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Gross alpha and beta activity analysis in water - A routine laboratory

method using liquid scintillation analysis

Article  in  Applied Radiation and Isotopes · August 2004

DOI: 10.1016/j.apradiso.2004.03.004 · Source: PubMed

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Ross Kleinschmidt
Queensland Health


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Applied Radiation and Isotopes ] (]]]]) ]]]–]]]

Gross alpha and beta activity analysis in water—a routine
laboratory method using liquid scintillation analysis
Ross I. Kleinschmidt
Queensland Health Scientific Services, P.O. Box 594 Archerfield, QD 4108, Australia

17 Abstract

19 The generally accepted method for gross alpha and beta activity analysis of drinking water in Australia is based on

ISO methods; ISO9696, water quality—measurement of gross alpha activity in non-saline water—thick source method,
21 and ISO9697, water quality—measurement of gross beta activity in non-saline water.

A liquid scintillation (LSA) based method that requires smaller sample quantities, less sample preparation time and
23 operator intervention, and produces adequate minimum detection levels for local drinking water guidelines has been
25 A synthetic groundwater sample was analysed using the LSA method and compared with results from ISO method
techniques used by two independent Australian laboratories. The results show that the LSA method exceeds
27 performance of the ISO methods in measurement accuracy.
r 2004 Published by Elsevier Ltd.

Keywords: Water; Gross alpha and beta radioactivity; Liquid scintillation analysis

1. Introduction methods is dependent on the water residue mass. It is 57
35 well recognized that sample presentation to the detector
The Australian Drinking Water Guidelines plays a significant role in producing reliable results, the 59

37 (NHMRC/ARMCANZ, 2001) have recommended a technique requiring a uniform thickness, homogeneous

dose of 1 mSv per year for radioactivity in drinking layer of residue material on the planchet. Multiple 61

39 water. Recently, this guideline has been extended to calibration standards are also required to cover a range
include irrigation waters, livestock drinking waters and of residue masses (Semkow and Parekh, 2001). The 63

41 recreational waters (ANZECC/ARMCANZ, 2000). APHA/AWWA/WEF (1998) co-precipitation method

Table 1 lists both artificial and naturally occurring has limited applicability for some radionuclides 65

43 radionuclides that may be found in drinking water (NHMRC/ARMCANZ, 2001). None of these methods
supplies. Screening levels have been derived from the is suitable for the determination of radon or low-energy 67

recommended guideline dose (Table 2). beta emitters in water.

Gross alpha and beta activity screening procedures The aim of this work was to develop a method to 69
47 have been developed to determine if radionuclide provide rapid results, adequate sensitivity, minimum

specific analysis is required to further characterize the sample preparation and operator intervention for waters 71
49 water. Recommended gross alpha and beta activity with widely varying chemical and physical properties.
screening methods generally employ gas proportional The low background, alpha/beta discriminating liquid 73
51 counting techniques (APHA/AWWA/WEF, 1998; AS- scintillation analyzer method fulfils these requirements
3550.5, 1990; NHMRC/ARMCANZ, 2001; ISO9696, while minimizing some of the disadvantages of GFPC 75
53 1991 and ISO9697, 1991). The efficiency of the ISO methods. The method can be adapted to allow
monitoring of low-energy beta emitters such as 14C 77
55 E-mail address: ross (R.I. and 3H. Radon in water measurement may be deter-
Kleinschmidt). 79

0969-8043/$ - see front matter r 2004 Published by Elsevier Ltd.

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1 Table 1 time resolved electronics (Passo and Cook, 1996). Pulse 57

Artificial and naturally occurring radionuclide dose contribu- decay analysis is used to differentiate between count
3 tions based on annual adult water consumption rate of 730 l pulses generated by either alpha or beta emissions. 59
(adapted from NHMRC/ARMCANZ, 2001) When dealing with low-level counting methods, the
5 Source Radionuclide Dose by water effects of background variations can adversely impact 61
ingestion on analysis results and minimum detection level. Even
7 (mSvBq1year1) though internal standardization is used to determine the 63
238 2 overall counting efficiency of the system, that method
Uranium series U 3.3  10
9 234
U 3.6  102
does not allow for calculation of misclassification of 65
Th 1.5  101 alpha and beta counts in the sample and spiked
11 226
Ra 2.0  101 duplicate backgrounds. Background characterization 67
Pb 5.0  101 was determined by adding 2 ml of 2 M H3PO4 to a
13 210
Po 8.8  101 counting vial and then 12 ml of UGAB scintillation 69
Thorium series 232
Th 1.7  101 cocktail to simulate sample preparation chemistry. As it
Ra 5.0  101 has been shown that alpha/beta misclassification 71

Th 5.3  102 changes with quench (Passo Jr. and Cook, 1996), it
17 Fission products 134
Cs 1.4  102 follows that the alpha and beta background will vary 73

Cs 9.5  103
with quench as well. This was confirmed by adding
Sr 2.0  102
19 131
I 1.6  102 increasing volumes of CCl4 as a chemical quench agent 75

Others 3
H 1.3  105 to the background samples. Each sample was counted
21 14
C 4.2  104 for 1000 min (5  200 min counts) and alpha and beta 77

Pu 1.8  101 counts plotted against a suitable quench indicator, in
23 241
Am 1.5  101 this case the transformed Spectral Index, or tSIE 79
(Kessler, 1989). Fig. 1 shows the alpha and beta count
25 variation associated with misclassification by quench 81
27 Table 2 83
Gross alpha and beta activity screening levels for various water
2.2. Procedure

29 use applications (NHMRC/ARMCANZ, 2001) 85

Water use Screening value (Bq l ) The procedure is designed to be simple, efficient and
31 87
Gross alpha Gross beta involve minimal operator intervention. Fig. 2 shows the

method schematic, detailing steps involved in sample

33 Drinking—human 0.5 0.5 89
Drinking—livestock 0.5 0.5 Typical water samples are collected from surface and
35 Irrigation 0.5 0.5 91
ground water supplies. Acid washed, 500 ml polyethy-
Recreational 0.1 0.1
lene bottles are recommended for sample collection.

37 93
Water samples are preserved to reduce loss of radio-

39 mined separately using alternative liquid scintillation 95

methods (NHMRC/ARMCANZ, 2001; AMHS/ 9.5

41 AWWA/WES, 1998; USEPA, 1987). 9.0 97



43 7.0 99
2. Method 6.5
45 101

2.1. Liquid scintillation analysis 4.5
47 4.0 103

Liquid scintillation analysis (LSA) has become a 3.0
49 useful tool in the analysis of environmental level 2.5 105
radionuclide concentrations. Advanced LSA systems 1.5
51 provide discrimination between alpha and beta radia- 0.5 107
tions, and reliable passive and active background 0.0
53 reduction systems. The instrument used for this work 100 200 300 400 500 600 700 800 900 109
(Packard Tricarb 3170 TR/SL) incorporates an active
55 background reduction system based on a Bismuth Fig. 1. Alpha () and beta (~) background count rate as a 111
Germanate (BGO) guard detector and programmable function of transformed Spectral Index (tSIE).
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1 5 x 20mL aliquots
to eliminate dissolved radon isotopes in the sample 57
of acidified sample (Sanchez-Cabeza and Pujol, 1995). To achieve adequate
3 water in poly vial minimum detection levels, a concentration factor of 10 59
was derived using instrument background levels.
5 To reduce operator intervention, evaporation of the 61
duplicate sample
for spike samples is conducted in a block heater. The heater holds
7 standard 20 ml liquid scintillation vials and is main- 63
N2 purge tained at 80 C, the maximum temperature recom-
9 mended for the polyethylene vials. The vials are 65
block heater
80°C to dry topped up in 20 ml increments until the desired volume
11 of sample has been evaporated, typically 100 ml in total. 67
add 2mL 2M H3PO4 A duplicate sample is prepared under the same condi-
13 tions for spiking and efficiency calculation. Evaporation 69
times are reduced by injecting nitrogen gas into the vial
15 block heater headspace to reduce the water vapour partial pressure. 71
50°C, ~2hrs

After evaporation, 2 ml of 2 M H3PO4 acid is added to
17 both the sample and duplicate to dissolve residual 73

add 0.02g spike: add 12mL UGAB
Am ~ 5 Bq
material. The use of orthophosphoric acid over nitric
19 90
S/Y ~ 5 Bq acid has been shown to reduce sample colour and reduce 75

chemical quench effects (Burnett et al., 2000).
21 α /β LSA A spike solution containing less than 10 Bq of both 77

alpha and beta radionuclide reference surrogates is
23 added to the duplicate sample before addition of the 79
Fig. 2. Method schematic showing steps involved in preparing liquid scintillation cocktail. To minimize the quenching
25 water samples for analysis. effects of the spike addition, a small volume, typically 81
20 ml is used for spiking. Details of the radionuclide
27 nuclides by adsorption onto container surfaces (AMHS/ concentration are provided in the following section. 83
AWWA/WES, 1998). If obviously free of high sus- Packard UltimaGold AB scintillation cocktail has been

29 pended solid loadings, the samples are acidified in the shown to mix well with the orthophosphoric acid based 85
field with nitric acid (approximately 15 ml per 1000 ml of sample (Burnett et al., 2000) and was used throughout
31 sample). Samples containing suspended solids are first this work. 12 ml of UltimaGold AB was found to 87
filtered through a 0.45 mm glass fibre filter paper and maintain the prepared samples in a homogeneous

33 then preserved with the acid. The filter papers may be mixture suitable for counting (Fig. 3). 89
submitted for analysis if required. While it has been All prepared samples are stored in the LSA for at least
35 observed that the addition of strong acids adversely 60 min to allow dark adaption prior to counting. 91
effects liquid scintillation counting by increasing quench Optimum counting time was determined by plotting

37 (Sanchez-Cabeza and Pujol 1995), it is common for minimum detection level (MDL), as calculated by 93
water samples to be collected at locations remote from

39 the laboratory, up to several 1000 km, and preservation 10 95

is justified. On arrival of the sample in the laboratory,

41 the pH of the sample is determined using a portable pH 97

meter to establish if the sample has been preserved. If it
reference activity (Bq/L)

has not been preserved, 15 ml of concentrated HNO3 is

43 99
added per litre of sample and left stand for at least 12 h
to allow dissolution of radionuclides from the container 5
45 101

surfaces. The presence of radium and radon in water, in 4

47 conjunction with long sample holding times, have been 3 103


observed to provide inconsistency in gross activity 2

49 analysis (Oural et al., 1988; Parsa, 1998). It is suggested 1 105

that a radon analysis be conducted on samples that have 0
51 been stored for a period of greater than 3 months, to 100 200 300 400 500 600 700 800 900 107
establish the possibility of in-growth of decay progeny, tSIE
53 thereby elevating gross alpha activity. 109
Fig. 3. Gross alpha () and beta (r) activity concentrations
This method relies on the concentration, by evapora- determined during quench effect validation trials. The broken
55 tion, of the water sample directly in a liquid scintillation line indicates reference alpha activity of 7.370.1 Bq l1, the 111
counting vial. Concentration by heating has been shown solid line being the beta reference activity of 6.270.1 Bq l1.
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1 Kessler (1989) and Passo and Cook (1996), against tion surrogates for alpha and beta radionuclides of 57
count time. A suitable MDL was considered to be at 241
Am (a energy B5.64 MeV) and 90Sr (bmean energy
3 least one-fifth of the screening level value for both alpha B0.20 MeV+90Y progeny bmean energy B0.93 MeV), 59
and beta activities (Table 2). From Fig. 4a count time of respectively, were chosen. The radionuclides were
5 250 min for a 100 ml sample meets the MDL target prepared from standard solutions traceable to the US 61
value. National Institute of Science and Technology (NIST). A
7 spiking standard containing approximately 350 Bq g1 63
2.3. Calibration of both radionuclides was prepared in a 0.5 M HNO3
9 carrier solution. Quench experiments to determine alpha 65
To maintain the lowest possible detection limits, and beta background misclassification and other instru-
11 analytical grade reagents and high-purity deionized ment parameters used CCl4 as the quenching agent, 67
water were used throughout this work. Ideally, reference typically in volumes between 0.01 and 0.3 ml.
13 radioisotopes used for calculation of system efficiency The method used to determine the optimum pulse 69
should be similar to those expected to be measured. In decay discriminator (PDD) and Time-Resolved Liquid
15 the case of natural radionuclides this is difficult to Scintillation Counting (TR-LSCt) settings for the liquid 71

achieve due to the complex nature of the numerous scintillation analyzer are those described by Passo and
17 decay chains and source equilibrium systems. An Cook (1996). The optimum PDD setting was determined 73

alternative method is to choose artificial sources with a for a low quench sample containing only the scintillation
19 similar emission type and energy range. Table 3 shows cocktail and 2 ml of 2 M H3PO4 acid. A TR-LSCt burst 75

the emission energies for various artificial radionuclides before delay setting of 100 ns and a PDD setting of 130
21 commonly employed as calibration surrogates in gross were used for this work. 77

alpha and beta activity analysis. In this work, calibra-
23 2.4. Quality assurance and method validation 79
25 0.28
Minimum detection level 81
100mL water, tSIE = 850 Each batch (or cassette of 12 vials) is run with a
0.26 control and blank sample to ensure measurement
27 0.24 beta
quality. The blank sample consists of 2 ml of 2 M 83
minimum detection level (Bq.L-1)

0.22 H3PO4 plus 12 ml UltimaGold AB scintillation cocktail.


29 0.20 The blank sample, and duplicate, is counted for the 85

0.18 same time period as the test samples. A control standard
31 0.16 is prepared under similar conditions to the test samples. 87
A QC solution is made up with alpha and beta activities

33 of less than 10 Bq l1 each. A vial, and duplicate for 89
0.10 spiking, is filled with 20 ml of the QC solution and
35 91
0.08 evaporated with the test samples. Results from both QC
sample and blank are recorded and monitored for

37 variations. If the results are outside of 2 standard 93
deviations of the expected value, the results for the batch

39 are not reported until the anomily has been investigated. 95
Even though the sample preparation method provides

41 0 100 200 300 400 500 600 700 800 900 1000
relatively constant quench conditions (500otSIEo900), 97
time (minutes)
performance over a range of quench conditions was

43 Fig. 4. Minimum detection level optimization for a given test tested by the addition of CCl4 to a number of artificially 99
sample counting time (tSIE=850, sample volume=100 ml).
spiked samples with an alpha/beta activity ratio of
45 101

Table 3
47 103

Emission energies for various alpha and beta emitting radionuclides commonly used for calibration of gross alpha and beta
measurement systems
49 105
Radionuclide Alpha energy (MeV) Beta energy (MeV)
51 Maximum Mean 107
53 Am 5.49 (85%), 5.44 (12%) — 109
K — 1.31 (89%), 1.51 (11%) 0.522
Sr/90Y — 0.546 (100%) / 2.28 (100%) 0.565
55 137 111
Cs — 1.17 (5%), 0.51 (95%) 0.186
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1 approximately 1:1. The CCl4 volumes ranged from 0 to samples with tSIE value between 140 (highly quenched) 57
0.3 ml, representing tSIE values between 850 and 140, and 800 (minimum quench). All sample results were
3 respectively. In addition to the quench tests, a number of within 2d total uncertainty bars of the reference value 59
artificial water samples were made up to simulate (Fig. 3).
5 conditions were alpha to beta activity ratios were not To determine the effects of low beta activity in the 61
equal to 1, and hence establish if the data reduction presence of high alpha activity, and visa versa,
7 algorithms were performing as expected. additional validation samples were counted at a fixed 63
A 3 l artificial water intercomparison sample was quench value. Table 4 shows the mean results of the
9 made to simulate a typical ground water sample. The validation samples over three separate analysis. All 65
sample was split and 1000 ml aliquots were sent to two sample results are within 2d total uncertainty bars of the
11 independent Australian laboratories for gross alpha and reference values. 67
beta activity analysis. Both laboratories use GFPC
13 methods (ISO9696 and ISO9697, 1991) for gross alpha 3.2. Intercomparison samples 69
and beta activity analysis.
15 The simulated ground water sample 71

(TDS=300 mg l1) was spiked with 1.470.1 Bq l1 of
17 3. Results and discussion alpha activity (as 241Am) and 1.170.1 Bq l1 beta 73

activity (as 90Sr/Y). The laboratories selected for the
19 3.1. Validation samples intercomparison trial routinely perform gross alpha and 75

beta activity analysis on a range of drinking and
21 It is assumed that by using an internal standard environmental waters using the ISO series standard 77

method for total efficiency determination, chemical, methods (ISO 9696, 1991 and ISO 9697, 1991). Table 5
23 colour and detection efficiency are all accounted for. shows the results from the trials. The LSA method 79
Reference values for the alpha activity and beta activity performed well with results within the expected range for
25 were 7.370.1 Bql1 (241Am equivalent) and both alpha and beta activities. Results from laboratory 81
1 90
6.270.1 Bq l ( Sr/Y equivalent), respectively. The A show the impact that varying residue masses may have
27 validation samples confirmed that the data reduction on results using the GFPC method, specifically alpha 83
algorithm compensates for varying chemical quench in activity. Laboratory A checked the alpha activity

29 85

31 Table 4 87
Validation results for varying alpha and beta activity ratios

33 89
Sample Reference activity (Bq l1) Mean measured activity(n=3) (Bq l1)
35 Alpha Beta Alpha Beta 91

37 A=B 7.970.1 6.270.1 7.870.2 6.370.3 93

LoA/HiB 0.870.1 5.770.1 0.970.1 6.170.2

HiA/LoB 7.670.1 1.770.1 7.970.4 1.670.1

39 95

41 97

Table 5

43 99
Results of intercomparison studies for LSA and GFPC analysis methods
45 Results (Bq l1) 101

Laboratory Method

Alpha Beta
47 103

QHSS LSA (90 ml sample) 1.4070.14 1.1570.10

49 Laboratory A ISO 9696/9697 (0.1999 g residue) 0.7070.09 0.9870.05 105
Laboratory A ISO 9696/9697 (0.0994 g residue) 0.9370.11 1.0270.07
51 Laboratory A ISO 9696/9697 (0.0834 g residue) 1.0270.12 1.0870.08 107
Laboratory A Gamma ray spectrometry 1.470.1 —
53 Laboratory B ISO 9696/9697 1.2270.08 1.2070.06 109
Reference activity Am+90Sr/Y solution 1.470.1 1.170.1
55 Gross beta activity results have been corrected for 40
K concentration as required under the drinking water guidelines (NHMRC/ 111
ARMCANZ, 2001).
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1 component of the sample by recovering the residues for References 57

gamma spectrometry, results indicating that the alpha
3 activity present in the sample as 241Am corresponds to ANZECC/ARMCANZ, 2000. Australian and New Zealand 59
the stated reference activity of the simulated water Guidelines for Fresh and Marine Water Quality. National
5 sample provided. Laboratory A beta results were within Water Quality Management Strategy Paper No. 4, Aus- 61
tralian and New Zealand Environmental and Conservation
the stated uncertainty bounds. Results from Laboratory
Council & Agricultural and Resource Management Council
7 C indicated some inaccuracy in alpha activity measure- 63
of Australia and New Zealand, Australian Government
ment, beta results being within the stated uncertainty Publishing Service, Canberra.
9 bounds. APHA/AWWA/WEF, 1998. Standard Methods for the Exam- 65
Both Laboratory A and Laboratory B used 241Am ination of Water and Wastewater, 20th Edition. American
11 and 40K as calibration surrogates for gross alpha and Public Health Association, Washington, DC. 67
beta activity analysis. It would appear that the use of AS 2550.5, 1990. Australian Standard, Waters—Part 5 Deter-
13 different beta calibration radionuclides between the LSA mination of Gross Alpha and Gross Beta Activities. 69
and GPFC methods had little effect on the gross beta Standards Association of Australia, Sydney, NSW.
15 activity result. Burnett, W.C., Christoff, J., Stewart, B., Winters, T., Wilbur, 71

P., 2000. Reliable gross alpha-/beta-particle analysis of
environmental samples via liquid scintillation counting.
17 73

Radioact. Radiochem. 11 (4), 26–44.
ISO 9696, 1991. Water quality—measurement of gross alpha
19 4. Summary and conclusions activity in non-saline water—thick source method. Interna- 75

tional Standard 9696. International Organization for
21 Australian drinking, recreational, irrigation and live- Standardization, Geneva, Switzerland. 77

stock waters are screened for the presence of radio- ISO 9697, 1991. Water quality—measurement of gross beta
23 activity in non-saline water. International Standard 9696. 79
nuclides using gross alpha and beta activity screening
International Organization for Standardization, Geneva,
techniques. The liquid scintillation method described Switzerland.
25 provides an alternative method to the more commonly 81
ISO 9698, 1991. Water quality—measurement of tritium
used ISO methods that use gas flow proportional activity concentration—liquid scintillation method. Inter-
27 counting. 83
national Standard 9698. International Organization for
The method overcomes the self attenuation problems Standardization, Geneva, Switzerland.

29 typical of high dissolved solid waters and gas flow Kessler, M.J., 1989. Liquid Scintillation Analysis—Science and 85
proportional counting. Additionally, the need to evapo- Technology. Publication No. 169-3052, Packard Instrument
31 rate large volumes of water, quantitatively transfer Company, Meriden, USA. 87
residues to counting lancets and developing operator NHMRC/ARMCANZ, 2001. Australian drinking water guide-

33 lines 1996—update 2001. National Water Quality Manage- 89

skills in producing homogeneous, evenly distributed
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35 minimized during sample preparation and counting. It is 91
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Government Publishing Service, Canberra.

37 radionuclides such as 14C and 3H in the gross beta 93
Oural, C.R., Upchurch, S.B., Brooker, H.R., 1988. Radon
counting window if desired. progeny as sources of gross-alpha radioactivity anomalies in

39 Intercomparison trials have indicated that the method ground water. Health Phys. 55, 889–894. 95
provides a more accurate alpha activity result for a Parsa, B., 1998. Contribution of short-lived radionuclides to

41 simulated ground water sample than ISO gas flow alpha particle radioactivity in drinking water and their 97
proportional counting methods, and that the method impact on the safe drinking water act regulations. Radioact.

43 Radiochem. 9 (4), 41–50. 99

provides reliable results for samples with varying quench
Passo Jr., C.J., Cook, G.T., 1996. Handbook of Environmental
and alpha to beta activity ratios. Alpha and beta activity Liquid Scintillation Spectrometry. A Compilation of
45 101

minimum detection levels of 0.05 and 0.08 Bq l1, Theory and Methods. Packard Instrument Company,
respectively, are achievable with 100 ml of acidified Meriden, USA.
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sample and a total count time of 270, 250 min for sample Sanchez-Cabeza, J.A., Pujol, L., 1995. A rapid method for the
counting (assuming activity levels are near background), simultaneous determination of gross alpha and beta
49 and 30 min for counting the spiked duplicate. activities in water samples using a low background liquid 105
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51 Semkow, T.M., Parekh, P.P., 2001. Principles of gross alpha 107
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53 (5), 567–574. 109
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