Rapid fusion method for determination of actinides in fecal samples

A new rapid fusion method for the determination of actinides in fecal samples has been developed at the Savannah River National Laboratory that can be used for emergency response or routine bioassay analyses. If a radiological dispersive device, improvised nuclear device or nuclear accident occur, there will be an urgent need for rapid analyses of environmental, food and bioassay matrices. If an inhalation event occurs and there is confirmed radionuclide activity present via urine analyses of individuals, fecal analyses will typically be required to determine the soluble/insoluble fraction of actinides present as a result of the event to allow a more reliable estimate of radiological dose. The new method for actinides in fecal samples uses accelerated furnace heating, a rapid sodium hydroxide fusion method, a lanthanum fluoride matrix removal step, and a column separation process with stacked TEVA, TRU and DGA resin cartridges. The rapid fusion method provides rugged digestion of any refractory particles present, essential for reliable analysis of actinides in fecal samples. Alpha spectrometry was used to determine the actinide isotopes, but this method can be adapted for assay by inductively-coupled plasma mass spectrometry for actinide isotopes with longer half-lives that have sufficient mass to allow measurement. The method showed high chemical recoveries and effective removal of interferences. The determination of actinides in fecal samples can be performed in less than 12 h in an emergency with excellent quality for emergency samples. The new method, which is much less tedious and time-consuming than other reported methods, can be used for emergency or routine fecal sample analyses. This enables more timely estimates of radiological dose to be performed that utilize soluble/insoluble actinide ratios.     

Spectroscopic Determination of the Electronic Structure of a Uranium Single-Ion Magnet

Early actinide ions have large spin-orbit couplings and crystal field interactions, leading to large anisotropies. The success in using actinides as single-molecule magnets has so far been modest, underlining the need for rational strategies. Indeed, the electronic structure of actinide single-molecule magnets and its relation to their magnetic properties remains largely unexplored. A uranium(III) single-molecule magnet, [U^III{SiMe₂NPh}₃-tacn)(OPPh₃)] (tacn=1,4,7-triazacyclononane), has been investigated by means of a combination of magnetic, spectroscopic and theoretical methods to elucidate the origin of its static and dynamic magnetic properties.     

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 separation of actinides and radiostrontium in vegetation samples

A new rapid method for the determination of actinides and radiostrontium in vegetation samples has been developed at the Savannah River Site Environmental Lab (Aiken, SC, USA) that can be used in emergency response situations or for routine analysis. The actinides in vegetation method utilizes a rapid sodium hydroxide fusion method, a lanthanum fluoride matrix removal step, and a streamlined column separation process with stacked TEVA, TRU and DGA Resin cartridges. Lanthanum was separated rapidly and effectively from Am and Cm on DGA Resin. Alpha emitters are prepared using rare earth microprecipitation for counting by alpha spectrometry. The purified ⁹⁰Sr fractions are mounted directly on planchets and counted by gas flow proportional counting. The method showed high chemical recoveries and effective removal of interferences. The actinide and ⁹⁰Sr in vegetation sample analysis can be performed in less than 8 h with excellent quality for emergency samples. The rapid fusion technique is a rugged sample digestion method that ensures that any refractory actinide particles or vegetation residue after furnace heating is effectively digested.     

Rapid radiochemical method for determination of actinides in emergency concrete and brick samples

A new rapid method for the determination of actinides in emergency concrete and brick samples has been developed at the Savannah River Site Environmental Lab (Aiken, SC, USA) that can be used in emergency response situations or for routine analysis. If a radiological dispersive device (RDD), Improvised Nuclear Device (IND) or nuclear accident occurs, there will be a urgent need for rapid analyses of many different environmental matrices, including building materials such as concrete and brick, to support dose mitigation and environmental clean-up. The new method for actinides in concrete and brick method utilizes a rapid sodium hydroxide fusion method, a lanthanum fluoride matrix removal step, and a column separation process with stacked TEVA, TRU and DGA Resin cartridges. Alpha emitters are prepared using rare earth microprecipitation for counting by alpha spectrometry. The method showed high chemical recoveries and effective removal of interferences. The determination of actinides in concrete and brick sample analysis can be performed in less than 8 h with excellent quality for emergency samples. The rapid fusion technique is a rugged sample digestion method that ensures that any refractory actinide particles are effectively digested.     

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.     

Two step hydrothermal synthesis of flowerbud-like magnetite/graphene oxide hybrid with high-performance microwave absorption

A novel flowerbud-like magnetite/graphene oxide (GO) hybrid was synthesized from facile two-step hydrothermal process by using FeCl₃ as iron source, ethylene glycol as the reducing agent, and graphene oxide as template. The magnetite nanoparticles with the diameters of 70–80 nm were attached onto the surface of graphene oxide through the two-step self-assembly process which enhanced the magnetic properties of the hybrids. The final flowerbud-like magnetite/graphene oxide hybrid emerged with the saturated magnetization of ~84.5 emu g^–1. More importantly, owing to the combined contribution of enhanced dielectric and magnetic properties, the maximum microwave absorption of as-prepared magnetite/GO hybrid reached 30 dB with a thickness of 4 mm. Besides, the absorption bandwidth with a reflection loss above 23 dB ranged from 6.0 to 11.5 GHz.     

Behavior of neptunium in the separation process of actinides from irradiated targets

Radiochemical separations of trace amounts of actinides produced in heavy ion reactions with actinide targets are described. The neptunium behavior in the separation process using extraction chromatography with HDEHP is investigated. To select the optimal separation conditions for Np from the other actinides and from each other, their extraction by HDEHP has been studied in such solutions as HCl, NHO₃, HClO₄, HF, H₂C₂O₄ and H₃PO₄. A two-step separation procedure yields fractions of individual actinide elements.     

Determination of transuranic and thorium isotopes in ocean water: In solution and in filterable particles

A sensitive technique for the measurement of dissolved and particulate actinide concentrations and water column distributions is described. Pu, Am, and Th isotopes are collected using large-volume, wire-mounted electrical pumping systems. Particles were removed by filtration, and actinides by absorption on MnO₂-coated filters. The very large volumes processed (up to 4000 liters) result in very sensitive and precise concentration measurements after analyses of the samples by standard radiochemical and alpha spectrometric techniques.     

An improved actinide separation method for environmental samples

This paper presents a rapid method of separation of five actinide elements (Th, U, Np, Pu, and Am) for aqueous media samples. This separation method utilizes the unique chemistries of the actinides at low concentrations^1,2 and the properties of the EIChroM TRU-Resin^TM extraction resin. In order to cleanly recover the five actinides from aqueous samples or solubilized soil samples, the sample is passed through the column twice. The sample is first loaded in an HCl solution with hydrogen peroxide. This allows the Am and most matrix ions to pass through the column. Then the Th is eluted using dilute HCl followed by the Np and Pu which are eluted together with oxalic acid in dilute HCl solution. Finally, the U is eluted with ammonium oxalate solution. A calcium-oxalate coprecipitation is performed on the original load solution containing the Am ions and the dissolved precipitate is then reloaded onto the TRU-Resin^TM column in HNO₃ with ascorbic acid. The procedure requires approximately 1.5 working days for experienced technicians, greatly reduces waste, and generally results in actinide recoveries of 80–100%.     

Rapid determination of actinides in emergency food samples

A new rapid method for the determination of actinides in food samples has been developed at the Savannah River Site Environmental Lab (Aiken, SC, USA) that can be used for emergency response or routine food samples. If a radiological dispersive device or improvised nuclear device event occurs, there will be a urgent need for rapid analyzes of many different environmental matrices, as well as food samples, to support dose mitigation and protect general populations from radioactivity that may enter the food chain. The recent accident at Fukushima nuclear power plant in March, 2011 reinforces the need to have rapid analyzes for radionuclides in environmental and food samples. The new method to determine actinides in food samples utilizes a furnace ashing step, a rapid sodium hydroxide fusion method, a lanthanum fluoride matrix removal step, and a column separation process with stacked TEVA, TRU, and DGA resin cartridges. The furnace ashing and rapid fusion steps are performed in relatively inexpensive, reusable zirconium crucibles. Alpha emitters are prepared using rare earth micro precipitation for counting by alpha spectrometry. The method showed high chemical recoveries and effective removal of interferences. The determination of actinides in food samples can be performed in less than 8 h for 10 g samples with excellent quality for emergency samples using short count times. Larger food samples (100 g) may be processed in 24 h or less. The rapid fusion technique is a rugged sample digestion method that ensures that any refractory actinide particles are effectively digested. This method can be used to meet the derived intervention level guidelines recommended by the U.S. Food and Drug Administrations.     

Role of Magnetite Nanoparticles Size and Concentration on Hyperthermia under Various Field Frequencies and Strengths

Magnetite (Fe₃O₄) nanoparticles were synthesized using the chemical coprecipitation method. Several nanoparticle samples were synthesized by varying the concentration of iron salt precursors in the solution for the synthesis. Two batches of nanoparticles with average sizes of 10.2 nm and 12.2 nm with nearly similar particle-size distributions were investigated. The average particle sizes were determined from the XRD patterns and TEM images. For each batch, several samples with different particle concentrations were prepared. Morphological analysis of the samples was performed using TEM. The phase and structure of the particles of each batch were studied using XRD, selected area electron diffraction (SAED), Raman and XPS spectroscopy. Magnetic hysteresis loops were obtained using a Lakeshore vibrating sample magnetometer (VSM) at room temperature. In the two batches, the particles were found to be of the same pure crystalline phase of magnetite. The effects of particle size, size distribution, and concentration on the magnetic properties and magneto thermic efficiency were investigated. Heating profiles, under an alternating magnetic field, were obtained for the two batches of nanoparticles with frequencies 765.85, 634.45, 491.10, 390.25, 349.20, 306.65, and 166.00 kHz and field amplitudes of 100, 200, 250, 300 and 350 G. The specific absorption rate (SAR) values for the particles of size 12.2 nm are higher than those for the particles of size 10.2 nm at all concentrations and field parameters. SAR decreases with the increase of particle concentration. SAR obtained for all the particle concentrations of the two batches increases almost linearly with the field frequency (at fixed field strength) and nonlinearly with the field amplitude (at fixed field frequency). SAR value obtained for magnetite nanoparticles with the highest magnetization is 145.84 W/g at 765.85 kHz and 350 G, whereas the SAR value of the particles with the least magnetization is 81.67 W/g at the same field and frequency.     

Study of the An–Cl bond contraction in actinide trichlorides

The variation of the An–Cl bond distance in ground-state actinide trichloride (AnCl₃) molecules has been studied by density functional theory calculations using the B3LYP exchange–correlation functional in conjunction with small-core relativistic energy-consistent pseudopotentials for the actinides. The ground electronic states and the ground-state molecular properties of the trichlorides of heavy actinides (An = Bk–Lr) are reported in this paper the first time. Extending the present results with literature data on the light actinide trichlorides (AnCl₃, An = Th–Cm), the trend in the bond distance has been evaluated for the whole actinide row. The contraction is well manifested in the major part of the actinide row (An = U–Fm). The deviations at the beginning (Th, Pa) and end of the row (Md, No) have been explained by minor differences in the bonding interactions.     

Comparative structural and chemical studies of ferritin cores with gradual removal of their iron contents

Transmission Electron Microscopy (TEM), X-ray Absorption Near Edge Spectroscopy (XANES), Electron Energy-Loss Spectroscopy (EELS), Small-Angle X-ray Scattering (SAXS), and SQUID magnetic studies were performed in a batch of horse spleen ferritins from which iron had been gradually removed, yielding samples containing 2200, 1200, 500, and 200 iron atoms. Taken together, findings obtained demonstrate that the ferritin iron core consists of a polyphasic structure (ferrihydrite, magnetite, hematite) and that the proportion of phases is modified by iron removal. Thus, the relative amount of magnetite in ferritin containing 2200 to 200 iron atoms rose steadily from approximately 20% to approximately 70% whereas the percentage of ferrihydrite fell from approximately 60% to approximately 20%. These results indicate a ferrihydrite-magnetite core-shell structure. It was also found that the magnetite in the ferritin iron core is not a source of free toxic ferrous iron, as previously believed. Therefore, the presence of magnetite in the ferritin cores of patients with Alzheimer's disease is not a cause of their increased brain iron(II) concentration.     

Iron-modified light expanded clay aggregates for the removal of arsenic(V) from groundwater

Iron modified materials have been proposed as a filter medium to remove arsenic compounds from groundwater. This research investigated the removal of arsenate, As(V) from aqueous solutions by iron-coated light expanded clay aggregates (Fe-LECA). Arsenic is effectively adsorbed by Fe-LECA in the optimum pH range 6-7 by using a 10 mg mL^− 1 adsorbent dose. Kinetics experiments were performed to investigate the adsorption mechanisms. Electrostatic attraction and surface complexation were proposed to be the major arsenic removal mechanisms. The experimental data fitted the pseudo-first-order equation of Lagergren. For an arsenic concentration of 1 mg L^− 1, the rate constant (k₁) of pseudo-first-order was 0.098 min^− 1, representing a rapid adsorption in order to reach equilibrium early. Equilibrium sorption isotherms were constructed from batch sorption experiments and the data was best described by the Langmuir isotherm model. Large scale column experiments were conducted under different bed depths, flow rates, coating duration and initial iron salts concentration to determine the optimal arsenic removal efficiency by Fe-LECA column. Volumetric design as well as higher hydraulic detention time was proposed to optimize the efficiency of the column to remove arsenic. In addition, concentrated iron salts and longer coating duration were also found to be crucial parameters for arsenic removal. The maximum arsenic accumulation was 3.31 mg of As g^− 1 of Fe-LECA when the column was operated at a flow rate of 10 mL min^− 1 and the LECA was coated with 0.1 M FeCl₃ suspension for a 24 h coating duration.     

Rapid determination of actinides in seawater samples

A new rapid method for the determination of actinides in seawater samples has been developed at the Savannah River National Laboratory. The actinides can be measured by alpha spectrometry or inductively-coupled plasma mass spectrometry. The new method employs novel pre-concentration steps to collect the actinide isotopes quickly from 80 L or more of seawater. Actinides are co-precipitated using an iron hydroxide co-precipitation step enhanced with Ti⁺³ reductant, followed by lanthanum fluoride co-precipitation. Stacked TEVA Resin and TRU Resin cartridges are used to rapidly separate Pu, U, and Np isotopes from seawater samples. TEVA Resin and DGA Resin were used to separate and measure Pu, Am and Cm isotopes in seawater volumes up to 80 L. This robust method is ideal for emergency seawater samples following a radiological incident. It can also be used, however, for the routine analysis of seawater samples for oceanographic studies to enhance efficiency and productivity. In contrast, many current methods to determine actinides in seawater can take 1–2 weeks and provide chemical yields of ~30–60 %. This new sample preparation method can be performed in 4–8 h with tracer yields of ~85–95 %. By employing a rapid, robust sample preparation method with high chemical yields, less seawater is needed to achieve lower or comparable detection limits for actinide isotopes with less time and effort.     

Sorption of europium and actinides by means of octyl(phenyl)-N,N-diisobutyl carbamoylmethyl phosphine oxide (CMPO) loaded on silica

The octyl(phenyl)-N,N-diisobutylcarbamoylmethylphosphine oxide (CMPO), loaded as stationary phase on silica, has been used for the sorption of Eu and actinides from acidic aqueous solution. Different commerical solid support were investigated and, finally SiO₂ was chosen. Experiments were performed to obtain basic data on actinide removal. Distribution coefficients, kinetics, sorption isotherms (three adsorption model correlations were tested) and the acidic concentration effect were studied.     

Rapid column extraction method for actinides and strontium in fish and other animal tissue samples

The analysis of actinides and radiostrontium in animal tissue samples is very important for environmental monitoring. There is a need to measure actinide isotopes and strontium with very low detection limits in animal tissue samples, including fish, deer, hogs, beef and shellfish. A new, rapid separation method has been developed that allows the measurement of plutonium, neptunium, uranium, americium, curium and strontium isotopes in large animal tissue 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), neptunium (Np), uranium (U), americium (Am), and curium (Cm) using a single multi-stage column combined with alphaspectrometry. Strontium is collected on Sr Resin® from Eichrom Technologies (Darien, IL, USA). After acid digestion and furnace heating of the animal tissue samples, the actinides and ^89/90Sr are separated using column extraction chromatography. This method has been shown to be effective over a wide range of animal tissue matrices. Vacuum box cartridge technology with rapid flow rates is used to minimize sample preparation time.     

Adsorption of Mercury(II) on Amidoxime Chelating Resins with Magnetic Properties

Two amidoxime chelating resins were prepared. The preparation process was carried out through copolymerization of acrylonitrile with N,N′-methylene-bis-acrylamide (MBA) as a crosslinker in the presence and absence of magnetite (Fe₃O₄) particles. The resins obtained were subsequently treated with hydroxylamine to give the corresponding amidoxime chelating resins. The uptake behavior of the resins toward Hg(II) in aqueous solutions using batch and column techniques was studied. The oxide containing resin gave higher uptake capacities relative to oxide free resin confirming the advantage of embedded particles on the uptake capacity. Thermodynamic and kinetic parameters of the uptake process were calculated. Regeneration of the resins was carried out using 0.5 M KI and the desorption ratio was found to be more than 97%.