Separation and determination of <Superscript>241</Superscript>Am in urine samples from radiation workers using PC88-A and alpha spectrometry

Bioassay technique is used for the estimation of actinides present in the body based on their excretion rate through body fluids. For occupational radiation workers urine assay is the preferred method for monitoring of chronic internal exposure. Determination of low concentrations of actinides such as plutonium, americium and uranium at low level of mBq in urine by alpha spectrometry requires pre-concentration of large volumes of urine. This article deals with standardization of analytical method for the determination of ²⁴¹Am isotope in urine samples using Extraction Chromatography (EC) and ²⁴³Am tracer for radiochemical recovery. The method involves oxidation of urine followed by co-precipitation of americium along with calcium phosphate. This precipitate after treatment is further subjected to calcium oxalate co-precipitation. Separation of Am was carried out by EC column prepared by PC88-A (2-ethyl hexyl phosphonic acid 2-ethyl hexyl monoester) adsorbed on microporous resin XAD-7 (PC88A-XAD7). Am-fraction was electro-deposited and activity estimated using tracer recovery by alpha spectrometer. Ten routine urine samples of radiation workers were analyzed and consistent radiochemical recovery was obtained in the range 44–60% with a mean and standard deviation of 51 and 4.7% respectively.     

A method for estimation of Pu-isotopes in urine samples using TEVA resin and alpha spectrometry

The conventional method used for estimation of Pu-isotopes in urine samples involves anion exchange resin followed by alpha spectrometry, which takes nearly one working week for complete sample analysis. Since the results of the analysis form an important input for decision making by the plant authorities, it is always preferable to reduce overall analysis time for the estimation of Pu-isotopes in bioassay samples. This paper deals with standardization of a relatively faster method for estimation of Pu-isotopes in bioassay samples using TEVA resin and ²³⁶Pu tracer for radiochemical recovery. The method involves oxidation of urine followed by co-precipitation of plutonium along with calcium phosphate and separation of Pu was carried out using TEVA resin. Pu-fraction was electrodeposited and activity estimated using tracer recovery by alpha spectrometer. Routine urine samples of radiation workers were analyzed and consistent radiochemical tracer recovery was obtained in the range 65–87 % with a mean and SD of 75 and 7.4 %, respectively. The standardized chromatographic technique reduces the analysis time by about 1 day as compared to conventional method for estimation of Pu-isotopes in urine samples.     

Determination of uranium isotopes in urine samples from radiation workers using 232U tracer, anion-exchange resin and alpha-spectrometry

Bioassay technique is used for the estimation of actinides present in the body based on the excretion rate of body fluids. For occupational radiation workers urine assay is the preferred method for monitoring of chronic internal exposure. Determination of low concentrations of actinides such as plutonium, americium and uranium at low level of mBq in urine by alpha-spectrometry requires pre-concentration of large volumes of urine. This paper deals with standardization of analytical method for the determination of U-isotopes in urine samples using anion-exchange resin and ²³²U tracer for radiochemical recovery. The method involves oxidation of urine followed by co-precipitation of uranium along with calcium phosphate. Separation of U was carried out by Amberlite, IRA-400, anion-exchange resin. U-fraction was electrodeposited and activity estimated using tracer recovery by alpha-spectrometer. Eight routine urine samples of radiation workers were analyzed and consistent radiochemical tracer recovery was obtained in the range of 51% to 67% with a mean and standard deviation of 60% and 5.4%, respectively.     

Feasibility studies to assess the use of <Superscript>236</Superscript>Pu as a radiochemical yield monitor in bioassay samples

Various plutonium compounds are handled in nuclear facilities of BARC. Hence, there is a possibility of occupational workers getting exposed to Pu. In vitro bioassay monitoring in which Pu is separated by chemical procedures from excreta samples and estimated by alpha-spectrometry, is the method of choice for the evaluation of internal dose to the occupational workers handling Pu. However, this method requires a suitable Pu tracer for reducing the uncertainties due to chemical yield in the separation, electro-deposition and counting efficiency. ²⁴²Pu is commonly used as a tracer but due to its non-availability, efforts were made earlier to indigenously synthesis ²³⁶Pu by proton irradiation of ²³⁷Np in BARC-TIFR pelletron facility. The present study, reports the feasibility of using ²³⁶Pu as a radiochemical yield monitor (tracer) in bioassay samples.     

ICP-MS analysis of plutonium activities and <Superscript>240</Superscript>Pu/<Superscript>239</Superscript>Pu ratio in alpha spectrometry planchet deposits

Plutonium isotopes were measured by alpha-spectrometry and ICP-MS in sediment samples from two European lakes: Blelham Tarn in U.K. and Stechlin lake in Germany. The ICP-MS measurements were made after alpha-spectrometry counting of the planchets. The planchets were prepared by traditional electrodeposition method after radiochemical extraction, separation and purification of the Pu fraction. A short radiochemical separation using plutonium selective resin, between the two spectrometry measures, is presented. The results show that these two complementary methods are in good agreement, the plutonium activity concentrations are the same. Alpha-spectrometry allows the ²³⁸Pu determination and ICP-MS individual measurement of ²³⁹Pu and ²⁴⁰Pu. ²³⁸Pu/^239+240Pu and ²⁴⁰Pu/²³⁹Pu ratios are calculated to determine the plutonium contamination source. With the results of these two techniques, it could be demonstrate that the plutonium is of global fallout origin.     

Purification and separation of <Superscript>239+240</Superscript>Pu and <Superscript>241</Superscript>Am in biological samples by anion-exchange and extraction chromatography for high resolution alpha-spectrometry analyses

Many biological samples (urines and faeces) have been analyzed by means of chromatographic extraction columns, utilizing two different resins (AG 1-X2 resin chloride and TRU), in order to detect the possible internal contamination of ^239+240Pu and ²⁴¹Am for some workers of a reprocessing nuclear plant in the decommissioning phase. The results obtained show on one hand the great suitability of the first resin for the determination of plutonium, and on the other, the great selectivity of the second one for the determination of americium.     

Synthesis and biodistribution of two novel 99mTc nitrido dithiocarbamate complexes containing heterocyclic linkage as potential brain perfusion imaging agents

Various plutonium compounds are handled in nuclear facilities of BARC. Hence, there is a possibility of occupational workers getting exposed to Pu. In vitro bioassay monitoring in which Pu is separated by chemical procedures from excreta samples and estimated by alpha-spectrometry, is the method of choice for the evaluation of internal dose to the occupational workers handling Pu. However, this method requires a suitable Pu tracer for reducing the uncertainties due to chemical yield in the separation, electro-deposition and counting efficiency. ²⁴²Pu is commonly used as a tracer but due to its non-availability, efforts were made earlier to indigenously synthesis ²³⁶Pu by proton irradiation of ²³⁷Np in BARC-TIFR pelletron facility. The present study, reports the feasibility of using ²³⁶Pu as a radiochemical yield monitor (tracer) in bioassay samples.     

Pilot measurements of <Superscript>237</Superscript>Np in forest litter from Poland

Described are results and the procedure for a pilot study on ²³⁷Np content in forest litter samples from Poland in relation to their plutonium activity. Neptunium was determined by inductively coupled plasma mass spectrometry (ICP-MS) and Pu by alpha spectrometry. Two samples originated from a location with pure global fallout and two others from a place with about 65% of the plutonium from Chernobyl. Plutonium activities were determined twice: at Krakow and in Monaco. The two results were consistent and ^239 + 240Pu activities ranged from about 1 to about 7 Bq/kg dry weight (dw). The chemical recovery for Np was between 27 and 89%. Results for ²³⁷Np activity concentrations were between 0.099 ± 0.005 and 2.21 ± 0.076 mBq/kg dw. Observed activity ratios were lower than expected and could be explained by fractionation of Np against Pu in forest litter.     

Sequential isotopic determination of plutonium,thorium, americium and uranium in the air filter and drinking water samples around the WIPP site

The simultaneous determination of actinides in air filter and water samples around the WIPP site have been demonstrated. The analytical method is based on the selective separation and purification by anion exchange and Eichrome-TEVA, TRU and DGA-resin followed by determination of actinides by alpha spectrometry. Counting sources for alpha spectrometric measurements were prepared by microcoprecipitation on neodymium fluoride (NdF₃). Radiochemical yields were determined using ²⁴²Pu, ²²⁹Th, ²⁴³Am and ²³²U as tracers. The validation of the method is performed through the analysis of reference materials or participating in laboratory intercomparison programs. The plutonium concentrations in aerosols varied seasonally, being highest in spring and summer due to the spring-time enhanced wind-storm transportation of radioactive aerosols from the stratosphere to the troposphere. The ²³⁸Pu/^239+240Pu activity ratio in the aerosol samples is typically close to that of global fallout from historic above-ground nuclear weapons testing. The results presented here indicate that the source of plutonium in the WIPP environment results mainly from global nuclear fallout and there is no evidence of increases in radiological contaminants in the region that could be attributed to releases from the WIPP.     

Systematic radiochemical separation for the determination of <Superscript>99</Superscript>Tc, <Superscript>90</Superscript>Sr, <Superscript>94</Superscript>Nb, <Superscript>55</Superscript>Fe and <Superscript>59,63</Superscript>Ni in low and intermediate radioactive waste samples

A simple and rapid separation procedure was systemized for the determination of ⁹⁹Tc, ⁹⁰Sr, ⁹⁴Nb, ⁵⁵Fe and ^59,63Ni in low and intermediate level radioactive wastes. The integrated procedure involves precipitation, anion exchange and extraction chromatography for the separation and purification of individual radionuclide from sample matrix elements and from other radionuclides. After separating Re (as a surrogate of ⁹⁹Tc) on an anion change resin column, Sr, Nb, Fe and Ni were sequentially separated as follows; Sr was separated as Sr (Ca-oxalate) co-precipitates from Nb, Fe and Ni followed by purification using Sr-Spec extraction chromatographic resin. Nb was separated from Fe and Ni by anion exchange chromatography. Fe was separated from Ni by anion exchange chromatography. Ni was separated as Ni-dimethylglyoxime precipitates after the removal of ^134,137Cs and ^110mAg by Cs-phosphotungstate and AgCl precipitation, respectively. Finally, the radionuclide sources were prepared by precipitation for their radioactivity measurements. The reliability of the procedure was evaluated by measuring the recovery of chemical carriers added to a synthetic radioactive waste solution.     

Plutonium and americium in sediment samples along the Romanian sector of the Danube river and the Black Sea coast

The concentrations of²³⁸Pu,^239,240Pu and²⁴¹Am were determined in eight sediment samples, collected from the bed of the Romanian sector of the Danube river and the Black Sea coast during 1994 and 1995. Fusion with potassium carbonate was used to achieve complete dissolution of the samples. Tracers,²⁴²Pu and²⁴³Am, were added and the separation of plutonium from americium, uranium and thorium was performed by anion exchange. Americium was separated from uranium in two steps, using a conventional anion exchange resin and an extraction chromatographic resin for transuranics. After electrodeposition on stainless steel discs the nuclides were counted with -spectrometry with -PIPS detectors. The total plutonium concentrations obtained by this method were compared with the acid leachable plutonium concentrations reported for the same samples in a previous paper.     

Rapid determination of actinides in urine by inductively coupled plasma mass spectrometry and alpha spectrometry: A hybrid approach

A new rapid separation method that allows separation and preconcentration of actinides in urine samples was developed for the measurement of longer lived actinides by inductively coupled plasma mass spectrometry (ICP-MS) and short-lived actinides by alpha spectrometry; a hybrid approach. This method uses stacked extraction chromatography cartridges and vacuum box technology to facilitate rapid separations. Preconcentration, if required, is performed using a streamlined calcium phosphate precipitation. Similar technology has been applied to separate actinides prior to measurement by alpha spectrometry, but this new method has been developed with elution reagents now compatible with ICP-MS as well. Purified solutions are split between ICP-MS and alpha spectrometry so that long- and short-lived actinide isotopes can be measured successfully. The method allows for simultaneous extraction of 24 samples (including QC samples) in less than 3 h. Simultaneous sample preparation can offer significant time savings over sequential sample preparation. For example, sequential sample preparation of 24 samples taking just 15 min each requires 6 h to complete. The simplicity and speed of this new method makes it attractive for radiological emergency response. If preconcentration is applied, the method is applicable to larger sample aliquots for occupational exposures as well. The chemical recoveries are typically greater than 90%, in contrast to other reported methods using flow injection separation techniques for urine samples where plutonium yields were 70-80%. This method allows measurement of both long-lived and short-lived actinide isotopes. ²³⁹Pu, ²⁴²Pu, ²³⁷Np, ²⁴³Am, ²³⁴U, ²³⁵U and ²³⁸U were measured by ICP-MS, while ²³⁶Pu, ²³⁸Pu, ²³⁹Pu, ²⁴¹Am, ²⁴³Am and ²⁴⁴Cm were measured by alpha spectrometry. The method can also be adapted so that the separation of uranium isotopes for assay is not required, if uranium assay by direct dilution of the urine sample is preferred instead. Multiple vacuum box locations may be set-up to supply several ICP-MS units with purified sample fractions such that a high sample throughput may be achieved, while still allowing for rapid measurement of short-lived actinides by alpha spectrometry.     

Determination of activity concentrations and activity ratios of plutonium,americium and curium isotopes in radioactive waste samples

This paper presents a rapid and quantitative radiochemical separation method for the Pu, Am and Cm isotopes with an anion exchange resin and a TRU resin. After the Pu isotopes were purified with an anion exchange resin method and the Am and Cm isotopes were purified with the TRU resin method, micro-coprecipitation method was applied for an alpha-source preparation. The activity concentrations and activity ratios for the Pu, Am and Cm isotopes in a radioactive sample were measured by radiation counting methods such as an alpha-spectrometry and a liquid scintillation counting as well as by a mass spectroscopic method such as a thermal ionization mass spectrometry.     

<Superscript>239, 240, 241</Superscript>Pu fingerprinting of plutonium in western US soils using ICPMS: solution and laser ablation measurements

Sector field inductively coupled plasma mass spectrometry (SF-ICPMS) has been used with analysis of solution samples and laser ablation (LA) of electrodeposited alpha sources to characterize plutonium activities and atom ratios prevalent in the western USA. A large set of surface soils and attic dusts were previously collected from many locations in the states of Nevada, Utah, Arizona, and Colorado; specific samples were analyzed herein to characterize the relative contributions of stratospheric fallout vs. Nevada Test Site (NTS) plutonium. This study illustrates two different ICPMS-based analytical strategies that are successful in fingerprinting Pu in environmental soils and dusts. Two specific datasets have been generated: (1) soils are leached with HNO₃-HCl, converted into electrodeposited alpha sources, counted by alpha spectrometry, then re-analyzed using laser ablation SF-ICPMS; (2) samples are completely dissolved by treatment with HNO₃-HF-H₃BO₃, Pu fractions are prepared by extraction chromatography, and analyzed by SF-ICPMS. Optimal laser ablation and ICPMS conditions were determined for the re-analysis of archived alpha spectrometry “planchette” sources. The best ablation results were obtained using a large spot size (200 μm), a defocused beam, full repetition rate (20 Hz) and scan rate (200 μm s⁻¹); LA-ICPMS data were collected with a rapid electrostatic sector scanning experiment. Less than 10% of the electroplated surface area is consumed in the LA-ICPMS analysis, which would allow for multiple re-analyses. Excellent agreement was found between ^239+240Pu activities determined by LA-ICPMS vs. activity results obtained by alpha spectrometry for the same samples ten years earlier. LA-ICPMS atom ratios for ²⁴⁰Pu/²³⁹Pu and ²⁴¹Pu/²³⁹Pu range from 0.038–0.132 and 0.00034–0.00168, respectively, and plot along a two-component mixing line (²⁴¹Pu/²³⁹Pu = 0.013 [²⁴⁰Pu/²³⁹Pu] – 0.0001; r ² = 0.971) with NTS and global fallout end-members. A rapid total dissolution procedure, followed by extraction chromatography and SF-ICPMS solution Pu analysis, generates excellent agreement with certified ^239+240Pu activities for standard reference materials NIST 4350b, NIST 4353, NIST 4357, and IAEA 385. ^239+240Pu activities and atom ratios determined by total dissolution reveal isotopic information in agreement with the LA-ICPMS dataset regarding the ubiquitous mixing of NTS and stratospheric fallout Pu sources in the regional environment. For several specific samples, the total dissolution method reveals that Pu is incompletely recovered by simpler HNO₃-HCl leaching procedures, since some of the Pu originating from the NTS is contained in refractory siliceous particles.     

Improvements on the method for determining of <Superscript>210</Superscript>Pb and <Superscript>210</Superscript>Po in lead

An improved method is proposed to determine the content of ²¹⁰Pb in lead using ²¹⁰Po measured by alpha-ray spectrometry. This improved method, which is based on radiochemical separation by DDTC–toluene extraction, employs EDTA and citrate as masking reagents for the lead ions. To selectively extract polonium from an alkaline solution, the pH dependency was examined using a liquid scintillation counting method. And pH 9 was chosen as an extraction condition. Then ²¹⁰Po was electrodeposited on a stainless steel disk, and the chemical recovery was followed by ²⁰⁹Po tracer. The effectiveness of the new method was validated by the agreement with the analytical results from five samples as determined by gamma-ray spectrometry.     

Enzymatic degradation of large vegetation samples for the simultaneous determination of129I,actinides and strontium

A radiochemical procedure is given for the simultaneous determination of low levels of¹²⁹I, actinides (Pu, Am, Cm) and⁹⁰Sr in vegetation samples. It is shown that grass samples up to 5 kg fresh weight can be wet ashed conveniently by hydrogen peroxide under alkaline conditions, subsequent to an initial enzymatic disintegration. After purification of the iodine fraction,¹²⁹I is determined by neutron activation analysis. Using alpha spectrometry,²³⁸Pu and^239,240Pu are determined in the plutonium fraction, and²⁴¹Am,²⁴²Cm, and²⁴⁴Cm in the americium/curium fraction. The⁹⁰Sr is determined after separation by beta counting its decay product⁹⁰Y.     

Separation and purification of <Superscript>249</Superscript>Cf and <Superscript>245</Superscript>Cm

There is a need to provide radioactivity standards of the higher actinides in support of both decommissioning and remediation activities as well as routine environmental analysis. In the case ²⁴⁹Cf, this will provide a useful calibration nuclide for both α-and γ-spectrometry as well as improving knowledge of the decay scheme for this nuclide. There is anecdotal evidence to suggest that the chemical yield of americium and curium may differ in radiochemical analysis. Thus, a chemical yield tracer of ²⁴⁵Cm may help to resolve this issue and will be suitable for both, suitable for use as a chemical yield tracer for both α-particle spectrometry and mass spectrometry. An aged source of ²⁴⁹Cf was used as the source material for the separation of these two nuclides by cation-exchange, using 2-hydroxy-2-methyl-propanoic acid at controlled pH as an eluant, ²⁴⁹Cf being eluted before the ²⁴⁵Cm daughter. The purity of both nuclides was measured by γ-ray spectrometry.     

Determination of thorium,uranium and plutonium isotopes in atmospheric samples

A new procedure for the radiochemical measurements of thorium, uranium and plutonium in atmospheric samples is described. Analysis involves coprecipitation of these actinides with iron hydroxide from a 40-to 50-dm³ sample of rainwater, followed by radiochemical separation and purification procedures by the use of ion exchange chromatography (Dowex AG1×8) and solvent extraction. The new procedure enables one to determine the isotopes of thorium, uranium and plutonium, which are found in rainwater at extremely low concentrations, with a chemical yield ranging from 60 to 80%.     

Determination of237Np in large volume samples of sea water by a radiochemical procedure

A radiochemical procedure followed by alpha spectrometry has been developed for the determination of²³⁷Np present at low activity concentrations in seawater. The analytical procedure is based on concentration of actinides from 1800 1 sea water samples by hydroxide precipitations. Neptunium is isolated by ion exchange, fluoride precipitation and extraction with TTA (thenoyltrifluoroacetone). As a radiochemical yield determinant²³⁹Np or²³⁵Np is used. Neptunium is electroplated onto stainless steel discs before alpha-spectrometry for about 10 days. The procedure allows for sequential separation of plutonium, americium, technetium and radiocaesium together with neptunium. The radiochemical yield for neptunium is only 20–50%, but the procedure has been applied with success on several samples contaminated with²³⁷Np at fallout or close to fallout levels.     

Alpha spectroscopic analysis of actinides (Th,U and Pu) after separation from aqueous solutions by cation-exchange and liquid extraction

The radioactivity concentration of ²³⁶Pu, ²³²U and ²²⁸Th in aqueous samples has been determined by means of alpha spectroscopy after chemical separation and pre-concentration of the radionuclides by cation exchange and liquid–liquid extraction using the Chelex-100 resin and 30% TBP/dodecan, respectively. Method calibration using a ²³⁶Pu standard solution containing the daughter radionuclides results in a detector efficiency of 18% and in a chemical recovery for cation-exchange which is (30 ± 7)%, (90 ± 5)% and (20 ± 5)% for plutonium, uranium and thorium, respectively. The chemical recovery for liquid–liquid extraction is found to be (60 ± 7)%, (50 ± 5)% and (70 ± 5)%, for plutonium, uranium and thorium, respectively. The differences in the efficiencies can be ascribed to the oxidation states, the different actinides present in solution. Taking into account that the electrodeposition of the radionuclides under study is quantitative, the total method efficiency is calculated to be (18 ± 15)%, (46 ± 7)% and (15 ± 5)%, for plutonium, uranium and thorium, respectively, at the mBq concentration range. The detection limit of the alpha spectrometric system has been found to be 0.2 mBq/L, suggesting that the method could be successfully applied for the radiometric analysis of the studied radionuclides and particularly uranium in aqueous samples.