Sequential Injection Approach for Simultaneous Determination of Ultratrace Plutonium and Neptunium in Urine with Accelerator Mass Spectrometry (original) (raw)
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Method intercomparison for the analysis of 239/240Pu in human urine
Journal of Analytical Atomic Spectrometry, 2008
Following a radiological or nuclear emergency, medical intervention requires rapid assessment of the exposure of people usually through determination of internal dose. For the plutonium urine bioassay, besides thermal ionization mass spectrometry (TIMS) and alpha spectrometry methods, inductively coupled plasma mass spectrometry (ICP-MS) methods have been recently developed, which can provide much higher sample throughput. In this work, three ICP-MS methods were compared with one TIMS method and two alpha spectrometry methods for the measurement of 239 Pu and 240 Pu in human urine samples spiked at different concentration levels. The sample throughputs for all three ICP-MS methods are similar: each instrument measures about 80 samples in the first 24 hours and 200 samples in the first 48 hours following the emergency event, if the samples arrive at the laboratory 8 hours after the event occurs. Method accuracy and precision were determined using ANSI N13.30. Method detection limits and minimum detectable amounts (MDA) were determined to evaluate method sensitivities. The sensitivities of the three ICP-MS methods were also compared with the derived urine action level (24 h urine, 500 mSv committed effective dose equivalent, inhalation exposure, maximum dose conversion factor) to evaluate their applicability to exposure situations.
AECL Nuclear Review
Ultra-trace analysis of actinides, such as Pu isotopes and 237Np, in bioassay samples is often needed for radiation protection programs at nuclear facilities. Accelerator mass spectrometry (AMS), particularly the compact ETH Zurich system “Tandy”, has evolved over the years as one of the most sensitive, selective, and robust techniques for actinide analysis. Employment of the AMS technique can reduce the demands on sample preparation chemistry and increase sample analysis throughput, due to very low instrumental detection limit, high rejection of interferences, and low susceptibility to adverse sample matrices. Initial research and development tests were performed to explore and demonstrate the analytical capability of AMS for Pu and Np urine bioassay. In this study, urine samples spiked with femtogram levels of Np and Pu isotopes were prepared and measured using compact ETH AMS system and the results showed excellent analytical capability for measuring Np and Pu isotopes at femtogr...
International Journal of Mass Spectrometry, 2004
A new analytical procedure has been developed for the determination of Pu in urine at the low ag ml −1 concentration level by double-focusing sector field inductively coupled plasma mass spectrometry (ICP-SFMS). One liter of urine doped with 4 pg 242 Pu was analyzed after co-precipitation with Ca 3 (PO 4) 2 followed by extraction chromatography on TEVA resin in order to enrich the Pu and remove uranium and matrix elements. Figures of merit of ICP-SFMS for the determination of Pu were studied using two nebulizers, PFA-100 and direct injection high-efficiency nebulizer (DIHEN), for solution introduction with uptake rates of 0.58 and 0.06 ml min −1 , respectively. The sensitivity for Pu in ICP-SFMS was determined to be 2000 and 1380 MHz ppm −1 for the PFA-100 and DIHEN nebulizers, respectively. Due to the low solution uptake rate of DIHEN the absolute sensitivity was about seven times better and yielded 1380 counts fg −1 in comparison to 207 counts fg −1 measured with the PFA-100 nebulizer. Recovery using 242 Pu tracer was about 70%. The limits of detection for 239 Pu in 1 l of urine, based on an enrichment factor of 100 for PFA-100 nebulizer and 1000 for DIHEN, were 9 × 10 −18 and 1.02 × 10 −18 g ml −1 , respectively. Measurements of 240 Pu/ 239 Pu isotopic ratio in synthetically prepared urine standard solution yielded a precision of 1.8 and 1.9% and accuracy of 1.5 and 1.8% for the PFA-100 and DIHEN nebulizers, respectively.
Journal of Analytical Atomic Spectrometry, 2012
Accelerator mass spectrometry (AMS) is a very sensitive and robust technique for analysis of long-lived radionuclides. Employment of the AMS technique can reduce the demands on sample preparation chemistry, due to its high rejection of interferences and low susceptibility to sample matrix. This is particularly of interest for ultra-trace determination of 239 Pu in bioassay and environmental samples, as other mass spectrometric methods such as inductively coupled plasma mass spectrometry (ICP-MS) can suffer from isobaric mass interferences by the presence of uranium in the sample. A rapid sample preparation method for analysis of Pu at femtogram levels in large volume urine samples is described.
Journal of Analytical Atomic Spectrometry, 2004
The Centers for Disease Control and Prevention has a mission to protect and promote public health, which includes investigation of environmental exposures to toxic substances that could threaten health. Plutonium is an environmentally available substance that is chemically and radiologically toxic and represents a potential health threat from excessive exposure. Inductively coupled plasma mass spectrometry (ICP-MS) is a sensitive method for assessing environmental or unintentional exposure to these and other actinides. We report here a magnetic sector instrument method in which a desolvating introduction system is used to provide rapid, sensitive emergency response analysis for 239 Pu in only 1 mL of urine without digestion or coprecipitation. 239 Pu was separated from U and interfering urine organic substances by solid phase extraction. The within run limit of detection (LOD) was 0.16 fg mL 21 for 1 mL of urine even though originally spiked to 1018 ng L 21 of depleted U. A more rigorous LOD of 1.4 fg mL 21 239 Pu was based on 3 ''total'' standard deviations in the presence of the same U concentration. At below 10 6 atoms of 239 Pu detectable in 1 mL of urine, this method is sufficiently sensitive for elevated emergency exposure assessment with high throughput. The precision for 10 duplicate samples was within 3.7% relative ''total'' standard deviation (RSD, within and between run) for a 9.96 fg mL 21 239 Pu-spiked urine sample and within 2.2% for a 99.6 fg mL 21 239 Pu-spiked urine sample. The method was demonstrated to be accurate within 2.6% of the Los Alamos National Laboratories target value at 99.6 fg mL 21 , to within 1.0% of target value at 9.96 fg mL 21 and within 1.2% at 0.996 fg mL 21 , just below the method LOD.
Individual determination of uranium and plutonium in a single aliquot
1983
Studies on the individual potentiometric determination of uranium and plutonium in a single aliquot have been initiated recently in our laboratory. It was required to adapt the reported procedures (for the precise determination of uranium and plutonium individually when present together in a sample) at various stages to make them suitable for the successive application of the procedures to the same aliquot. Two alternative schemes are proposed in the present work. In the first, plutonium is determined by HCIO4 oxidation followed by the determination of total uranium and plutonium by Zn(Hg) reduction. In the second, plutonium is determined by AgO oxidation following the determination of total uranium and plutonium by Zn(Hg) reduction. Amount of uranium is computed in both cases from the difference of two determinations. Precision for the assay of plutonium and uranium was found to be +-0.25% and +-0.35%, respectively, at milligram levels.
This paper describes the use of IBC0s Ana- LigPu-02 molecular recognition technology product to effectively and selectively pre-concentrate, separate and recover plutonium from urine samples. This method uses two-stage column separations consisting of two different commercial products, Eichrom’s Pre-filter Material and AnaLigPu-02 resin from IBC Advanced Technologies. By eliminating the co-precipitation techniques and the ashing steps to remove residual organics, the analysis time was reduced significantly. The method was successfully tested by adding known activities of reference solutions of 242Pu and 239Pu to urine samples.
Health Physics, 2006
Accidental exposure to depleted or enriched uranium may occur in a variety of circumstances. There is a need to quantify such exposure, with the possibility that the testing may post-date exposure by months or years. Therefore, it is important to develop a very sensitive test to measure precisely the isotopic composition of uranium in urine at low levels of concentration. The results of an interlaboratory comparison using sector field (SF)-inductively coupled plasma-mass spectrometry (ICP-MS) and multiple collector (MC)-ICP-MS for the measurement of uranium concentration and 235 U/ 238 U and 236 U/ 238 U isotopic ratios of human urine samples are presented. Three urine samples were verified to contain uranium at 1-5 ng L ؊1 and shown to have natural uranium isotopic composition. Portions of these urine batches were doped with depleted uranium (DU) containing small quantities of 236 U, and the solutions were split into 100 mL and 400 mL aliquots that were subsequently measured blind by three laboratories. All methods investigated were able to measure accurately 238 U/ 235 U with precisions of ϳ0.5% to ϳ4%, but only selected MC-ICP-MS methods were capable of consistently analyzing 236 U/ 238 U to reasonable precision at the ϳ20 fg L ؊1 level of 236 U abundance. Isotope dilution using a 233 U tracer demonstrates the ability to measure concentrations to better than ؎4% with the MC-ICP-MS method, though sample heterogeneity in urine samples was shown to be problematic in some cases. MC-ICP-MS outperformed SF-ICP-MS methods, as was expected. The MC-ICP-MS methodology described is capable of measuring to ϳ1% precision the 238 U/ 235 U of any sample of human urine over the entire range of uranium abundance down to <1 ng L ؊1 , and detecting very small amounts of DU contained therein. Health Phys. 90(2):127-138; 2006
Perspectives of uranium and plutonium analysis in urine samples by secondary ion mass spectrometry
Journal of Radioanalytical and Nuclear Chemistry, 1997
Secondary ion mass spectrometry (SIMS) is a well-established technique that permits rapid detection of stable and radioactive nuclides. Its resolving mass power provides an efficient analytical method and, in palticular, it makes possible accurate isotopic ratio determination. Tests were carried out to evaluate the performance of this technique for the assessment of trace concentrations of uranium and plutonium in mine samples prepared in thin sources. Special attention has been paid to the preparation of the Specimens which represents a critical step for the employment of this technique due to the erosion process used by SIMS. Fixation cs the matrix in Polypyrrole fdms have been proved to be suitable. Present results show that concentrations in the order of 10 -10 g. 1 -I of 238U (10 -6 Bq-1-1) and 10 -11 g. 1-1 of 239pu (10 -2 Bq. 1-1) can be rapidly measured.
Czechoslovak Journal of Physics, 2006
Measurement of plutonium isotopes in vivo is not feasible for radiation protection purposes. Considering the slow rate of plutonium excretion, the respect to annual dose limits, whenever risk of plutonium internal contamination occurs, implies the need of a monitoring programme based on very sensitive bioassay, i.e., measurement of plutonium content in samples of urine or feces, characterized by a very low minimum detectable activity. Alpha spectrometry is the most common measurement method applied in this field. The applicability of this method strictly depends on the procedure adopted for the sample radiochemical preparation preceding the real spectrometric counting and, particularly, on the element chemical recovery that is one of the parameters that mostly influence the minimum detectable activity achievable by the analysis. The aim of the present work is to compare the performances of four of the most widely adopted radiochemical procedures making use of different separation methods for the determination of plutonium in urine samples via alpha spectrometry.