Quantification of measurement uncertainty in the sequential determination of <Superscript>210</Superscript>Pb and <Superscript>210</Superscript>Po by liquid scintillation counting and alpha-particle spectrometry

Methodologies for the quantification of measurement uncertainties associated with the determination of ²¹⁰Pb- and ²¹⁰Po-specific activities by liquid scintillation counting (LSC) and alpha-particle spectrometry are presented, and are demonstrated using the soil reference material IAEA-326. Major contributors to the combined uncertainty associated with the measurement result of ²¹⁰Pb were the uncertainties of net count rates in the ²¹⁰Pb energy region of the sample spectrum and in the ²¹⁰Bi energy region of the blank spectrum. The predominant sources of uncertainty in the measurement of ²¹⁰Po were the uncertainties of net count rates in the regions of interest of ²⁰⁹Po and ²¹⁰Po. The relative standard uncertainty of ²¹⁰Po exponentially increases with the time interval between the sampling date and the separation date of Po, and this effect is strongly dependent on the ²¹⁰Po/²¹⁰Pb activity ratio. When the specific activity of ²¹⁰Pb is much higher than that of ²¹⁰Po in the sample, the relative standard uncertainty of the ²¹⁰Po determination increases significantly within a short time interval between the sampling date (or reference date) and the separation date of Po in samples.     

Marine Sediments and Snow from Ross Sea Region (Antarctica) Dating by 210Pb Method

Abstract

²¹⁰Pb is widely used to determine accumulation rates in order to obtain a time scale in environmental samples. The most accurate method uses the determination of ²¹⁰Pb via its grand-daughter ²¹⁰Po by alpha spectrometry. Unfortunately this method requires a complex wet-chemistry procedure to achieve the separation of ²¹⁰Po from its matrix. In this work a simplified procedure for the chemical separation of ²¹⁰Po is proposed and applied to three marine sediment cores and a 10 m snow core collected in Antarctica. The calculated sedimentation rates for marine sediments range from 0.053 to 0.071 cm y^?1. The mean annual accumulation rate for the snow is 16.6 cm y^?1 w.e. A comparison with literature data in the same region is given.     

The fractionation and determination procedures for the speciation of Pb and Po in soil samples

A method for speciation and determination of ²¹⁰Pb and ²¹⁰Po in soil samples was developed. The speciation was carried out by fractionating the soil samples into five fractions which are water soluble or exchangeable, bound to carbonates, bound to Fe-Mn oxides, bound to organic matter and bound to residue. After mineralisation, 10% solution of each fraction was used to spontaneously deposit polonium on a silver disk at 85-90 °C and pH 1.5, and ²¹⁰Po was measured by α-spectrometry; the remain solution was used to separate lead by anion-exchange resin and purified by precipitation as PbS and PbSO₄, and ²¹⁰Pb was determined by a low background β-counter. The IAEA-327 reference material (soil) was studied for ²¹⁰Pb and ²¹⁰Po speciation. The results show that: (1) the average yields are 88.7 ± 6.4% for ²¹⁰Pb and 93.8 ± 8.2% for ²¹⁰Po; (2) if compared to the total ²¹⁰Pb activity in the sample, ²¹⁰Pb fractions are 0.95% in exchangeable form, 10.6% bound to carbonates, 14.3% bound to Fe-Mn oxides, 7.0% bound to organic matter and 67.2% bound to residue or acid soluble, and the corresponding values for ²¹⁰Po are 0.17%, 0.97%, 21.0%, 0.47% and 77.4%, respectively; and (3) the obtained ²¹⁰Pb concentration is in good agreement with the recommended value given by the IAEA.     

Optimization of Pb determination via spontaneous deposition of Po on a silver disk

The accuracy of ²¹⁰Pb determination via spontaneous deposition of ²¹⁰Po on a silver disk and alpha spectrometric measurement was examined. The study focused on the storage conditions of the polonium-containing solutions, the tracer used in polonium analysis and the effect of storage time and acid concentration on ²¹⁰Po deposition. The intermediate precision and repeatability associated with the improved ²¹⁰Pb analysis of fresh groundwater samples was 5 and 14%, respectively. These improved values were achieved by using glass bottles as storage containers for the solution remaining from the first ²¹⁰Po deposition, by rinsing the sample container with concentrated hydrochloric acid after storage and by using different isotopes of polonium as the yield determinant tracer in the first and the second deposition. Less polonium adsorption onto the storage container walls occurred with HCl than with HNO₃. The overall uncertainty in ²¹⁰Pb analysis was (11 ± 7)% at the 95% confidence level. The minimum detectable activity concentration was 0.1 mBq l⁻¹ calculated from blank samples and 0.05 mBq l⁻¹ using the background counts of the alpha spectrometer.     

Radiochemical characterization of spring waters in Balaton Upland, Hungary, estimation of radiation dose to members of public

Hungary is rich in spring waters. A survey studying the naturally occurring alpha emitter radionuclides in 30 frequently visited and regularly consumed spring waters was conducted out in the Balaton Upland region of Hungary.²²⁶Ra, ²²⁴Ra, ²³⁴U, ²³⁸U and ²¹⁰Po activity concentrations were determined by using alpha spectrometry after separation from matrix elements. Average concentration (mBq L^{− 1}) of ²²⁶Ra, ²²⁴Ra, ²³⁴U, ²³⁸U and ²¹⁰Po in the spring waters is varied from 2.1 to 601, from < 1.1 to 65.4, from 3.9 to 741.9, from < 0.44 to 274.3 and from 2 to 15.2 respectively. In most cases radioactive disequilibrium was observed between uranium and radium isotopes. The doses for the analyzed samples of spring water are in the range 3.59–166.73 μSv y^{− 1} with an average 18.2 μSv y^{− 1} .This is well below the 100 μSv y^{− 1} reference level of the committed effective dose recommended by WHO. Only one water sample had a dose higher than 100 μSv y^{− 1}, mainly due to the contribution from radium (²²⁶Ra, ²²⁴Ra) and ²¹⁰Po isotopes. This study provides important information for consumers and authorities about their internal radiological exposure risk from spring water intake.     

Analytical methods for the characterization and the leachability evaluation of a solid waste generated in a phosphoric acid production plant

Naturally Occurring Radioactive Materials (NORM) are present in the environment and can be concentrated by technical activities, particularly those involving natural resources. These NORM deposits are highly stable and very insoluble under environmental conditions at the earth's surface. However reducing or oxidant conditions or pH changes may enable a fraction of naturally occurring radionuclides to eventually be released to the environment. In this paper the analytical methods to determine the chemical and radiochemical composition of a solid waste generated in an acid phosphoric production plant was shown. The sample, analysed by gamma spectrometry and radiochemical methods, contained ²¹⁰Pb and ²¹⁰Po and a high activity concentration of uranium isotopes but it shows a very low quantity of ²²⁶Ra. Also a sequential extraction method consisting of five operationally-defined fractions was used to evaluate the leachability of uranium isotopes, ²¹⁰Pb and ²¹⁰Po. The average leaching potential observed in the sample is 97.6% for ²³⁸U, 93.2% for ²¹⁰Pb and 82.4% for ²¹⁰Po. Moreover the results show that ²¹⁰Pb and ²¹⁰Po are leachable under only extreme conditions, whereas uranium is very more soluble.     

A comparison of two nuclear analytical techniques for determination of 210Pb-specific activity in solid environmental samples

Two nuclear analytical techniques for determination of ²¹⁰Pb-specific activity in solid environmental samples have been validated and compared. The first technique depends on determination of ²¹⁰Pb via its alpha emitting daughter ²¹⁰Po using alpha-particle spectrometry, while the second technique is based on direct determination of ²¹⁰Pb by measuring its activity at the 46-keV gamma line by low-energy gamma-ray spectrometry. Detection limits, repeatability, reproducibility, and surrogate recovery were the main validation parameters. Measurement uncertainties were estimated and compared for both techniques. Results of this study have shown that the expected activity of ²¹⁰Pb in the environmental samples and the required measurement uncertainty are the main factors influencing a selection of the appropriate method for the application.     

Comparison of analytical methods used to determine <Superscript>235</Superscript>U, <Superscript>238</Superscript>U and <Superscript>210</Superscript>Pb from sediment samples by alpha,beta and gamma spectrometry

An intercomparison of the methodology (alpha, beta and gamma spectrometry) used for ²³⁸U, ²³⁵U and ²¹⁰Pb determination was carried out based on 38 sediment samples. The activity range of the samples varied from 10–700 Bq/kg for ²¹⁰Pb, 1–35 Bq/kg for ²³⁵U and 10–800 Bq/kg for ²³⁸U. Results obtained using the three methods were not statistically different at high activity levels, but agreement between the results decreased at lower sample activity levels. For ²¹⁰Pb, the smallest difference was found between alpha and gamma spectrometry. A good correlation between results from alpha and gamma spectrometry was observed over the whole activity range. In beta spectrometry, the results were slightly higher than those obtained by alpha or gamma spectrometry due to the impurity of ²²⁸Ra. In ²³⁸U analysis, good correspondence was observed between ²³⁸U determined by gamma and alpha spectrometry, particularly at higher ²³⁸U activity concentrations over 100 Bq/kg. In ²³⁵U analysis, attention needs to be paid to interference from ²²⁶Ra and its reduction.     

Effective doses due to intake of radiotoxic radionuclides 226Ra, 210Po and 210Pb through drinking water of coastal Karnataka

The concentrations of ²²⁶Ra, ²¹⁰Po and ²¹⁰Pb have been measured, by high efficiency 5″ × 5″ NaI(Tl) gamma ray spectrometer and chemical deposition method, in surface water samples from major rivers Kali, Sharavathi and Netravathi of coastal Karnataka. Measurements of ²²⁶Ra, ²¹⁰Po and ²¹⁰Pb in surface water from these rivers are important because the river water is main source of potable water in this region due to inadequate supply of treated water. The mean activity of ²²⁶Ra, ²¹⁰Po and ²¹⁰Pb in the surface water of the river Kali was found to be 5.13 mBq L⁻¹, 1.28 and 1.37 Bq L⁻¹, for Sharavathi River the mean activity was found to be 3.37 mBq L⁻¹, 1.30 and 1.44 Bq L⁻¹. In Netravathi River the mean activity of ²²⁶Ra, ²¹⁰Po and ²¹⁰Pb was found to be 3.30 mBq L⁻¹, 1.00 and 1.20 Bq L⁻¹. From the measured concentration of ²²⁶Ra, ²¹⁰Po and ²¹⁰Pb, the Effective dose to the population of the region was computed. The results of these systematic studies are presented and discussed in the paper.     

Analysis of Pb in water samples with plastic scintillation resins

²¹⁰Pb is a radioactive lead isotope present in the environment as member of the ²³⁸U decay chain. Since it is a relatively long-lived radionuclide (T_1/2 = 22.2 years), its analysis is of interest in radiation protection and the geochronology of sediments and artwork. Here, we present a method for analysing ²¹⁰Pb using plastic scintillation resins (PSresins) packaged in solid-phase extraction columns (SPE cartridge). The advantages of this method are its selectivity, the low limit of detection, as well as reductions in the amount of time and reagents required for analysis and the quantity of waste generated. The PSresins used in this study were composed of a selective extractant (4′,4″(5″)-Di-tert-butyldicyclohexano-18-crown-6 in 1-octanol) covering the surface of plastic scintillation microspheres. Once the amount of extractant (1:1/4) and medium of separation (2 M HNO₃) were optimised, PSresins in SPE cartridges were calibrated with a standard solution of ²¹⁰Pb. ²¹⁰Pb could be fully separated from its daughters, ²¹⁰Bi and ²¹⁰Po, with a recovery value of 91(3)% and detection efficiency of 44(3)%. Three spiked water samples (one underground and two river water samples) were analysed in triplicates with deviations lower than 10%, demonstrating the validity of the PS resin method for ²¹⁰Pb analysis.     

Atmospheric deposition of 210Po and 210Pb in Malaysian waters during haze events

Biogenic burning as forest fire phenomena occurring from April to August each year in the Sumatra and Borneo islands are major sources of biogenic uranium–thorium decay series in marine systems. 30 samples were collected during the Ekspedisi Pelayaran Saintifik Perdana 2009 cruise (EPSP 2009 cruise) between 12th June and 1st August 2009 from the Straits of Malacca to the Sulu and Sulawesi Seas to study the effect of haze and the monsoon season on the deposition rate of ²¹⁰Po and ²¹⁰Pb in Malaysian waters. All samples were spiked with 1 ml of lead [Pb(NO₃)₂; 25 mg ml^?1] and 0.05 ml of Polonium-209 tracer (26.08 dpm ml^?1). ²¹⁰Po activity was determined by auto plating onto silver foil and counting using an alpha spectrometry system (Canberra model Alpha Analyst with a silicon-surface barrier detector). Lead that was collected via electrodeposition, formed lead sulphate (PbSO₄) precipitation. This precipitate was wrapped onto plastic discs and counted for ²¹⁰Pb beta activity using a gross alpha–beta counting system (Tennelec model LB-5100 low background gas-flowing anti-coincidence alpha/beta counter) after 1 month to allow bismuth ingrowths. The range of ²¹⁰Po activities varied between 51.08 ± 15.1 and 742.08 ± 220.34 Bq/kg, whereas the activity of ²¹⁰Pb ranged from 31.10 ± 4.20 to 880.23 ± 123.86 Bq/kg and ²¹⁰Po/²¹⁰Pb ratio value varied between sampling stations from 0.19 to 13.77. The contents of ²¹⁰Po were also statistically positively correlated with the amount of total suspended particulate especially those recorded during heavy haze period events.     

Determination of210Pb and210Po in human tissues of Japanese

To determine the levels of²¹⁰Pb and²¹⁰Po in human tissues of people in Japan, various tissue samples were obtained at autopsy from the cadavers of 22 oncologic cases, mainly in Niigata Prefecture in northern Japan, from 1986 to 1988.Wet ashing, followed by electrochemical deposition and alpha spectrometry were used to separate and determine the²¹⁰Pb and²¹⁰Po present. Among the tissues analyzed, the highest concentrations of²¹⁰Pb and²¹⁰Po were observed in bone (sternum), liver, and kidneys. The total body burden of²¹⁰Pb and²¹⁰Po was found to be approximately 427 pCi and 514 pCi, respectively. This estimated²¹⁰Po value did not differ significantly from values found in populations in the U.S.A. and European countries.     

Rapid determination of 210Po in water samples

A new rapid method for the determination of ²¹⁰Po in water samples has been developed at the Savannah River National Laboratory (SRNL) that can be used for emergency response or routine water analyses. If a radiological dispersive device event or a radiological attack associated with drinking water supplies occurs, there will be an urgent need for rapid analyses of water samples, including drinking water, ground water and other water effluents. Current analytical methods for the assay of ²¹⁰Po in water samples have typically involved spontaneous auto-deposition of ²¹⁰Po onto silver or other metal disks followed by counting by alpha spectrometry. The auto-deposition times range from 90 min to 24 h or more, at times with yields that may be less than desirable. If sample interferences are present, decreased yields and degraded alpha spectrums can occur due to unpredictable thickening in the deposited layer. Separation methods have focused on the use of Sr Resin?, often in combination with ²¹⁰Pb analysis. A new rapid method for ²¹⁰Po in water samples has been developed at the SRNL that utilizes a rapid calcium phosphate co-precipitation method, separation using DGA Resin^® (N,N,N′,N′ tetraoctyldiglycolamide extractant-coated resin, Eichrom Technologies or Triskem-International), followed by rapid microprecipitation of ²¹⁰Po using bismuth phosphate for counting by alpha spectrometry. This new method can be performed quickly with excellent removal of interferences, high chemical yields and very good alpha peak resolution, eliminating any potential problems with the alpha source preparation for emergency or routine samples. A rapid sequential separation method to separate ²¹⁰Po and actinide isotopes was also developed. This new approach, rapid separation with DGA resin plus microprecipitation for alpha source preparation, is a significant advance in radiochemistry for the rapid determination of ²¹⁰Po.     

Radiochemical determination of210Po and210Pb in water

A method for²¹⁰Po and²¹⁰Pb determination in water samples is described. The nuclides are concentrated, in presence of added²⁰⁸Po and lead carrier, by evaporation. Then the polonium is plated electroless from the acidic solution on a copper planchet and measured by alpha spectrometry.²¹⁰Pb separation from the other isotopes is based on the solutility of PbSO₄ in citrate.²¹⁰Pb content is determined by measuring the activity of its daughter²¹⁰Bi. The critical steps in the isolation of lead have been examined and discussed.     

The radiation dose and distribution coefficient of 210Po and 210Pb concentrations in aquatic environs of major rivers of coastal Karnataka

The activity of ²¹⁰Po and ²¹⁰Pb was measured in different matrices of aquatic ecosystem of the major rivers of Coastal Karnataka viz, Kali, Sharavathi and Netravathi. The environmental samples such as surface water, suspended particulate matter and sediment have been subjected to analyses. The activity of these two radionuclides were determined by radiochemical separation of ²¹⁰Po and counting the activity using a ZnS(Ag) alpha counter. The activity ratio of ²¹⁰Po and ²¹⁰Pb and correlation between the activity of these radionuclides were studied. From the measured concentration of ²¹⁰Po and ²¹⁰Pb, the internal Committed Effective Dose to the population for the study area was calculated. The distribution coefficient K_d between water, suspended particulate matter and sediments have been calculated to understand the distribution and accumulation of these radionuclides in different matrices of the aquatic environment.

     

Polonium–lead extractions to determine the best method for the quantification of clean lead used in low-background radiation detectors

Radiation detectors used to search for the existence of exceptionally rare phenomena, such as double-beta decay and dark matter interactions, as well as tiny traces of environmental radioactivity, require the elimination of background signals. Modern detection systems created from ultra pure materials and operated deep underground may be sensitive enough to “see” these rare phenomena, but background activity in Pb gamma-ray shielding could still be a critical stumbling block owing to alpha and beta emissions of Pb, Bi, and Po in the mass 210 chain. To minimize the probability of overwhelming activity from Pb, the alpha activity of ²¹⁰Pb is quantified. However, a reliable quantification procedure that does not require large volumes of chemicals has not yet been established. Two procedures created for this purpose have been tested for the quantification of alpha activity in lead. Both procedures were designed to start with less than 10 g Pb samples to reduce reagents needed and combined precipitation with column separation to isolate ²¹⁰Pb, followed by alpha spectrometry. One procedure shows promise for obtaining high recoveries and good separation.     

Radiological characterization of phosphate fertilizers: Comparison between alpha and gamma spectrometry

The natural radioactivity in phosphate fertilizers used in central Italy has been measured by alpha and gamma spectrometry. The results show that the specific activities of ²³⁸U, ²³⁴U and ²³⁵U ranged within interval from < 0.5 to 2628.8, from < 0.5 to 2826.3 and from < 0.9 to 138.0 Bq kg^{− 1} respectively and those of ²¹⁰Pb and ²¹⁰Po ranged within interval from < 15.0 to 401.5 and < 0.5 to 351.6 Bq kg^{− 1} respectively. The ²²⁸Th, ²³⁰Th and ²³²Th concentrations found by alpha spectrometry ranged from < 0.5 to 50.2, from 0.9 to 2727.2 and from < 0.5 to 60.8 Bq kg^{− 1} respectively. ²²⁶Ra and ²²⁸Ra activity concentrations ranged from < 14.3 to 290.9 and from < 2.9 to 24.9 respectively. ⁴⁰K specific activities ranged from 39.2 to 8263.7 Bq kg^{− 1}. A very good correlation exists between the activity concentrations found by alpha spectrometry and those found by gamma spectrometry.     

A biomonitoring study: 210Po and heavy metals in marine organisms from the Adriatic Sea (Italy)

In various samples of marine organisms from the central Adriatic Sea ²¹⁰Po was determined by alpha spectrometry and thirteen heavy metals (Mn, Fe, Co, Cr, V, Ni, Cu, Zn, Cd, As, Sn, Hg and Pb) by energy dispersive, polarised X ray fluorescence spectrometry (EDPXRF). ²¹⁰Po activity concentration ranged between 0.3 and 44.6 Bq kg⁻¹ fresh weight. The data obtained depend upon the type of the marine organism; among the pelagic species, anchovy displayed the highest polonium concentration. Typical concentration ( \upmu \textg·\textg_(\textfresh) ^{- 1} ) \left( {\upmu {\text{g}}\cdot{\text{g}}_{{({\text{fresh}})}}^{ - 1} } \right) ranges were as follows: Mn: <1.32–1.73; Fe: 4.11–94.27; Co < 0.13–0.23; Ni: <0.13–0.52; Cu: 0.37–145.31; Zn: 0.46–16.46; Cd: <0.10–0.25; As: 0.36–60.52; Hg: <0.13–0.70; Pb: <0.13–0.35, Sn: <0.20–12.67; V and Cr were always <1.32. The data obtained are also compared with those obtained by other authors for the same organism coming from other Italian seas.     

A study on 210Po activity concentration in soil at different depths along coastal Kerala

The paper presents systematic studies on the vertical profiles of ²¹⁰Po, an important decay product of ²³⁸U, in soils along coastal Kerala. Soil samples collected from different depth intervals 0–10, 10–20, 20–30 cm were analyzed for ²¹⁰Po activity concentration by radiochemical methods. The activity ²¹⁰Po in soil samples were counted using a ZnS(Ag) alpha scintillation counting system. The mean values of activity concentrations of ²¹⁰Po in soil of various depths were found to be 8.66, 5.63 and 4.95 Bq kg⁻¹ for depth intervals of 0–10, 10–20 and 20–30 cm, respectively. The overall activity concentration of ²¹⁰Po in soil was found to vary from 2.26 ± 0.19 to 14.02 ± 0.12 Bq kg⁻¹ with a mean value of 6.43 Bq kg⁻¹. Maximum activity concentration was found in soil samples of Kollam region with the mean value of 10.08 ± 0.92 Bq kg⁻¹. The activity of ²¹⁰Po was found to be comparatively high in surface soil. The variation of ²¹⁰Po activity concentration with organic matter contents was studied. ²¹⁰Polonium activity concentration was found to increase with increasing organic matter content.     

Distribution of <Superscript>210</Superscript>Po and <Superscript>210</Superscript>Pb in riverine environs of coastal Karnataka

The concentrations of ²¹⁰Po and ²¹⁰Pb have been measured in soil, sediment and rock samples collected from major rivers of coastal Karnataka, viz. Kali, Sharavathi and Netravathi. The activity of ²¹⁰Po and ²¹⁰Pb in the samples were separated by radiochemical methods and the activity was counted using ZnS(Ag) alpha-counter. The activity ratio of ²¹⁰Po and ²¹⁰Pb and the dependence of organic matter content on the activity of these radionuclides were studied.