Predominance of the alkaline earth(II) triscarbonatoactinyl(VI) complexes in different geochemical contexts: Review of existing data and estimation of potentially unidentified species.

From the available thermodynamic data in the literature, a review of the impact of the formation of complexes between triscarbonatoactinyl(VI) and alkaline earth(II) (Ae) is estimated under varying conditions. First, after analyzing the literature data and using the ascertained thermodynamic data available from the commissioned reviews from the Nuclear Energy Agency (Organization for the Economic Cooperation and Development) Thermochemical DataBank Project on actinides (An) U, Np, and Pu, and from recently determined AenUO2(CO3)3(4-2n)- thermodynamic functions, the formation of AenAnO2(CO3)3(4-2n)- complexes for Pu(VI) and Np(VI) are estimated using linear free energy relationships (LFERs). The data are in good agreement with the sole determination of AePuO2(CO3)32- from Jo et al. (Dalton Trans. 49, 11605), which gives a relative confidence in the LFERs, and allows the application to actual situations. From existing uranium data, first, the impact of the origin of the data on the calculated predominance is addressed under 0.1 M NaCl and atmospheric CO2(g); second, the influence of ionic strength and salinity on predominance is estimated; and finally, the influence of temperature up to 50 °C on the solubility of uraninite in a deep geological radioactive waste storage or disposal site is calculated. For neptunium and plutonium, the impact of the potential log10ß°(AenAnO2(CO3)3(4-2n)-) on Pourbaix diagrams of Pu and Np in Mg-Ca-CO3 media are estimated from Jo et al. (Dalton Trans. 49, 11605) and LFERs. Finally, the application to the speciation of Pu and Np in seawater is proposed.

Sorption behaviour of neptunium in marine and fresh water bottom sediments in Far East area of Russia (Lake Khanka and Amur Bay).

The concentration and sorption behavior of 237Np on the bottom sediments of water bodies in the Far East region of Russia (Lake Khanka and Peter the Great Bay) were studied for the first time. The 237Np concentrations vary from 1.06 × 10-6 to 4.43 × 10-5 mBq g-1 in the bottom sediments of Lake Khanka and from 1.05 × 10-4 to 2.52 × 10-3 mBq g-1 for Amur Bay. The experiment on the adsorption of Np on marine and lake sediment showed that it is sorbed through complexation with silicates (albite, leucite). The Np sorption isotherm on marine sediments is described by the Langmuir equation; the distribution coefficients (Kd) of Np vary from 57 to 588 mL g-1. For lake sediments, the isotherm is described by the Henry equation; the Kd value reaches 935 mL g-1.

Comparison for the simultaneous determination of 237Np and Pu isotopes between TEVA and TK200 resin.

A reliable and stable method was developed to accurately analyze neptunium (237Np) and plutonium isotopes in environmental samples using 242Pu or 236Pu as a tracer. Key parameters, including the valence adjustment conditions and the stabilities of Pu and Np in the different resins, were investigated using TK200 and TEVA resin. It was found that Pu and Np could be efficiently extracted simultaneously using TK200 resin under the optimal loading conditions (6-12 M HNO3) with the addition of 0.01-0.12 M NaNO2 for valence adjustment. These isotopes were subsequently stripped out using a solution containing 0.1 M HCl, 0.05 M HF, and 0.01 M NH2OH·HCl. The separation efficiencies of Pu and Np were >93%, and the chemical yield ratio between Np and Pu was maintained steady at an average of 1.00 ± 0.03 (n > 50) under the optimal conditions. The analytical method was validated by analyzing environmental soil samples spiked with known amounts of 239Pu and 237Np standard solutions or certified reference materials. The measured values of 237Np, 239Pu, and 240Pu obtained by inductively coupled plasma tandem mass spectrometry were consistent with their International Atomic Energy Agency literature values within a 95% confidence interval. These results confirm the reliability and high analytical precision (<6%) of this developed method using Pu as a non-isotopic tracer for monitoring the chemical yield of 237Np. The developed method can also be used for environmental pollutant monitoring and for tracer studies of the 237Np and Pu isotopes.

Assessment of soil-soil solution distribution coefficients of global fallout 237Np and 239Pu in Japanese upland soils.

Neptunium-237 and 239Pu are important radionuclides in the safety assessment related to geological disposal of radioactive waste because of the possibility of long-term exposure to humans. Mobilities of these radionuclides in the environment are of particular importance for their radiation dose evaluation; therefore, in this study, we have made the assessment of the soil-soil solution distribution coefficient (Kd, L/kg) using global fallout 237Np and 239Pu in Japanese upland soils. The Kd values were determined by extracting these radionuclides from 24 soil samples using a laboratory batch method. The desorption Kd values of 237Np ranged from 3.3 × 102 to 1.0 × 104 L/kg, and their geometric mean (GM) and arithmetic mean (AM) were 1.7 × 103 L/kg and 2.6 × 103 L/kg, respectively. The desorption Kd values of 239Pu were found to vary from 9.4 × 103 to 7.1 × 104 L/kg, and their GM and AM were 3.3 × 104 L/kg and 4.0 × 104 L/kg, respectively. In Japanese upland soils, the Kd value of 239Pu was one order of magnitude higher than that of 237Np.

Comparative uptake, translocation, and plant mediated transport of Tc-99, Cs-133, Np-237, and U-238 in Savannah River Site soil columns for the grass species Andropogon virginicus.

This study examines the ability of the grass species Andropogon virginicus to alter the subsurface transport and redistribution of a suite of radionuclides (99Tc, 133Cs (stable analog for 135Cs and 137Cs), 237Np, 238U) with varying chemical behaviors in a Savannah River Site soil via the use of vegetated and unvegetated soil columns. After an acclimation period, a small volume of solution containing all radionuclides was introduced into the columns via Rhizon© pore water sampling tubes. Plants were grown for an additional 4 weeks before shoots were harvested, and columns were prepared for sampling. Plant presence led to decreased radionuclide release from the columns, mainly due to radionuclide specific combinations of system hydrology differences resulting from plant transpiration as well as plant uptake. For the most mobile radionuclides, 99Tc followed by 237Np, plant presence resulted in significantly different soil concentration profiles between vegetated and unvegetated columns, including notable upward migration for 237Np in columns with plants. Additionally, plant uptake of 99Tc was the greatest of all the radionuclides, with plant tissues containing an average of 44 % of the 99Tc, while plant uptake only accounted for <2 % of 237Np and <0.5 % of 133Cs and 238U in the system. Although overall plant uptake of 133Cs and 238U were similar, the majority of 133Cs taken up by plants was associated with 133Cs already available in the aqueous phase while 238U uptake was mainly associated with the solid phase, meaning that plant activity resulted in a fraction of the native 238U being mobilized and thus, made available for plant uptake. Overall, this study quantified the influence of several plant-mediated physical and biogeochemical factors that have significant influence on radionuclide mobility and transport in this complex system which can be further utilized in future system or site-specific environmental transport and risk assessment models.

Hyphomonas sediminis sp. nov., isolated from marine sediment.

A Gram-staining-negative, aerobic and pear-shaped bacterial strain, designated WL0036T, was isolated from coastal sediment sample collected in Nantong city, Jiangsu province of China (120° 51' 13″ E, 32° 6' 26″ N) in October 2020. Strain WL0036T was found to grow at 20-37 °C (optimum, 28 °C) with 0-9.0% NaCl (optimum, 2.5-4.0%) and displayed alkaliphilic growth with the pH range of pH 6.0-10.0 (optimum, pH 7.0-8.0). The polar lipids profile of strain WL0036T included phosphatidylcholine, phosphatidylethanolamine, glycolipid and an unidentified lipid. The major isoprenoid quinone was determined to be Q-11 and the major fatty acids were C16:0, 11-methyl-C18:1ω7c, and summed features 8 (C18:1ω6c and/or C18:1ω7c). The G + C content of genomic DNA was 61.8%. Phylogenetic trees constructed based on 16S rRNA gene sequence and bac120 gene set (a collection of 120 single-copy protein sequences prevalent in bacteria) indicted that strain WL0036T clustered with strains Hyphomonas neptunium ATCC 15444T and H. polymorpha PS728T. The average nucleotide identities between strain WL0036T and strains H. neptunium ATCC 15444T and H. polymorpha PS728T were 80.7% and 81.2%, respectively. Strain WL0036T showed 22.8% and 23.2% of digital DNA-DNA hybridization identities with H. neptunium ATCC 15444T and H. polymorpha PS728T, respectively. As inferred from the phenotypic and genotypic characteristics and the phylogenetic trees, strain WL0036T ought to be recognized as a novel species in genus Hyphomonas, for which the name Hyphomonas sediminis sp. nov. is proposed. The type strain is WL0036T (= MCCC 1K05843T = JCM 34658T = GDMCC 1.2413T).

Highly efficient uptake of neptunium from acidic feeds using two solid phase extraction resins containing diglycolamide-functionalized calix[4]arene ligands.

Two solid phase extraction resins (SPER) were prepared by impregnating solutions of two diglycolamide-functionalized calix[4]arenes in 10% isodecanol in n-dodecane into Chromosorb W, as the stationary phase. While SPER-I contained n-propyl functionalized calix[4]arene, SPER-II contained the calix[4]arene with isopentyl groups at the carboxamide nitrogen atoms. The SPERs were characterized by SEM, TGA, FTIR, etc. and were used for the batch uptake of neptunium(IV) from nitric acid feed solutions. While the uptake of Np(IV) was extremely high with SPER-I (Kd: 47,544 at 3 M nitric acid, ca. 8% extractant loading), SPER-II displayed a significantly lower extraction efficiency (Kd: 13,724 under identical conditions) as indicated by the batch uptake studies. Sorption isotherm studies were carried out which indicated good fitting to the Langmuir model suggesting uptake conforming to monolayer sorption. Fitting to the D-R isotherm model conformed to a chemisorption model. Column studies were also carried out and the elution profiles, obtained with solutions of oxalic acid and nitric acid indicated very sharp peaks suggesting that the column can be used for the separation of Np(IV) from acidic radioactive feeds.

Uranium and neptunium retention mechanisms in Gallionella ferruginea/ferrihydrite systems for remediation purposes.

The ubiquitous ß-Proteobacterium Gallionella ferruginea is known as stalk-forming, microaerophilic iron(II) oxidizer, which rapidly produces iron oxyhydroxide precipitates. Uranium and neptunium sorption on the resulting intermixes of G. ferruginea cells, stalks, extracellular exudates, and precipitated iron oxyhydroxides (BIOS) was compared to sorption to abiotically formed iron oxides and oxyhydroxides. The results show a high sorption capacity of BIOS towards radionuclides at circumneutral pH values with an apparent bulk distribution coefficient (Kd) of 1.23 × 104 L kg-1 for uranium and 3.07 × 105 L kg-1 for neptunium. The spectroscopic approach by X-ray absorption spectroscopy (XAS) and ATR FT-IR spectroscopy, which was applied on BIOS samples, showed the formation of inner-sphere complexes. The structural data obtained at the uranium LIII-edge and the neptunium LIII-edge indicate the formation of bidentate edge-sharing surface complexes, which are known as the main sorption species on abiotic ferrihydrite. Since the rate of iron precipitation in G. ferruginea-dominated systems is 60 times faster than in abiotic systems, more ferrihydrite will be available for immobilization processes of heavy metals and radionuclides in contaminated environments and even in the far-field of high-level nuclear waste repositories.

Combining EXAFS and Computer Simulations to Refine the Structural Description of Actinyls in Water.

EXAFS spectroscopy is one of the most used techniques to solve the structure of actinoid solutions. In this work a systematic analysis of the EXAFS spectra of four actinyl cations, [UO2]2+, [NpO2]2+, [NpO2]+ and [PuO2]2+ has been carried out by comparing experimental results with theoretical spectra. These were obtained by averaging individual contributions from snapshots taken from classical Molecular Dynamics simulations which employed a recently developed [AnO2]2+/+ -H2O force field based on the hydrated ion model using a quantum-mechanical (B3LYP) potential energy surface. Analysis of the complex EXAFS signal shows that both An-Oyl and An-OW single scattering paths as well as multiple scattering ones involving [AnO2]+/2+ molecular cation and first-shell water molecules are mixed up all together to produce a very complex signal. Simulated EXAFS from the B3LYP force field are in reasonable agreement for some of the cases studied, although the k= 6-8 Å-1 region is hard to be reproduced theoretically. Except uranyl, all studied actinyls are open-shell electron configurations, therefore it has been investigated how simulated EXAFS spectra are affected by minute changes of An-O bond distances produced by the inclusion of static and dynamic electron correlation in the quantum mechanical calculations. A [NpO2]+-H2O force field based on a NEVPT2 potential energy surface has been developed. The small structural changes incorporated by the electron correlation on the actinyl aqua ion geometry, typically smaller than 0.07 Å, leads to improve the simulated spectrum with respect to that obtained from the B3LYP force field. For the other open-shell actinyls, [NpO2]2+ and [PuO2]2+, a simplified strategy has been adopted to improve the simulated EXAFS spectrum. It is computed taking as reference structure the NEVPT2 optimized geometry and including the DW factors of their corresponding MD simulations employing the B3LYP force field. A better agreement between the experimental and the simulated EXAFS spectra is found, confirming the a priori guess that the inclusion of dynamic and static correlation refine the structural description of the open-shell actinyl aqua ions.

First study of 237Np in Chinese soils: Source, distribution and mobility in comparison with plutonium isotopes.

In this study, the distribution and migration of 237Np and 239+240Pu in soils in the vicinity (<5 km) of Qinshan and Tianwan Nuclear Power Plants in China were studied, which is the first specific study of global fallout 237Np in Chinese soils. The 237Np and 239+240Pu concentrations in surface soils showed large spatial inhomogeneity. A remarkable 239+240Pu concentration (4.783 mBq/g) was observed in a surface soil near Qinshan NPP and stands for the ever reported highest value in the Chinese soils. The inventories of 239+240Pu in two Qinshan and Tianwan soil cores were estimated to be 128.8 Bq/m2 and 121.0 Bq/m2, respectively; while the 237Np inventories were 0.039 Bq/m2 and 0.035 Bq/m2 at these sites, respectively. The 240Pu/239Pu atomic ratios in these soils indicated that the global fallout is the main source of Pu in these regions. However, the non-isotopic 237Np/239Pu atomic ratio in environmental soil is not a sensitive indicator for source identification. Furthermore, we conducted pilot study on the migration behaviors of 237Np and 239+240Pu in soil core at Qinshan site with the Convection-Dispersion Equation (CDE) model. The obtained apparent dispersion coefficients of 237Np (2.82 ± 2.06 cm2/y) was 5 times higher than that of 239+240Pu (0.57 ± 0.16 cm2/y), proving that 237Np has stronger migration ability than Pu isotopes in the Qinshan soil. Finally, we predicted that with the increase of migration time, both 237Np and 239+240Pu concentration in the soil will gradually become more evenly distributed among different soil layers due to the dominant dispersion effects.

Dosimetric modeling of Tc-99, Cs-137, Np-237, and U-238 in the grass species Andropogon Virginicus: Development and comparison of stylized, voxel, and hybrid phantom geometry.

This paper discusses the development, comparison, and application of three anatomically representative computational phantoms for the grass species Andropogon virginicus, an indigenous grass species in the Southeastern United States. Specifically, the phantoms developed in this work are: (1) a stylized phantom where plant organs (roots or shoots) are represented by simple geometric shapes, (2) a voxel phantom developed from micro-CT imagery of a plant specimen, and (3) a hybrid phantom resulting from the refinement of (2) by use of non-uniform rational basis spline (NURBS) surfaces. For each computational phantom, Monte Carlo dosimetric modeling was utilized to determine whole-organism and organ specific dose coefficients (DC) associated with external and internal exposure to 99Tc, 137Cs, 237Np, and 238U for A. virginicus. Model DCs were compared to each other and to current values for the ICRP reference wild grass in order to determine if noteworthy differences resulted from the utilization of more anatomically realistic phantom geometry. Modeled internal DCs were comparable with ICRP values. However, modeled external DCs were more variable with respect to ICRP values; this is proposed to be primarily due to differences in organism and source geometry definitions. Overall, the three anatomical phantoms were reasonably consistent. Some noticeable differences in internal DCs were observed between the stylized model and the voxel or hybrid models for external DCs for shoots and for cases of crossfire between plant organs. Additionally, uptake data from previous hydroponic (HP) experiments was applied in conjunction with hybrid model DCs to determine dose rates to the plant from individual radionuclides as an example of practical application. Although the models within are applied to a small-scale, hypothetical scenario as proof-of-principle, the potential, real-world utility of such complex dosimetric models for non-human biota is discussed, and a fit-for purpose approach for application of these models is proposed.

Kinetics of neptunium sorption and desorption in the presence of aluminum (hydr)oxide minerals: Evidence for multi-step desorption at low pH.

Kinetics analyses of sorption and desorption provide important insight into reaction mechanisms occurring at the mineral-water interface. They are also needed to determine when equilibrium is achieved, identify intermediate chemical species, and inform models describing neptunium mobility. Neptunium sorption to and desorption from four different aluminum (hydr)oxides - bayerite (α-Al(OH)3), gibbsite (γ-Al(OH)3), corundum (α-Al2O3), and γ-alumina (γ-Al2O3) - were investigated as a function of mineral concentration (5 - 170 m2 L-1), neptunium concentration (10-9 - 10-7 M), and pH (5.5 - 10.5). Neptunium sorption was characterized by a two-step reaction with an initial fast sorption step occurring within minutes followed by a slower equilibrium process, which was attributed to initial sorption of neptunium to a small number of strong sorption sites followed by sorption of neptunium to a larger number of weak sorption sites. The kinetics data were modeled using the linear and non-linear forms of the pseudo-first and pseudo-second order rate equations and the goodness of fit parameters were compared. Non-linear pseudo-second order rate constants described neptunium sorption to aluminum (hydr)oxides most accurately and were used to determine the reaction orders with respect to mineral concentration and [H+]. Neptunium desorption experiments demonstrated that the desorption mechanism changed as a function of pH and that the forward and reverse reactions were not equivalent. At pH ≥ 7.5, desorption reached steady-state within an hour and was accurately described by the non-linear pseudo-second order rate equations. A desorption plateau was observed at pH 5.5 that could not be described by either pseudo-first or -second order kinetics, suggesting the possibility of a multi-step desorption reaction. The comparatively slow desorption kinetics observed here suggests that sorbed neptunium could be slowly released back into the aqueous phase and act as a continuous source of contamination to the environment.

Determination of kinetic parameters of redox reactions using CE-ICP-MS: A case study for the reduction of Np(V) by hydroxylamine hydrochloride.

The rate constants k of the reduction of 5 × 10-5  M Np(V) to Np(IV) by hydroxylamine hydrochloride (HAHCl) in 1 M HCl have been determined by CE-ICP-MS in the temperature range of ϑ = 30-70°C and with varying concentrations of HAHCl from 1 to 7.2 M. The reaction was found to have (pseudo)first order kinetics with respect to HAHCl. The experimental results for k ranged from 0.0029(1) min-1 (ϑ = 40°C, c(HAHCl) = 3 M) to 0.039(7) min-1 (ϑ = 60°C, c(HAHCl) = 7.2 M). The activation energy of the reaction was determined as EA  = (72 ± 10) kJ/mol. These results and a comparison with literature data show that the coupling of CE to ICP-MS provides a powerful analytical tool for the investigation of the kinetic aspects of redox reactions of actinides at low concentrations. On the basis of this proof-of-principle study, the method presented here can be extended to the investigation of the kinetic parameters of other redox systems containing different actinides (or transition metals) and oxidants/reductants.

A neptunium(v)-mediated interwoven transuranium-rotaxane network incorporating a mechanically interlocked [c2]daisy chain unit.

As an extension of actinide-rotaxane complexes from uranium to transuranium, we report the first crystal structure of a neptunium-rotaxane complex, NRCP-1, in which an interwoven neptunium(v)-rotaxane coordination network incorporating a mechanically-interlocked [c2]daisy chain unit is promoted via the simultaneous coordination of cucurbituril (CB6) and axle molecules in [2]pseudorotaxane to NpV.

Separation of neptunium (IV) from actinides by solid phase extraction using a resin containing Aliquat 336.

An extraction chromatographic resin material containing Aliquat 336 as the liquid anion exchanger extractant and Chromosorb W as the solid support was prepared and tested for the uptake of UO22+, Np4+, Pu4+, and Pu3+ from nitric acid feed solutions. The resin beads were characterized by thermogravimetry/differential thermogravimetry (TG/DTG) and scanning electron microscopy (SEM) surface morphology analysis. The uptake trend for the metal ions from 3 M HNO3 was found to be Pu4+ >> Np4+ >> UO22+ > Pu3+ which clearly followed the trend of their ionic potentials. In view of the significant difference in the uptake of Np4+ with respect to those of UO22+ and Pu3+, a separation scheme was developed for the selective separation of Np from feeds containing U, Np and Pu in nitric acid. The purity of the product was verified by alpha spectrometry.

Dose-response relationships between internally-deposited uranium and select health outcomes in gaseous diffusion plant workers, 1948-2011.

OBJECTIVE: To examine dose-response relationships between internal uranium exposures and select outcomes among a cohort of uranium enrichment workers. METHODS: Cox regression was conducted to examine associations between selected health outcomes and cumulative internal uranium with consideration for external ionizing radiation, work-related medical X-rays and contaminant radionuclides technetium (99 Tc) and plutonium (239 Pu) as potential confounders. RESULTS: Elevated and monotonically increasing mortality risks were observed for kidney cancer, chronic renal diseases, and multiple myeloma, and the association with internal uranium absorbed organ dose was statistically significant for multiple myeloma. Adjustment for potential confounders had minimal impact on the risk estimates. CONCLUSION: Kidney cancer, chronic renal disease, and multiple myeloma mortality risks were elevated with increasing internal uranium absorbed organ dose. The findings add to evidence of an association between internal exposure to uranium and cancer. Future investigation includes a study of cancer incidence in this cohort.

Mobility of Aqueous and Colloidal Neptunium Species in Field Lysimeter Experiments.

Due to its radiotoxicity, long half-life, and potentially high environmental mobility, neptunium transport is of paramount importance for risk assessment and safety. Environmental transport of neptunium through field lysimeters at the Savannah River Site was observed from both oxidized (Np(V)) and reduced (Np(IV)) source materials. While transport from oxidized neptunium sources was expected, the unexpected transport from reduced neptunium sources spurred further investigation into transport mechanisms. Partial oxidation of the reduced neptunium source resulted in significant release and transport into the mobile aqueous phase, though a reduced colloidal neptunium species appears to have also been present, enhancing neptunium mobility over shorter distances. These field and laboratory experiments demonstrate the multiple controls on neptunium vadose zone transport and chemical behavior, as well as the need for thorough understanding of radionuclide source terms for long-term risk prediction.

Comparison of partial least squares and random forests for evaluating relationship between phenolics and bioactivities of Neptunia oleracea.

BACKGROUND: Neptunia oleracea is a plant consumed as a vegetable and which has been used as a folk remedy for several diseases. Herein, two regression models (partial least squares, PLS; and random forest, RF) in a metabolomics approach were compared and applied to the evaluation of the relationship between phenolics and bioactivities of N. oleracea. In addition, the effects of different extraction conditions on the phenolic constituents were assessed by pattern recognition analysis. RESULTS: Comparison of the PLS and RF showed that RF exhibited poorer generalization and hence poorer predictive performance. Both the regression coefficient of PLS and the variable importance of RF revealed that quercetin and kaempferol derivatives, caffeic acid and vitexin-2-O-rhamnoside were significant towards the tested bioactivities. Furthermore, principal component analysis (PCA) and partial least squares-discriminant analysis (PLS-DA) results showed that sonication and absolute ethanol are the preferable extraction method and ethanol ratio, respectively, to produce N. oleracea extracts with high phenolic levels and therefore high DPPH scavenging and α-glucosidase inhibitory activities. CONCLUSION: Both PLS and RF are useful regression models in metabolomics studies. This work provides insight into the performance of different multivariate data analysis tools and the effects of different extraction conditions on the extraction of desired phenolics from plants. © 2017 Society of Chemical Industry.

On the sequential separation and quantification of 237Np, 241Am, thorium, plutonium, and uranium isotopes in environmental and urine samples.

The implementation of the one-pass-through separation technique using two stacked chromatography columns of TEVA - TRU resins for the separation of 237Np, 241Am, thorium, plutonium and uranium from environmental and urine samples was investigated. The sequential separation technique proved to be successful and gave similar results to those obtained when using individual separations. The analysis time was considerably improved. The amount of chemical waste was also reduced by 50% and the use of HClO4 was avoided. The technique of ICP-MS was also investigated as a complementary technique to alpha-spectrometry.

Enzymatic activity of the CaM-PDE1 system upon addition of actinyl ions.

The threat of a dirty bomb which could cause internal contamination has been of major concern for the past decades. Because of their high chemical toxicity and their presence in the nuclear fuel cycle, uranium and neptunium are two actinides of high interest. Calmodulin (CaM) which is a ubiquitous protein present in all eukaryotic cells and is involved in calcium-dependent signaling pathways has a known affinity for uranyl and neptunyl ions. The impact of the complexation of these actinides on the physiological response of the protein remains, however, largely unknown. An isothermal titration calorimetry (ITC) was developed to monitor in vitro the enzymatic activity of the phosphodiesterase enzyme which is known to be activated by CaM and calcium. This approach showed that addition of actinyl ions (AnO2n+), uranyl (UO22+) and neptunyl (NpO2+), resulted in a decrease of the enzymatic activity, due to the formation of CaM-actinide complexes, which inhibit the enzyme and alter its interaction with the substrate by direct interaction. Results from dynamic light scattering rationalized this result by showing that the CaM-actinyl complexes adopted a specific conformation different from that of the CaM-Ca2+ complex. The effect of actinides could be reversed using a hydroxypyridonate actinide decorporation agent (5-LIO(Me-3,2-HOPO)) in the experimental medium demonstrating its capacity to efficiently bind the actinides and restore the calcium-dependent enzyme activation.