Behavior Of Np Research Articles

Confocal Surface-Enhanced Raman Imaging of the Intestinal Barrier Crossing Behavior of Model Nanoplastics in Daphnia Magna.

Nanoplastics (nP) pose hazards to aquatic animals once they are ingested. Significant knowledge gaps exist regarding the nP translocation across the animal intestine, which is the first barrier between the ingested nP and the animal body. We examined the intestinal barrier crossing behavior of nP in an aquatic animal model (Daphnia magna) and determined the translocation mechanism with the help of model "core-shell" polystyrene nanoplastics (nPS) and confocal surface-enhanced Raman spectroscopy (SERS). The Raman reporter (4-mercaptobenzoic acid)-tagged gold "core" of the model nPS enables sensitive and reliable particle imaging by confocal SERS. This method detected SERS signals of model nPS concentration as low as 4.1 × 109 particles/L (equivalent to 0.27 μg/L PS "shell" concentration). The translocation was observed with the help of multilayer stacked Raman maps of SERS signals of the model nPS. With a higher concentration or longer exposure time of the model nPS, uptake and translocation of the plastic particles increased. In addition, we demonstrated that clathrin-dependent endocytosis and macropinocytosis were two major mechanisms underlying the translocation. This study contributes to a mechanistic understanding of nP translocation by using the pioneering model nPS and an analytical toolkit, which undergird further investigations into nP behavior and health effects in aquatic species.

Collision Oxidation Behavior of Silver Nanoparticles in Alkaline Solution.

In recent years, silver nanoparticles (Ag NPs) have been used as positive electrode material for zinc/silver batteries, and the silver oxides formed during the charging process determine the discharge performance of batteries. Therefore, it is important to study the oxidation behavior of Ag NPs in alkaline solution. Single-nanoparticle collision is an important tool for analyzing oxidation behavior of individual nanoparticles. Based on thermodynamic information from collision events, it is known that oxidation products are potential-dependent and size-dependent. Based on dynamic information, including collisional peak shapes and duration time, it was observed that the Ag NP collision oxidation process changed from stepwise oxidation to direct oxidation as the potential increased or size decreased. This work provides guidance for application of Ag NPs in zinc/silver batteries and proposed a strategy for oxidation behavior of individual NP that could be tracked in situ through an all-encompassing view of thermodynamic and dynamic information.

Np(V) Retention at the Illite du Puy Surface.

In this study, Np(V) retention on Illite du Puy (IdP) was investigated since it is essential for understanding the migration behavior of Np in argillaceous environments. The presence of structural Fe(III) and Fe(II) in IdP was confirmed by Fe K-edge X-ray absorption near-edge structure (XANES) and 57Fe Mössbauer spectroscopy. In batch sorption experiments, a higher Np sorption affinity to IdP was found than to Wyoming smectite or iron-free synthetic montmorillonite. An increase of the relative Np(IV) ratio sorbed onto IdP with decreasing pH was observed by solvent extraction (up to (24 ± 2)% at pH 5, c0(Np) = 10-6 mol/L). Furthermore, up to (33 ± 5)% Np(IV) could be detected in IdP diffusion samples at pH 5. Respective Np M5-edge high-energy resolution (HR-) XANES spectra suggested the presence of Np(IV/V) mixtures and weakened axial bond covalency of the NpO2+ species sorbed onto IdP. Np L3-edge extended X-ray absorption fine structure (EXAFS) analysis showed that significant fractions of Np were coordinated to Fe─O entities at pH 9. This highlights the potential role of Fe(II/III) clay edge sites as a strong Np(V) surface complex partner and points to the partial reduction of sorbed Np(V) to Np(IV) via structural Fe(II).

Simultaneous determination of femtogram levels of 237Np, 239Pu, and 240Pu in environmental solid samples using extraction chromatography and ICP-MS/MS

An analytical method based on triple quadrupole inductively coupled plasma mass spectrometry (ICP-MS/MS) was developed for simultaneous determination of femtogram levels of 237Np, 239Pu, and 240Pu in environmental samples. By carefully controlling the valence states of Np and Pu in the entire separation procedure using a simple single extraction chromatographic column (TK200), the consistent behavior of Np and Pu was achieved, allowing for the reliable application of 242Pu as the chemical yield tracer for 237Np, 239Pu, and 240Pu. A high decontamination factor of 3.2 × 107 for the most critical interfering element, uranium, was achieved in the chemical separation step. The interferences of 238U1H+ and peak tailing of 238U+ during the measurement of plutonium isotopes were effectively eliminated by utilizing 7.5 mL/min He–1.1 mL/min CO2 as reaction gases in the octupole collision/reaction cell and employing sequential quadrupole mode for mass separation in ICP-MS/MS. Specifically, the interference of 238U1H+ was reduced to 10−6 and the peak tailing of 238U+ to 10−10, surpassing the performance of measurement method without reaction gases by 3 orders of magnitude. The developed method enables the accurate determination of femtogram levels of 237Np, 239Pu, and 240Pu in the samples with U/Np and U/Pu atom ratios of up to 1017 and 1012, respectively. The developed method was validated by analyzing standard reference materials and spiked soil samples.

Effect of ply structure on mechanical hysteresis behavior in 3D needle-punched C/SiC composites

For 3D needle-punch C/SiC composite, four ply structures were adopted to fabricate the composite using the chemical vapor deposition (CVD) and reactive infiltration (RI) methods. Effects of ply structure on the mechanical hysteresis behavior of the 3D NP C/SiC composites were analyzed. The hysteresis-based damage parameters (i.e., unloading/reloading inverse tangent modulus (UITM/RITM), interface slip parameter, and hysteresis width) were analytically derived from the hysteresis theory. Evolution of the hysteresis-based damage parameters with increasing peak stress was analyzed. Comparison analysis of the mechanical hysteresis behavior between the 3D NP-C/SiC with four ply structures were conducted. The hysteresis-based damage parameters reflect the internal damages under cyclic loading. The higher the values of hysteresis-based damage parameters, the more seriously of the damages occurred in the composite.

Behavior of Np(V) in HCOOH Solutions Containing H2O and HClO4

Behavior of Np(V) in HCOOH Solutions Containing H2O and HClO4

Hydroxypyridinone-based stabilization of Np(IV) enabling efficient U/Np/Pu separations in the Adapted PUREX process

The classical process to recover uranium (U) and plutonium (Pu) from used nuclear fuel using tributyl phosphate (TBP), namely the Plutonium Uranium Redox EXtraction (PUREX) process, is complicated by the persistent presence of neptunium (Np) and thus requires extra purification steps. The concept of Adapted PUREX seeks to achieve Np recovery by adjusting the valence of the metal more effectively, thereby controlling its behavior more precisely. This study introduces the use of an aqueous hydroxypyridinone chelator, 3,4,3-LI(1,2-HOPO) (abbreviated as HOPO), to dictate the behavior of Np for recovery and meanwhile simplify cumbersome reprocessing steps. The interactions between Np and HOPO were probed mechanistically by way of absorption spectrophotometry, in conjunction with cyclic voltammetry. UV–Vis-NIR spectra illustrated the reduction of NpO22+ to Np4+, with a fast reaction rate. Cyclic voltammetry revealed quasi-reversible processes between the oxidized and reduced forms of the ligand and its Np complexes. The corresponding heterogeneous rate constants (k0) were estimated from the peak-to-peak separation potentials (ΔEp), at ~ 4 – 35 μm/s for both HOPO and NpHOPO, with scan rates of 0.01 – 0.4 V/s. Meanwhile, the electromotive force (EMF) as well as the change of Gibbs free energy (ΔG) were assessed from the half-wave potential (E1/2), demonstrating the completeness of NpO22+ reduction to Np4+ by HOPO. The cumulative formation constant of the resulting NpHOPO complex (logβ101) was determined by metal competition titration to be 42.0 ± 0.6, corroborating the extraordinarily high affinity of HOPO to tetravalent metal ions. The prowess of valence control by HOPO and the high stability of the formed complex resulted in enhanced separations of Np from U and of Pu from U, with a maximum separation factor of ~7000 for both, nearly 90- and 10300-fold higher, respectively, than the values obtained using conventional PUREX formulae.

Distribution of TiO2 Nanoparticles in Acidic and Alkaline Soil and Their Accumulation by Aspergillus niger

The nanoparticles of TiO2 (TiO2 NP) have been used as a plant-growth stimulant or catalyst in pesticide formulas. However, due to high resistance of TiO2 NP to abiotic weathering, dissolved Ti is unlikely to act as an active compound in these preparations. Even if soil is acidic, TiO2 NP do not dissolve easily and preferably remain as undissolved particles. The low dissolution rates of inorganic nanoparticles in the soil environment make Ti in TiO2 NP largely unavailable for plants and soil microorganisms. To characterize the behavior of TiO2 NP in soil under different pH conditions, we analyzed TiO2 NP-size distribution in two soil materials, an alkaline and acidic one. We also cultivated Aspergillus niger, a fungus ubiquitously found in soils, in the growth medium spiked with TiO2 NP to assess accumulation of the nanoparticles in fungus. In soil suspensions, the dissolved Ti was present in low concentrations (up to 0.010 mg L−1). Most of the TiO2 NP remained in particulate form or appeared as aggregates sized 100–450 nm. In experiment on Ti accumulation by A. niger, TiO2 NP either settled down to the bottom of the flask with growth medium or were actually accumulated by the fungus; about 7.5% of TiO2 NP were accumulated in fungal mycelia. Most of the TiO2 NP remain in particulate form in soil solutions, regardless of soil pH. Filamentous fungus A. niger has the ability to accumulate bioavailable TiO2 NP, which hints at the possibility that some soil fungi can affect spatial distribution of this type of nanoparticles in soils.

Sorption of Cs(I) and Np(V) onto Clays from the Ostrozhanskoe Deposit (Belarus)

The sorption behavior of Np(V) and Cs(I) on natural and acid-treated bentonite-like clay of Ostro-zhanskoe deposit (Belarus) was studied in a wide range of radionuclide concentrations and pH values of the suspension. The sorption equilibrium with both radionuclides is attained within the first minutes of the interac¬tion. The sorption behavior on the untreated and treated clay is similar. Based on the experimental data, ther-modynamic modeling of the Cs(I) and Np(V) sorption onto the clays was performed.

Effects of soil organic carbon (SOC) content and accessibility in subsoils on the sorption processes of the model pollutants nonylphenol (4-n-NP) and perfluorooctanoic acid (PFOA)

Subsoils control the release of hydrophobic pollutants to groundwater systems, but the role of subsoil soil organic carbon (SOC) in sorption processes of hydrophobic organic pollutants remains unclear. Thus, this study aimed to understand the role of subsoil SOC in sorption processes of 4-n-nonylphenol (NP) and perfluorooctanoic acid (PFOA) as model pollutants. To characterize the sorption behavior of NP and PFOA, 42 sub- and 54 topsoil samples were used for batch experiments. Differences in NP and PFOA sorption between sub- and topsoil samples and its mechanisms were identified using multiple regression analysis. Generally, the sorption of NP and PFOA was linear in all samples. The sorption of NP to soil samples (logKD = 1.78–3.68) was significantly higher and less variable than that of PFOA (logKD = −0.97–1.44). In topsoils, SOC content had the highest influence on NP and PFOA sorption. For NP, hydrophobic interactions between NP and SOC were identified as the most important sorption mechanism. For PFOA, hydrophobic as well as electrostatic interactions were determined depending on soil pH. In subsoils, the relevance of SOC content for pollutant sorption decreased drastically. For NP, not SOC content but rather SOC quality was relevant in SOC poor subsoils. For PFOA, clay and iron oxide content were found to be relevant for pollutant interactions with the solid phase. Thus, especially in SOC depleted subsoils, the sorption potential for PFOA remained unpredictable.

Effect of Soil Organic Matter, Soil pH, and Moisture Content on Solubility and Dissolution Rate of CuO NPs in Soil.

The objectives of this research were to quantify the impact of organic matter content, soil pH and moisture content on the dissolution rate and solubility of copper oxide nanoparticles (CuO NPs) in soil, and to develop an empirical model to predict the dissolution kinetics of CuO NPs in soil. CuO NPs were dosed into standard LUFA soils with various moisture content, pH and organic carbon content. Chemical extractions were applied to measure the CuO NP dissolution kinetics. Doubling the reactive organic carbon content in LUFA 2.1 soil increased the solubility of CuO NP 2.7-fold but did not change the dissolution rate constant. Increasing the soil pH from 5.9 to 6.8 in LUFA 2.2 soil decreased the dissolution rate constant from 0.56 mol1/3·kg1/3·s-1 to 0.17 mol1/3·kg1/3·s-1 without changing the solubility of CuO NP in soil. For six soils, the solubility of CuO NP correlated well with soil organic matter content ( R2 = 0.89) independent of soil pH. In contrast, the dissolution rate constant correlated with pH for pH < 6.3 ( R2 = 0.89), independent of soil organic matter content. These relationships predicted the solubility and dissolution rate constants of CuO NP in two test soils (pH 5.0 and pH 7.6). Moisture content showed negligible impact on the dissolution kinetics of CuO NPs. Our study suggests that soil pH and organic matter content affect the dissolution behavior of CuO NP in soil in a predictable manner.

Unexpected Behavior of Np in Oxo-selenate/Oxo-selenite Systems.

A study of neptunium (Np) chemistry in the complex oxo-selenium system has been performed. Hereby, two sets of precipitation experiments were conducted, investigating the influence of the initial oxidation state of selenium using SeIVO2 and H2SeVIO4 with NpV in alkali nitrate solution, keeping the ratio of Np/Se constant. Surprising results were observed. Five novel neptunium and selenium bearing compounds have been obtained by slow evaporation from aqueous solution. The novel NpIV phase K4-x[Np(SeO3)4-x(HSeO3)x]·(H2O)1.5 (1) crystallizes in green-colored, plate-shaped crystals and was obtained by adding SeO2 and ANO3 to a NpV stock solution. Single-crystal X-ray diffraction reveals one-dimensional chain structures composed of square antiprismatic NpO8 polyhedra linked via four trigonal pyramidal SeO3 and HSeO3 units. Raman spectral analysis supports the presence of both selenite and hydroselenite due to the presence of corresponding modes within the spectra. The addition of selenic acid to a NpV stock solution resulted in the precipitation of elongated rose prisms of K2[(NpO2)2(SeO4)3(H2O)2]·(H2O)1.5 (2), Rb2[(NpO2)2(SeO4)3(H2O)2]·(H2O)2 (3) and K9[(NpO2)9(SeO4)13.5(H2O)6]·(H2O)12 (4) as well as light red plates of Cs2[(NpO2)2(SeO4)3] (5). To our knowledge, this is the first report of NpVI selenates. All four structures show two-dimensional layered structures with alkali cations acting as charge balancing counter cations. Hereby the layers of compounds 2 and 3 are found to be orientational geometric isomers. Distinctly different phenomena are made responsible for the phase formation within these systems. The kinetically driven process of NpV disproportionation led to the formation of the NpIV selenites in the SeIV-based system, whereas the oxidation of NpV by reduction of nitrate in acidic conditions is responsible for the formation of the NpVI selenates in the SeVI system. The influence of air oxygen is also discussed for the latter reaction.

Influence of metal-support interaction on nitrate hydrogenation over Rh and Rh-Cu nanoparticles dispersed on Al2O3 and TiO2 supports

Well-defined Rh and Rh-Cu nanoparticles (NP's) of 1.6nm and 1.3nm, respectively, were synthesized by alkaline polyol method and then dispersed on insulating (Al2O3) and semiconducting (TiO2) supports. Both colloidal NP's and supported NP's were characterized using various experimental methods (TEM, XPS, XRD, etc.) to gather information about their specific morphology, structure and chemical state. The effects of size and support on the catalytic behavior of NP's for nitrate hydrogenation reaction were analyzed. Oxide supports, especially TiO2, were found to have a strong positive effect on the catalytic activity of metallic NP's. The non-supported, colloidal, Rh and Rh-Cu NP's are either inactive or posses very low hydrogenation activity. For supported materials, the intimate contact between two metals (i.e. Rh-Cu) is required to attain good hydrogenation activity. The strong metal-support interaction, induced by hydrogen spillover, is a key point in determining hydrogenation activity. The Rh-Cu NP's dispersed on TiO2 are extremely active for NO3− and NO2− (intermediate) deep hydrogenation, with high selectivity for NH4+. The hydrogenation activity of Rh-Cu NP's supported on Al2O3 is hindered considerably, the main products of NO3− hydrogenation being NO2− intermediate.

Sorption Behavior of Np(V) on Microbe Pure Culture and Consortia

The sorption of Np(V) by microbe consortia and by a single pure culture of the Fe-reducing bacterium Shewanella putrefaciens was studied at pH levels between 3 and 7 under resting cell conditions. The sorption of Np(V) by S. putrefaciens obtained under inert conditions and by the consortia in the aerated condition was higher than that by S. putrefaciens under aerobic conditions at low pH below 5, strongly suggesting the presence of another mechanism other than the adsorption of Np(V) on the microbial cell surface, i.e., by reduction to Np(IV).

Temporal evolution of 137Cs, 237Np, and 239+240Pu and estimated vertical 239+240Pu export in the northwestern Mediterranean Sea

The evolution of 137Cs, 237Np and 239+240Pu at the DYFAMED station (NW Mediterranean) is discussed in relation to physical processes, downward fluxes of particles, and changes in the main input sources. The data set presented in this study represents the first complete 237Np vertical profiles (0.12–0.27μBqL−1), and constitutes a baseline measurement to assess future changes. A similar behavior of Cs and Np has been evidenced, confirming that Np behaves conservatively. While the 137Cs decrease has been driven by its radioactive decay, the vertical distribution of 237Np has not substantially changed over the last decade. In the absence of recent major inputs, a homogenization of their vertical distribution occurred, partly due to deep convection events that became more intense during the last decade. In contrast, 239+240Pu surface levels in the NW Mediterranean waters have fallen in the past four decades by a factor of 5. This decrease in surface has been balanced by higher concentrations in the deep-water layers. A first estimate of the downward 239+240Pu fluxes in the NW Mediterranean Sea is proposed over more than two decades. This estimation, based on the DYFAMED sediment trap time-series data and published 239+240Pu flux measurements, suggests that sinking particles have accounted for 60–90% of the upper layer (0–200m) Pu inventory loss over the period 1989–2013. The upper layer residence time of Pu is estimated to be ~28years, twice as long as the residence time estimated for the whole western Mediterranean (~15years). This difference highlights the slow removal of Pu in the open waters of the NW Mediterranean and confirms that most of the Pu removal occurs along the coastal margin where sedimentation rates are high.

Np(V) uptake by bentonite clay: Effect of accessory Fe oxides/hydroxides on sorption and speciation

Batch sorption experiments on thoroughly characterized bentonites and thermodynamic modeling studies were conducted to reveal the role of iron-containing accessory phases on the interfacial behavior of Np(V). Bentonite clays from different industrial deposits with varying total iron contents were selected for the studies. The samples were characterized by XRD, Mossbauer spectroscopy, XRF, HRTEM, SEM-EDX and other techniques, and wherever possible, the accessory iron phases were identified and quantified. Thermodynamic modeling using available surface complexation data revealed the dominant role of the goethite accessory phase, which was present as nanoparticles, in Np(V) sorption at trace level concentrations (10−14 M). This fact is independently supported by the combination of SEM-EDX and α-track radiography. These studies illustrate the important role that accessory minerals can play in radionuclides sorption data. This is important to the understanding and modeling of the molecular-level speciation of radionuclides.

Controls on the Fate and Speciation of Np(V) During Iron (Oxyhydr)oxide Crystallization.

The speciation and fate of neptunium as Np(V)O2(+) during the crystallization of ferrihydrite to hematite and goethite was explored in a range of systems. Adsorption of NpO2(+) to iron(III) (oxyhydr)oxide phases was reversible and, for ferrihydrite, occurred through the formation of mononuclear bidentate surface complexes. By contrast, chemical extractions and X-ray absorption spectroscopy (XAS) analyses showed the incorporation of Np(V) into the structure of hematite during its crystallization from ferrihydrite (pH 10.5). This occurred through direct replacement of octahedrally coordinated Fe(III) by Np(V) in neptunate-like coordination. Subsequent analyses on mixed goethite and hematite crystallization products (pH 9.5 and 11) showed that Np(V) was incorporated during crystallization. Conversely, there was limited evidence for Np(V) incorporation during goethite crystallization at the extreme pH of 13.3. This is likely due to the formation of a Np(V) hydroxide precipitate preventing incorporation into the goethite particles. Overall these data highlight the complex behavior of Np(V) during the crystallization of iron(III) (oxyhydr)oxides, and demonstrate clear evidence for neptunium incorporation into environmentally important mineral phases. This extends our knowledge of the range of geochemical conditions under which there is potential for long-term immobilization of radiotoxic Np in natural and engineered environments.

Np(V) solubility, speciation and solid phase formation in alkaline CaCl2 solutions. Part II: Thermodynamics and implications for source term estimations of nuclear waste disposal

Abstract The results of comprehensive solubility experiments with Np(V) in dilute to concentrated CaCl2 solutions which included the spectroscopic investigation of the predominant aqueous Np(V) species and the thorough analysis of the solubility controlling Np(V) solid phases [1](Fellhauer, D., Rothe, J., Altmaier, M., Neck, V., Runke, J., Wiss, T., Fanghänel, Th., Np(V) solubility, speciation and solid phase formation in alkaline CaCl2 solutions. Part I: Experimental solubility (Radiochim. Acta, DOI 10.1515/ract-2015-2489), in the following referred to as “Part I”), showed that the concentration of Np(V) in these systems is limited by equilibrium reactions between previously unknown (qua)ternary solid compounds, CaNpO2(OH)2.6Cl0.4 · 2H2O(s) (I), Ca0.5NpO2(OH)2 · 1.3H2O(s) (II) and Ca0.5NpO2(OH)2(s) (III), and ternary aqueous complexes of Np(V) with the general formulae Ca x [NpO2(OH)2]2x–1, Ca y [NpO2(OH)5]2y–4 with y ≈ 2.4 ± 1.5 (EXAFS result) and innersphere Np(V) chloro complexes, Ca z [NpO2Cl]2z+ with z = 0 and 1 (EXAFS result). A systematic thermodynamic evaluation of the experimental solubility data based on the specific ion interaction theory (SIT) and the Pitzer approach is performed. The stoichiometries of the ternary hydrolysis complexes are assessed as Ca[NpO2(OH)2]+ and Ca3[NpO2(OH)5]2+. The corresponding thermodynamic solubility and complex formation constants at I = 0 as well as the ion interaction parameters (SIT and Pitzer) were derived yielding a comprehensive geochemical model for the Np(V) solubility behavior in pH neutral and alkaline CaCl2 solutions over a large range of ionic strengths. This significantly improves source term estimations for scenarios with calcium dominated aquatic systems. The principally different behavior of Np(V) in NaCl and CaCl2 solutions is highlighted, and the impact of the new findings on geochemical modelling of systems relevant for nuclear waste disposal is discussed.

Np(V) solubility, speciation and solid phase formation in alkaline CaCl2 solutions. Part I: Experimental results

Abstract The aqueous chemistry of Np(V) in alkaline 0.01 to 5.5 M CaCl2 solutions at T = 23 ± 2 ℃ was thoroughly studied by long-term batch solubility experiments from both over- and undersaturation. Applying a comprehensive set of experimental and spectroscopic techniques including Vis/NIR and Np L3-edge EXAFS, the solubility controlling Np(V) solid phases and the predominant aqueous Np(V) species were identified. The results demonstrate that the solubility behavior of Np(V) in alkaline CaCl2 solutions differs completely from the one reported for alkaline NaCl and NaClO4 solutions: as solubility limiting solid phases, three so far not considered Ca-Np(V)-OH compounds were identified and their solubility and stability in CaCl2 solutions analyzed: CaNpO2(OH)2.6Cl0.4 · 2H2O(s) (I) (metastable), Ca0.5NpO2(OH)2 · 1.3H2O(s) (II) (long-term metastable) and Ca0.5NpO2(OH)2(s) (III) (stable). The considerably higher stability of these (qua)ternary phases which readily form in alkaline CaCl2 solutions from oversaturation (addition of NpO2 +) and undersaturation (addition of binary NpO2OH(am)) limit the Np(V) equilibrium concentrations to values that are up to 3 log-units lower compared to those for NpO2OH(am) in NaCl and NaClO4 systems. Based on systematic evaluation of the pH dependence (solubility curve slopes), Vis/NIR and EXAFS spectroscopic information, unhydrolysed NpO2 + and innersphere chloro complexes, NpO2Cl(aq) and Ca z [NpO2Cl]2z+ with z = 1 (EXAFS, Vis/NIR), were identified as prevailing Np(V) species in less alkaline solutions with pHm &lt; 10.5 for [CaCl2] ≤ 2.0 M and [CaCl2] &gt; 2.0 M, respectively. The steep increase of the Np(V) solubility for pHm &gt; 11 with slopes of approximately + 2.5 (for solid phase (I)) and + 3 (for solids (II) and (III)) as well as the Np L3-edge EXAFS results for the aqueous Np(V) species in 4.5 M CaCl2/pHm ≈ 12 confirm the presence of ternary Ca-Np(V)-OH complexes Ca x [NpO2(OH)2]2x–1 (x ≈ 1 is estimated within the thermodynamic evaluation in a subsequent paper (Fellhauer, D., Altmaier, M., Gaona, X., Lützenkirchen, J., Fanghänel, Th., Np(V) solubility, speciation and solid phase formation in alkaline CaCl2 solutions. Part II: Thermodynamics and implications for source term estimations of nuclear waste disposal (Radiochim. Acta, DOI 10.1515/ract-2015-2490), in the following referred to as “Part II” [1]) and Ca y [NpO2(OH)5]2y–4 with y ≈ 2.4 ± 1.5 (EXAFS result) as predominant Np(V) hydrolysis species in solution for [CaCl2] ≥ 0.25 and pHm &gt; 10.5. The thermodynamic evaluation and implications of the new findings with respect to source term estimations for nuclear waste disposal scenarios are discussed in “Part II” [1]).

Distribution Behavior of Neptunium by Extraction with N,N-dialkylamides (DEHDMPA and DEHBA) in Mixer-Settler Extractors

ABSTRACTThe extraction properties of N,N-di(2-ethylhexyl)-2,2-dimethylpropanamide (DEHDMPA) and N,N-di(2-ethylhexyl)butanamide (DEHBA) for Np(V) and Np(VI) were studied by a batch method using various nitrate ion concentrations. The distribution ratios of Np(VI) obtained with DEHDMPA and DEHBA exceeded unity when the nitrate ion concentration was > 3 mol/dm3, while DEHDMPA and DEHBA barely extracted Np(V). A continuous counter-current experiment using mixer-settler extractors was performed to evaluate the behavior of Np in a process comprising two cycles using DEHDMPA and DEHBA as extractants. The feed was nitric acid containing U, Pu, Np, and several fission products. The results indicated that part of Np(V) changed its valence state to Np(IV) or Np(VI) after the 1st experimental cycle. The recoveries of Np in the streams of U fraction and U-Pu fraction were 63.7% and 29.1%, respectively.