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Progress in Chemistry 2011, No.7 Previous issue Next issue

In this issue:

Some Thinking of Nuclear Fuel Reprocessing/Recycling in China
Gu Zhongmao, Chai Zhifang
2011, 23 (7): 1263-1271 |
Published: 24 July 2011
Abstract
Based on the uranium-plutonium fuel cycle, the once-through fuel cycle, closed fuel cycle for thermal reactors and closed fuel cycle for fast reactors are analyzed and compared from the view point of sustainable development of nuclear fission energy. It is pointed out that both the once-through fuel cycle and the closed fuel cycle of thermal reactor could not meet the strategic needs of sustainable development of nuclear energy and fast reactor with multi-recycling of nuclear fuel is the best option to develop the nuclear fission energy in a sustainable way. The present status and the major trend of reprocessing/recycling technologies in the world are introduced and the gap between China and the major nuclear energy countries is evaluated. Keeping the domestic situation in mind, we try to explore the general considerations of the development of nuclear fuel reprocessing/recycling technologies in China and the technical options to be taken. The key techniques to be solved and the associated supporting measures are also proposed. Contents
1 Introduction
2 Two options of nuclear fuel cycle-once-through fuel cycle and closed fuel cycle
2.1 Concept of nuclear fuel cycle
2.2 Problems of once-through fuel cycle
2.3 Characteristics of closed fuel cycle for thermal reactors
2.4 Advantages of closed fuel cycle for fast reactors
3 Present status and development trends of reprocessing/recycling technologies at home and abroad
3.1 World status and development trends of reprocessing/recycling technologies
3.2 China’s present status of reprocessing/recycling technologies and the gaps from the world advanced level
4 Preliminary considerations of China’s development strategy of reprocessing/recycling technologies
4.1 Recycle plutonium directly in fast reactors is adaptable in China
4.2 Follow the route of “breeder first, burner second” is adaptable in China
5 Key technologies to be developed for reprocessing/recycling in China
5.1 Reprocessing of spent fuel from thermal reactors
5.2 Reprocessing of spent fuel from fast reactors
6 Conclusions
Special issues
Progress and Discussion on Chemical Separation Technologies for Nuclear Fuel Reprocessing Abroad
Wei Yuezhou
2011, 23 (7): 1272-1288 |
Published: 24 July 2011
Abstract

Reprocessing technologies can be divided into wet process using aqueous solution and dry process. The wet process includes solvent extraction (liquid-liquid extraction), ion exchange, precipitation, etc. The PUREX process which uses TBP as extractant and can recover about 99.5% of the U and Pu from spent fuel is the only successfully commercialized reprocessing technology nowadays.However, the PUREX process still has some significant drawbacks such as complicated extraction procedures, generation of a great amount of waste and utilization of large scale equipment. In addition, it can not effectively recover the long-lived nuclides such as minor actinides (Np, Am, Cm) and Tc, which will result in a long term radiological effect on the environment. In recent years, many efforts have been devoted to the improvement of the PUREX process and the study of advanced wet reprocessing technologies. Dry process utilizing electro-refining in molten salt, reductive extraction in liquid metal or volatilization of fluorides is attracting wide attention, because it has the advantages of compact equipment, high radiation resistance and critical safety. But relatively low separation factor and corrosion of materials at high temperature are the main problems of the dry process. This article reviews the progress in the chemical separation technologies for nuclear fuel reprocessing abroad. Furthermore, some chemical problems in separation processes are analyzed and discussed.

Contents
1 Necessity for the development of advanced reprocessing technologies
2 Progress and discussion on advanced wet reprocessing technologies
2.1 Extraction processes based on the improvement of PUREX
2.2 Separation processes using novel extractants
2.3 Other wet separation processes
2.4 Separation processes for MA and FP
2.5 Summary of wet separation processes
3 Progress and discussion on dry reprocessing technologies
3.1 The principle and characteristics of dry separation processes
3.2 Molten salt electro-refining process for metalic nuclear fuel
3.3 Molten salt electro-reduction process for oxide nuclear fuel
3.4 Hybrid process of dry and wet separation technologies
3.5 Summary of dry separation processes
4 Concluding remarks

A Review on the Development of Spent Nuclear Fuel Reprocessing and Its Related Radiochemistry
Ye Guoan, Zhang Hu
2011, 23 (7): 1289-1294 |
Published: 24 July 2011
Abstract

The development and its corresponding technical features of spent nuclear fuel reprocessing were reviewed systematically according to the changes of its applications to different spent fuels and separation improvements. Aiming at the partition and transmutation (P&T) technologies in future advanced nuclear energy system, the improvements of the Purex process from Generation Ⅱ reprocessing to Generations Ⅲ and Ⅳ reprocessing were highlighted. The key radiochemical issues which should pay much attention in the Purex process and following partition processes as well as the dry reprocessing for spent nuclear fuel of fast reactors were summarized.

Contents
1 Introduction
2 Development of reprocessing technologies
3 Reprocessing for P&T
4 Radiochemical issues for further explorations

Abstract

Complexation of actinide elements with various ligands has become a subject of significant interest in recent years, due to the rapid development of nuclear energy and the demand for advanced actinide separation processes. Some ligands play very important roles in actinide separations, while other ligands determine the speciation of actinides and their transport in the environment. Therefore, fundamental understanding of actinide complexation is critical to the development of advanced fuel cycles, including the used fuel reprocessing and the safe management of nuclear wastes. A number of thermodynamic and spectroscopic techniques can be applied to the studies of actinide complexation in solution, providing fundamental information on the nature (e.g., ionic bonding vs covalency, outer sphere vs inner sphere), energetics (e.g., free energy, enthalpy, entropy and heat capacity) and structures of actinide complexes. This paper briefly reviews the application of selected thermodynamic and spectroscopic techniques that have been frequently used in recent years for studying actinide complexation, including microcalorimetry, optical absorption and fluorescence spectroscopy, and X-ray absorption spectroscopy. Emphasis is placed on demonstrating, with examples, the scientific information that can be extracted from the measurements with the techniques.

Application of Supercritical Fluid Extraction in Reprocessing of Spent Nuclear Fuel
Zhu Liyang, Wen Mingfen, Duan Wuhua, Xu Jingming, Zhu Yongjun
2011, 23 (7): 1308-1315 |
Published: 24 July 2011
Abstract

PUREX process is used in the reprocessing of spent nuclear fuel (SNF) for many years. But the operation of the process produces large volume of secondary waste and encounters difficulties in dealing with new type of spent nuclear fuel in the future, such as UO2 spent fuel with higher burn up and MOX (mixed oxide) spent fuel. Supercritical fluid extraction (SFE) as a novel non-aqueous technology has potential to use in nuclear industry. The current researches on application of SFE in nuclear industry include decontamination of solid radioactive waste, volume reduction of liquid radioactive waste and reprocessing of SNF. To use SFE in the reprocessing of SNF can simplify the process and reduce the secondary waste greatly. The reprocessing conceptual flow sheets based on supercritical fluid extraction are developed in Japan and Russia, which show promising prospect to be applied in the future. It is being investigated to use supercritical fluid extraction for the reprocessing of high temperature gas cooled reactor (HTGR) SNF in INET (Institute of Nuclear and New Energy Technology, Tsinghua University). The pebble fuel of HTGR is disintegrated by electrochemical intercalation method, and then the UO2 kernels are converted into nitrate by N2O4 and extracted by supercritical CO2 fluid containing TBP (tri-butyl phosphate). The recovery rate of uranium is 99.93%. The experimental results indicated the possibility of using electrochemical intercalation technology and SFE technology in reprocessing of HTGR spent nuclear fuel.

Contents
1 Introduction
2 Development trend of SNF reprocessing
2.1 Improvement of PUREX process
2.2 Development of pyrochemical process
3 Application of SFE in reprocessing
3.1 Principal of supercritical fluid extraction
3.2 Extraction of metal ions from solid matrix
3.3 Extraction of metal ions from aqueous solution
3.4 Direct extraction of actinide and lanthanide oxides
3.5 N2O4 nitration combined with SFE
3.6 Concept flow sheets of SNF reprocessing on SFE
4 R&D on reprocessing of HTGR SNF by SFE
4.1 Disintegration of pebble fuel of HTGR by electrochemical intercalation method
4.2 Supercritical fluid extraction of fuel kernel
5 Conclusion

Progress in Theoretical Research of Metallic Plutonium and its Compounds
Chen Piheng, Lai Xinchun, Wang Xiaolin
2011, 23 (7): 1316-1321 |
Published: 24 July 2011
Abstract

Plutonium is an element that its 5f electrons are in the transition border between delocalized and localized, and is therefore considered one of the most complex elements. It has six allotropes normally and a seventh under pressure, each of which have very similar energy levels but with significantly varying densities, making it very sensitive to changes in temperature or pressure, and allowing for dramatic volume changes following phase transitions. Moreover, plutonium and its compounds age with time because the plutonium undergoes alpha decay, which leads to self-irradiation inducing structural damage and chemical changes in the materials. The aging properties are driven by a combination of materials composition, processing history, and self-irradiation effects. Understanding these driving forces requires knowledge of both thermodynamic and kinetic properties of these materials. Advances in computer power and simulation techniques have allowed us to simulate the materials behavior on different scales. Recent progress in applications of density functional theory (DFT), molecular dynamics (MD) and kinetic Monte Carlo (KMC) to study of the properties of plutonium and its compounds in China has been reviewed.

Contents
1 Introduction
2 Electronic structure of plutonium and its compounds
2.1 Electronic structure of plutonium
2.2 Electronic structure of plutonium compounds
3 Adsorption of gases on surfaces of plutonium and its oxides
4 Self-radiation damage in plutonium
5 Conclusions and outlook

Progress on Uranium Surface Science
Luo Lizhu, Lai Xinchun, Wang Xiaolin
2011, 23 (7): 1322-1328 |
Published: 24 July 2011
Abstract

Uranium is very important in nuclear energy industry and national defense, while uranium and its alloys corroded seriously during storage because of its chemical activity. In order to find ways preventing further surface corrosion, studies are carried out on behavior of surface corrosion and surface modified technology, and provided technical supports for engineering application. Progress in last decade on uranium surface science has been reviewed, and some suggestions for further study are given.

Contents
1 Introduction
2 Progress on uranium surface science
2.1 Surface corrosion and reaction kinetics of uranium and its alloys in O2
2.2 Surface corrosion and reaction kinetics of uranium and its alloys in H2
2.3 Surface modification of uranium
2.4 Interactions of membrane and substrate
2.5 Preparation and characterization of U film
2.6 The first principle applied in physical and chemical properties of uranium surface
3 Summary and prospect

Theoretical Studies on Fluorescence Spectra of Actinide Complexes
Su Jing, Li Jun
2011, 23 (7): 1329-1337 |
Published: 24 July 2011
Abstract

In this mini-review, we have briefly summarized the experimental research on fluorescence spectra of actinide complexes, the electronic structures of actinyl complexes, and the basic principle for computational simulations of fluorescence spectra.Although numerous fluorescence spectroscopy data had been available experimentally, there were no theoretical investigations on vibrationally resolved fluorescence spectra of actinide complexes. Recently we have performed for the first time computational modeling of vibrationally resolved fluorescence spectra of uranyl complexes using Heller’s time-dependent theory for electronic spectroscopy. Herein reviewed are the theoretical results from computational chemistry modeling on the coordination structures, stabilization energies and fluorescence properties of uranyl-glycine-water complexes. Our research has shown that the vibrationally resolved electronic spectra and the unusually high intensity of the illustrious uranyl hot-band can be interpreted by combining state-of-the-art computational chemistry and contemporary experimental techniques. This integrated theory and experiment approach can lead to a detailed understanding of the geometries, energetics, and luminescence properties of actinide compounds, including those with bio-ligands.

Contents
1 Introduction
1.1 Actinide speciation
1.2 Fluorescence of actinide compounds
1.3 Theoretical studies of electronic spectra of actinides
2 Electronic structure of actinyl ions
3 Principles of fluorescence spectroscopy simulation
4 Computational study of uranyl-glycine-water complexes
4.1 Structure and stability
4.2 Thermodynamic properties
4.3 Fluorescence spectra simulation
5 Conclusions and outlook

Studies on Separating Trivalent Actinides from Lanthanides by Dialkyldithiophosphinic Acid Extraction
Chen Jing, Wang Fang, He Xihong, Pan Dengfang
2011, 23 (7): 1338-1344 |
Published: 24 July 2011
Abstract

The effective separation of trivalent actinides from lanthanides is one of key steps to realizing the advanced nuclear fuel cycle based on “partitioning-transmutation”. However, their effective separation is always one of difficulties in the separation field because of the very similar physical and chemical properties between trivalent actinides and lanthanides. In the separation by solvent extraction, ligands containing soft donor S, N show good performance to separate trivalent actinides from lanthanides. In 1995, Cyanex 301, a commercial reagent, was found to be able to separate trivalent actinides from macro amount of lanthanides, and then the purified product bis(2,4,4-trimethylpentyl)dithiophosphinic acid was proven to have remarkable ability to separate actinides from both micro and macro amount of lanthanides. The separation process was studied and demonstrated by hot test. The dominant complex in extraction is of cubic structure with a coordination number of 8. The phenyl, chlorophenyl-substituted compounds had no separation ability, but achieved a good separation performance with the synergistic extraction of neutral extractants such as trialkylphosphate. Recently, o-trifluoromethylphenyl- substituted extractant compound was proven to have an excellent separation performance. Although the improvement in stability is desired and the further investigation to the separation mechanism is needed, dialkyldithiophosphinic acids are promising reagents for trivalent actinides/lanthanides separation because of the outstanding separation performance.

Contents
1 Introduction
2 Separation of trivalent actinides from lanthanides
3 Separation of trivalent actinides from lanthanides by Cyanex 301 extraction
4 Separation of trivalent actinides from lanthanides by dialkyldithiophosphinic acids extraction
5 Future of dialkyldithiophosphinic acid-based separation technology

Calixarene Derivatives for An(Ⅲ)/Ln(Ⅲ) Separation in Nuclear Fuel Reprocessing
Yang Yanqiu, Luo Shunzhong, Yang Tongzai, Hao Fanhua
2011, 23 (7): 1345-1354 |
Published: 24 July 2011
Abstract

In the process of partitioning HLW, an urgent subject is focus on the development of extraction ligands for actinides (An(Ⅲ)) over lanthanides (Ln(Ⅲ)) with excellent selectivity. It is well known that the preorganization of ligands considerably improves their extraction capacity and selectivity to certain cations. Calixarenes offer ideal platforms to such preorganization.From the 1990s on, large amounts of calixarene derivatives bearing various complexation functionalites to An(Ⅲ) have been synthesized. Many of them showed improved extraction properties and higher extraction selectivity to An(Ⅲ). In this review, the An(Ⅲ)/Ln(Ⅲ) extraction properties of various calixarene derivatives bearing ligands, such as carbamoylmentylphosphine oxide, dialkylphosphine oxide, picolinamide, and other function moities, were summarized at large. Emphasis was placed on the relationship of the structures of the calixarene derivatives to the preorganization of ligands, the extraction properties and the separation factor of An(Ⅲ)/Ln(Ⅲ). The developing directions and the potential application of such derivatives for An(Ⅲ)/Ln(Ⅲ) separation were described.

Contents
1 Introduction
2 Effect of the Preorganization of Ligands on the Extraction Properties
3 The Extraction Properties of Calixarene Derivatives Bearing CMPO Moieties
3.1 Upper rim CMPO Calixrenes
3.2 Lower rim CMPO Calixrenes
3.3 CMPO Adamantyl Calixarenes
3.4 Other Calixarene-CMPO Derivatives
4 The Extraction Properties of Phosphine Oxide Derivatives of Calixarenes
5 The Extraction Properties of Picolinamide Derivatives of Calixarenes
6 Summary and outlook

Development of Silica-Based Supramolecular Recognition Materials in Reprocessing of Nuclear Spent Fuel
Zhang Anyun, Xiao Chengliang, Chai Zhifang
2011, 23 (7): 1355-1365 |
Published: 24 July 2011
Abstract

The new materials and new technologies are considered to play important roles in the advanced nuclear energy systems. Supramolecular recognition materials (SMRM) have received worldwide attention for several decades, and are becoming a hot research field in the spent nuclear fuel reprocessing. The research progress of the macroporous silica-based supramolecular recognition materials in spent fuel reprocessing are reviewed. The synthesis and characterization of silica-based supramolecular recognition materials and their respective adsorption properties for Cs(I)/Sr(Ⅱ) are summarized. The effects of various factors on the adsorption of the silica-based supramolecular recognition materials are evaluated. The SPEC process for strontium/cesium partitioning by extraction chromatography was discussed. It is found that the extraction chromatography processes based on the silica-based supramolecular recognition materials have following advantages: (1) high separation efficiency and excellent selectivity, (2) a minimal organic solvent utilization and less waste accumulation, (3) compacted equipment and simple operation, and (4) a real “salt-free” treatment, etc.

Contents
1 Introduction
2 Synthesis and characterization
2.1 Synthesis of silica-based SiO2-P support
2.2 Synthesis of silica-based supramolecular recognition materials
2.3 Characterization of silica-based supramolecular recognition materials
3 Development of silica-based materials in spent nuclear fuel reprocessing
3.1 Crown ether/SiO2-P
3.2 Calix[4]arene-crown-6/SiO2-P
3.3 Silica-basedsynergistic supramolecular recogni-tion materials
3.4 Other silica-based materials
4 Conclusions and outlooks

Overview of 30 Years Research on TRPO Process for Actinides Partitioning from High Level Liquid Waste
Chen Jing, Wang Jianchen
2011, 23 (7): 1366-1371 |
Published: 24 July 2011
Abstract

Safe treatment and disposal of radioactive waste, especially high level waste, are attracting much attention from governments of many countries and the public and becoming one of key factors affecting the sustainable development of nuclear energy. High level liquid waste (HLLW) is the raffinate from Purex process and contains more than 95% radioactivity of spent fuel. HLLW must be vitrified and disposed in the geological repository which should be isolated from biosphere for more than 100 000 years because of the α activity. “partitioning-transmutation” method for the treatment of HLLW can effectively reduce the isolation period of geological repository from biosphere. TRPO with good physico-chemical properties and irradiation stability has excellent extraction selectivity to tri-, tetra- and hexa-valent actinides. TRPO process for actinides removal from HLLW has been invented in China. Several times hot tests and the pilot test demonstrated that the HLLW could be conditioned into non-α waste after treatment by TRPO process. TRPO with self-owned intellectual property rights has a bright future in the treatment of defense HLLW and civil HLLW.

Contents
1 Significance of high level liquid waste partitioning
2 Composition of TRPO and its extraction properties
3 Principle TRPO process for actinides partitioning from high level liquid waste
4 Research and development of TRPO process
5 Future of TRPO process

Synthesis and Crystal Structure of Uranyl Complexes
Liu Chunli, Wang Luhua
2011, 23 (7): 1372-1378 |
Published: 24 July 2011
Abstract

Uranium is one of the most important nuclear materials. It is the core of the nuclear fuel cycle and the element to which much attention has been paid since it is inevitable that uranium is released in the process of uranium mining, enrichment, oxide fuel manufacturing and spent nuclear fuel reprocessing. Inorganic acid and carboxylic acid group of the humus can be coordinated to uranyl thus change its migration and sorption behavior in the environment. By analyzing the synthesis and crystal structure of uranyl complexes we can provide essential structure data for sorption modeling and sorption mechanism in the molecular level. The structural characters of uranyl primary building units and the complexes that may form with common inorganic and organic acids in the aquatic solutions have been reviewed. A proposal followed by the summary and analysis of the work carried out in the groups in the world of uranyl complexes based on environmentally concerned acids and some other oxo containing ligands is presented.

Tritium Chemistry and Techniques
Peng Shuming, Wang Heyi, Fu Yibei
2011, 23 (7): 1379-1385 |
Published: 24 July 2011
Abstract

As one of the most important resources, tritium is widely used in the scientific researches of national defense and national economy. To satisfy the development of national defense, China Academy of Engineering Physics (CAEP)has obtained great progress in the tritium chemistry and techniques, and the research fields are focused on the whole period of the tritium, including tritium production, isotopes separation, tritium storage, tritium application and tritium waste treatment, etc. Some of the recently progress in the fundamental research of CAEP are reviewed in this paper, which mainly introduces the physical and chemical property of metal tritide, tritium storage materials, hydrogen isotopes separation techniques, tritide heavy water treatment techniques and ITER related tritium techniques, and some directions for further researches have also been proposed.

Contents
1 Introduction
2 Metal tritide
2.1 Physical and chemical property of metal tritide
2.2 Helium behaviors in metal tritide
3 Tritium storage materials
3.1 La series metals
3.2 Zr series metals and alloys
3.3 Ti and Mg series alloys
4 Hydrogen isotopes separation techniques
4.1 Gas chromatograph(GC) technique
4.2 Cryogenic distil ion(CD) technique
5 Tritiated heavy water treatment techniques
5.1 Ensemble technique
5.2 Electrolyze technique
5.3 Catalysis exchange technique
5.4 Catalysis oxidation technique
5.5 Gas chromatograph(GC) technique
6 ITER related tritium techniques
6.1 Preparation and properties of tritium breeders
6.2 Techniques of tritium extraction in liquid LiPb cycle
6.3 Techniques of tritium safety
7 Summary

Applications of Typical Supramolecular Systems in the Field of Radiochemistry
Shen Xinghai, Zhang Jingjing, Gao Song, Fu Suzhen, Sun Taoxiang, Fu Jing, Zhang Hongjuan, Chen Qingde, Gao Hongcheng
2011, 23 (7): 1386-1399 |
Published: 24 July 2011
Abstract

Supramolecular chemistry is defined as “chemistry beyond the molecule”, bearing on the organized entities of higher complexity that result from the association of two or more chemical species held together by intermolecular forces. Now, the applications of supramolecular chemistry in the realm of radiochemistry have attracted much attention. In this article, the separation of important metal ions by two kinds of supramolecular systems and ionic imprinted polymers (IIP) is discussed, which demonstrates the significant roles of supramolecular systems in the field of radiochemistry. Meanwhile, the first type is supermolecules resulted from the intermolecular association of a host molecule and its substrates, where the host molecules are mainly macrocyclic compounds (such as crown ethers, calixarene, calix crown ethers and so on). The second type is supramolecular assemblies induced by the spontaneous association of a large undefined number of components into a specific phase, including reversed micelles, microemulsions and liquid membranes. IIPs can recognize and separate metal ions selectively, which realizes the recognition function of supramolecular chemistry. The transport function of supramolecular chemistry is also well interpreted in the separation of metal ions by liquid membrane. Besides, the perspectives of supramolecular chemistry in the field of radiochemistry are also presented.

Models Used in Deep Geological Deposit of High-Level Radioactive Waste
Wang Xiangyun, Chen Tao, Liu Chunli
2011, 23 (7): 1400-1410 |
Published: 24 July 2011
Abstract

China has decided to deposit high level radioactive waste (HLW) that will be produced by quickly developing nuclear power industry. In order to assess the repository safety and predict the migration behavior of radionuclides that could be released when HLW canisters would be damaged. In addition to experimental investigations modeling has also to be used for these purposes. In this paper models involved in deep geological deposit of HLW, relevant software, and necessitated databases are reviewed with emphasis on geochemical models for chemical speciation. Multi-field coupling models are also described briefly. Finally, methods and programs for treatment of migration experimental data used in our laboratory are schematically reported.

A Review of Beneficial Effects of Ruducing Environment at the Near-field of KBS-3 Repository
Daqing Cui
2011, 23 (7): 1411-1428 |
Published: 24 July 2011
Abstract

The recent research activities, i.e. relevant publications and the authors experiments on chemical behaviors of spent nuclear fuel (SNF) and canister materials at near-field of KBS-3 deep geological repository were reviewed. The advantages of reductive substances at KBS-3 repository to the spent fuel disposal safety were discussed. Using data from literatures and experiments, the author demonstrated the blocking effect of hydrogen generated for iron canister corrosion on SNF dissolution, and discussed the reaction mechanism. It is also proved that the γ radiation expected at the early stage of disposal and micro mole level oxidative species in water solution can only slightly enhance the corrosion rate of copper canister to μm/y level, still 103 times slower than that at air saturated conditions. During a long period of time after copper canister leaks, under combined effects of iron canister material, hydrogen and fission product alloy particle catalysts, SNF dissolution can be depressed or blocked, and most radiotoxic multivalent radionuclides U, Np, Tc and Se released from SNF can be reduced and precipitated. This paper supplies scientific bases for the sitting of a SNF repository at a stable reducing area, and designing of canisters with massive iron material.

Radionuclide Sorption on Solid-liquid Surfaces: Models and Applications
Fan Qiaohui, Guo Zhijun, Wu Wangsuo
2011, 23 (7): 1429-1445 |
Published: 24 July 2011
Abstract

Sorption of a radionuclide on the solid-liquid interface is one of its most important physicochemical behaviors in environmental medium. Sorption dynamics and thermodynamics research proceedings are introduced in this work. Surface complexation model (SCM) and metastable equilibrium adsorption (MEA) theory are mainly discussed here. In addition, some advanced spectroscopy technologies and modeling methods for surface characterization, theoretical calculations are also introduced detailedly in this paper.

Adsorption of Uranium by Carbon Materials from Aqueous Solutions
Li Xingliang, Song Qiang, Liu Bijun, Liu Chunxia, Wang Hang, Geng Junxia, Chen Zhen, Liu Ning, Li Shoujian
2011, 23 (7): 1446-1453 |
Published: 24 July 2011
Abstract

Uranium is both the major constituent of nuclear fuel and one of the key nuclides in spent fuel reprocessing. Separation of uranium in various aqueous effluent streams via adsorption or solid-phase extraction can not only recycle this precious resource, but also reduce the cost for the final disposal of radioactive wastes. Carbon based sorbents, at least potentially, should play a correspondingly important role for this purpose. Carbon materials were chosen as the adsorbing material because of their large specific surface area, better acid and alkaline stability and higher radiation and thermal resistance. The adsorption capacity of carbon materials can be improved by surface oxidization and other chemical or physical modifications, such as impregnating, coating, or grafting functional molecules or groups that can extract uranium selectively from liquid solution. Comparing with other modification methods, grafting technology is a promising method because of its excellent affinity and high selectivity. Uranium in aqueous wastes can be effectively removed by electrosorption onto electrode made of carbon fibers. It seems that electrosorption process for the removal of uranium has a prospect of industrialization because of the high electrosorption efficiency and the low-cost regeneration of carbon fiber electrode.

Contents
1 Introduction
2 Adsorption of uranium on activated carbon
2.1 Adsorption of uranium on raw carbon
2.2 Adsorption of uranium on modified carbon
3 Adsorption of uranium on mesoporous carbon
4 Adsorption of uranium on carbon nanotubes
5 Electrosorption of uranium on carbon fiber electrode
6 Conclusion and prospects

Radiation Effects on Imidazolium Ionic Liquids and Their Extraction Systems
Yuan Liyong, Peng Jing, Zhai Maolin
2011, 23 (7): 1469-1477 |
Published: 24 July 2011
Abstract

Room-temperature ionic liquids (RTILs), especially those containing imidazolium cations, for instance 1,3-dialkylimidazolium, associated with various inorganic anions are receiving an ever-increasing amount of interest as environmentally benign alternatives to volatile organic solvents for traditional liquid-liquid extraction of high level radioactive nuclides in nuclear fuel reprocessing, because of their low volatility, good thermal and chemical stability, as well as excellent extraction capacity. The application of RTILs in nuclear fuel reprocessing, however, requires a comprehensive knowledge of radiation effects on RTILs and their extraction systems. Herein, we reviewed our recent investigations of γ-radiation effects on two widely used hydrophobic RTILs X and X-based extraction systems, where + is 1-butyl-3-methylimidazolium and X is hexafluorophosphate (PF-6) and bis(trifluoromethylsulfonyl)imide ( -), respectively. The investigations involved radiation effects on chemical structure and some properties, especially phase behavior and fluorescence properties of neat RTILs under nitrogen atmosphere and of RTILs in the presence of nitric acid, separation and analysis of radiolytic products of RTILs, and influence of γ-irradiation on RTILs-based extraction systems during extraction of metal ions. Based on the results, the feasibility of RTILs as alternative media for the separations of high level radioactive nuclides from spent nuclear fuel was evaluated, and further studies on the radiation effects on RTILs and RTILs-based extraction system are prospected.

A Preview of Nano-Materials and Nano-Technologies Applied in Advanced Nuclear Energy System
Shi Weiqun, Zhao Yuliang, Chai Zhifang
2011, 23 (7): 1478-1484 |
Published: 24 July 2011
Abstract

With the rapid growth of human demands for nuclear energy, in response to the challenges of nuclear energy development, the world's major nuclear countries have started the R&D of advanced nuclear energy systems, in which new materials and new technologies are considered to play important roles. Nano-materials and nano-technologies, which have gain extensive attention in recent years, have shown a wide range of potential applications in future nuclear energy system. In this paper, the basic research progress of nano-materials and nano-technologies in advanced nuclear fuel fabrication, spent nuclear fuel reprocessing, nuclear waste disposal and nuclear environmental restoration was reviewed. Furthermore, the R&D trends of nano-materials and nano-technologies in future advanced nuclear energy system are discussed.

Contents
1 Introduction
2 The applications of nano-materials and nano-technologies in advanced nuclear fuel fabrication
3 The applications of nano-materials and nano-technologies in advanced nuclear fuel reprocessing
4 The applications of nano-materials and nano-technologies in nuclear waste disposal and management
5 The applications of nano-materials and nano-technologies in recognition and detection of radionuclides
6 Conclusions and outlook

Advances in Domestic Brain, Heart, Tumor Radioactive Diagnosis Drugs
Zeng Huahui, Zhang Huabei
2011, 23 (7): 1485-1492 |
Published: 24 July 2011
Abstract

In recent years, radiopharmaceutical has played an increasingly important role in the medical diagnosis and treatment of diseases and the fundamental research of medicine, with the rapid development of the radiopharmaceutical. A diagnosis radiopharmaceutical is a biological agent or small molecule labeled with radioactive nuclide, which is applied in medical diagnosis of diseases in vivo. In this paper, a brief introduction to domestic recent development and applications of diagnosis radiopharmaceutical in the nervous system, cardiovascular and tumor imaging is given. Some main existing problems in the research of radiopharmaceuticals are advanced and the new research aspects may be provided in the coming years. We should devote major efforts to developing the PET tracer in our country, and the key aspect is to design and develop all kinds of the brain receptors imaging agents, receptor binding tumor imaging agents, the myocardium metabolism imaging agents and so on. These developments and achievements of radiopharmaceuticals to improve the peoples health are highly significant in our country.

Contents
1 Introduction
2 Development of nervous system imaging agent
3 Development of cardiovascular imaging agent
4 Development of tumor imaging agent
5 Outlook

Technetium-99m Radiopharmaceutical Chemistry
Mei Lei, Chu Taiwei
2011, 23 (7): 1493-1500 |
Published: 24 July 2011
Abstract

Technetium based radiopharmaceuticals have been widely used in scientific research and clinic. A large amount of new radiopharmaceuticals have been exploited and used. However, how to develop pharmaceuticals with better treatments and wider applicability to meet the need of clinic is still an urgent problem. The introduction of new ligands and cores and development of new strategies of labeling have become a hot subject in the technetium based radiopharmaceutical field. In order to provide some references to the researchers,introduction of some new labeling methods used for technetium-99m-labeled radiopharmaceuticals, including new ligands and methods for 99mTc-tricarbonyl technetium labeling, preparation and application of the high-valent technetium, are carried out in this paper.

Contents
1 Introduction
2 Recent progress of labeling with tricarbonyl technetium
2.1 New ligands for labeling of tricarbonyl technetium
2.2 New strategy for labeling of tricarbonyl technetium
3 Complex of high-valent technetium
4 Conclusion and outlook

New Methods and Techniques for F-18-labeled Radiopharmaceuticals
Huang Huafan, Liang Kun, Liu Yupeng, Huang Shitang, Chu Taiwei
2011, 23 (7): 1501-1506 |
Published: 24 July 2011
Abstract

The availability of radiopharmaceuticals is one prerequisite for positron emission tomography (PET) investigation. 18F appears to be the best candidates among a number of positron emission nuclides. Nevertheless, the chemistry of fluorine limits 18F labeling strategies, the preparation of many 18F-labeling radiopharmaceuticals is still laborious and time-consuming. In this review, new 18F-labeling methods and techniques are described in radiopharmaceutical chemistry, including detagging 18F-labeled methodology, direct radiolabeling of peptides with FDG, Al18F-chelated labeling, aqueous 18F-labeling of boronic esters, microfluidics-based radiochemical synthesis technologies for PET probes and so on. This review will provide an overview in new 18F-labeling methods and techniques for researchers.

Contents
1 Introduction
2 Detagging 18F-labeling methodology
3 18F-labeling of peptides
3.1 Direct radiolabeling of peptides with [18F]FDG
3.2 Al 18F-labeling of NOTA conjugated peptides
4 Aqueous 18F-labeling of boronic esters
5 Microfluidics-based radiochemical synthesis technologies for PET probes
5.1 FDG synthesis using microfluidic devices
5.2 Other 18F-labeled PET probes prepared by microfluidics
6 Conclusion and outlook

Synthesis and Chemical Properties of Superheavy Elements
Qin Zhi, Fan Fangli, Wu Xiaolei, Bai Jing, Ding Huajie, Lei Fuan, Tian Wei, Guo
2011, 23 (7): 1507-1519 |
Published: 24 July 2011
Abstract

Superheavy elements are those with high atomic number, beginning with element 104 (Rf). The research of superheavy elements is frontier topics in nuclear physics and nuclear chemistry. The present status of synthesis of superheavy elements is introduced, including the three synthesis methods——“hot fusion”, “cold-fusion” and “warm fusion” and the discovery of a new chemical element with atomic number Z=117. The current gas chemistry experimental studies of element 108 and element 112 are discussed in detail. And the prospects of the development of superheavy elements are also reviewed.

Contents
1 Introduction
2 Status of synthesis of superheavy elements
3 The influence of relativistic effects on superheavy elements
4 Chemical properties of superheavy elements
4.1 Element 108
4.2 Element 112
5 Status of the heavy elements in China
6 Conclusions and prospects

Current Status and Prospect of Radioanalytical Chemistry in the National Defense
Yang Tongzai, Wang Xiaolin
2011, 23 (7): 1520-1526 |
Published: 24 July 2011
Abstract

Radioanalytical chemistry is very important in the national defense. In this article, recent progress of radioanalytical chemistry in the national defense are reviewed from the following aspects: radiochemical separation of gas and solid sample, radiation detection for α、β、γ spectrometer, analysis of mass spectrometry for isotope, preparation and performance of lithium ceramic breeder materials, hydrogen isotope chemistry, fusion fuel cycle. Finally, some challenges and prospects in this field are suggested.

Contents
1 Introduction
2 Radioanalytical chemistry
2.1 Analysis of radionuclide for gas sample
2.2 Analysis of radionuclide for solid sample
2.3 Detection of radionuclide
3 Tritium chemistry
3.1 Preparation and performance of lithium ceramic breeder materials
3.2 Hydrogen isotope chemistry
3.3 Fusion fuel cycle
4 Outlook

Radioanalytical Methods in Nanotoxicology Studies
Zhang Zhiyong, Zhao Yuliang, Chai Zhifang
2011, 23 (7): 1527-1533 |
Published: 24 July 2011
Abstract

With the rapid development of nanotechnology and its applications, the potential interactions of nanomaterials with living systems and the environment have attracted increasing attention from the public, as well as from manufacturers of nanomaterial-based products, academic researchers and policymakers. Nanotoxicology is emerging as an important subdiscipline of nanotechnology as well as toxicology. Nanotoxicology studies rely on many analytical methods for the characterization of nanomaterials and detection of nanomaterials in living systems. In this case, radioanalytical methods can play an important role due to their intrinsic merits such as high sensitivity, good accuracy, ability to distinguish the endogenous or exogenous sources of materials, and ability of in situ and in vivo analysis. This article reviews recent progress of applications of radioanalytical methods in nanotoxicology studies, and the emphasis is radiolabeling methods of nanomaterials.

Contents
1 Introduction
2 Chemical impurity analysis of carbon nanotubes using neutron activation analysis
3 Radiolabelling of nanomaterials for in vivo radiotracer studies
3.1 Radiolabeling of carbon nanomaterials
3.2 Radiolabeling of metallic and metal oxide nanomaterials
3.3 Radiolabeling of nanomedicines and other nanoparticles
4 Conclusions and outlook

Synchrotron Radiation and Related Nuclear Analytical Techniques for the Study on Biological Effects of Nanomaterials
Qu Ying, Li Yufeng, Chen Chunying
2011, 23 (7): 1534-1546 |
Published: 24 July 2011
Abstract

With the rapid development of nanotechnology, studies on biological effects of nanomaterials have becoming hotspots. However, the fully understanding of fate and toxicological behavior of nanomaterials as a result of interactions with complex biosystem are highly dependent on the reliable analytical techniques. Synchrotron radiation is an advanced light source with notable quality such as high brightness, high level of polarization, high collimation, high brilliance, high intensity and tide tunability in energy/wavelength. It provides particular advantages in elemental mapping and structure characterization of nanomaterials. In this paper, the applications of synchrotron radiation and related nuclear analytical techniques in the studies on the toxicological or biological behaviors of nanomaterials in biological systems are critically reviewed, along with their advantages and limitations. Mentioned techniques include synchrotron radiation X ray fluorescence (SRXRF), X-ray absorption fine structure (XAFS, XANES and EXAFS), synchrotron radiation circular dichroism spectroscopy (SRCD), inductively coupled plasma mass spectrometry (ICP-MS), neutron activation analysis (NAA), and isotopic tracing. High throughput quantification of nanomaterials can be achieved by ICP-MS and NAA. The distribution mappings of nanomaterials can be performed by SRXRF and isotopic tracing. Structural characterization can be acquired by XAFS and SRCD. All together, these novel techniques will help to lead a better understanding of the biological effects of nanomaterials.

Contents
1 Introduction
2 Synchrotron radiation and related nuclear analytical techniques for the study on biological effects of nanomaterials
2.1 Size characterization of nanomaterials
2.2 Oxidation state and structural analysis of nanomaterials
2.3 In vivo quantification of nanomaterials
2.4 Biodistribution of nanomaterials
2.5 Oxidation state and structural analysis of nanomaterials in the body
3 Conclusions and Outlook

Article
Application of Radiation Technology in Environmental Protection
Wu Minghong, Liu Ning, Xu Gang, Bu Tingting, He Yaqin, Wang Liang
2011, 23 (7): 1547-1557 |
Published: 24 July 2011
Abstract

The progress in the investigation of radiation technology applied in the environmental protection is reviewed. Radiation technology including electron beam and γ-ray irradiation has great potential in the field of environmental protection due to its special characteristics. The investigations and applications of radiation technology in the treatment of wastewater, waste gas and solid waste are introduced in this paper, including the treatment of printing and dyeing wastewater, papermaking wastewater, nitroanilines, halogenated flame retardants, endocrine disrupting chemicals, algal toxin, volatile organic contaminants and sludge etc and the removing of SOx and NOx in coal-fired and automobile exhaust. The degradation efficiency of these organic pollutants by electron beam or γ-ray radiolytic degradation is discussed in various conditions, such as different initial concentrations, irradiation doses, pH values, solvents, radiolysis systems and the addition of H2O2 etc. Besides, the radiolysis products of certain pollutants are listed and radiolytic degradation mechanisms of these organic pollutants are illustrated. These results demonstrated that radiation technology is an effective method to degrade the organic contaminants, especially the persistentorganic pollutants, OH and e-aq played significant roles in the radiolysis of organic pollutants. In addition, the limitations and the future tends of radiation technology applied in the environmental protection are also discussed.

Contents
1 Introduction
2 Applications of radiation technology in wastewater treatment
2.1 Printing and dyeing wastewater
2.2 Wastewater from papermill
2.3 Nitroanilines
2.4 Halogenated flame retardants
2.5 Endocrine disrupting chemicals
2.6 Algal toxin
3 Applications of radiation technology in waste gas treatment
3.1 Removal of sulfur dioxide and nitrogen oxides
3.2 Volatile organic contaminants
4 Applications of radiation technology in solid waste treatment
4.1 Sludge
4.2 Polymer solid waste
5 Conclusions and outlook

Marine Radiochemistry
Liu Guangshan
2011, 23 (7): 1558-1565 |
Published: 24 July 2011
Abstract

Marine radiochemistry deals with the content and speciation of radionuclides in the oceans. Using their distributions in the oceans, the source and sink, migration and transport processes of the radionuclides were studied, and their inventories in some compartments are often evaluated. In this paper, the development history for marine radiochemistry in the world and China was briefly introduced. The main fields of oceanography applying radiochemistry are general circulation, seawater mixing, particle dynamics, and marine radiochronology. The future major subjects of marine radiochemistry are the fluxes and time scales of biogeochemical cycles, post marine environment change and accumulation and ecological effect of radionuclide in the sea area adjacent nuclear power plants. The main issues of marine radiochemistry are addressed in this paper as well.

Contents
1 Introduction
2 Historical marine radiochemistry
2.1 International study for marine radiochemistry
2.2 Marine radiochemistry in China
3 The circulation and mixing of ocean traced by radionuclide
3.1 General circulation
3.2 Sea water mixing and matter transport
4 Marine particle dynamics
4.1 Modeling
4.2 Export production and new production
5 Marine radiochronology
6 Perspectives of expecting major oceanographical fields applying radiochemistry
6.1 Flux and time scale of marine biogeochemical cycle
6.2 Past marine environment change
6.3 Accumulation and ecological effect of radionuclides discharged by nuclear power plant in adjacent sea area
7 Existing problems

Recent Advances in Computational Actinide Chemistry
Dongqi Wang, Wilfred F. van Gunsteren
2011, 23 (7): 1566-1581 |
Published: 24 July 2011
Abstract

We briefly reviewed the recent advances in computational actinide chemistry during the past ten years. They cover two issues: the geometrical and electronic structures, and reactions. The former addresses the An—O and M—An (M is another metal atom including An) bonds in the actinide molecular systems, and the latter the hydration and ligand exchange, the disproportionation, the oxidation, the reduction of uranyl, hydroamination, and the photolysis of uranium azide.

Contents
1 Introduction
2 Treatment of relativistic effects
3 Computational Models
3.1 Density functional theory
3.2 Wavefunction based ab initio methods
4 Applications in actinide chemistry
4.1 The role of 5f orbitals
4.2 Geometry and electronic structure
4.3 Reactions
5 Conclusion and outlook
6 Acknowledgement