 1124 1513.
40 1125 103.H. Ramebäck, U. Nygren, P. Lagerkvist, A. Verbruggen, R. Wellum, and G.
41 1126 Skarnemark, Basic characterization of 233U: Determination of age and 232U content
42
43 1127 using sector field ICP-MS, gamma spectrometry and alpha spectrometry, Nucl. Instr.
44 1128 Meth. Phys. Res., 2008, B 266, 807–812.
45 1129 104.J. Kang and F. N. von Hippel, U-232 and the proliferation-resistance of U-233 in
46
1130 spent fuel, Science & Global Security, 2001, 9, 1-32.
47
48 1131 105.S.K.Aggarwal, P.M.Shah, D.Alamelu and N.N.Mirashi, Preparation and
49 1132 characterization of working standards for 238Pu, Radiochim. Acta, 2007, 95, 233-237.
50 1133 106.D.Alamelu, P.M.Shah, and S.K.Aggarwal, A comparative evaluation of 238Pu
51
52 1134 determination in NIST-SRM-947-Pu by alpha spectrometry and thermal ionization
53 1135 mass spectrometry, Radiochim. Acta, 2005, 93, 259-263.
54 1136 107.S.K.Aggarwal, A.I.Alamula, P.M.Shah, P.A.Ramasubramanian, A.R.Parab and H.C
55
1137 Jain, Determination of 241Am in plutonium, Radiochem. Radioanal. Lett., 1980, 45,
56
57 1138 73-77.
58
59
60
View Article Online
DOI: 10.1039/C6AY00920D
1
2
3 1139 108.N.N.Miarshi, P.M.Shah, and S.K.Aggarwal, Comparison of alpha-spectrometry and
4 1140 alpha/gamma ratio method for the determination of americium in plutonium bearing
5
6 1141 fuel materials, J. Radioanal. Nucl. Chem., 2008, 275, 479-482.
7 1142 109.S.K.Aggarwal, N.N.Mirashi, S. Chakraborty, and V.M.Telmore, Determination of
8 1143 americium in plutonium based nuclear fuel materials: an assessment of different
9 1144 methodologies, J. Nucl. Mat., 2010, 406, 271-275.
10
11 1145 110.S.K. Aggarwal, A.V. Jadhav, S.A.Chitambar, A.R.Parab, P.M.Shah, A.I.Almaula, K.

Raghuraman, C.K.Sivaramkrishnan, and H.C.Jain, Half-life of 242Cm, Radiochem.
12 1146
13 1147 Radioanal. Lett., 1982, 54, 99-104.
14
15
1148 111.S.K.Aggarwal, Precise and accurate determination of alpha decay half-life of 244Pu
16 1149 by relative activity method using thermal ionization mass spectrometry and alpha
17 1150 spectrometry, Radiochim. Acta, 2006, 94, 397-401.
18 1151 112.S.S.Rattan, A.V.R.Reddy, V.S.Mallapurkar, R.J.Singh, and Satya Prakash, A
19
20 1152 method for the simultaneous estimation of 228Th and 229Th, J. Radioanal. Chem.,
21 1153 1981, 67, 95-99.
22 1154 113.S.K.Aggarwal, D.Alamelu, and P.M.Shah, Isotope correlations for alpha specific
23
1155 and isotopic composition of plutonium, Radiochim. Acta, 1998, 81, 129-133.
24
25 1156 114.D.Alamelu and S.K.Aggarwal, Isotope correlations for determining the isotopic
26 1157 composition of plutonium, Radiochim. Acta, 2001, 89, 131-134.
27 1158 115.S.K.Aggarwal and D.Alamelu, Isotope correlation for determining the isotopic
28
29 1159 composition of plutonium produced in research and power reactors using the
30 1160 experimental data obtained by alpha and mass spectrometry, Int. J. Nucl. Energy Sci.
31 1161 Technol., 2005, 1, 215-219.
32 1162 116.D.Alamelu and S.K.Aggarwal, Application of chemometry for identification of the
33
34 1163 source of plutonium, Int. J. Nucl. Energy Sci. Technol., 2011, 6, 30-36.
35 1164 117.J. L. Orrell, C. E. Aalseth, I. J. Arnquist, T.A. Eggemeyer, B.D. Glasgow, E. W.
36 1165 Hoppe, M.E. Keillor, S. M. Morley, A. W. Myers, C.T. Overman, S.M. Shaff, and K.
37
38
1166 S. Thommasso, Assay methods for 238U, 232Th, and 210Pb in lead and calibration of
210
39 1167 Bi bremsstrahlung emission from lead, PNNL-SA-115123 (2015).
40 1168 118.J. J. Harrison, T. E. Payne, K. L. Wilsher, S. Thiruvoth, D.P. Child, M.P. Johansen,
41 1169 and M.A.C. Hotchkis, Measurement of 233U/234U ratios in contaminated groundwater
42
43 1170 using alpha spectrometry, J. Environ. Radioactivity, 2016, 151, 537-541.
44 1171 119.P.I. Mitchell, E. Holm, L. L. Vintró, O.M. Condren, and P. Roos, Determination of
45 1172 the 243Cm/244Cm ratio alpha spectrometry and spectral deconvolution in
46
1173 environmental samples exposed to discharges from the nuclear fuel cycle, Appl.
47
48 1174 Radiat. Isot., 1998, 49, 1283-1288.
49 1175 120.F. Amoudry and P. Burger, Determiantion of the 239Pu/240Pu isotopic ratio by high
50 1176 resolution alpha spectrometry, Nucl. Instrum. Meth. Phys. Res., 1984, 223, 360-367.
51
52 1177 121.W. Raab and J.L.Parus, The measurement of 240Pu/239Pu and 238Pu/239Pu isotopic
53 1178 ratios by alpha-particle spectrometry, Nucl. Instrum. Meth. Phys. Res., 1994, A 339,
54 1179 116–121.
55
1180 122.S. Srinivasan, H. Seshadri, T. Kumar, and S.K. Rajan, Determination of the
56 240
57 1181 Pu/239Pu ratio by alpha spectrometry using the WinALPHA program, Appl. Radiat.
58 1182 Isot., 2006, 64, 591–593.
59
60
View Article Online
DOI: 10.1039/C6AY00920D
1
2
3 1183 123.S.K.Aggarwal and D.Alamelu, High resolution alpha-particle spectrometry for the
4 1184 determination of 240Pu/239Pu atom ratio in Pu samples from PHWR, J. Alloys and
5
6 1185 Compounds, 2007, 444-445, 656-659.
7 1186 124.D. Alamelu, and S.K. Aggarwal, Determination of uranium isotopes in irradiated
8 1187 thorium dioxide by alpha spectrometry using WinALPHA for deconvolution of
9 1188 complex spectra, J. Radioanal. Nucl. Chem., 2012, 294, 405-408.
10
11 1189 125.A.L. Nichols, Decay data: review of measurements, evaluations and compilations,

Appl. Radiat. Isot., 2001, 55, 23-70.
12 1190
13 1191 126.M.A. Kellett, F.G. Kondev, A.L. Nichols, IAEA coordinated research project :
14
15
1192 updated decay data library for actinides, Appl. Radiat. Isot., 2008, 66, 694-700.
16 1193 127.E. García-Toraño, M.L. Aceña, G. Bortels, and D. Mouchel, Alpha-particle emission
17 1194 probabilities in the decay of 243Am, Nucl. Instr. Methods Phys. Res., 1992, A312,
18 1195 317-322.
19
20 1196 128.G. Bortels, D.Mouchel, E.García-Toraño, and M.L. Aceña, Alpha-particle emission
21 1197 probabilities in the decay of 236Pu , Appl. Radiat. Isot., 1992, 43, 247-252.
22 1198 129.C. J. Bland and J. Truffy, Alpha-particle emission probabilities for 239Pu and 240Pu,
23
1199 Appl. Radiat. Isot., 1992, 43, 1241-1245.
24
25 1200 130.E.García-Toraño, M.L. Aceña, G. Bortels, D. Mouchel, Alpha-particle emission
26 1201 probabilities in the decay of 239Pu, Nucl. Instr. Methods Phys. Res., 1993, A 334,
27 1202 477-484.
28
29 1203 131.E. García-Toraño, Alpha-Particle emission probabilities in the decay of U-238, Appl.
30 1204 Radiat. Isot., 2000, 52, 591-594.
31 1205 132.G. Sibbens and S. Pomme´, Study of alpha-particle emission probabilities and
32 1206 energies in the decay of 240Pu, Appl. Radiat. Isot., 2004, 60, 155–158.
33
34 1207 133.E. García-Toraño, M. T. Crespo, M. Roteta, G. Sibbens, S. Pommé, A. Martín
35 1208 Sánchez, M. P. Rubio Montero, S. Woods, and A. Pearce, α-particle emission
36 1209 probabilities in the decay of 235U, Nucl. Instr. Meth. Phys. Res., 2005, A 550, 581-
37
38
1210 592.
39 1211 134.F.G. Kondev, I.Ahmad, J.P. Greene, M.A. Kellett, and A.L. Nichols, Measurements
40 1212 of the half-life of 246Cm and the α-decay emission probabilities of 246Cm and 250Cf,
41 1213 Appl. Radiat. Isot., 2007, 65, 335–340.
42
43 1214 135.G. Sibbens, S.Pomme´, T. Altzitzoglou, E. Garcıa-Torano, H. Janßen, R. Dersch, O.
44 1215 Ott, A. M. Sanchez, M.P.R. Montero, M.Loidl, N. Coron, P. deMarcillac, and T. M.
45 1216 Semkow, Alpha-particle emission probabilities in the decay of 240Pu, Appl. Radiat.
46
1217 Isot., 2010, 68, 1459-1466.
47
48 1218 136.M. Marouli, S. Pommé, J. Paepen, R. Van Ammel, V. Jobbágy, A. Dirican, G.
49 1219 Suliman, H. Stroh, C. Apostolidis, K. Abbas, and A. Morgenstern, High-resolution
50 1220 alpha-particle spectrometry of the U-230 decay series, Appl. Radiat. Isot., 2012, 70,
51
52 1221 2270-2274.
53 1222 137.M. Marouli, S. Pommé, V. Jobbágy, R. Van Ammel, J. Paepen, H. Stroh, and L.
54 1223 Benedik, Alpha-particle emission probabilities of 236U obtained by alpha
55
1224 spectrometry, Appl. Radiat. Isot., 2014, 87, 292-296.
56
57
58
59
60
View Article Online
DOI: 10.1039/C6AY00920D
1
2
3 1225 138.S. Pommé, E. García-Toraño, M. Marouli, M.T. Crespo, V. Jobbágy, R. Van
4 1226 Ammel, J. Paepen, and H. Stroh, High-resolution alpha-particle spectrometry of 238U,
5
6 1227 Appl. Radiat. Isot., 2014, 87, 315-317.
7 1228 139.B.C.Marroyo, A. M. Sanchez, and M. J. Vargas, Improvements to alpha-particle
8 1229 spectrometry techniques, Appl. Radiat. Isot., 2014, 87, 328-330.
9 1230 140.S. Pommé, M. Loidl, E. García-Toraño, M. Marouli, C. Le-Bret, M. T. Crespo, J.
10
11 1231 Paepen, X. Mougeot, V. Jobbágy, M. Rodrigues, R. Van Ammel, H. Stroh, and A.

Luca, Lessons learned from nuclear decay data measurements in the European
12 1232
13 1233 metrology research programme ‘Metro Fission’, 2014, IEEE Transactions on Nucl.
14
15
1234 Sci., 2014, 61, 2066-2070.
16 1235 141.S.K.Aggarwal and H.C.Jain, Half-life of 241Pu: past and present, J. Radioanal. Nucl.
17 1236 Chem., Articles, 1987, 109, 183-200.
18 1237 142.S.K. Aggarwal, S.N. Acharya, A.R. Parab, and H.C. Jain, Half-life of 241Pu by
19 241
20 1238 Am growth method using isotope dilution alpha spectrometry, Radiochim. Acta,
21 1239 1981, 29, 65-70.
22 1240 143.S.K.Aggarwal, D.Alamelu, P.M.Shah, and N.N.Mirashi, Precise and accurate
23
1241 determination of alpha decay half-life of 243Am using 241Am as a reference isotope,
24
25 1242 Nucl. Instr. Meth. Phys. Res., 2007, A571, 663-668.
26 1243 144.S.K.Aggarwal, D.Alamelu, P.M.Shah and N.N.Mirashi, Determination of
27 1244 241
Am/243Am ratios, J. Radioanal. Chem., 2007, 273, 771-774.
28
29 1245 145.S.K.Aggarwal, S.N.Acharya, A.R.Parab and H.C.Jain, Half-life of 242Pu, Phys. Rev.
30 1246 C, 1979, 20, 1135-1144.
31 1247 146. S.K.Aggarwal, S.B.Manohar, S.N.Acharya, Satya Prakash and H.C.Jain, Half-life
32 1248 of 232U, Phys. Rev. C , 1979, 20, 1533-1541.
33
34 1249 147.S.K. Aggarwal and H.C. Jain, Determination of the half-lives of transactinium isotopes
35 1250 by the relative activity method, J. Radioanal. Nucl. Chem., Letters, 1986, 103, 213-224.
36 1251 148.S. Pommé, E. García-Toraño, G. Sibbens, S. Richter, R. Wellum, A. Stolarz, and A.
37
38
1252 Alonso, 234U/235U activity ratios as a probe for the 238U/235U half-life ratio, J.
39 1253 Radioanal. Nucl. Chem., 2008, 277, 207–210.
40 1254 149.W. J. Oldham Jr, D. E. Dry, and A. H. Mueller, Synthesis of functional monolayer
41 1255 surfaces for rapid radiometric determination of plutonium, J. Radioanal. Nucl.
42
43 1256 Chem., 2009, 282, 585−589.
44 1257 150.R.S. Addleman, O.B. Egorov, M.J. O’Hara, B. Busche, T.S. Zemanian, and G.J.
45 1258 Fryxell, Preconcentration and assay of radionuclides with self assembled monolayers
46
1259 on mesoporous supports, J. Radioanal. Nucl. Chem., 2005, 263, 59−64.
47
48 1260 151.C. Labrecque, L.W. Leveille, and D. Lariviere, Cloud point extraction of plutonium
49 1261 in environmental matrixes coupled to ICPMS and α spectrometry in highly acidic
50 1262 conditions, Anal.Chem., 2013, 85, 10549−10555.
51
52 1263
53
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3 1264
4 1265 Table 1. Some of the commonly determined radionuclides by α-particle spectrometry in
5 1266 various samples
6
1267
7
8 Element Isotope α-decay half-life Main α-particle Remarks
9 energies
10 (in MeV)
11 208
Po Po 2.898 yr 5.115 -

12 209
Po 120 ± 6 yr (Pomme, 4.880 Used as a tracer
13 Stroh and and
14
15
Benedik, 2015)
16 125.2 ± 3.3 yr (Cole
17 et al, 2014)
210
18 Po 138.38 d 5.304 Used to determine 210Bi
212
19 Po 0.298 µsec, 45s 8.784, 11.65 -
20 224
Ra Ra 3.63 d 5.685, 5.449 -
21 226
Ra 1600 yr 4.785, 4.602 -
22 228
Ra 5.75 yr (beta emitter) 0.039, 0.015, 0.026 -
23 228
24 Th Th 1.912 yr 5.423, 5.340 Progeny of 232U
229
25 Th 7400 yr 4.845, 4.901, 4.814 Progeny of 233U
230
26 Th 7.56 x 104 yr 4.688, 4.621 Progeny of 234U
27 232 10
Th 1.40 x 10 yr 4.012, 3.947 Natural thorium
232
28 U U 70.6 yr 5.320,5.263 Present in 233U obtained by
29 neutron irradiation of 232Th
30 233 5
31
U 1.592 x 10 yr 4.824, 4.784 Obtained by neutron irradiation
32 of 232Th
234 5
33 U 2.455 x 10 yr 4.725, 4.776 Present in natural U (0.005%)
235
34 U 7.04 x 108 yr 4.398, 4.366 Present in natural U (0.72%)
236
35 U 2.342 x 107 yr 4.494, 4.445 Present in reactor irradiated U,
36 natural fossil reactor
37 238
U 4.47 x 109 yr 4.197, 4.147 Present in natural U (99.275%)
38 237
Np Np 2.14 x 106 yr 4.788, 4.771 Present in irradiated U fuel
39 236
40 Pu Pu 2.87 yr 5.767, 5.721 Artificially produced by
41 charged particle irradiation;
42 used as a tracer; interference
43 from 244Cm and 224Ra
44 238
Pu 87.74 yr 5.499, 5.456 Present in reactor produced Pu;
45 Progeny of 242Cm
46 239
Pu 24100 yr 5.156, 5.144, 5.105 Present in reactor produced Pu
47
48
(maximum abundance among
49 all the Pu isotopes)
240
50 Pu 6560 yr 5.168, 5.124 Present in reactor produced Pu;
51 Progeny of 244Cm
241
52 Pu 14.4 (β), 6 x 105 (α) 4.897, 4.853 Major decay is by β-particle
53 emission
54 242
Pu 5
3.76 x 10 yr 4.901, 4.856 Present in reactor produced Pu
55 244
Pu 8.1 x 107 yr 4.589, 4.546 Produced by high flux isotope
56
57 reactor (HFIR) irradiation of
243
58 Am
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2
241
3 Am Am 432.7 yr 5.486, 5.443 Progeny of 241Pu
4 243
Am 7370 yr 5.276, 5.234 Produced by HFIR irradiation
5 of 242Pu
6 242
Cm Cm 162.8 d 6.113, 6.069 Obtained by neutron irradiation
7
8 of 241Am; present in irradiated
9 fuels
243
10 Cm 29.1 yr 5.785, 5.742 Present in irradiated fuels
244
11 Cm 18.11 yr 5.808, 5.763 Present in irradiated fuels

245
12 Cm 8500 yr 5.362 Produced by neutron

13 irradiation of 244Cm
14 246
Cm 4770 yr 5.386, 5.342, 5.242 Produced by neutron
15
16
irradiation of 244Cm
247
17 Cm 1.56 x 107 yr 4.870, 5.267 Produced by neutron
18 irradiation of 244Cm
248
19 Cm 3.48 x 105 yr 5.078, 5.035 Progeny of 252Cf
20 1268
21 1269 Ref: E.M.Baum, M.C.Ernesti, H.D.Knox, T.R.Miller, A.M.Watson and S.D.Travis,
22
23 1270 Seventeenth Edition, Nuclides and Isotopes, Chart of the Nuclides, Knolls Atomic Power
24 1271 Laboratory, 2009.
25 1272
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
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3 1273 Table 2. Typical examples of electrodeposition methods used for actinide elements
4 1274
5
6 No. Actinide Electrolyte Current Cathode & Deposit Detector Reference
7 element density anode ion area &
8 (matrix) & time & resolution
9 voltage yield
10 1 Th, 1M 1.2 A Electropol 40 min/ - Talvitie,
11 U,Pu,Am ammoniu ished SS/ 98.8% 1972 (17)

12 (Pu from m Pt-Ir disk to

13
soil) sulphate, 99.8%
14
15
pH 2
16 2. Np, Pu 0.3 M 0.6 Polished 1 hr 50 mm2, Tsoupko-
17 and Am Na2SO4, mA/cm2 SS/ RDE (90% 8-8.5 keV Sitnikov,
18 pH 4.5 for Np 2000 (23)
19 & Am),
20 3 hr
21 (80%
22 for Pu)
23
24
3. U, Pu,0.3 M 0.9A Polished 600 mm2
2hr / Janda et al.,
25 Am, Cm ammoniu SS / Pt 90.1%
(PIPS) 2010 (24)
26 (aqueous m oxalate, spiral to
27 solutions) 0.36 M 96.2%
28 ammoniu
29 m sulfate,
30 0.1 M
31 hydroxyl
32 ammoniu
33
34
m sulfate,
35 0.005 M
36 DTPA, pH
37 2
38 4. U (1 H2SO4 and 1500mA, Polished 90%, 1 1200 mm2, Dumitru et
39 -1
Bq.mL ) Na2SO4, 9V SS/ Spiral hr 100 keV al., 2013 (31)
40 pH 2 to Pt wire
41 2.2
42
1275
43
44 1276
45
46
47
48
49
50
51
52
53
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3 1277 Table 3. Various alpha spectrometric systems available commercially
4 1278
5
6 No. Supplier System Vacuum chamber Details
7 1. ORTEC Alpha Aria Single chamber, Up to 51 mm sample
8 (Ametek) compact diameter, detector area up
9 to 1200 mm2
10 Alpha Mega Single chamber, For filters up to 106 mm
11 large in diameter, using large

12 area detectors (3000 mm2)

13
14
Alpha Duo Dual-chamber (2) Up to 51 mm sample
15 diameter, detector area up
16 to 1200 mm2
17 Alpha ensemble Multi–chamber Up to 51 mm sample
18 (8) diameter, detector area up
19 to 1200 mm2
20 2. CANBERRA Model 7401 Single chamber Samples up to 50 mm
21 diameter, detector area up
22
to 1200 mm2
23
24 1279
25 1280 Optional alpha recoil protection system available from ORTEC (www.ortec-online.com)
26 1281
27
1282
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
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2
3 1283 Table 4. Tracers (Spikes) commonly used for chemical recovery and isotope dilution alpha
4 1284 spectrometry (IDAS) for concentration determination
5
6 1285
7 1286
8 Element Tracer (spike) Remarks
9 Po 209
Po -
10 225
Ra Ra (β) Measured via its daughter product 217At
11 229
Th Th Progeny of 233U

12 232
13 U U Thermal neutron irradiation of 231Pa
14 Np - No useful alpha emitting tracer
236
15 Pu Pu Decays by α-particles of energy “higher” than
16 all the commonly determined Pu isotopes
17 238
Pu Can be used, but needs one extra analysis
18
without tracer if 238Pu in sample is also to be
19
20
determined
242
21 Pu Gives α-particles of energy “lower” than all
22 the commonly determined Pu isotopes
243
23 Am Am High flux isotope irradiation (HFIR) of 242Pu
248
24 Cm Cm,243Am 248
Cm is daughter product of 252Cf
25 1287
26
27 1288
28 1289
29 1290
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
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3 1291 Table 5. Radionuclides with close-lying main α-particle energies that require high resolution
4 1292 α-particle spectrometry (HRAS)
5
6 1293
7 No. Low energy High energy ∆E (keV) Remarks
8 isotope isotope between main
9 alpha energies
10 233 234
1 U U 67 Both present in reactor
11 irradiated Th

12 232 228 228

13
2 U Th 100 Th is a progeny of
232
14 U; limits the use of
232
15 U as a tracer for U
239 240
16 3 Pu Pu 13 Required for nuclear
17 forensics; identification of
18 type of reactor
19 4 238
Pu 241
Am 13 Source preparation only
20 by drop deposition
21 243 244
22
5 Cm Cm 23 Both present in reactor
23 produced Cm
241 242
24 6 Pu Pu 4 Both present in reactor
25 produced Pu; of interest
26 in enriched isotopes of
241
27 Pu and 242Pu
28 1294
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
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12 928 americium-241/uranium-233 and curium-244/uranium-233 alpha activity ratios

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12 Cm 8500 yr 5.362 Produced by neutron

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12 (Pu from m Pt-Ir disk to

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12 area detectors (3000 mm2)

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12 232 228 228

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