Actinide cyanometallates

Simple salts of the tetracyanoplatinate (TCP) anions with the general formula M[Pt(CN)₄] _x ·H₂O have been described for over 200 years. A major structural feature of these compounds are pseudo one dimensional Pt···Pt interactions between the square planar tetracyanoplatinate anions. These interactions form quasi one-dimensional chains in the solid state and are believed to be the source of their unique spectroscopic and emission properties. The lanthanides offer the ability to tune the Pt···Pt spacing of these pseudo one dimensional chains, predictably by taking advantage of the lanthanide contraction. Here, we describe the emission and structural characteristics of new actinide tetracyanometallates.     

Lanthanide und Actinide

Ohne Zusammenfassung     

Reduced inorganic phosphorus in the natural environment: significance, speciation and determination

It is commonly assumed that phosphorus occurs almost exclusively in the environment as fully oxidized phosphate (primarily H₂PO₄⁻ and HPO₄²⁻, where the oxidation state of phosphorus is +V). Recent developments in the field of microbiology and research on the origin of life have suggested a possibly significant role for reduced, inorganic forms of phosphorus in bacterial metabolism and as evolutionary precursors of biological phosphate compounds. Reduced inorganic forms of phosphorus include phosphorus acid (H₃PO₃, P(+III)), hypophosphorus acid (H₃PO₂, P(+I)) and various forms of phosphides (P(−III)). Reduced phosphorus has been detected in anaerobic sediments, sewage treatment facilities and in industrial and agricultural processes.Microbiological evidence suggests a significant role for reduced phosphorus species in metabolic processes and raises interesting questions regarding the biogeochemistry of this nutrient in the environment. However, the paucity of data on the presence and cycling of reduced phosphorus compounds in the environment requires attention in order to elucidate the role of these compounds in natural systems. This paper discusses the significance of reduced phosphorus in the natural environment, its speciation and methods of detection.     

Occurrence and chemical speciation analysis of organotin compounds in the environment: A review

Environmental concerns regarding organotin compounds have increased remarkably in the past 20 years, due in large part to the use of these compounds as active components in antifouling paints [mainly tributyltin (TBT)] and pesticide formulations [mainly triphenyltin (TPhT)]. Their direct introduction into the environment, their bio-accumulation and the high toxicity of these compounds towards “non-target” organisms (for example: oysters and mussels) causes environmental and economic damage around the world. As a consequence, the presence and absence of organotin compounds is currently monitored in a range of environmental matrices (e.g., water, sediment and shellfish) to examine the utility of controls meant to regulate the level of contamination as required in some EC Directives and the Water Framework Directive 2000/60/EC. To evaluate the environmental distribution and fate of these compounds and to determine the effectives of legal provisions adopted by a number of countries, a variety of analytical methods have been developed for organotin determination in the environment. Most of these methods include different steps such as extraction, derivatisation and clean up. The aim of the present review is to evaluate the environmental distribution, fate and chemical speciation of organotin compounds in the environment.     

Seventeen-Coordinate Actinide Helium Complexes

The geometries and electronic structures of molecular ions featuring He atoms complexed to actinide cations are explored computationally using density functional and coupled cluster theories. A new record coordination number is established, as AcHe₁₇³⁺, ThHe₁₇⁴⁺, and PaHe₁₇⁴⁺ are all found to be true geometric minima, with the He atoms clearly located in the first shell around the actinide. Analysis of AcHe_n³⁺ (n=1–17) using the quantum theory of atoms in molecules (QTAIM) confirms these systems as having closed shell, charge-induced dipole bonding. Excellent correlations (R²>0.95) are found between QTAIM metrics (bond critical point electron densities and delocalization indices) and the average Ac−He distances, and also with the incremental He binding energies.     

Actinide bioassays by ICPMS

The ever-increasing sensitivity of ICPMS continues to expand the technique’s application in the field of health physics. Enhancements in sample introduction and instrument design over the last few years have resulted in improving the ICPMS detection limit from ∼10 ng/l to≤0.1 ng/l. This additional sensitivity provides greater flexibility in the analysis of long-lived radionuclides in biological fluids, and requires only minimal sample preparation of urine for uranium analysis; the described 3-minute abbreviated matrix separation provides detection limits that are comparable to or better than alpha counting. For urine samples tested having concentrations that exceed the accepted administrative limit for total uranium (0.2 μg/day), isotopic analysis by ICPMS (e.g., determining the presence of²³⁶U, or measuring appropriate uranium isotope ratios) provides a reliable indication of occupational exposure. Our laboratory also utilizes ICPMS in a study examining uranium dissolution rate classification of dust collected at the perimeter of a nuclear facility. Specific details regarding these and other health physics applications are featured, including our group’s participation in assisting the DOE with the evaluation of ICPMS as a cost-effective alternative to fission-track analysis for the routine determination of²³⁹Pu in urine.     

锕系计算化学进展

本文简要总结了过去十年中应用量子力学方法研究锕系化学的若干结果。我们将其大致归为几何与电子结构和化学反应两类。对于前者,简要总结了锕系元素化合物中的An-O键和金属-金属键;而后者则涉及水合反应和配体交换反应,歧化反应,氧化反应,铀酰离子的还原,氢胺化反应以及铀的叠氮化合物的光解反应等。     

化学计量学在锕系元素分析中的应用

锕系元素的化学性质相似,各元素的分离和分析都很困难,用传统的数据解析手段,难以实现各元素的同时、快速分析。化学计量学是一种高效、功能强大的数据解析方法,对于样品复杂,基体干扰严重以及多组分样品的分析具有独特优势。将化学计量学应用于锕系元素的分析中,利用数学分离代替化学分离,可直接对样品进行测定。化学计量学方法也可用来指导试样的科学采集,进行实验设计、仪器分析操作条件选择等。从吸收光谱、ICP–AES及放射性测量3个方面综述了化学计量学在锕系元素分析中的应用,阐明了化学计量学在锕系元素分析中的应用难点及发展前景。     

Actinide pollutants and the oxygen/water couple

The redox potential of environmental water influences the speciation of pollutants like plutonium. This potential cannot be reliably predicted from diagrams for irreversible couples like oxygen/water.Mound is operated for the U. S. Department of Energy by EG&G Mound Applied Technologies Incorporated under Contract No. DE-AC04-88DP43495.     

Actinide behavior on crushed rock columns

The interactions of dissolved or colloidal actinides with tuffaceous rock are being studied at Los Alamos National Laboratory in support of the Nevada Nuclear Waste Storage Investigations project. We have used small columns of crushed tuff to obtain information on the sorption of neptunium, plutonium and americium during short (<1 day) time spans. Data from these experiments supplement information obtained from longer term batch-type experiments and provide insight concerning sorption kinetics, speciation, and colloid migration. We find that Np(V), Pu(VI) and Pu(V) show limited sorption on crushed tuff. Pu(IV) polymer and Am(III) are largely retained by the tuff, with a small fraction of the imput material moving through the column as colloids.     

Actinide(III) carbonate complexation

The following equations have been developed to estimate trivalent actinide and lanthanide carbonate stability constants: log B₁⁰ = −6.128+35.206R−21.557R²; log B₂⁰ = 14.797+7.945R−10.304R², where B₁⁰ = aMCO₃⁺/(aM³⁺aCO₃²⁻, B₂⁰ = aM(CO₃)₂⁻(aM³⁺(aCO₃²⁻), aX is the activity of ion X, M indicates a metal ion and R is the effective ionic radius of the metal ion in six-fold coordination. These equations describe carbonate stability constants for cerium, europium and ytterbium at zero ionic strength. Constants at zero ionic strength were estimated from experimental determinations made in 0.68 molal NaClO₄ by accounting for medium effects.     

Actinide accumulation and some radiochemical problems

The state of Soviet research on the improvement of spent fuel reprocessing (deep TPE extraction included) and some applied radiochemicstry problems are discussed.     

Microstructures and speciation of radionuclides in natural environment studied by advanced spectroscopy and theoretical calculation

The environmental behavior of radionuclides is mainly dependent on their speciation and microstructures at solid particles.The speciation and microstructures of radionuclides at molecular level can be achieved from advanced spectroscopy techniques and theoretical calculations.In this perspective,we give a brief introduction of the advanced X-ray absorption fine structure(XAFS) technique and theoretical calculation in the analysis of the speciation and microstructures of radionuclides in the natural environment,which is crucial to evaluate the physicochemical behavior of radionuclides in the environment.     

R&D Activities on Actinide Separation in China

A brief status of the development of actinide separation in china is presented. The activities on actinide separation include:1) Neptunium chemistry and its separation in Purex Process;2) actinide separation from HLLW;3) separation of actinides from rare earth; and4) preliminary studies on uranium cathode deposit by pyrochemical process.     

Actinide uptake onto zeolite-L and SAPO-34

The characteristics of ion exchange of uranyl and americium, which are -emitting radioactive nuclides, were examined by batch and column methods. SAPO-34 showed good selectivity for uranyl ion at pH 2–3.5, and distribution coefficients of Am³⁺ and UO ₂ ²⁺ increased with equilibrium pH. -irradiation (2 MGy) did not show any significant effect on the uptake of both of actinide ions onto L and SAPO-34. Higher does of -irradiation (up to 10 MGy) created a change of equilibrium pH, and hence uptake, due to radiolysis of water and heat localization generated by -radiation and annealing processes.     

Seventeen‐Coordinate Actinide Helium Complexes

The geometries and electronic structures of molecular ions featuring He atoms complexed to actinide cations are explored computationally using density functional and coupled cluster theories. A new record coordination number is established, as AcHe₁₇³⁺, ThHe₁₇⁴⁺, and PaHe₁₇⁴⁺ are all found to be true geometric minima, with the He atoms clearly located in the first shell around the actinide. Analysis of AcHe_n ³⁺ (n =1–17) using the quantum theory of atoms in molecules (QTAIM) confirms these systems as having closed shell, charge‐induced dipole bonding. Excellent correlations (R ²>0.95) are found between QTAIM metrics (bond critical point electron densities and delocalization indices) and the average Ac−He distances, and also with the incremental He binding energies.