Uranium contamination of bivalve Mytilus galloprovincialis, speciation and localization.

Uranium is a natural radioelement (also a model for heavier actinides), but may be released through anthropogenic activities. In order to assess its environmental impact in a given ecosystem, such as the marine system, it is essential to understand its distribution and speciation, and also to quantify its bioaccumulation. Our objective was to improve our understanding of the transfer and accumulation of uranium in marine biota with mussels taken here as sentinel species because of their sedentary nature and ability to filter seawater. We report here on the investigation of uranium accumulation, speciation, and localization in Mytilus galloprovincialis using a combination of several analytical (Inductively Coupled Plasma Mass Spectrometry, ICP-MS), spectroscopic (X ray Absorption Spectroscopy, XAS, Time Resolved Laser Induced Fluorescence Spectroscopy, TRLIFS), and imaging (Transmission Electron Microscopy, TEM, µ-XAS, Secondary Ion Mass Spectrometry, SIMS) techniques. Two cohorts of mussels from the Toulon Naval Base and the Villefranche-sur-Mer location were studied. The measurement of uranium Concentration Factor (CF) values show a clear trend in the organs of M. galloprovincialis: hepatopancreas â‰« gill > body ≥ mantle > foot. Although CF values for the entire mussel are comparable for TNB and VFM, hepatopancreas values show a significant increase in those from Toulon versus Villefranche-sur-Mer. Two organs of interest were selected for further spectroscopic investigations: the byssus and the hepatopancreas. In both cases, U(VI) (uranyl) is accumulated in a diffuse pattern, most probably linked to protein complexing functions, with the absence of a condensed phase. While such speciation studies on marine organisms can be challenging, they are an essential step for deciphering the impact of metallic radionuclides on the marine biota in the case of accidental release. Following our assumptions on uranyl speciation in both byssus and hepatopancreas, further steps will include the inventory and identification of the proteins or metabolites involved.

Exploring uranium bioaccumulation in the brown alga Ascophyllum nodosum: insights from multi-scale spectroscopy and imaging.

Legacy radioactive waste can be defined as the radioactive waste produced during the infancy of the civil nuclear industry's development in the mid-20th Century, a time when, unfortunately, waste storage and treatment were not well planned. The marine environment is one of the environmental compartments worth studying in this regard because of legacy waste in specific locations of the seabed. Comprising nearly 70% of the earth's service, the oceans are the largest and indeed the final destination for contaminated fresh waters. For this reason, long-term studies of the accumulation biochemical mechanisms of metallic radionuclides in the marine ecosystem are required. In this context the brown algal compartment may be ecologically relevant because of forming large and dense algal beds in coastal areas and potential important biomass for contamination. This report presents the first step in the investigation of uranium (U, an element used in the nuclear cycle) bioaccumulation in the brown alga Ascophyllum nodosum using a multi-scale spectroscopic and imaging approach. Contamination of A. nodosum specimens in closed aquaria at 13 °C was performed with a defined quantity of U(VI) (10-5 M). The living algal uptake was quantified by ICP-MS and a localization study in the various algal compartments was carried out by combining electronic microscopy imaging (SEM), X-ray Absorption spectroscopy (XAS) and micro X-ray Florescence (µ-XRF). Data indicate that the brown alga is able to concentrate U(VI) by an active bioaccumulation mechanism, reaching an equilibrium state after 200 h of daily contamination. A comparison between living organisms and dry biomass confirms a stress-response process in the former, with an average bioaccumulation factor (BAF) of 10 ± 2 for living specimens (90% lower compared to dry biomass, 142 ± 5). Also, these results open new perspectives for a potential use of A. nodosum dry biomass as uranium biosorbent. The different partial BAFs (bioaccumulation factors) range from 3 (for thallus) to 49 (for receptacles) leading to a compartmentalization of uranium within the seaweed. This reveals a higher accumulation capacity in the receptacles, the algal reproductive parts. SEM images highlight the different tissue distributions among the compartments with a superficial absorption in the thallus and lateral branches and several hotspots in the oospheres of the female individuals. A preliminary speciation XAS analysis identified a distinct U speciation in the gametes-containing receptacles as a pseudo-autunite phosphate phase. Similarly, XAS measurements on the lateral branches (XANES) were not conclusive with regards to the occurrence of an alginate-U complex in these tissues. Nonetheless, the hypothesis that alginate may play a role in the speciation of U in the algal thallus tissues is still under consideration.

Interaction Between the Transferrin Protein and Plutonium (and Thorium), What's New?

Transferrin (Tf) is a glycoprotein that transports iron from the serum to the various organs. Several studies have highlighted that Tf can interact with metals other than Fe(III), including actinides that are chemical and radiological toxics. We propose here to report on the behavior of Th(IV) and Pu(IV) in comparison with Fe(III) upon Tf complexation. We considered UV-Vis and IR data of the M2 Tf complex (M=Fe, Th, Pu) and combined experimental EXAFS data with MD models. EXAFS data of the first M-O coordination sphere are consistent with the MD model considering 1 synergistic carbonate. Further EXAFS data analysis strongly suggests that contamination by Th/Pu colloids seems to occur upon Tf complexation, but it seems limited. SAXS data have also been recorded for all complexes and also after the addition of Deferoxamine-B (DFOB) in the medium. The Rg values are very close for apoTf, ThTf and PuTf, but slightly larger than for holoTf. Data suggest that the structure of the protein is more ellipsoidal than spherical, with a flattened oblate form. From this data, the following order of conformation size might be considered:holoTf

Uranium Speciation in a Chalky Soil.

In this article, the speciation and behavior of anthropogenic metallic uranium deposited on natural soil are approached by combining EXAFS (extended X-ray absorption fine structure) and TRLFS (time-resolved laser-induced fluorescence spectroscopy). First, uranium (uranyl) speciation was determined along the vertical profile of the soil and bedrock by linear combination fitting of the EXAFS spectra. It shows that uranium migration is strongly limited by the sorption reaction onto soil and rock constituents, mainly mineral carbonates and organic matter. Second, uranium sorption isotherms were established for calcite, chalk, and chalky soil materials along with EXAFS and TRLFS analysis. The presence of at least two adsorption complexes of uranyl onto carbonate materials (calcite) could be inferred from TRLFS. The first uranyl tricarbonate complex has a liebigite-type structure and is dominant for low loads on the carbonate surface (<10 mgU/kg(rock)). The second uranyl complex is incorporated into the calcite for intermediate (∼10 to 100 mgU/kg(rock)) to high (high: >100 mgU/kg(rock)) loads. Finally, the presence of a uranium-humic substance complex in subsurface soil materials was underlined in the EXAFS analysis by the occurrence of both monodentate and bidentate carboxylate (or/and carbonate) functions and confirmed by sorption isotherms in the presence of humic acid. This observation is of particular interest since humic substances may be mobilized from soil, potentially enhancing uranium migration under colloidal form.

Investigation of the Plutonium(IV) Interactions with Two Variants of the EF-Hand Ca-Binding Site I of Calmodulin.

Due to its presence in the nuclear industry and its strong radiotoxicity, plutonium is an actinide of major interest in the event of internal contamination. To improve the understanding of its mechanisms of transport and accumulation in the body, the complexation of Pu(IV) to the most common protein calcium-binding motif found in cells, the EF-hand motif of calmodulin, was investigated. Visible and X-ray absorption spectroscopies (XAS) in solution made it possible to investigate the speciation of plutonium at physiological pH (pH 7.4) and pH 6 in two variants of the calmodulin Ca-binding site I and using Pu(IV) in different media: carbonate, chloride, or nitrate solutions. Three different species of Pu were identified in the samples, with formation of 1:1 Pu(IV):calmodulin peptide complexes, Pu(IV) reduction, and formation of peptide-mediated Pu(IV) hexanuclear cluster.

Optimized Coordination of Uranyl in Engineered Calmodulin Site 1 Provides a Subnanomolar Affinity for Uranyl and a Strong Uranyl versus Calcium Selectivity.

As an alpha emitter and chemical toxicant, uranium toxicity in living organisms is driven by its molecular interactions. It is therefore essential to identify main determinants of uranium affinity for proteins. Others and we showed that introducing a phosphoryl group in the coordination sphere of uranyl confers a strong affinity of proteins for uranyl. In this work, using calmodulin site 1 as a template, we modulate the structural organization of a metal-binding loop comprising carboxylate and/or carbonyl ligands and reach affinities for uranyl comparable to that provided by introducing a strong phosphoryl ligand. Shortening the metal binding loop of calmodulin site 1 from 12 to 10 amino acids in CaMΔ increases the uranyl-binding affinity by about 2 orders of magnitude to log KpH7 = 9.55 ± 0.11 (KdpH7 = 280 ± 60 pM). Structural analysis by FTIR, XAS, and molecular dynamics simulations suggests an optimized coordination of the CaMΔ-uranyl complex involving bidentate and monodentate carboxylate groups in the uranyl equatorial plane. The main role of this coordination sphere in reaching subnanomolar dissociation constants for uranyl is supported by similar uranyl affinities obtained in a cyclic peptide reproducing CaMΔ binding loop. In addition, CaMΔ presents a uranyl/calcium selectivity of 107 that is even higher in the cyclic peptide.

Correction: Formation of plutonium(IV) silicate species in very alkaline reactive media.

Correction for 'Formation of plutonium(IV) silicate species in very alkaline reactive media' by Paul Estevenon et al., Dalton Trans., 2021, 50, 12528-12536, DOI: 10.1039/D1DT02248B.

Characterization of a Hexanuclear Plutonium(IV) Nanostructure in an Acetate Solution via Visible-Near Infrared Absorption Spectroscopy, Extended X-ray Absorption Fine Structure Spectroscopy, and Density Functional Theory.

A new hexanuclear plutonium cluster has been stabilized in aqueous media with acetate ligands. To probe the formation of such a complex structure, visible-near infrared (vis-NIR) absorption spectroscopy, extended X-ray absorption fine structure (EXAFS) spectroscopy, and density functional theory (DFT) were combined. The presence of Pu6O4(OH)4(CH3COO)12 species in solution was first detected by vis-NIR and EXAFS spectroscopy. To confirm unambiguously this structure, EXAFS spectra were simulated from ab initio calculations. Debye-Waller factors and structural parameters were derived from DFT calculations. A large number of 5f electrons were treated as valence or core electrons using small- and large-core relativistic effective pseudopotentials. It is possible to reproduce accurately the EXAFS spectrum of the octahedral hexamer cluster at both levels of calculations. Further DFT and EXAFS calculations were performed on clusters of lower or higher nuclearities and of different geometries using the 5f-core approximation. The result shows that trimer, tetramer, flat hexamer, and even 16-mer clusters exhibit different EXAFS patterns and confirm the very specific octahedral hexanuclear EXAFS signature.

Accumulation and Speciation of Cobalt in Paracentrotus lividus.

Since the first human release of radionuclides on Earth at the end of the Second World War, impact assessments have been implemented. Radionuclides are now ubiquitous, and the impact of local accidental release on human activities, although of low probability, is of tremendous social and economic consequences. Although radionuclide inventories (at various scales) are essential as input data for impact assessment, crucial information on physicochemical speciation is lacking. Among the metallic radionuclides of interest, cobalt-60 is one of the most important activation products generated in the nuclear industry. In this work, a marine model ecosystem has been defined because seawater and more generally marine ecosystems are final receptacles of metal pollution. A multistep approach from quantitative uptake to understanding of the accumulation mechanism has been implemented with the sea urchin Paracentrotus lividus. In a well-controlled aquarium, the day-by-day uptake of cobalt and its quantification in different compartments of the sea urchin were monitored with various conditions of exposure by combining ICP-OES analysis and γ spectrometry. Cobalt is mainly distributed following the rating intestinal tract ≫ gonads > shell spines. Cobalt speciation in seawater and inside the gonads and the intestinal tract was determined using extended X-ray absorption fine structure (EXAFS). The cobalt inside the gonads and the intestinal tract is mainly complexed by the toposome, the main protein in the sea urchin P. lividus. Complexation with purified toposome was characterized and a complexation site combining EXAFS and AIMD (ab initio molecular dynamics) was proposed implying monodentate carboxylates.

X-ray absorption spectroscopy and actinide electrochemistry: a setup dedicated to radioactive samples applied to neptunium chemistry.

A spectroelectrochemical setup has been developed to investigate radioactive elements in small volumes (0.7 to 2 ml) under oxidation-reduction (redox) controlled conditions by X-ray absorption spectroscopy (XAS). The cell design is presented together with in situ XAS measurements performed during neptunium redox reactions. Cycling experiments on the NpO22+/NpO2+ redox couple were applied to qualify the cell electrodynamics using XANES measurements and its ability to probe modifications in the neptunyl hydration shell in a 1 mol l-1 HNO3 solution. The XAS results are in agreement with previous structural studies and the NpO22+/NpO2+ standard potential, determined using Nernst methods, is consistent with measurements based on other techniques. Subsequently, the NpO2+, NpO22+ and Np4+ ion structures in solution were stabilized and measured using EXAFS. The resulting fit parameters are again compared with other results from the literature and with theoretical models in order to evaluate how this spectroelectrochemistry experiment succeeds or fails to stabilize the oxidation states of actinides. The experiment succeeded in: (i) implementing a robust and safe XAS device to investigate unstable radioactive species, (ii) evaluate in a reproducible manner the NpO22+/NpO2+ standard potential under dilute conditions and (iii) clarify mechanistic aspects of the actinyl hydration sphere in solution. In contrast, a detailed comparison of EXAFS fit parameters shows that this method is less appropriate than the majority of the previously reported chemical methods for the stabilization of the Np4+ ion.

Interaction of Th(IV), Pu(IV) and Fe(III) with ferritin protein: how similar?

Ferritin is the main protein of Fe storage in eukaryote and prokaryote cells. It is a large multifunctional, multi-subunit protein consisting of heavy H and light L subunits. In the field of nuclear toxicology, it has been suggested that some actinide elements, such as thorium and plutonium at oxidation state +IV, have a comparable `biochemistry' to iron at oxidation state +III owing to their very high tendency for hydrolysis and somewhat comparable ionic radii. Therefore, the possible mechanisms of interaction of such actinide elements with the Fe storage protein is a fundamental question of bio-actinidic chemistry. We recently described the complexation of Pu(IV) and Th(IV) with horse spleen ferritin (composed mainly of L subunits). In this article, we bring another viewpoint to this question by further combining modeling with our previous EXAFS data for Pu(IV) and Th(IV). As a result, the interaction between the L subunits and both actinides appears to be non-specific but driven only by the density of the presence of Asp and Glu residues on the protein shell. The formation of an oxyhydroxide Th or Pu core has not been observed under the experimental conditions here, nor the interaction of Th or Pu with the ferric oxyhydroxide core.

Formation of plutonium(IV) silicate species in very alkaline reactive media.

Studying the speciation of Pu(IV) in very alkaline and silicate ion rich reactive media allowed identification of the formation of plutonium(IV)-silicate colloidal suspensions which were stable for months. These colloids were stabilized in aqueous solution for pH > 13 and for concentrations around 10-2 mol L-1. Successive filtration processes allowed evaluation of their size, which was found to be smaller than 6 nm. Their structural characterization by XAS evidenced that their structure was similar to those identified for the other tetravalent actinide-silicate colloidal systems like thorium, uranium and neptunium. Their formation could explain the increase of plutonium solubility usually observed in alkaline silicate-rich solutions and could affect the plutonium mobility as a result in contaminated sites or in other environmental permeable media.

Structural and Thermodynamics Studies on Polyaminophosphonate Ligands for Uranyl Decorporation.

The development of actinide decorporation agents with high complexation affinity, high tissue specificity, and low biological toxicity is of vital importance for the sustained and healthy development of nuclear energy. After accidental actinide intake, sequestration by chelation therapy to reduce acute damage is considered as the most effective method. In this work, a series of bis- and tetra-phosphonated pyridine ligands have been designed, synthesized, and characterized for uranyl (UO22+) decorporation. Owing to the absorption of the ligand and the luminescence of the uranyl ion, UV-vis spectroscopy and time-resolved laser-induced fluorescence spectroscopy (TRLFS) were used to probe in situ complexation and structure variation of the complexes formed by the ligands with uranyl. Density functional theory (DFT) calculations and X-ray absorption fine structure (XAFS) spectroscopy on uranyl-ligand complexes revealed the coordination geometry around the uranyl center at pH 3 and 7.4. High affinity constants (log K ∼17) toward the uranyl ion were determined by displacement titration. A preliminary in vitro chelation study proves that bis-phosphonated pyridine ligands can remove uranium from calmodulin (CaM) at a low dose and in the short term, which supports further uranyl decorporation applications of these ligands.

Uranium retention on iron oxyhydroxides in post-mining environmental conditions.

Investigating uranium migration mechanisms related to the weathering of waste rocks is essential for developing strategies that can address the potential environmental issues caused by uranium mining. This work is based on environmental samples containing 2 L ferrihydrite, lepidocrocite and goethite collected in the technosols from granitic waste rock piles, mine drainage conduits and mine waters. The results show the important role of iron oxyhydroxide in U immobilization and re-concentration. EXAFS spectroscopy combined with mineralogical and geochemical studies (Scanning electronic microscopy, Wavelength-dispersive X-ray spectroscopy microprobe, inductively coupled plasma - optical emission spectrometry/mass spectrometry and X-ray diffraction) allowed for the identification of uranyl ternary surface complexes at the ferrihydrite surface that were either composed of phosphate groups or organic matter. Moreover, goethite and lepidocrocite were also identified as a secondary trap for U immobilization. U(VI) is known to be mobile in oxidizing conditions. This study highlights the control of the uranyl mobility by various iron oxyhydroxides in supergene conditions.

How Does Iron Storage Protein Ferritin Interact with Plutonium (and Thorium)?

The impact of the contamination of living organisms by actinide elements has been a constant subject of attention since the 1950s. But to date still little is understood. Ferritin is the major storage and regulation protein of iron in many organisms, it consists of a protein ring and a ferrihydric core at the center. This work sheds light on the interactions of early actinides (Th, Pu) at oxidation state +IV with ferritin and its ability to store those elements at physiological pH compared to Fe. The ferritin-thorium load curve suggests that ThIV saturates the protein (2840 Th atoms per ferritin) in a similar way that Fe does on the protein ring. Complementary spectroscopic techniques (spectrophotometry, infrared spectroscopy, and X-ray absorption spectroscopy) were combined with molecular dynamics to provide a structural model of the interaction of ThIV and PuIV with ferritin. Comparison of spectroscopic data together with MD calculations suggests that ThIV and PuIV are complexed mainly on the protein ring and not on the ferrihydric core. Indeed from XAS data, there is no evidence of Fe neighbors in the Th and Pu environments. On the other hand, carboxylates from amino acids of the protein ring and a possible additional carbonate anion are shaping the cation coordination spheres. This thorough description from a molecular view point of ThIV and PuIV interaction with ferritin, an essential iron storage protein, is a cornerstone in comprehensive nuclear toxicology.

High-efficient microbial immobilization of solved U(VI) by the Stenotrophomonas strain Br8.

The environmental impact of uranium released during nuclear power production and related mining activity is an issue of great concern. Innovative environmental-friendly water remediation strategies, like those based on U biomineralization through phosphatase activity, are desirable. Here, we report the great U biomineralization potential of Stenotrophomonas sp. Br8 CECT 9810 over a wide range of physicochemical and biological conditions. Br8 cells exhibited high phosphatase activity which mediated the release of orthophosphate in the presence of glycerol-2-phosphate around pH 6.3. Mobile uranyl ions were bioprecipitated as needle-like fibrils at the cell surface and in the extracellular space, as observed by Scanning Transmission Electron Microscopy (STEM). Extended X-Ray Absorption Fine Structure (EXAFS) and X-Ray Diffraction (XRD) analyses showed the local structure of biogenic U precipitates to be similar to that of meta-autunite. In addition to the active U phosphate biomineralization process, the cells interact with this radionuclide through passive biosorption, removing up to 373 mg of U per g of bacterial dry biomass. The high U biomineralization capacity of the studied strain was also observed under different conditions of pH, temperature, etc. Results presented in this work will help to design efficient U bioremediation strategies for real polluted waters.

Electrochemical and Spectroscopic Study of EuIII and EuII Coordination in the 1-Ethyl-3-methylimidazolium Bis(trifluoromethylsulfonyl)imide Ionic Liquid.

Separation processes based on room temperature ionic liquids (RTIL) and electrochemical refining are promising strategies for the recovery of lanthanides from primary ores and electronic waste. However, they require the speciation of dissolved elements to be known with accuracy. In the present study, Eu coordination and EuIII /EuII electrochemical behavior as a function of water content in 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([EMIm][NTf2 ]) was investigated using UV-visible spectrophotometry, time-resolved laser fluorescence spectroscopy, electrochemistry, and X-ray absorption spectroscopy. In situ measurements were performed in spectroelectrochemical cells. Under anhydrous conditions, EuIII and EuII were complexed by NTf2 , forming Eu-O and Eu-(N,O) bonds with the anion sulfoxide function and N atoms, respectively. This complexation resulted in a greater stability of EuII , and in quasi-reversible oxidation-reduction with an E0 ' potential of 0.18 V versus the ferrocenium/ferrocene (Fc+ /Fc) couple. Upon increasing water content, progressive incorporation of water in the EuIII coordination sphere occurred. This led to reversible oxidation-reduction reactions, but also to a decrease in stability of the +II oxidation state (E0 '=-0.45 V vs. Fc+ /Fc in RTIL containing 1300 mm water).

Carboxylate- and Phosphonate-Modified Polyethylenimine: Toward the Design of Actinide Decorporation Agents.

Plutonium (Pu) is an anthropogenic element involved in the nuclear industry cycle. Located at the bottom of the periodic table within the actinide family, it is a chemical toxic but also a radiological toxic, regardless of isotopy. After nearly 80 years of Pu industrialization, it has become clear that inhalation and wounds represent the two main ways a person may become contaminated after an accident. In order to reduce the deleterious health effects of Pu, it is crucial to limit chronic exposure by removing it or preventing its incorporation into the body. Diethylenetriaminepentaacetic acid (DTPA) has emerged as the gold standard for Pu decorporation, although it suffers from very short retention time in serum. Other molecules like the hydroxypyridonate family with high chemical affinity have also been considered. We have been considering alternative polymeric chelates and, in particular, polyethylenimine (PEI) analogues of DTPA (the carbonate or phosphonate version), which may present a real breakthrough in Pu decorporation not only because of their higher loading capacity but also because of their indirect vectorization properties correlated with a specific biodistribution into the lungs, bone, kidney, or liver. In the first part of this Forum Article, new data on the structural characterization of the complexation of PuIV with polyethylenimine methylphosphonate (PEI-MP) were obtained using the combination of extended X-ray absorption fine structure spectroscopy and ab initio molecular dynamics (AIMD) calculations. The use of thorium (Th) as a Pu chemical surrogate is also discussed because its unique oxidation state is IV+ in solution. In the second part of the paper, we put this new set of data on PEI-MP-Pu into perspective with use of the PEI platform to complex ThIV and PuIV. Uptake curves of ThIV witth polyethylenimine methylcarboxylate (PEI-MC) are compared with those of PEI-MP and DTPA, and the AIMD data are discussed.

Direct conversion of uranium dioxide UO2 to uranium tetrafluoride UF4 using the fluorinated ionic liquid [Bmim][PF6].

The industrial fluorination of UO2 to UF4 is based on a complex process involving the manipulation of a large amount of HF, a very toxic and corrosive gas. We present here a safer way to accomplish this reaction utilizing ionic liquid [Bmim][PF6] as a unique reaction medium and fluoride source.

Interdisciplinary Round-Robin Test on Molecular Spectroscopy of the U(VI) Acetate System.

A comprehensive molecular analysis of a simple aqueous complexing system-U(VI) acetate-selected to be independently investigated by various spectroscopic (vibrational, luminescence, X-ray absorption, and nuclear magnetic resonance spectroscopy) and quantum chemical methods was achieved by an international round-robin test (RRT). Twenty laboratories from six different countries with a focus on actinide or geochemical research participated and contributed to this scientific endeavor. The outcomes of this RRT were considered on two levels of complexity: first, within each technical discipline, conformities as well as discrepancies of the results and their sources were evaluated. The raw data from the different experimental approaches were found to be generally consistent. In particular, for complex setups such as accelerator-based X-ray absorption spectroscopy, the agreement between the raw data was high. By contrast, luminescence spectroscopic data turned out to be strongly related to the chosen acquisition parameters. Second, the potentials and limitations of coupling various spectroscopic and theoretical approaches for the comprehensive study of actinide molecular complexes were assessed. Previous spectroscopic data from the literature were revised and the benchmark data on the U(VI) acetate system provided an unambiguous molecular interpretation based on the correlation of spectroscopic and theoretical results. The multimethodologic approach and the conclusions drawn address not only important aspects of actinide spectroscopy but particularly general aspects of modern molecular analytical chemistry.