Rapid analysis of emergency urine and water samples

There is a need for fast, reliable methods for the determination of actinides and ^89/90Sr analysis on environmental and bioassay samples in response to an emergency radiological incident. The Savannah River Site (SRS) Environmental Laboratory participated in the National Institute of Standards and Technology Radiochemistry Intercomparison Program (NRIP-06) and analyzed water and urine samples within 8 hours of receipt. The SRS Environmental Laboratory was the only lab that participated in the program that analyzed these samples for both actinides and ^89/90Sr within an eight hour turnaround time. A rapid actinide and ^89/90Sr separation method was used for both urine and water samples. This method uses stacked TEVA Resin®, TRU Resin® and Sr-Resin® cartridges from Eichrom Technologies (Darien, IL, USA) that allows the rapid separation of plutonium (Pu), neptunium (Np), uranium (U), and americium (Am), curium (Cm) and thorium (Th) using a single multi-stage column combined with alpha-spectrometry. Vacuum box cartridge technology with rapid flow rates was used to minimize sample preparation time. This paper discusses the technology and conditions employed for both water and urine samples and presents the SRS performance data on the NRIP-06 samples.     

Rapid method for determination of plutonium, americium and curium in large soil samples

The analysis of actinides in environmental soil and sediment samples is very important for environmental monitoring. There is a need to measure actinide isotopes with very low detection limits. A new, rapid actinide separation method has been developed and implemented that allows the measurement of plutonium, americium and curium isotopes in large soil samples (100–200 g) with high chemical recoveries and effective removal of matrix interferences. This method uses stacked TEVA Resin®, TRU Resin® and DGA-Resin® cartridges from Eichrom Technologies (Darien, IL, USA) that allows the rapid separation of plutonium (Pu), americium (Am), and curium (Cm) using a single multi-stage column combined with alpha-spectrometry. The method combines an acid leach step and innovative matrix removal using cerium fluoride precipitation to remove the difficult soil matrix. This method is unique in that it provides high tracer recoveries and effective removal of interferences with small extraction chromatography columns instead of large ion-exchange resin columns that generate large amounts of acid waste. By using vacuum box cartridge technology with rapid flow rates, sample preparation time is minimized.     

Rapid column extraction method for actinides and 89/90Sr in water samples

Summary The SRS Environmental Laboratory analyzes water samples for environmental monitoring, including river water and ground water samples. A new, faster actinide and ^89/90Sr separation method has been developed and implemented to improve productivity, reduce labor costs and add capacity to this laboratory.This method uses stacked TEVA Resin^ò, TRU Resin^òand Sr-Resin^òcartridges from Eichrom Technologies (Darien, IL, USA) that allows the rapid separation of plutonium, neptunium, uranium, americium, curium and thorium using a single multi-stage column combined with alpha-spectrometry. By using vacuum box cartridge technology with rapid flow rates, sample preparation time is minimized. The method can be used for routine analysis or as a rapid method for emergency preparedness. Thorium and curium are often analyzed separately due to the interference of the daughter of ²²⁹Th tracer, actinium (²²⁵Ac) on curium isotopes when measured by alpha-spectrometry. This new method also adds a separation step using DGA Resin^ò, (diglycolamide resin, Eichrom Technologies) to remove ²²⁵Ac and allow the separation and analysis of thorium isotopes and curium isotopes at the same time.     

Rapid column extraction method for actinides in soil

Summary The determination of actinides in environmental soil and sediment samples is very important for environmental monitoring as well as for emergency preparedness. A new, rapid actinide separation method has been developed and implemented that provides total dissolution of large soil samples, high chemical recoveries and effective removal of matrix interferences. This method uses stacked TEVA Resin^ò, TRU Resin^ò and DGA-Resin^ò cartridges from Eichrom Technologies (Darien, IL, USA) that allows the rapid separation of plutonium, neptunium, uranium, americium, and curium using a single multi-stage column combined with alpha-spectrometry. The method combines a rapid fusion step for total dissolution to dissolve refractory analytes and matrix removal using cerium fluoride precipitation to remove the difficult soil matrix. By using vacuum box cartridge technology with rapid flow rates, sample preparation time is minimized.     

New fecal method for plutonium and americium

A new fecal analysis method that dissolves plutonium oxide was developedat the Westinghouse Savannah River Site. Diphonix Resin . (Eichrom Technologies),is used to pre-concentrate the actinides from digested fecal samples. A rapidmicrowave digestion technique is used to remove the actinides from the DiphonixResin ., which effectively extracts plutonium and americium from acidic solutionscontaining hydrofluoric acid. After resin digestion, the plutonium and americiumare recovered in a small volume of nitric acid that is loaded onto small extractionchromatography columns, TEVA Resin and TRU Resin (Eichrom Technologies). Themethod enables complete dissolution of plutonium oxide and provides high recoveryof plutonium and americium with good removal of thorium isotopes such as ²²⁸Th.     

Electrofission and photofission as tools to measure actinides in environmental and biological samples

Photofission and electrofission cross sections for fissionable isotopes of uranium, thorium, plutonium and other actinides have been known for several decades. Published data on electrofission and photofission reactions for energies lower than 60 MeV indicate that the²³⁸U cross sections range from a fraction of one mbarn up to about 2.0 mbam for the first of these reactions, and for the second is about 150 nbarn. However, the use of photofission and electrofission as analytical tools to measure uranium, thorium, plutonium and other fissionable actinides is still quite recent. This work examines the potential use of photofission and electrofission to measure thorium, uranium, neptunium, plutonium, americium and curium in environmental and biological samples.Work partially supported by FINEP, CNPq, FAPERJ (ASP), and FAPESP (JDTAN).     

Rapid determination of 239,240Pu, 238Pu, 241Am and 90Sr in high contaminated samples waste using combined SPE sorbents AnaLig® Pu-02, AnaLig® Sr-01 and DGA® Resin

A rapid separation method has been developed which allows measurement of plutonium, americium and strontium isotopes in the high active sample from CBRN Training and Testing Centre in Zemianske Kostolany (Slovakia) with high chemical recoveries and effective removal of matrix interferences. This method uses different commercial products stacked AnaLig^® Pu-02, AnaLig^® Sr-01 and DGA^® Resin cartridges from IBC Advanced Technologies and Eichrom Technologies. The method allows rapid separation of plutonium, strontium and americium using a single multi-stage column in the vacuum box (cartridge technology) with rapid flow rates to minimize sample separation time. The ^239,240Pu, ²³⁸Pu and ²⁴¹Am were determined by alpha spectroscopy, ⁹⁰Sr was counted on TRICARB 2900 TR by Cerenkov counting of its progeny ⁹⁰Y.     

Rapid determination of actinides in asphalt samples

A new rapid method for the determination of actinides in asphalt samples has been developed that can be used in emergency response situations or for routine analysis. If a radiological dispersive device, improvised nuclear device or a nuclear accident such as the accident at the Fukushima Nuclear Power Plant in March, 2011 occurs, there will be an urgent need for rapid analyses of many different environmental matrices, including asphalt materials, to support dose mitigation and environmental clean-up. The new method for the determination of actinides in asphalt utilizes a rapid furnace step to destroy bitumen and organics present in the asphalt and sodium hydroxide fusion to digest the remaining sample. Sample preconcentration steps are used to collect the actinides and a new stacked TRU Resin + DGA Resin column method is employed to separate the actinide isotopes in the asphalt samples. The TRU Resin plus DGA Resin separation approach, which allows sequential separation of plutonium, uranium, americium and curium isotopes in asphalt samples, can be applied to soil samples as well.     

Rapid determination of 239,240Pu, 238Pu, 241Am and 90Sr in radioactive waste using combined SPE sorbents AnaLig? Pu02, AnaLig? Sr01 and TRU? Resin

A rapid separation method has been developed which allows measurement of plutonium, americium and strontium isotopes in the radioactive sludge from Nuclear power plant A1 Jaslovske Bohunice (NPP A1) with high chemical recoveries and effective removal of matrix interferences. This method uses different commercial products stacked AnaLig^? Pu02, AnaLig^? Sr01 and TRU^? Resin cartridges from IBC Advanced Technologies and Eichrom Technologies. The method allows the rapid separation of plutonium, strontium and americium using a single multi-stage column in the vacuum box (cartridge technology) with rapid flow rates to minimize sample separation time. The ^239,240Pu, ²³⁸Pu and ²⁴¹Am were determined by alpha spectroscopy, ⁹⁰Sr was counted on TRICARB 2900 TR by Cerenkov counting of its progeny ⁹⁰Y.     

Separation of neptunium, plutonium, americium and curium from uranium with di-(2-ethylhexyl)-phosphoric acid (HDEHP) for radiometric and ICP-MS analysis

The possibility of using di-(2-ethylhexyl)-phosphoric acid (HDEHP) in solvent extraction for the separation of neptunium, plutonium, americium and curium from large amounts of uranium was studied. Neptunium, plutonium, americium and curium (as well as uranium) were extracted from HNO₃, whereafter americium and curium were back-extracted with 5M HNO₃. Thereafter was neptunium back-extracted in 1M HNO₃ containing hydroxylamine hydronitrate. Finally, plutonium was back-extracted in 3M HCl containing Ti(III). The method separates²³⁸Pu from²⁴¹Am for α-spectroscopy. For ICP-MS analysis, the interferences from²³⁸U are eliminated: tailing from²³⁸U, for analysis of²³⁷Np, and the interference of²³⁸UH⁺ for analysis of²³⁹Pu. The method has been used for the analysis of actinides in samples from a spent nuclear fuel leaching and radionuclide transport experiment.     

Rapid method for determination of radiostrontium in emergency milk samples

A new rapid separation method for radiostrontium in emergency milk samples was developed at the Savannah River Site (SRS) Environmental Bioassay Laboratory (Aiken, SC, USA) that will allow rapid separation and measurement of radiostrontium within 8 hours. The new method uses calcium phosphate precipitation, nitric acid dissolution of the precipitate to coagulate residual fat/proteins and a rapid strontium separation using Sr Resin (Eichrom Technologies, Darien, IL, USA) with vacuum-assisted flow rates. The method is much faster than the previous method that use calcination or cation-exchange pretreatment, has excellent chemical recovery, and effectively removes beta-interferences. When a 100 mL sample aliquot is used with a 20 minute count time, the method has a detection limit of 0.5 Bq·L⁻¹, well below generic emergency action levels.     

Various flowsheets of actinides recovery with diamides of heterocyclic dicarboxylic acids

Solvents on the base of diamides of heterocyclic dicarboxylic acids are promising alternatives for studied Grouped ActiNide EXtraction (GANEX) solvents. Advantage of these ligands is the possibility of simultaneous extraction not only of residual uranium and plutonium, but also minor actinides—neptunium, americium and curium. Two flowsheets on the base of diamides of heterocyclic dicarboxylic acids for separation of actinides form acidic solutions were developed, tested in laboratory scale and compared. Both flowsheets allow separation of more than 99.95% of actinides from raffinates with high content of lanthanides.     

Sequential separation of neptunium,plutonium, americium and curium using coprecipitation with bismuth phosphate

The reaction of neptunium, plutonium and americium with oxidizing or reducing agents in phosphoric acid solution has been studied to design a separation procedure of the actinide elements using coprecipitation with bismuth phosphate. In the presence of uranium, successive separation of neptunium, plutonium, americium and curium was accomplished by combining the coprecipitation and redox reaction of the elements. The coprecipitation behaviour of fission products during the course of sequential separation of the actinide elements on bismuth phosphate was also discussed.     

Measurement of radionuclides using ion chromatography and on-line radiation detection

Summary A technique is presented for the relatively rapid measurement of actinide and beta-emitting radionuclides in waste streams and environmental samples. It uses ion chromatography for elemental selectivity and flow-through scintillation counting with dual parameter pulse-height and pulse-shape analysis for alpha/beta detection and discrimination. The system was tested for one surrogate sample (spiked groundwater from the southeastern U.S.) and two actual samples from the Savannah River Site (supernatant from a highactivity drain tank and sludge from a high level waste tank). For the spiked groundwater, recoveries were quantitative for all of the analytes (americium, curium, plutonium, and strontium) except uranium. For the actual samples, which contained americium, curium, plutonium, strontium, and cesium, the results using the system were within 20% of those obtained independently. Based on these tests, it is concluded that the system is capable of analyzing alpha- and beta-emitting radionuclides in samples that are representative of those encountered at contaminated former weapons sites.     

Sequential Isotopic Determination of Strontium, Thorium, Plutonium, Uranium, and Americium in Bioassay Samples

A procedure is presented to provide sequential determination of isotopic strontium, thorium, plutonium, uranium, and americium in a single biological sample. The method begins with digestion and dissolution of the sample. Tracers and/or carriers are added to the sample for the purpose of chemical yield monitoring. Strontium is first separated from the actinides and from most of the interfering constituents of the sample by precipitation as carbonates. Strontium isotopes are purified, and ⁸⁹Sr and ⁹⁰Sr are measured by gas proportional counting. Actinides are separated and purified by ion exchange chromatography, co-precipitated with neodymium fluoride, filtered, and counted by alpha-particle spectrometry.     

RFNC-VNIIEF capabilities to production high pure isotopes for scientific and medical applications

This technical paper presents information on the basic equipment and more than thirty-year experience of RFNC-VNIIEF activities in the sphere of producing highly enriched isotopes of actinide elements - thorium, uranium, neptunium, plutonium, americium and curium - for scientific research and practical applications. Electromagnetic separator and radiochemical methods are used to produce super pure isotope samples for nuclear-physical radiometric and mass-spectrometric equipment, and also as tracers when analyzing environmental contamination. There are stated science and engineering elaborations of technologies aimed at producing alpha-ray radiating radionuclides - thorium-229, thorium-228, actinium-225, radium-224 - for the purpose of anti-cancer therapy using bismuth-212 and bismuth-213 produced by specially developed generators.     

Effects of ammonium molybdophosphate (AMP) on strontium, actinides, and RCRA metals in SRS simulated waste

Three radionuclide-spiked salt solutions have been prepared that simulate a range of typical compositions in Savannah River Site waste solutions. The Savannah River National Laboratory performed a series of tests with the three salt solutions designed to determine the propensity of ammonium molybdophosphate (AMP) to bind some of the common analytes such as the actinides (Pu, Am, Np, U), strontium, or the elements (Ag, As, Ba, Cd, Cr, Hg, Pb, Se) regulated by the Resource Conservation Recovery Act (RCRA). The results of the tests indicate that within the protocol conditions, AMP exhibited no appreciable affinity for plutonium, neptunium, uranium and strontium. AMP showed a possible minor affinity for americium; however, the data is not as clear due to continued americium solubility changes during the duration of the experiment. Of the eight RCRA elements studied, AMP exhibited affinity for only silver under our experimental conditions.     

Pre-concentration and separation of thorium, uranium, plutonium and americium in human soft tissues by extraction chromatography

An extraction chromatographic method is described for the pre-concentration and separation of thorium, uranium, plutonium and americium in human soft tissues. Tissues such as lung and liver are oven dried at 120°C, ashed at 450°C and the ashed sample is alternately wet (HNO₃/H₂O₂) and dry ashed, and then dissolved in 8M HCl. Because of the complex matrix and large sample samples (up to 1500 g), the actinides were preconcentrated from the tissue solution using the TRU^TM resin (EIChroM) prior to elemental separation by extraction chromatography and determination of americium, plutonium, uranium and thorium by alpha spectrometry. The actinides were eluted from the preconcentration column and each actinide was individually eluted on TEVA^TM and TRU^TM resin columns in a tandem configuration. Actinide activities were then determined by alpha spectrometry after electrodeposition from a sulfate medium. The method was validated by analyzing human tissue samples previously analyzed for americium, plutonium, uranium and thorium in the United States Transuranium and Uranium Registries (USTUR). Two National Institute of Standards and Technology (NIST) Standard Reference Materials, SRM 4351-Human Lung and SRM 4352-Human Liver were also analyzed. United States Transuranium and Uranium Registries, Washington State University, Pullman, WA, 99163, USA.     

Tris-{hydridotris(1-pyrazolyl)borato}actinide Complexes: Synthesis,Spectroscopy, Crystal Structure,Bonding Properties and Magnetic Behaviour

The isostructural compounds of the trivalent actinides uranium, neptunium, plutonium, americium, and curium with the hydridotris(1-pyrazolyl)borato (Tp) ligand An[η³-HB(N₂C₃H₃)₃]₃ (AnTp₃) have been obtained through several synthetic routes. Structural, spectroscopic (absorption, infrared, laser fluorescence) and magnetic characterisation of the compounds were performed in combination with crystal field, density functional theory (DFT) and relativistic multiconfigurational calculations. The covalent bonding interactions were analysed in terms of the natural bond orbital (NBO) and quantum theory of atoms in molecules (QTAIM) models.     

Development of radiochemical analysis of uranium isotopes in highly contaminated soil samples

An accurate and reliable analytical technique of uranium isotopes in highly contaminated soil samples was developed and applied to the IAEA reference samples. The conventional TBP method of uranium isotopes is insufficient to completely purify uranium from actinides such as plutonium and americium isotopes in highly contaminated soil samples. For overcoming the demerits of the conventional TBP extraction method, sample materials were decomposed with HNO₃ and HF, and uranium isotopes were purified by TBP extraction and anion exchange columns and extraction chromatography. Among the purifying methods of uranium, with a TRU Spec resin column after TBP solvent extraction, uranium was completely separated from the radionuclides in a highly contaminated samples. With the modified TBP extraction method, it was found that the concentrations of uranium isotopes were consistent with the reference values reported by the IAEA.