Actinide elements and their chemistry have a significant number of applications. Bringing together contributions from the leading experts in the field, Recent Advances in Actinide Science covers six main topics: * Analysis, the environment and biotransformations * Coordination and organometallic chemistry * Heavy elements * Nuclear fuels, materials and waste forms * Separations and solution chemistry * Spectroscopy, magnetism and superconductivity Covering a wide range of research from pure academic studies to applied industrial science and technology, this book distils the knowledge and achievements gained in actinide science over the last four years. This high level book is aimed at researchers, both industrial and academic, and provides a comprehensive overview of the current status of actinide science.
Innehållsförteckning
Chapter One: Analysis, the Environment and Biotransformations; Biotransformation of Actinides; Microbial Transformations of Actinides in Transuranic- and Mixed-Wastes: Implications for Radioactive-Waste Disposal; A Brief Review of the Enzymatic Reduction of Tc, U, Np, and Pu by Bacteria; Actinides – A Challenge for Nuclear Forensics; Non-Exchangeable Binding of Radionuclides by Humic Substances: A Natural Chemical Analogue; On the Multi-Spectroscopic Approach for Radionuclide/Mineral Interaction Modelling in Aqueous Solutions; Compact Accelerator Mass Spectrometry: A Powerful Tool to Measure Actinides in the Environment; Interaction Mechanisms of Uranium with Bacterial Strains Isolated from Extreme Habitats; High Sensitivity Plutonium Isotopic Analysis in Environmental and Monitoring Samples; Speciation of the Oxidation States of Np and Pu in Aqueous Solutions by CE-ICP-MS and CE-RIMS; Soft X-Ray Spectromicroscopy of Actinide Particulates; Uranium Colloid Analysis by Single Particle Inductively Coupled Plasma – Mass Spectrometry; Status of The European Network for Actinide Sciences, ACTINET; Using Surface Imaging and Analytical Techniques to Study the Calcite Surface in Contact with Aqueous UO22+ Ions; Production of High-Purity 236Pu From 237Np by a Photonuclear Reaction; Decontamination of Soils in Liquid ?O2; A Novel Hydrogen Uranyl Phosphate-Based Bio-Inorganic Ion Exchanger for the Removal of 60Co, 85Sr And 137Cs from Aqueous Solutions; Effect of Closo-Dodecacarborane Ion Exchangers on the Potentiometric Response of Ionophore-Based Ion-Selective Electrodes; Geochemical and Microbial Controls on Decomposition and Dispersion of Depleted Uranium (DU) in the Environment: An Overview of Current Research and the Development of Methods for Handling DU Microparticulates; Fibrous ’Filled’ Sorbents for the Preconcentration of Actinides and Technetium; Np(V) Sorption to Goethite in the Presence of Natural and Hydroquinone-Enriched Humic Acids; Sorption of Np(IV) and Np(V) by Depleted Uranium Dioxide; The Recommended Values of 239Pu and 240Pu Concentrations in IAEA Standard Reference Material Estimated by Three Measuring Methods: Isotope Dilution-Thermal Ionizaton Mass Spectrometry, Inductively Coupled Plasma Mass Spectrometry and Alpha Spectrometry; A Sequential Separation Procedure for Pu, Am, U and Np Isotopes in Soils and Liquid Samples; Combination of Alpha Track Analysis, Fission Track Analysis with SEM-EDX and SIMS to Study Spatial Distribution of Actinides; Aspects of UO3 Dissolution Kinetics; Determining the Radiation Damage Effect on Glovebox Glove Materials; Plutonium-Humate Complexation in Natural Groundwater by XPS; Uranium Sorption and Solubility Under Conditions Relevant for the Radioactive Waste Repository in Morsleben / Germany; The Application of Colloidal Photocatalysis in Actinide Photoredox Chemistry; Study of the Chemical Scheme of ?-TUPD Solid Solution Alteration; Solubility Studies of Uranium(IV) by Laser-Induced Breakdown Detection (LIBD); Resonance Ionisation Mass Spectrometry for Element- and Isotope-Selective Trace Analysis of Actinides in Environmental Micro-Particles; The Romanian Uranium Industry- Its Past and Future in the Context of The Strengthening and Integration of the European Research Area; Uranium and Neptunium Sorption onto Magnetite Under Suboxic Conditions; The Application of Avalanche Photodiodes for the Measurement of Actinides by Alpha Liquid Scintillation Counting; The Effect of Uranium on the Corrosion of Stainless Steel in High Temperature Molten Salts in the Presence of Moisture; Reactions of the Feldspar Surface: Surface Composition and Microtopography After Contact with Radionuclides and Heavy Metals; The Influence of Oxalate on the Partitioning of Trivalent f-Elements to Hematite; Mechanisms for the Reduction of Actinide Ions by Geobacter Sulfurreducens; Oxidation and Surface Complexation of Actinyl Species by Oxides; Chapter Two: Coordination and Organometallic Chemistry; Structure-Property Relationships in Novel Actinide Compounds with Heavy Oxoanions; On the Role of f-Obitals in the Bonding in f-Element Complexes: the ’Feudal’ Model as Applied to Organoactinide and Actinide Aquo Complexes; New Catalytic Reactions Promoted by Organoactinides; Octacoordinate Soft Donor Complexes of Trivalent and Tetravalent Lanthanide and Actinide Cations; Structure and Stability of Peroxo Complexes of Uranium and Plutonium in Carbonate Solution; Sequestered Plutonium: Structural Characterisation and Complex Formation of Pu(IV) Complexes with Siderophore-Like Ligands; Extraction of Actinides by Functionalised Calixarenes; 5f Element Complexes with ’Soft’ Donor Atom Ligands: Eight Coordinate Pu(III) Pyrazinyl and Thioether Complexes; Plutonium(V) Chemistry in Neutral Aqueous Complexing Media: New Crystal Compounds Synthesis and Study of their Structure and Properties; Management of Transuranic Actinide Containing Materials in Nuclear Clean up in the UK; Extending the Chemistry of the Uranyl Ion: {UO2}2+ Acting as a Lewis Acid and a Lewis Base; Covalency in Uranium Complexes and New f-Element Chemistry that Exploits Soft Organometallic Carbene Ligands; Variability in the Crystal Structures of Uranium(VI), Neptunium(VI) and Plutonium(VI) Phthalates; Novel Neptunyl(V) and Plutonyl(V) Bi-Oxalate Compounds: Synthesis, Properties and Structure; Synthesis and Crystal Structure of a New Np(V) Oxalate, Na4(Np O2)2(C2O4)3.6H2O; Plutonyl(V) Malonate Compounds: Synthesis and Properties; Crystal Compounds of Plutonyl(V) Monooxalate Complex; Solid Compounds of Np(V) with 2, 4, 6-Tri-(2-Pyridyl)-1, 3, 5-Triazine: Crystal Structure, Spectral and Thermal Properties; Complex Formation of Np(V) with Picolinic, Nicotinic and Isonicotinic Acids; The Stability of a Uranyl(V) Benzoyl Acetonate Complex in Dimethyl Sulfoxide; Preparation of Uranium(III) Perchlorate in N, N-Dimethylformamide and Other Aprotic Media; Bent Metal Carbenes – Electrostatic Bonds vs Covalency in Organometallic Actinide Chemistry; Uranyl Complexation by a Hinged Polypyrrolic Macrocycle; Hydrogen Bonding with the Uranyl Oxo Atom and Enforced ??Stacking in the Equatorial Plane; Structure of Trivalent Americium and Lanthanide Complexes with Phosphoryl Acetic Acid Amides; Surprising Activity of Organoactinide Complexes in the Polymerization of Cyclic Mono- and Diesters; The Affinity of N Donor Ligands in An O22+ Complexes and Synthetic Routes to New Neptunyl Chemistry; Synthesis and Crystal Structure Determination of Some Mixed Oxalates of Actinide(s) and/or Lanthanide and Monovalent Cations (NH4+ or N2H5+); Complexation of a B-Type Unsaturated Polyoxoanion, [Bi W9O33]9-, to Actinyl, {UO2}2+, {Np O2}+ and {Pu O2}2+, Cations; Uranium Coordination to Environmentally Relevant Polyhydroxycarboxylate Ligands; Co-Crystallisation Processes in a Study of Physiochemical Properties of Actinides and Lanthanides in Lower Oxidation States; Monocarboxylate Complexes of Uranyl: a Relativistic Density Functional Study; Coordination Chemistry of Americium: Synthesis, Structure of Am(III) Iodates; The Performance of Time-Dependent Density Functional Theory in the Simulation of the Electronic Spectra of Molecular Uranium Complexes; The Effect of Solvent on the Modelling of the Geometry and Vibrations of UO2(H2O)52+; Chapter Three: Heavy Elements; Chemistry of Transactinides; Unusual Volatility of Oxides Formed by Some Actinides; SISAK Liquid-Liquid Extraction Studies of Rutherfordium and Future Plans to Study Heavier Transactinides; Development of a System for Chemical Studies of Rutherfordium by Liquid-Liquid Extraction From Sulphuric Acid Solutions with SISAK; Influence of KCl on the Extraction of Rutherfordium Homologues Hafnium and Zirconium from Sulphuric Acid with Tri-Octylamine in Toluene; Thermochromatographic Adsorption Studies of Curium and Berkelium; Self-Diffusion Coefficients and Structure of the Trivalent f-Element Ions, Eu3+, Am3+ and Bk3+ in Aqueous Solution; Ceramic Plutonium Target Development for the MASHA Separator for the Synthesis of Element 114; Chapter Four: Nuclear Fuels, Materials and Waste Forms; Understanding and Predicting Self-Irradiation Effects in Plutonium Alloys: A Coupled Experimental and Theoretical Approach; Identifying and Quantifying Actinide Radiation Damage in Zr Si O4 Minerals and ceramics with Nuclear Magnetic Resonance; Lessons Drawn From Studies of the Transmutation of Fuels Carried Out in the Framework of the French Law of December 1991 on the Management of Long Lived Waste; Properties of Minor Actinide Compounds Relevant to Nuclear Fuel Technology; Transformation Characteristics of Isothermal Martensite in Pu-Ga Alloys; Reactivity of Mixed Uranium and Plutonium Nitride with Silicon Carbide as Materials for Gas Cooled Fast Reactors; Confinement of Plutonium and Thorium in Monazite/Brabantite, in View of Actinide Conditioning; Physical and Electronic Properties Changed by Aging Plutonium; Corrosion Resistance of Uranium Metal Surface with CO and SCCO2 Treatment; Pyrochemical Processing of Plutonium at AWE; Uranium Ion Valences in Perovskite, Zirconolite and Pyrochlore from Near Infrared Diffuse Reflectance Spectroscopy; Thermal and Mechanical Properties of Simulated High Burnup Uranium Oxide Fuels; Thermodynamic Modelling and Analyses of Molten Salt Reactor Fuel; Structure of the Americium Pyrochlore Am2Zr2O7 and its Evolution Under Alpha Self-Irradiation; Local Structure of Th1-XMXO2 Solid Solutions with M = U, Pu; First-Principles Phase Diagram of the Ce-Th System; Crystal Stability and Equation of State for Am: Theory; XPS Study of High Temperature Oxidation of a Plutonium Alloy Under Vacuum; Phase Relation of Mixed Oxide Fuel Containing Np and Am; Study on Corrosion Resistance Improvement of U and U-Nb Alloys by Ion Implantation with Niobium; Simulation by External Irradiation of Self-Irradiation Effects on Thorium Phosphate Diphosphate (?-TPD) – Consequences for Its Dissolution; From Thorium Phosphate-Hydrogenphosphate Hydrate to Thorium Phosphate-Diphosphate : A New Way of Preparation of ? TPD and Associated Solid Solutions with Actinides; Invariant Equilibria in Binary Plutonium Phase Diagrams, Relationships; Photoemission and Secondary Ion Mass Spectrometry Study of Uranium Passivation by C+ Implantation; Optical Metallography of Plutonium; New Family of Intermetallic Hydrides: U2T2In Hx and U2T2Sn Hx; Self-Propagating High-Temperature Synthesis of Actinide-Containing Pyrochlore-Type Matrices; Relation Between Solubility and Local Environment of Actinides and Surrogates in Borosilicate Glasses; Electrochemical Studies of Uranium Metal Corrosion Mechanism and Kinetics in Water; The Effect of Oxygen Potential on the Sintering Behaviour of MOX Fuel Containing Americium; Variation of Lattice Parameter and Thermal Expansion Coefficient of (U, Er)O2 as a Function of Er O1.5 Content; An Experimental Investigation of Effects of Americium Addition to (U, Pu)O2-X on Phase Relation; Molecular Dynamics Studies of Uranium-Plutonium Mixed Oxide Fuels; Thermodynamic Modelling of the Uranium-Zirconium-Iron-Oxygen System; Nanoindentation Studies of Uranium Intermetallic Compounds; Self-Irradiation of Ceramics and Single Crystals Doped with Plutonium-238; Actinoid Phosphates of Kosnarite Structure; Monazite and Kosnarite-Based Ceramics Containing Uranium and Plutonium; Application of ?eramicrete Matrices for Low-Temperature Solidification of Liquid Actinides-Containing Wastes; Ab Initio Study of Uranium and Plutonium Carbides and Nitride; Effect of High Static Pressure on Crystaline and Electronic Structures of Transition, Lanthanide and Actinide Metals; Positron Annihilation Spectroscopy: A Powerful Tool to Investigate the Early Stages of Self-Irradiation Effects in ?-Pu Alloys; High Pressure X-Ray Diffraction Study of a Pu0.92Am0.08 Binary Alloy; Calculation of the Critical Concentration of Helium Release From Uranium Tritide; Recycle of Calcium in Incineration Process of Low Level Radioactive Wastes; Vaporization Behaviour of Pu-Cd Intermetallic Compounds; Development of the Scientific Concept of the Phosphate Methods for Actinide-Containing Waste Handling (Pyrochemical Fuel Reprocessing); Synthesis and Investigations of the Phosphates of Th, U, Np, Pu, Am and Lanthanides with Monazite, Zircon, Kosnarite and Langbenite Mineral-Like Structures; Basic Concept of Hydro-Pyro Hybrid Type Sulfide Process for Spent Fuel; Low Temperature Selective Reduction of U3O8 in the Presence of Sulfurizing Agents; Chapter Five: Separation and Solution Chemistry; Actinide Solution Chemistry And Chemical Separations: Structure-Function Relationships In The Grand Scheme Of Actinide Separations Science; X-Ray Absorption Spectroscopy of Actinides Involved in Toxicological Processes; Solubility and Redox Reactions of Plutonium(IV) Hydrous Oxide in the Presence of Oxygen; Uranium Speciation in Molten Salts from X-Ray Absorption and Electronic Absorption Spectroscopy Measurements; The Separation of Plutonium from Uranium by Solvent Extraction: Recent Developments for Advanced Fuel Cycles; Ternary Complex Formation and Coordination Modes of Am, Cm and Rare Earths with EDTA+NTA: Stability Constants, TRLFS and 13C NMR Studies; Influence of Temperature and Ionic Strength on the Hydration of Curium(III) in Aqueous Solution Studied with TRLFS; Insights into Third Phase Formation Using Neptunium; Investigation of the Behavior of Am (IV), (V) And (VI) in Alkaline Media; A Comparative Study of the Complexation Of Uranium(VI) with Oxydiacetic Acid and its Amide Derivatives; Actinide Electrochemistry in Low Temperature Ionic Liquids; New Data on Extraction of Nitric Acid with 30% TBP from Solutions Containing Uranyl Nitrate; New Data on Extraction of Tetravalent Uranium With 30% TBP from Solutions Containing Uranyl Nitrate; Behaviour Of Some Anhydrous U(IV) Complexes in Hydrophobic Room Temperature Ionic Liquids; The Hydrolysis of Protactinium(V): Equilibrium Constants and Determination of the Standard Thermodynamic Data; The Study of Polymerization of Pu(OH)4 and its Solubility in 0.01M Na Cl Solutions at Various p H Values; Dissolution Of Actinide Oxides In Some Organic Reagents Saturated With Nitric Acid; Separation of Uranium and Plutonium by the Method of Countercurrent Chromatography; Alkaline Sequestrants in Hanford Tank Waste Processing; Anion Control in Hanford Leachates by Solid-Liquid Separation; Uranium Removal From Process Effluents Containing Chromate And Aluminum Nitrate; Diffusion Coefficients of Actinide and Lanthinde Elements in Liquid Metal for Reductive Extraction; Electrochemical and Spectroscopic Characteristics of Uranium Ions in a Hydrate Melt; Spectroscopic Study for the Oxychloride Precipitation of Neodymium and Uranium in Chloride Melts; Extraction of Transuranium Elements and T?(VII) from Acid Solutions by Neutral Phosphorous Compounds; Transuranium, Rare Earth Elements and Technetium (VII) Extraction by Calix[4]Arenes From Acidic and Alkaline Media; Adsorption Properties of Amidoxime Resins for Uranium(VI) and Some Fission Products Soluble in Aqueous Carbonate Solutions; Solubility of UO2(?-Diketonato)2DMSO Complexes (?-Diketonate = Acetylacetonate, Trifluoroacetylacetonate, Hexafluoro-Acetylacetonate; DMSO = Dimethyl Sulfoxide) In Supercritical CO2; Kinetic Study on Exchange Reaction of Hexafluoroacetyl-Acetonate in Bis (Hexafluoroacetylacetonato) (Dimethyl Sulfoxide) Dioxouranium(VI) in Supercritical CO2 by 19F NMR; Heat Oscillating Extraction of Rare Earth Elements; Mathematical Model of Extraction Separation of f-Elements in Non-Stationary Conditions; Final Tests using the BNFL Electrorefiner at Harwell; Behaviour Of FPs And TRU in a Fluoride Volatility Process; Specific Features of Kinetics and Mechanism of Np(IV) Oxidation with Nitric Acid in Aqueous and TBP Solutions; Lanthanide Salt Solutions: Representation Of Osmotic Coefficients Within the Binding Mean Spherical Approximation; The Reduction of Np(VI) by Acetohydroxamic Acid in Nitric Acid Solution; Photoreduction Of UO2F2 Enriched with 18O in Isopropanol Solution; Electrorefining of Plutonium in Calcium Chloride; Separation of Minor Actinides and Lanthanides from Nitric Acid Solution by R-BTP Extraction Resin; UC Electrochemical Behaviour in Aqueous Solution; Redox Behaviour of Plutonium(IV) in Acidic Solutions; The Effect of Fission Product Elements on the Chlorination of Uranium Metal in Molten Salts; Spectroelectrochemical Studies of Uranium Behavior in (Li-K)Cleut Based Melts At 450 ?C; Evaluation of Nuclear Fuel Cycle Systems for Actinide Recycle in Feasibility Study on Commercialized Fast Reactor Cycle Systems; Extraction of Transplutonium and Rare-Earth Elements with the use of Zirconium Salt of Dibutyl Phosphoric Acid; The Effect of Dibutylphosphoric Acid on Actinide (IV) Extraction by 30% TBP from Solutions Containing Uranyl Nitrate; Sorption Properties of New Solid Extractants Based on Malonamide Compounds; Direct Extraction of Uranium and Plutonium with Supercritical Carbon Dioxide from MOX Fuel; Modelling the Hydrolysis of Actinide Complexed Hydroxamic Acid Ligands; A New Approach for Estimating Stability Constants Between Actinides and Organic Ligands by Semi-Empirical Gibbs Energy Fragmental Method; Measurement of Some Actinides Redox Potentials in TBP Medium With Ultramicroelectrode; Development of High Throughput Electrorefining of Uranium in the Metallic Fuel Cycle; Experimental Data Points to Existence of Plutonium (VIII) in Alkaline Solutions; Control of Neptunium Routing During the Reprocessing of Spent Nuclear Fuel Using PUREX; Crystallization Behavior of Uranium and Plutonium in Nitric Acid Solution; A Hot Test on Minor Actinides Separation from High-Level-Waste by CMPO/Si O2-P Extraction Resin; Recovery Of Uranium and Plutonium Metals Through Cathode Processing of Electrodeposits from Reduced Oxide Fuel Anodes; Kinetics of Electrochemical Generation of Silver(II); Ionic Liquids for Actinides and Lanthanides Chemistry; Solvent Extraction of Actinides by Tetraalkylpyridine-N-Oxide-Bis Phosphine Oxide Complexants; Kinetics and Mechanism of Actinide Complexation by Polydentate Ligands; The Significance of Minor Actinide Based Fuel Cycles in Advanced Fuel Cycles; Separation of Uranium from Radioactive Waste using Supercritical Carbon Dioxide with Nitric Acid – Tri-n-Butylphosphate Complex; Chapter Six: Spectroscopy and Magnetism; Spectroscopic Actinide Speciation for Nuclear Waste Disposal; Superconductivity in Actinide Materials; Neutron Scattering Studies of Np TGa5 (T = Fe, Co, Ni and Rh); Tuning the Superconducting Behaviour of the Pu TGa5 Compounds; The Electronic Structure of the Pu-Based Superconductor Pu Co Ga5: LSDA and LSDA+U Investigations; Ground State and Solution Behaviour of Actinide Ions Investigated by Nuclear Magnetic Resonance Methods; Polarization Effects in EXAFS Spectra at the Uranium L1 and L3 Edge – A Comparison Between Theory and Experiment; A Study of the Competition Between Delocalization and Spin-Orbit Splitting in the Actinide 5f States; A Crossover Effect of the 5f Electrons of Uranium Compounds: From Itinerant to Localized, With Increasing Temperature; Localization of 5f Electrons and Phase Transitions in Americium; Orbital Ordering in Actinide Oxides: New Perspectives on Old Problems; Electronic Structure of ?-Pu: Theories and PES Experiments; Magnetic Properties of Radiation Damage in Pu and Pu Alloys; A Photoelectron Spectroscopy Investigation of the Early Stages of Neptunium Oxidation; Electronic Structure of Molecular Actinide Compounds Through Spectroscopic Experiments Combined with Theoretical Modelling; Influence of Self-Irradiation Damage on the Superconducting Behaviour of Plutonium-Based Compounds; MARS Beamline, A New Facility for Studying Radioactive Matter from a Synchrotron Source; Solid State Synthesis and X-Ray Diffraction Characterization of Pu3+(1-2x)Pu4+x Ca2+x PO4; Chemiluminescence in Solid-Phase Reactions of Uranium (IV) and Terbium (III) Compounds; Chemiluminescent Reactions of Uranium and the Role of UO2+; Magnetic Anisotropy of U2Co17-x Six Single Crystals; High-Field Magnetization of a UIr Ge Single Crystal; Comparative Photoemission Study of Actinide Metals, Nitrides and Hydrides; Cathodoluminescence of Actinide Ions in Crystalline Host Phases Electronic Structure of the Americium Monopnictides: Ab Initio Calculations and Photoemission Experiments; Using Nano-Focussed Bremstrahlung Isochromat Spectroscopy (n BIS) to Determine the Unoccupied Electronic Structure of Pu: A Proposed Study Fluorescence Spectroscopy of Protactinium(IV); Pu, Np and U Valence States and the Determination of their Molecular Form by Chemiluminescence and Pulsed Laser Spectroscopy; Air-Oxidation Behaviour of UO2 and Gd-Doped UO2 by XAS; Speciation Of Radionuclides With Bioligands Using Time-Resolved Laser-Induced Fluorescence (TRLIF) and Electrospray Mass Spectrometry (ES-MS); Magnetic Diagrams of Pu Ga3 Under Pressure; Magnetic Ordering of U and Co Moments in (Th, U)Co2X2 (X = Si, Ge) Solid Solutions; Spectroscopic Investigations of Uranium Species in Alkali Chloride Molten Salts; Magnetic and Electrical Properties of UCu3M2Al7 Alloys; X-Ray Photoelectron Spectroscopy Study of Neptunium-Containing Ceramics on the Basis of Ferrite and Titanate (6P23); Subject Index