The new QST bioassay laboratory in Chiba, Japan.

Japan's National Institutes for Quantum Science and Technology (QST) was designated as the core radiation emergency medical support center by the country's Nuclear Regulation Authority (NRA) in 2019. One of the main missions of the QST is to maintain and improve its dose assessment capability for radiation-exposed individuals. Toward the goal of effectively fulfilling this mission, a new facility-the Dose Assessment Building for Advanced Radiation Emergency Medicine-was constructed at the Chiba base of the QST in 2020. An integrated bioassay laboratory was installed in this facility for assessing subjects' internal doses, along with a new integrated in vivo counter. The bioassay capability of the new laboratory is currently expected to screen 5-10 persons simultaneously assuming internal contamination with actinides such as Pu, Am/Cm and U, although this is dependent on the specific contamination circumstances.

Bioavailable actinide fluxes to the Irish Sea from Sellafield-labelled sediments.

Nuclear discharges to the oceans have given rise to significant accumulations of radionuclides in sediments which can later remobilise back into the water column. A continuing supply of radionuclides to aquatic organisms and the human food chain can therefore exist, despite the absence of ongoing nuclear discharges. Radionuclide remobilisation from sediment is consequently a critical component of the modelled radiation dose to the public. However, radionuclide remobilisation fluxes from contaminated marine sediments have never been quantitatively determined in-situ to provide a valid assessment of the issue. Here, we combine recent advances in the Diffusive Gradients in Thin Films (DGT) sampling technique with ultrasensitive measurement by accelerator mass spectrometry (AMS) to calculate the remobilisation fluxes of plutonium, americium and uranium isotopes from the Esk Estuary sediments (UK), which have accumulated historic discharges from the Sellafield nuclear reprocessing facility. Isotopic evidence indicates the local biota are accumulating remobilised plutonium and demonstrates the DGT technique as a valid bioavailability proxy, which more accurately reflects the elemental fractionation of the actinides in the biota than traditional bulk water sampling. These results provide a fundamental evaluation of the re-incorporation of bioavailable actinides into the biosphere from sediment reservoirs. We therefore anticipate this work will provide a tool and point of reference to improve radiation dose modelling and contribute insight for other environmental projects, such as the near-surface and deep disposal of nuclear waste.

α-Aminophosphonates, -Phosphinates, and -Phosphine Oxides as Extraction and Precipitation Agents for Rare Earth Metals, Thorium, and Uranium: A Review.

α-Aminophosphonates, -phosphinates, and -phosphine oxides are a group of organophosphorus compounds that were investigated as extraction agents for rare earth (RE) metals and actinoids for the first time in the 1960s. However, more systematic investigations of their extraction properties towards REs and actinoids were not started until the 2010s. Indeed, recent studies have shown that these α-amino-functionalized compounds can outperform the commercial organophosphorus extraction agents in RE separations. They have also proven to be very efficient extraction and precipitation agents for recovering Th and U from RE concentrates. These actinoids coexist with REs in some of the commercially important RE-containing minerals. The efficient separation and purification of REs is becoming more and more important every year as these elements have a pivotal role in many existing technologies. If one also considers the facile synthesis of α-amino-functionalized organophosphorus extractants and precipitation agents, it is expected that they will be increasingly utilized in the extraction chemistry of REs and actinoids in the future. This review collates α-aminophosphonates, -phosphinates, and -phosphine oxides that have been utilized in the separation chemistry of REs and actinoids, including their most relevant synthetic routes and molecular properties. Their extraction and precipitation properties towards REs and actinoids are also discussed.

Risk of colloidal and pseudo-colloidal transport of actinides in nitrate contaminated groundwater near a radioactive waste repository after bioremediation.

The possible role of biogeochemical processes in the transport of colloidal and pseudo-colloidal U, Np, and Pu during bioremediation of radionuclide- and nitrate-contaminated groundwater was investigated. In two laboratory experiments with water samples taken from contaminated aquifers before and post bioremediation, we found that microbial processes could cause clayed, ferruginous, and actinide colloids to coagulate. The main mechanisms are biogenic insoluble ferrous iron species formations (goethite, pyrrhotite, siderite, troilite, and ferrihydrite), the aggregation of clay particles by microbial metabolites, and the immobilization of actinides in the bacterial cells, large polymers, and iron and clayed sediments. This process decreases the risk of colloidal and pseudo-colloidal transport of actinides.

Simultaneous determination of actinides and 90Sr in large-size soil and sediment samples.

A simultaneous analytical method for sequential separation and determination of actinides and 90Sr in large-size environmental samples has been developed. In this method, successive co-precipitation steps were firstly conducted to remove matrix elements, then sequential column separation method was applied for simultaneous separation and purification of actinides and 90Sr/90Y. By using vacuum box technology, the total analytical time was minimized and batch processing allowed analyzing 12 samples in four days. The activity of 90Sr was obtained immediately by measuring its daughter radionuclide (90Y) with triple-to-double coincidence ratio (TDCR) Cherenkov counting, while the concentrations of Pu isotopes and 241Am could be measured by alpha spectrometry and mass spectrometric techniques. The overall recoveries of Pu, Am, Sr and Y were higher than 70% for the entire procedure, while the recovery ratios of Sr/Y were between 0.95 and 1.04 before chromatographic separation. The developed method was verified using 20 g and 50 g of environmental soil samples spiked with certified reference materials IAEA-384 or IAEA-385 and standard solution of 90Sr/90Y, and good agreement between the expected values and measured results has been achieved.

Microfluidic In-Situ Spectrophotometric Approaches to Tackle Actinides Analysis in Multiple Oxidation States.

The study and development of present and future processes for the treatment/recycling of spent nuclear fuels require many steps, from design in the laboratory to setting up on an industrial scale. In all of these steps, analysis and instrumentation are key points. For scientific reasons (small-scale studies, control of phenomena, etc.) but also with regard to minimizing costs, risks, and waste, such developments are increasingly carried out on milli- or microfluidic devices. The logic is the same for the chemical analyses associated with their follow-up and interpretation. Due to this, over the last few years, opto-microfluidic analysis devices adapted to the monitoring of different processes (dissolution, liquid-liquid extraction, precipitation, etc.) have been increasingly designed and developed. In this work, we prove that photonic lab-on-a-chip (PhLoC) technology is fully suitable for all actinides concentration monitoring along the plutonium uranium refining extraction (plutonium, uranium, reduction, extraction, or Purex) process. Several PhLoC microfluidic platforms were specifically designed and used in different nuclear research and development (R&D) laboratories, to tackle actinides analysis in multiple oxidation states even in mixtures. The detection limits reached (tens of µmol·L-1) are fully compliant with on-line process monitoring, whereas a range of analyzable concentrations of three orders of magnitude can be covered with less than 150 µL of analyte. Finally, this work confirms the possibility and the potential of coupling Raman and ultraviolet-visible (UV-Vis) spectroscopies at the microfluidic scale, opening the perspective of measuring very complex mixtures.

State-of-the-art progress for the selective crystallization of actinides, synthesis of actinide compounds and their functionalization.

Crystallization and immobilization of actinides to form actinide compounds are of significant importance for the extraction and reutilization of nuclear waste in the nuclear industry. In this paper, the state-of-art progress in the crystallization of actinides are summarized, as well as the main functionalization of the actinide compounds, i.e., as adsorbents for heavy metal ions and organic pollutant in waste management, as (photo)catalysts for organic degradation and conversion, including degradation of organic dyes and antibiotics, dehydrogenation of N-heterocycles, CO2 cycloaddition, selective alcohol oxidation and selective oxidation of sulfides. This review will give a comprehensive summary about the synthesis and application exploration of solid actinide crystalline salts and actinide-based metal organic frameworks in the past decades. Finally, the future perspectives and challenges are proposed in the end to give a promising direction for future investigation.

Biological, biomolecular, and bio-inspired strategies for detection, extraction, and separations of lanthanides and actinides.

Lanthanides and actinides are elements of ever-increasing technological importance in the modern world. However, the similar chemical and physical properties within these groups make purification of individual elements a challenge. Current industrial standards for the extraction, separation, and purification of these metals from natural sources, recycled materials, and industrial waste are inefficient, relying upon harsh conditions, repetitive steps, and ligands with only modest selectivity. Biological, biomolecular, and bio-inspired strategies towards improving these separations and making them more environmentally sustainable have been researched for many years; however, these methods often have insufficient selectivity for practical application. Recent developments in the understanding of how lanthanides are selectively acquired and used by certain bacteria offer the opportunity for a newer, more efficient take on these designs, as well as the possibility for fundamentally new designs and strategies. Herein, we review current cell-based and biomolecular (primarily small-molecule and protein-based) methods for detection, extraction, and separations of f-block elements. We discuss how the increasing knowledge regarding the selective recognition, uptake, trafficking, and storage of these elements in biological systems has informed and will continue to promote development of novel approaches to achieve these ends.

Comparison of decomposition techniques for solid samples with emphasis on actinide content determination.

Comparison of conventional acid digestion with mixtures of acids HNO3, HClO4, and HF and thermal fusion utilizing Li borate as a fusion agent was made for solid samples. In the study, various parameters such as amount of the sample taken for the analysis, as well as addition of tracers before and after dissolution procedures were investigated. The obtained results showed that dissolution without any residue was achieved only when the fusion method was used. Thus, no filtration was needed prior to the loading of the sample on the resin to perform radiochemical separation. Alpha-particle spectrometry and neutron activation analysis were used for determination of the actinides content in the investigated samples as well as in residues obtained after dissolution.

An Overview of Analytical Methods for in Vitro Bioassay of Actinides.

The bioassay of urine and fecal samples has been used since the 1940s to determine an individual's uptake of uranium and actinide elements such as americium and plutonium. Over the years, several analytical separation methods and techniques have been employed for these types of analyses. Analytical separations, ranging from solvent extraction and anion exchange to chromatography, and analytical techniques, ranging from autoradiography to kinetic phosphorescence to fission-track analysis and high-resolution solid-state alpha spectroscopy, have been used at one time or another. Over the last few decades, there have been significant advances in radiochemical separations, as well as an increased use of mass spectroscopy, to determine trace and ultratrace levels of actinides in urine and fecal samples. This review summarizes and discusses developments in radiochemical separation methods and advancements in analytical techniques for actinide bioassay since the early 1940s to the present, followed by a recent development and trend in the bioassay of actinides-particularly in urine and fecal samples.

Evaluation of Uncertainties in lung measurements of actinides due to counting statistics.

Counting statistics is an important parameter that can introduce uncertainties in the lung activity measurements of actinides in radiation workers. Evaluation of uncertainties due to counting statistics is practically difficult as it requires monitoring various radiation workers having different levels of lung actinide content, multiple times, each for 50 min of monitoring period. However, different activities in lungs can be simulated by combining uncontaminated male data with LLNL phantom data acquired with 241Am and natural uranium lung sets at various short periods. Therefore, multiple measurements were carried out on realistic thorax LLNL phantom with 241Am and natural uranium lung sets for 15-600 s. The mean counts with the phantom at various time intervals, corresponds to different actinide activities in lungs, assuming they are obtained for 50 min of monitoring interval. Using propagation of error, standard deviations were evaluated for combined phantom and uncontaminated adult male data. The combined standard deviations and mean phantom counts are used to evaluate scattering factors (SFs) for uncertainties due to counting statistics for Phoswich and HPGe array detectors. The SFs due to counting statistics are found to be the function of lung activities of radionuclides as well as energies and yields of the photons emitted by radionuclides. SFs are found to increase with decrease in lung activity. For similar yields photons, SFs are found to be lower for higher energy photons compared to lower energy photons. For photons of similar energies, the SFs are lower when yield is higher compared to lower yield photons.

Speciation of actinides in groundwater samples collected near deep nuclear waste repositories.

Actinide binding to colloidal particles of different nature was studied under oxic and anoxic conditions of an underground nuclear waste disposal site using successive micro- and ultrafiltration techniques. According to the actinide redox speciation, under oxic conditions they were present in high oxidation states except for plutonium, for which a significant part was found in the tetravalent state. In case of the anoxic conditions, the share of An (IV) was proportional to the total U(IV) concentration. This indicated formation of intrinsic U(IV) hydroxocolloids, which bound other actinides. Formation of the intrinsic actinide colloids was proven by the secondary ion mass spectrometry (SIMS) with the submicron resolution. In contrast, under the oxic conditions uranium and plutonium were sorbed by natural colloids (amorphous hydrous ferric oxide and Mn oxides).

Sequential analyses of actinides in large-size soil and sediment samples with total sample dissolution.

There is a growing demand for the determination of actinides in soil and sediment samples for environmental monitoring and tracing, radiological protection, and nuclear forensic reasons. A total sample dissolution method based on lithium metaborate fusion, followed by sequential column chromatography separation, was developed for simultaneous determination of Pu, Am and Cm isotopes in large-size environmental samples by alpha spectrometry and mass spectrometric techniques. The overall recoveries of both Pu and Am for the entire procedure were higher than 70% for large-size soil samples. The method was validated using 20 g of soil samples spiked with known amounts of 239Pu and 241Am as well as the certified reference materials IAEA-384 (Fangataufa Lagoon sediment) and IAEA-385 (Irish Sea sediment). All the measured results agreed very well with the expected values.

Evaluation of uncertainties in lung measurement of actinides due to non-uniform distribution of activity in lungs.

Various parameters can introduce uncertainties in the lung activity measurements of actinides. In this study, uncertainties due to non-uniform distribution of activity in the lungs are evaluated. To study the effect of non-uniform distribution, lungs of ICRP male thorax voxel and resized phantoms are divided into upper and lower parts of both right and left lungs as well as into anterior and posterior lung regions. Simulation of uniform and non-uniform distribution of activity in lungs is carried out using thorax voxel phantoms in FLUKA for Phoswich and an array of three HPGe detectors for 18-238keV photons. Source sampling for non-uniform distribution of activity is carried out by selecting the source points by varying the weightage to 0.4, 0.5, 0.6 and 1 in different parts of lungs. Uncertainties in lung activity estimation at different energies are quantified in the form of scattering factors (SFs) which are geometric standard deviations. The SFs due to non-uniform distribution of activity of the order of 0.4-0.6 in different parts of the lungs are found to be ~ 1.25 for Phoswich and HPGe array detectors above 18keV.

Rare earth elements and select actinoids in the Canadian House Dust Study.

Nationally representative baseline data are presented for rare earth elements (REE), thorium (Th) and uranium (U) in house dust sampled from 1025 urban homes, in units of concentrations (µg g-1 ), loadings (µg m-2 ), and loading rates (ng m-2  d-1 ). Spearman rank correlations indicate that, in addition to outdoor sources, consumer products and building materials can influence indoor dust concentrations of REE, Th, and U. Correlations (P<.01) with numbers of occupants, dogs, and cats suggest soil track-in. Correlations (P<.01) with hardwood floors suggest release of REE additives used in pigments and coatings during daily wear and tear. Concentrations of light REE are elevated in smokers' homes compared to non-smokers' homes (P<.001), suggesting that a key source is "mischmetal," the REE alloy used in cigarette-lighter flints. Indoor sources include geological impurities in raw materials used in consumer products, such as U and Th impurities in bentonite clay used in cat litter, and REE impurities in phosphates used for a variety of applications including dog food and building materials. Median gastric bioaccessibility (pH 1.5) of most REE in dust ranges from about 20% to 29%. Household vacuum samples correlate with fresh dust samples from the same homes (P<.001 for all investigated elements).

Analysis methodology and development of a statistical tool for biodistribution data from internal contamination with actinides.

The aim of this work was to develop a computational tool that integrates several statistical analysis features for biodistribution data from internal contamination experiments. These data represent actinide levels in biological compartments as a function of time and are derived from activity measurements in tissues and excreta. These experiments aim at assessing the influence of different contamination conditions (e.g. intake route or radioelement) on the biological behavior of the contaminant. The ever increasing number of datasets and diversity of experimental conditions make the handling and analysis of biodistribution data difficult. This work sought to facilitate the statistical analysis of a large number of datasets and the comparison of results from diverse experimental conditions. Functional modules were developed using the open-source programming language R to facilitate specific operations: descriptive statistics, visual comparison, curve fitting, and implementation of biokinetic models. In addition, the structure of the datasets was harmonized using the same table format. Analysis outputs can be written in text files and updated data can be written in the consistent table format. Hence, a data repository is built progressively, which is essential for the optimal use of animal data. Graphical representations can be automatically generated and saved as image files. The resulting computational tool was applied using data derived from wound contamination experiments conducted under different conditions. In facilitating biodistribution data handling and statistical analyses, this computational tool ensures faster analyses and a better reproducibility compared with the use of multiple office software applications. Furthermore, re-analysis of archival data and comparison of data from different sources is made much easier. Hence this tool will help to understand better the influence of contamination characteristics on actinide biokinetics. Our approach can aid the optimization of treatment protocols and therefore contribute to the improvement of the medical response after internal contamination with actinides.

Pore-Filled Scintillating Membrane as Sensing Matrix for α-Emitting Actinides.

Pore-filled membranes with scintillating properties have been synthesized for sensing α-emitting radionuclides. The membranes have been prepared by in situ UV-initiator-induced polymerization of monomer bis[2-(methacryloxy)ethyl] phosphate in pores of the host membranes, poly(propylene) and poly(ethersulfone). The polymerization has been carried out in the presence of scintillating molecules, 2,5-diphenyloxazole. These scintillating molecules are physically trapped in the thus formed microgel in the membrane. Much higher α-scintillation efficiency has been obtained for the (241)Am-loaded poly(ethersulfone)-based grafted membrane compared to poly(propylene)-based membrane. This was attributed to the aromatic backbone of the poly(ethersulfone) membrane. The scintillation response of poly(ethersulfone)-based membranes has been found to be linear over the range of (241)Am activity studied. The pore-filled scintillating membranes have been found to be selective toward Pu(4+) ions at higher HNO3 concentration compared to Am(3+). The analytical performance of the pore-filled scintillating membranes has been evaluated. The membranes have been found to be stable and reusable. The scintillating membrane with optimized composition has been applied for quantification of Pu in a soil sample.

DEVELOPMENT OF A RAPID PROCEDURE TO ANALYSE Pu, Am AND 90Sr IN EMERGENCY URINE BIOASSAY IN CIEMAT BIOELIMINATION LABORATORY: METHOD VALIDATION BY EMERGENCY BIOASSAY INTERCOMPARISON EXERCISES.

After a radiological or nuclear incident, it is necessary to give a prompt response and to know the number of persons exposed to internal contamination, to evaluate the contamination levels in each person and even and to identify the radionuclides involved. In vitro laboratories routine monitoring measurements employed to quantify (90)Sr and actinides in urine require radiochemical separation and long counting time, which implies a minimum of 1 or 2 weeks to obtain the results, respectively. In this work, rapid radiochemical separation method applied directly to urine samples is presented. It is based on minimal sample preparation, without co-precipitation phase, using extraction resin columns and vacuum box technology. Pu isotopes and (241)Am are isolated, electrodeposited and measured by alpha spectrometry, whereas (90)Sr is measured by liquid scintillation counting. Finally, results of the participation in European Radiation Dosimetry Group intercomparison on Emergency Bioassay exercise and Bundesamt für Strahlenschutz exercise validate the accuracy of this procedure.

The pentavalent actinide solution chemistry in the environment.

With regard to environmental monitoring of certain nuclear facilities, pentavalent actinides, in particular neptunium and plutonium, play a key role, as the chief soluble, mobile forms of actinides. In the past five years, investigations carried out by hyphenating capillary electrophoresis to ICP-MS (CE-ICP-MS) have allowed a number of hitherto unknown thermodynamic data to be determined for Np(V) and Pu(V) interactions with the chief environmentally abundant anions. For the first time, data were provided for Pu(V) interactions with carbonate, sulfate, oxalate, chloride, and nitrate ions, allowing the Np(V)/Pu(V) analogy to be verified experimentally. Knowledge of Np(V) chemistry, especially in carbonate, and sulfate media, was also refined. These CE-ICP-MS studies, combined with some earlier findings, have brought about a renewal in the knowledge of An(V) chemistry in solution.

Decreased Salinity and Actinide Mobility: Colloid-Facilitated Transport or pH Change?

Colloids have been implicated in influencing the transport of actinides and other adsorbed contaminants in the subsurface, significantly increasing their mobility. Such colloid-facilitated transport can be induced by changes in groundwater chemistry that occur, for example, when high ionic strength contaminant plumes are displaced by infiltrating rainwater. We studied the transport and mobility of Th(IV), as an analogue for Pu(IV) and other tetravalent actinides [An(IV)], in saturated columns packed with a natural heterogeneous subsurface sandy sediment. As expected, decreases in ionic strength both promoted the mobilization of natural colloids and enhanced the transport of previously adsorbed Th(IV). However, colloid-facilitated transport played only a minor role in enhancing the transport of Th(IV). Instead, the enhanced transport of Th(IV) was primarily due to the pH-dependent desorption of Th(IV) caused by the change in ionic strength. In contrast, the adsorption of Th(IV) had a marked impact on the surface charge of the sandy sediment, significantly affecting the mobility of the colloids. In the absence of Th(IV), changes in ionic strength were ineffective at releasing colloids while in the presence of Th(IV), decreases in ionic strength liberated significant concentrations of colloids. Therefore, under the conditions of our experiments which mimicked acidic, high ionic strength groundwater contaminant plumes, Th(IV) had a much greater effect on colloid transport than colloids had on Th(IV) transport.