Band 110, Heft 6-9

On the occasion of the diamond jubilee of Radiochimica Acta ( RCA ), this article briefly describes the progress made by the journal during the last 10 years; a detailed account of the developments during the first 50 years having been given earlier ( Radiochimica Acta 2012, 100, 483–492). Publishing responsibility for the journal was taken over in 2014 by Walter De Gruyter, a traditional German publishing company founded in 1749. This allowed RCA also to maintain its established traditional standard of publishing. Being broad-based, the journal encompasses all chemical aspects of nuclear science and technology. It has kept pace with the changing trends in radiochemical research. Today, besides fundamental nuclear chemistry, applied topics, such as chemical behaviour and mobility of actinides and fission products, accelerator-based radiochemistry, development of novel radiochemical techniques, study of radiation chemical effects, etc., are well represented. The journal is supported by a group of international Editors and Advisors who are distinguished radiochemists themselves. It follows a strict peer-review system and is assisted by a network of about 500 referees. About 200 manuscripts are received per year, out of which 40–45% are rejected. The impact factor (IF) of RCA is comparable to those of other radiochemistry-related journals, but the cited half-life (CHL) of RCA is by far the highest of all related journals. A list of top highly cited 100 articles has been provided alongside this article. In the past, most of the articles originated from Europe and North America, but in recent years the number of contributions from China and several developing countries has been increasing. All articles are published in English, and the journal is presently available to read both online and in a printed format.

Superheavy element research has been a strong pillar of the research program at GSI Darmstadt since its foundation. Six new elements were discovered along with many new isotopes. Initial results on chemical properties of the heaviest elements were obtained that allowed for comparing their behavior with that of their lighter homologs and with theoretical predictions. Main achievements of the past five decades of superheavy element research at GSI are described along with an outlook into the future of superheavy element research in Darmstadt.

Studies of the chemical properties of the elements at the uppermost end of the Periodic Table are extremely challenging both experimentally and theoretically. One of the most important and interesting subjects is to clarify the basic chemical properties of these elements as well as to elucidate the influence of relativistic effects on their electronic configuration. Isotopes of these elements produced at accelerators, however, are short-lived, and the number of produced atoms is so small; any chemistry to be performed must be done on an atom-at-a-time basis that imposes stringent limits on experimental procedures. Here we describe our recent achievements in the effective production of low-energy ion-beams of the elements at the end of the actinide series, fermium (Fm, atomic number Z  = 100), mendelevium (Md, Z  = 101), nobelium (No, Z  = 102), and lawrencium (Lr, Z  = 103), using a surface ionization ion-source installed in the ISOL (Isotope Separator On-Line) at the Tandem accelerator facility of JAEA (Japan Atomic Energy Agency). Then the successful measurements of the first ionization potentials (IP 1 ) of these elements with the ISOL setup are reviewed. The measured IP 1 values increased up to No via Fm and Md, while that of Lr was the lowest among the actinides. Based on the variation of the IP 1 values of the heavy actinides with the atomic number in comparison with those of the heavy lanthanides, the results clearly demonstrated that the 5 f orbitals are fully filled at No, and the actinide series ends with Lr. Furthermore, the IP 1 value of Lr provoked controversy over its position in the Periodic Table, so a short introduction to this issue is presented. The feasibility of the extension of chemical studies to still heavier elements with their ion-beams generated by ISOL is briefly discussed.

Sonochemistry studies chemical and physical effects in liquids submitted to power ultrasound. These effects arise not from a direct interaction of molecules with sound waves, but rather from the acoustic cavitation: the nucleation, growth, and implosive collapse of microbubbles in liquids submitted to power ultrasound. The violent implosion of bubbles leads to the formation of chemically reactive species. In principle, each cavitation bubble can be considered as a microreactor initiating chemical reactions at mild conditions. In addition, microjets and shock waves accompanied bubble collapse produce fragmentation, dispersion and erosion of solid surfaces or particles. Microbubbles oscillating in liquids also enable nucleation and precipitation of nanosized actinide compounds with specific morphology. This review focuses on the versatile sonochemical processes with actinide ions and particles in homogenous solutions and heterogenous systems. The redox reactions in aqueous solutions, dissolution or precipitation of refractory solids, synthesis of actinide nanoparticles, and ultrasonically driving decontamination are considered. The guideline for further research is also discussed.

In the advanced spent fuel cycle, the control and adjustment of neptunium valence state is greatly important for the highly efficient separation of neptunium. Hydrazine and its derivatives as salt-free reagents can selectively reduce Np(VI) to Np(V), but their reduction mechanisms are still unclear. We explored the reduction of [Np VI O 2 (H 2 O) 2 (NO 3 ) 2 ] by N 2 H 4 and its two derivatives HOC 2 H 4 N 2 H 3 and CHON 2 H 3 using scalar relativistic density functional theory. The thermodynamic energy of the reactions [Np VI O 2 (H 2 O) 2 (NO 3 ) 2 ] with three reductants are sensitive to the substitution group, HOC 2 H 4 N 2 H 3 enhances thermodynamic ability of the reaction and CHON 2 H 3 shows contrary result. Both HOC 2 H 4 N 2 H 3 and CHON 2 H 3 have lower energy barrier compared to N 2 H 4 based on the potential energy profiles (PEPs), which probably attributes to the intramolecular hydrogen bond of hydrazine derivatives. The nature of these redox reactions is that the hydrogen atom of reductants is gradually transferred to the axis oxygen atom of neptunyl, which accompanies the N–H bond dissociation and O ax –H bond formation. The reduction of Np(VI) with HOC 2 H 4 N 2 H 3 is the most favorable reaction based on the thermodynamic and kinetic results. This work provides theoretical perspective into the reduction of Np(VI) to Np(V), which is beneficial to the development of more effective free-salt reductants for the separation of neptunium from uranium and plutonium in spent fuel reprocessing.

This review concerns the speciation of protactinium in aqueous solution under its both oxidation states +IV and +V. Emphasis is placed on experimental data obtained at trace level but also in macroscopic amount leading to the determination of thermodynamic and structural data. Thus, the complexation of Pa(V) with mineral acids and organic acids, mainly polyaminocarboxylic acids (iminodiacetic acid [IDA], nitrilotriacetic acid [NTA], ethylenediaminetetraacetic acid [EDTA] and diethylenetriaminepentaacetic acid [DTPA]) are highlighted and compared. The review also includes the actual knowledge about the Pa(IV) aqueous chemistry pinpointing its spectroscopic features.

A multi-target recoil chamber technique was applied to study online chemical properties of protactinium in chlorinating and brominating gas media using 226 Pa ( T 1/2  = 1.8 min) decaying by alpha emission (74%) and β + /EC decay (26%). A 58 MeV proton beam passing 15 × 50 μg/cm 2 thick 232 Th targets enabled production of 226 Pa formed in the reaction 232 Th(p,7n). Isothermal gas chromatography in quartz columns allowed for the determination of adsorption enthalpies of oxohalides and pure halides of Pa 5+ compounds. On the basis of empirical correlations, these adsorption enthalpies (ΔH 0 ads ) could be converted to sublimation enthalpies (ΔH 0 subl ). Resulting values for the assumed compounds PaCl 5, PaOCl 3, PaBr 5 , and PaOBr 3 were 113 ± 15, 329 ± 16, 165 ± 5 and 235 ± 17 kJ/mol, respectively. These values are rather similar to known ΔH 0 subl data for group-5 elements Nb, Ta and Db in support of the assumption that Pa is a pseudo-group 5 element.

Available literature data on the aqueous chemistry of radium are compiled. There are limited available experimental data and a significant portion of the data has been estimated using electrostatic techniques, typically based on the corresponding data of barium. The available data are compared with the corresponding data of barium (and strontium) and a methodology for estimating additional radium thermochemical data is described.

An innovative-SANEX process for the selective separation of the trivalent actinides americium and curium from a simulated PUREX raffinate solution was successfully demonstrated on the laboratory scale using a 16-stage 1 cm annular centrifugal contactor setup. The solvent was composed of 0.2 mol L −1 N , N , N′ , N′ -tetra- n -octyl-diglycolamide (TODGA) and 5% v/v 1-octanol in a kerosene diluent. Zr(IV) and Pd(II) co-extraction was prevented using trans -1,2-diaminocyclohexane- N , N , N′ , N′ -tetraacetic acid (CDTA) as a masking agent in the feed. The actinide(III) selective back-extraction was achieved using 2,6-bis[1-(propan-1-ol)-1,2,3-triazol-4-yl]pyridine (PyTri-Diol) in 0.45 mol L −1 HNO 3 as a CHON alternative to the sulfur-containing stripping agent used in a previous version of the innovative-SANEX process. The new process described in this paper showed excellent performance for the recovery of An(III). An An(III) product with a quasi-quantitative recovery of americium and curium (≥99.9%) and very good separation from fission and activation products was obtained (decontamination factors ≥4000). Only a slight contamination with Zr and Ru was observed. This test demonstrates the successful use of molecules containing only carbon, hydrogen, oxygen, and nitrogen atoms (so-called CHON molecules) for the selective separation of An(III) from a simulated PUREX raffinate solution. By avoiding sulfur- or phosphorous-containing molecules, the generation of secondary radioactive waste during process operation can be reduced drastically.

Neptunium, with a half life of 2.14 million years is one of the most notorious activation products in the nuclear fuel cycle. It has been more than 5 decades in the reprocessing of nuclear fuels by the well documented PUREX process, but the fate of Np in the PUREX cycle is still not well controlled. Although Np being stable in its pentavalent state in low acid media, its starts to undergo disproportionation at higher acidities. This disproportionation along with the oxidizing conditions of the HNO 3 medium makes Np to exits as Np(IV), Np(V) and Np(VI) in the dissolver solution. The overall extractability of Np in the co-decontamination step of the PUREX cycle is dependent on its oxidation state in the medium as Np(VI) and Np(IV) being extractable while Np(V) being least extractable. The present review article discusses about the speciation of Np in HNO 3 and its disproportionation. The variety of redox reagents are discussed for their effectiveness towards controlling Np redox behavior in the HNO 3 media. The extraction of Np with the different class of extractant has also been discussed and the results are compared for better understanding. Solid phase extraction of Np using both commercially available resin and lab based synthesized resins were discussed. The anion exchange resins with the different cationic centers were shown to behave differently towards the uptake of Np form the acidic medium. The present review also highlight the chemical conditions required for controlling or minimizing the fate of Np in different process streams of the nuclear fuel cycle.

Surface adsorption has a major influence on the environmental mobility of radionuclides, including uranium. Six decades ago, the description of the sorption process relied predominantly on simple descriptive parameters of solid–liquid partitioning (such as Kd values). There have since been numerous systematic investigations of the processes controlling U adsorption, including the affinity of U for different types of geologic materials, the influence of factors such as pH, the effects of complexing ligands, and the role of microorganisms. Mathematical descriptions of sorption processes have adopted various models – including sorption isotherms, surface complexation models and other types of modelling approaches, aided by advances in computational and analytical techniques. In recent years, mechanistic models have incorporated structural insights gained from spectroscopic techniques (such as EXAFS and TRLFS). Throughout the period, the nuclear waste community has sought to develop models for U sorption in complex systems associated with radioactive waste disposal, involving a range of mineral surfaces and incorporating numerous interactions and processes. To some extent, the ongoing questions concerning U adsorption can be considered as being common to many environmental metal contaminants. However, uranium is a unique and significant case, particularly for the radiochemical community, where the long-term behaviour of actinides is a central issue.

Inorganic ion-exchange materials show potential application for toxic radioactive ions due to their remarkable high efficiency and selectivity features. Here, two type of carbon-supported titanate (C@TNFs and C@TNFs(H)) nanofibers have been synthesized by a cost-effective in suit growth method. The resulting C@TNFs and C@TNFs(H) microspheres present uniform flower-like morphology and large surface area. The interlayer Na + in the titanate shell provides docking sites for ion-exchange of radioactive ions (U(VI), Ba(II), and Sr(II)). Interestingly, the exceeding theoretical cation-exchange capacities (CECs) are achieved on C@TNFs for U(VI) ∼4.76 meq g −1 and Ba(II) ∼2.65 meq g −1 and C@TNFs(H) for Ba(II) ∼2.53 meq g −1 and Sr(II) ∼2.24 meq g −1 , respectively. The impressive adsorption performance is mainly attributed to the synergistic effects of ion-exchange and surface complexation. More significantly, C@TNFs and C@TNFs(H) maintain high distribution coefficients ( K d U ) of >104 mL g −1 over a wider pH range (pH = 3.5–9.0) and high adsorption rate with short equilibrium time within 50 min. Competitive ion-exchange investigation shows a selectivity order of U(VI) > Ba(II) > Sr(II) at individual 10 ppm concentration, pH = 6.0 and T = 298 K. The related spectroscopic studies reveal the intercalative mechanism of radionuclides in the deformed titanate structure, as a result of target ions firmly trapped in the interlayer of C@TNFs and C@TNFs(H). These advantageous features allow the C@TNFs and C@TNFs(H) to be promising candidates for the remediation of toxic radioactive ions polluted water.

The field of radiochemistry in the Republic of Korea has expanded greatly over the last three decades to meet the rapid growth of technological demands in various areas such as nuclear energy and nuclear technologies for human health and environmental protection. Major research activities, which were initially centered at the Korea Atomic Energy Research Institute (KAERI), have gradually spread to major universities and the commercial sector. In this review, progress and recent research trends in nuclear and radiochemistry in Korea are summarized. The main research outcomes achieved by KAERI scientists are highlighted, with emphasis on basic actinide chemistry in nuclear fuel cycles, the radioanalytical chemistry of various radionuclides from radioactive waste and the environment, and medical radionuclide production. In addition, recent efforts to promote radiochemical education and future perspectives are briefly outlined.

We have consulted existing half-life data available in Nuclear Data Sheets for radionuclides with Z  < 89 in the range between 30 and 10 8 years with emphasis on their uncertainty. Based on this dataset, we have highlighted the lack of reliable data by giving examples for nuclides relevant for astrophysical, environmental and nuclear research. It is shown that half-lives for a substantial number of nuclides require a re-determination since existing data are either based on one single measurement, are contradictory or are associated with uncertainties above 5%.

Recommended half-lives and specific well-defined emission energies and absolute emission probabilities are important input parameters that should be well-defined to assist in ensuring the diagnostic and therapeutic efficacy of individual radionuclides when applied in the field of nuclear medicine. Bearing in mind the nature of these requirements, approximately one hundred radionuclides have been considered and re-assessed as to whether their decay data are either adequately quantified, or require further in-depth measurements to improve their existing status and merit full re-evaluations of their decay schemes. The primary aim of such a review is to provide sufficient information on the existing and future requirements for such atomic and nuclear data.

The standardisation of nuclear reaction cross section data is an integral part of optimisation of production routes of medical radionuclides. The production cross sections are available for the reactor and cyclotron produced radionuclides to be used for diagnostics or therapeutic procedures. The types of nuclear data needed, and the sources of their availability are summarized. The method of standardisation of charged-particle data is briefly described. A historical overview of research work in Pakistan in this direction is given. Examples of a few medically important radionuclides, such as 64 Cu, 86 Y, 89 Zr, 103 Pd, 186 Re, etc., whose data were standardised and evaluated are highlighted. Calculated thick target yields from the recommended data are given. Some new directions in the nuclear data research are outlined.

Over the last several decades, our research group has been working on nuclear data measurements using a J-25 Neutron Generator, a TRIGA Mark II Research Reactor and a Tandem Accelerator at Savar, as well as an Am/Be neutron source at Rajshahi. The spectrum of fast neutrons having energies from 0.5 to 20 MeV in the core of the TRIGA reactor as well as from 1.5 to 11 MeV of the Am/Be source was well characterized for validation of evaluated data of neutron threshold reactions. Spectrum-averaged cross sections were determined by integral measurements. The integral values measured at both the reactor and the Am/Be source were compared with the integrated data deduced from measured and evaluated excitation functions of some nuclear reactions given in some data libraries. As example, the details on the integral and integrated cross sections of the 64 Zn(n,p) 64 Cu and 60 Ni(n,p) 60 Co reactions are discussed. In both cases, integral test shows that further improvement of the evaluated excitation function reported in data libraries is needed. The use of a newly developed facility at the 3 MV Tandem Accelerator in measurement of proton induced reaction cross sections in the energy region below 5 MeV is outlined, and new results on the 64 Ni(p,n) 64 Cu and nat Ni(p,x) 61 Cu processes below 3 MeV are discussed.

Measurement and evaluation of nuclear data of radioisotopes used as tracers are continuously underway in many laboratories to reach high accuracy for their use in production. We briefly mention some of the radionuclides useful for medical diagnostics and other industrial applications. The research group at the Egyptian cyclotron facility (EGCF) performed in collaboration with nuclear research centres and universities in many countries (Germany, Hungary, Finland, USA, Japan and Saudi Arabia) some measurements and evaluations of interesting nuclear reaction data. Nuclear reactions induced by p, d and α-particles on a wide variety of targets were extensively studied from threshold energy up to 50 MeV. Nuclear model code calculations, mainly using EMPIRE and TALYS, were performed for nuclear data validation. Proton and neutron activation of some industrially interesting samples were also studied as technological application of nuclear analytical techniques. Since the cyclotron facility is dedicated to development of the production routes of medical radioisotopes, this overview presents examples of optimization experiments to establish good production conditions.

Whatever the radionuclide to be used in nuclear medicine, it is essential to know the expected yield during the production process, but also of all the possible radionuclidic impurities coproduced, that can have an impact on the product final quality, as well as in the related waste management. The availability of the majority of emerging radioisotopes, including the theranostic ones or pairs, is mainly limited by the fact that, for most of them, the optimal production route still needs to be strengthened if not defined in some cases. The aim of this work is to present a review on the charged particle induced nuclear cross sections to produce some emerging radionuclides for medical applications to show that all types of projectiles should be considered in the quest of producing medical radionuclides. An accurate analysis of the production routes is presented for some radionuclides ( 67 Cu, 47 Sc, 89 Zr, 103 Pd, 186g Re, 97 Ru, 211 At) chosen as examples to highlight (i) how the quality of the final product strongly depends on the chosen target/projectile/energy parameters set, (ii) how deuteron production routes may sometimes be more effective than the proton ones or lead to a different impurity profile and (iii) how α-particle beams may allow to bypass the limitations occurring when using Z = 1 beams. An overview of possible advantages and drawbacks of the cited production routes and of potential cross sections that still need to be measured, is also reported.

Radiochemical separations used in large scale routine production of diagnostic and therapeutic radionuclides at a particle accelerator for patient care are briefly outlined. The role of chemistry at various stages of development of a production route of a novel radionuclide, namely nuclear data measurement, high-current targetry, chemical processing and quality control of the product, is discussed in detail. Special attention is paid to production of non-standard positron emitters (e.g. 44g Sc, 64 Cu, 68 Ga, etc.) at a cyclotron and novel therapeutic radionuclides (e.g. 67 Cu, 225 Ac, etc.) at an accelerator. Some typical examples of radiochemical methods involved are presented.

The attempts to produce neutron deficient radioisotopes of rare Earth elements by heavy ion activation are discussed in this review. The heavy ion induced reaction products have large atomic number difference with that of the target; therefore, radiochemical separation of no-carrier-added radio-lanthanides from the target matrix becomes easier. Heavy ion induced reactions also allow the production of rare Earth radionuclides from non-rare Earth target by tailor-made target-projectile combinations, and in those cases, radiochemical separations become even more easier. In general, the cross sections of heavy ion induced reactions are less than those of light charged particle induced reactions. However, some of the heavy ion induced reactions have comparable cross sections with those of light ion induced reactions. The range of heavy ions is also much smaller in the target matrix than that of lighter charged particles. These points hinder application of heavy ion induced reactions to produce radionuclides for nuclear medicine.

Enriched tungsten disulfide ( 186 WS 2 ) was evaluated at increasing proton beam currents (20–50 μA) and times (up to 4 h) on a GE PETtrace cyclotron for production of high specific activity (HSA) 186 Re. The HSA 186 Re was separated from the irradiated target as [ 186 Re][ReO 4 ] – by a liquid–liquid extraction method and radiolabeled with a new N 2 S 2 ligand (222-MAMA- N -ethylpropionate). The enriched 186 W was recovered from the extraction process, analyzed for purity and enrichment, and converted back to the disulfide ( 186 WS 2 ). The results demonstrate that the 186 WS 2 is an easily pressed target material that can withstand relatively high currents and can be readily recovered and recycled. The 186 Re produced was isolated in high specific activity and readily formed the radiotracers [ 186 Re][ReO(222-MAMA- N -ethylpropionate)] and [ 186 Re][Re(CO) 3 (OH 2 ) 3 ] + .

National Institutes for Quantum Science and Technology (QST), formerly known as the National Institute of Radiological Sciences (NIRS), has been engaged in work on radiopharmaceutical science using cyclotrons since 1974. Eight pioneering researchers founded the basis of this field of research at NIRS, and to the present, many researchers and technicians have accumulated both scientific and technical achievements, as well as inherited the spirit of research. Besides, in recent years, we have developed production systems with AVF-930 cyclotron for various ‘non-standard’ radioisotopes applied in both diagnosis and therapy. Here, we review the past 50 years of our activities on radioisotope and radiopharmaceutical development, as well as more recent activities.

This review provides an essential overview on the progress of rapidly-developing China’s radiopharmaceuticals in recent years (2014–2021). Our discussion reflects on efforts to develop potential, preclinical, and in-clinical radiopharmaceuticals including the following areas: (1) brain imaging agents, (2) cardiovascular imaging agents, (3) infection and inflammation imaging agents, (4) tumor radiopharmaceuticals, and (5) boron delivery agents (a class of radiopharmaceutical prodrug) for neutron capture therapy. Especially, the progress in basic research, including new radiolabeling methodology, is highlighted from a standpoint of radiopharmaceutical chemistry. Meanwhile, we briefly reflect on the recent major events related to radiopharmaceuticals along with the distribution of major R&D forces (universities, institutions, facilities, and companies), clinical study status, and national regulatory supports. We conclude with a brief commentary on remaining limitations and emerging opportunities for China’s radiopharmaceuticals.

Many scientists who are members of the Japan Society of Nuclear and Radiochemical Sciences have been involved in academic activities in response to the Fukushima Daiichi Nuclear Power Plant accident. Projects had been implemented that include determining radionuclides in environmental samples, identifying the distribution of radionuclides by large-scale soil monitoring, tracing radionuclide discharge time series, clarifying environmental dynamics of radionuclides, etc. For the last 10 years, these results have been shared and discussed in annual workshops partly sponsored by the society. This review summarizes the studies yielding these results, and they include reconstruction of the 131 I distribution on soil by long-lived 129 I analysis, reconstruction of the radioactive plume transport, identification of biological resuspension sources, discovery and characterization of cesium particles, and parameterization of the environmental behavior of radiocesium for dose assessment.