Acidic Nuclear Waste Research Articles

BHOEOCC6/n-dodecane: A new solvent extraction media for Cs removal from nuclear waste without using any phase modifier

Modifier-free diluent is most advantageous in hydrometallurgical route for separation of any radioactive element from high level liquid waste (HLLW). However there is not even a single calix crown reported in the literature that is soluble in pure n-dodecane and shows very high Cs extraction from such high nitric acid condition of 4.0 M prevalent in HLLW. Herein we designed a new calix crown-6-ether with an aim to reduce polarity so as to increase solubility in n-dodecane for extraction of Cs by density functional theory (DFT). The theoretically designed calix crown has been synthesised by introducing two 2-(hexyloxy)ethoxy alkyl arms at 1, 3 position calix[4]-arene framework and abbreviated as BHOEOCC6. Characterisation of BHOEOCC6 was carried out using 1H NMR, 13C NMR, and ESI-MS etc. techniques. 0.1 M BHOEOCC6/n-dodecane mixture shows exceptionally high stability as well as high Cs extraction ability (DCs = 10.75 @ 4.0 M HNO3) from highly acidic nuclear waste solution. The mechanism and interaction of Cs with BHOEOCC6 were also probed by experimental distribution ratio studies and instrumental techniques of UV–VIS titration and NMR studies of Cs-BHOEOCC6 complex.

Highly efficient and selective adsorption of palladium(II) from simulated nuclear waste solution using Amberlite XAD-7 resin impregnated with a phenanthroline-derived diamide

The increasing demand and limited natural resources for rare precious metal palladium render its separation and recovery from secondary sources such as acidic nuclear liquid waste greatly interesting. Herein, a novel Et-Tol-DAPhen extraction resin was prepared by impregnating Amberlite XAD-7 resin with a phenanthroline-derived diamide extractant N,N′-diethyl-N,N′-ditolyl-2,9-diamide-1,10-phenanthroline (Et-Tol-DAPhen), and the adsorption behavior of this new extraction resin towards Pd2+ in HNO3 solution was investigated through the batch and column experiments. The Et-Tol-DAPhen extraction resin exhibited strong adsorbability, high adsorption capacity, excellent selectivity and good reusability for Pd2+ in highly acidic HNO3 solution. In addition, the pseudo-second-order and Langmuir models were applied to understand the adsorption process of Pd2+ on Et-Tol-DAPhen extraction resin, respectively. It demonstrated the characteristics of a uniform single-layer chemisorption. The maximum uptake capacity could reach as high as 74.6 mg g−1 for Pd2+ in 3.0 mol/L HNO3 solution which is much higher than most adsorbent materials of palladium reported before. Furthermore, Et-Tol-DAPhen extraction resin could selectively uptake Pd2+ from a simulated acidic nuclear waste solution containing 20 different kinds of ions with the separation factor SFPd/M values as high as 100 to 10,000. Moreover, although the adsorption efficiency had a slight decrease after 5 times of adsorption-desorption process, it still remained at a high level. This new extraction resin displayed a potential application prospect in the field of separation and recovery of Pd2+ from acidic nuclear liquid waste.

Modulating Anion Nanotraps via Halogenation for High-Efficiency 99TcO4-/ReO4- Removal under Wide-Ranging pH Conditions.

Efficient and sustainable methods for 99TcO4- removal from acidic nuclear waste streams, contaminated water, and highly alkaline tank wastes are highly sought after. Herein, we demonstrate that ionic covalent organic polymers (iCOPs) possessing imidazolium-N+ nanotraps allow the selective adsorption of 99TcO4- under wide-ranging pH conditions. In particular, we show that the binding affinity of the cationic nanotraps toward 99TcO4- can be modulated by tuning the local environment around the nanotraps through a halogenation strategy, thereby enabling universal pH 99TcO4- removal. A parent iCOP-1 possessing imidazolium-N+ nanotraps showed fast kinetics (reaching adsorption equilibrium in 1 min), a high adsorption capacity (up to 1434.1 ± 24.6 mg/g), and exceptional selectivity for 99TcO4- and ReO4- (nonradioactive analogue of 99TcO4-) removal in contaminated water. By introducing F groups near the imidazolium-N+ nanotrap sites (iCOP-2), a ReO4- removal efficiency over 58% was achieved in 60 min in 3 M HNO3 solution. Further, introduction of larger Br groups near the imidazolium-N+ binding sites (iCOP-3) imparted a pronounced steric effect, resulting in exceptional adsorption performance for 99TcO4- under super alkaline conditions and from low-activity waste streams at US legacy Hanford nuclear sites. The halogenation strategy reported herein guides the task-specific design of functional adsorbents for 99TcO4- removal and other applications.

Experimental and theoretical studies (DFT) on technetium extraction as HTcO4 using dicyclohexano-18-crown-6 in a blend of isodecyl alcohol and n-dodecane from acidic medium

Fundamental studies on technetium extraction from acid medium using a versatile supramolecule, dicyclohexano-18-crown-6 (DCH18C6) in isodecyl alcohol-n-DD diluent system from acidic nuclear waste have been reported here. It was observed that the maximum extraction (DTc ∼ 2.03) and ∼99% recovery of technetium can be achieved when an organic phase of 0.4 M DCH18C6 in 50% isodecyl alcohol + n-dodecane was used to extract technetium from 4.0 M HNO3 solution followed by three successive stripping contact with water. Two types of mechanisms are found to be operative depending on the acidity of feed solution, an extraction mechanism like, H+aq. + TcO4−aq. + DCH18C6org = HTcO4.DCH18C6org up to 4.0 M feed acidity and HTcO4.DCH18C6org + H +aq. + NO3−aq = DCH18C6org.HNO3 + TcO4−aq.+ H +aq. for feed acidity beyond 4.0 M HNO3. Almost identical interaction energies of adducts DCH18C6-HTcO4 & DCH18C6–HNO3 obtained in the DFT calculations. The extraction is driven by low hydration energy of pertechnate compared to nitrate up to 4.0 M HNO3 and beyond 4.0 M HNO3 concentration of nitrate dominates the hydration energy effect causing decrease in the technetium extraction irrespective of the equal interaction energies.

Efficient removal of Se-79 from highly acidic solution using SiO2 particles functionalised with iron hydroxide

Due to its high solubility, radioactivity and toxicity, the separation of selenium from spent fuel reprocessing waste and industrial wastewater has attracted much attention. In this study, a novel adsorbent FeOOH@SiO2 with particle size of ∼100 μm was successfully prepared by loading FeOOH on micron-sized silica with emulsion methods. FeOOH@SiO2 with good acid resistance, γ-irradiation and thermal stability exhibits excellent adsorption abilities for Se(IV) and Se(VI) including fast adsorption kinetics, great adsorption capacities (11.0 mg/g for Se(IV) and 6.04 mg/g for Se(VI)) and preferable adsorption selectivity. It is worth noting that FeOOH@SiO2 can still remove nearly 90 % of Se(IV) and 80 % of Se(VI) even in 3 mol/L HNO3 system. Combined with the observations from X-ray photoelectron spectroscopic characterization and surface potential measurement, the adsorption mechanism caused with electrostatic attraction and the formation of inner complexes for Se(IV), and reduction reaction and partial formation of outer complexes for Se(VI) can be deduced. After 4 adsorption–desorption cycles, FeOOH@SiO2 still exhibits satisfactory reusability. Dynamic column experiments also demonstrated that FeOOH@SiO2 exhibited excellent removal capabilities towards Se(IV) and Se(VI) from real water samples. The present work demonstrates that FeOOH@SiO2 has great potential application for 79Se removal in highly acidic nuclear waste.

Polyphosphate‐Grafted Fe3O4 Nanomagnets for the Removal of Trivalent Radionuclides from Acidic Nuclear Waste Solution

AbstractThe removal of radionuclides from nuclear waste solution is one of the biggest environmental challenges in today's world. In this aspect, polyphosphate grafted Fe3O4 nanomagnets (PPNMs) were investigated for its efficiency in removal of trivalent radionuclides from acidic nuclear waste solution. Various characterization techniques like XRD, FTIR, TEM and DLS were used to characterize these PPNMs, which showed successful formation of single phase, polyphosphate functionalized aqueous stable Fe3O4 nanostructure with average size ∼10 nm. The kinetics of sorption for Am(III) and Eu(III) by the PPNMs was found to be very fast with equilibrium being attained within ∼5 min. The sorption of both the radionuclides was following pseudo second order kinetic model. With increasing pH of the solution, the sorption efficiency of PPNMs for both the radionuclides was found to increase, whereas it decreased with increasing ionic strength of the medium. These observations clearly suggested that the sorption process proceeds through electrostatic interaction between the nanomagnets and trivalent radionuclides. Moreover, the PPNMs retained their sorption efficiency for at least 10 successive cycles when desorbed with 0.2 M HNO3. Thus, these magnetic nanosorbents can be used as highly effective, separable and reusable materials for removal of trivalent radionuclides from acidic nuclear waste solution.

A H-Bonding and Electrostatic Interaction Combined Strategy for TcO4- Separation by a Nitrotriacetate-Derived Amine-Amide Extractant.

Effective and selective separation of technetium from acidic nuclear liquid waste is highly desirable for partitioning and transmutation but is of significant challenge. Highly efficient extraction of pertechnetate can be achieved by taking H-bonding and electrostatic interaction combined strategy. Base on this strategy, an amine-amide ligand NTAamide(n-Oct) was employed to extract TcO4- in HNO3 solution. Using n-dodecane as a diluent, NTAamide(n-Oct) demonstrated excellent extractability and good selectivity toward TcO4- with a rapid extraction equilibrium that could be reached in less than 1 min. Its maximal loading capacity for TcO4- was almost 100 times as much as that of traditional amine extractant Aliquat-336 nitrate. Meanwhile, TcO4- could be efficiently stripped from the loaded organic phase by (NH4)2CO3 solution. Slope analysis indicated the formation of a 1:1 complex of NTAamide(n-Oct) with TcO4-. The extraction conformed to the anion exchange extraction model, as confirmed by analyses of single-crystal X-ray diffraction, 1H NMR titration, FTIR, and ESI-MS.

Diluents induced tuning of the extraction characteristics of radioactive Cs from acidic nuclear waste solution using calix crown ether

The present investigation deals with understanding the effect of different diluents on the extraction properties of Cs+ using novel calix crown ether. The extraction efficiency was found follow the same order as the dielectric constant of the diluents. The extraction mechanism and the species involved during extraction were evaluated. The extraction process was found to be fast. Suitable stripping procedure was also optimized using different aqueous complexing agents. The effect of radiation exposure on the performance of these solvent systems in extraction of Cs+ ion was investigated up to 1000 kGy. The performance of octanol and isodecyl alcohol was found to be optimized with respect to radioactive plant scale operations.

Distinctive Two-Step Intercalation of Sr2+ into a Coordination Polymer with Record High 90Sr Uptake Capabilities

Summary 90Sr2+ remediation from acidic nuclear waste solution and contaminated seawater attracts great public attention but is very challenging because the removal performance toward soft Sr2+ by traditional oxidic ion-exchange materials are greatly affected by hard cations including H+, Na+, and Ca2+. We report a layered oxidic coordination polymer [(CH3)2NH2][ZrCH2(PO3)2F] (SZ-4) showing a notable advance over existing ion-exchange materials in 90Sr removal efficiencies with elevated distribution coefficients and record-high uptake capacities under acidic conditions. Moreover, the removal of Sr2+ is not significantly affected by the presence of a large excess of hard cations, leading to the successful cleanup of 90Sr-contaminated seawater samples. Such superior capabilities are directly visualized by well-refined single-crystal structures during in situ Sr2+ sorption process, revealing a distinctive two-step intercalation mechanism and a unique soft cation uptake selectivity achieved through collaborative coordination by the host layer and the interlayer dimethylamine (DMA) as a soft N-donor ligand.

Determination of the secondary phases at the acidic LNW disposal

ABSTRACTThe migration behavior of the long-lived actinides was studied under the conditions of the deep disposal of the acidic liquid nuclear waste (LNW). Composition of LNW varies significantly including acidic technological wastes (pH ∼2.4), which consist of sodium nitrate, acetic acid, corrosion products (Fe, Cr, Mn, Ni, Al), fission products and actinides. Corrosion products tend to precipitate under the LNW disposal conditions that favor forming of the phases with high sorption capacity towards actinides. Sands of reservoir bed have their own initial sorbent surfaces besides new secondary phases that have formed as a result of interaction with acidic LNW. The nearest to the injection well conditions are gradually changing from pH ∼2.4 till neutral values due to the dilution by groundwater with formation of new precipitated phases of corrosion products. The solid phases characterization is a necessary step on the path of knowledge of migration behavior of actinides. The secondary phases of both corrosion products and sands of reservoir bed under LNW disposal conditions were characterized using XRD, SEM and Mössbauer spectroscopy. The recent results of the analyses of the behavior of actinides (Pu. U, Np, Am) under the conditions of the injection of the acid LNW are presented in the paper.

Process development for separation of cesium from acidic nuclear waste solution using 1,3-dioctyloxycalix[4]arene-crown-6 + isodecyl alcohol/n-dodecane solvent

A new process for selective separation of cesium from acidic nuclear waste solution has been described using 1,3-dioctyloxycalix[4]arene-crown-6 (CC6)/n-dodecane modified with isodecyl alcohol. The process solvent was optimized as 0.03M CC6+30% isodecyl alcohol/n-dodecane for efficient recovery of cesium. The solvent has shown strong extraction ability for cesium between 1 and 6.0M nitric acid. Stoichiometry of the extracted complex determined by slope analysis method reveals 1:1:1 molar ratio for Cs+, CC6 and HNO3. Extraction of cesium was found to be independent of nitrate ion concentration, possibly due to formation of solvated free ions CsCC6+·HNO3 and NO3− in the organic medium. Extracted cesium from organic phase was readily stripped with deionized water. Radiolysis of the process solvent up to an absorbed dose of 0.6MGy produces essentially no deterioration in its performance. Counter-current mixer–settler experiments with four extraction, two scrubbing and four stripping stages gave about 99% recovery of cesium with very high selectivity from simulated high level waste solution. The results demonstrated the effective use of CC6+isodecyl alcohol/n-dodecane for separation of cesium from acidic high level waste solution.

Theoretical prediction of distribution coefficients of Sr2+ in nuclear waste/ionic liquid phases using COSMO-RS model

Extraction of radio-strontium from acidic nuclear waste streams was studied by COSMO-RS in presence and in absence of strontium-selective crown ethers. The crown ethers studied in this work were dicyclohexano-18-crown-6 and di-tert-butyl-dicyclohexano-18-crown-6. The ionic liquids studied were [BuMeim] [PF6], [HeMeim] [PF6], [OcMeim] [PF6], [BuMeim] [NTf2], [HeMeim] [NTf2] and [OcMeim] [NTf2]. Two different strategies were used in our modeling approach. In the first approach, strontium was inserted in the crown ether whereas, in the second approach, an equimolar composition of crown ether and strontium nitrate was used. The former approach described the effects of crown ethers, alkyl chain length and presence of acidic medium successfully. The COSMO-RS model was further benchmarked by predicting the experimental trend of distribution coefficient of CsNO3 in ionic liquid with respect to the length of alkyl chain.

A Mathematical Model for Size and Number Scale Up of Hollow Fiber Modules for the Recovery of Uranium from Acidic Nuclear Waste using the DLM Technique

In practice, raffinate generated from a nuclear facility is either neutralized or evaporated or diluted and dispersed. Value recovery from such lean raffinate streams (≈0.6 g/l U+6) is of immense importance in view of the potential uranium resource. The HFDLM technique was found to be quite stable and promising for the complete recovery of uranium from plant raffinate. A model was developed for simulating transport phenomena of U from the given raffinate. Here, the developed model is extended to address the large-scale application of HF contactors. Mass transfer coefficients evaluated from the module of 1.4 m2 area have been utilized to predict the performance of the module of 8.1 m2 area. Successful large-scale tests were accomplished by employing a bigger membrane contactor with 8.1 m2 membrane area. Large scale set up has a throughput of 51 l/hr for raffinate taken. The overall mass transfer coefficient of a system of 3 contactors of 1.4 m2 area combined in series is obtained as 1.55 × 10−2 cm/s; stage efficiency of each contactor is found as 60%. A flux of 9.2 × 10−3 moles/m2/hr was obtained for uranium which is about 3–4 times of supported liquid membrane in the HF module and about 10–50 times of solvent extraction in the conventional contactor.

Palladium-catalyzed cross-coupling of various phosphorus pronucleophiles with chloropyrazines: synthesis of novel Am(iii)-selective extractants

Palladium-catalyzed cross-coupling of (di)chloropyrazines with phosphorus pronucleophiles in the presence of a base gave the phosphorylated pyrazines in 81-95% yields. Based on this methodology a series of appropriately functionalized pyrazines was prepared as potential extractants of trivalent cations from highly acidic nuclear waste. A few hydrophilic derivatives exhibited a very good selectivity for Am(3+) over Eu(3+) with separation factors up to 40 at pH 1 at 0.01 mol L(-1) ligand concentration.

Effect of irradiation on AMP based resins for cesium separation from HNO3 feed solutions: batch and column studies

Three different resins containing ammonium molybdophosphate (AMP), viz. PMMA (polymethylmethacrylate) resin, composite AMP resin and ALIX (a bisphenol based resin), were evaluated for their irradiation stability. The studies included batch as well as column studies and were carried out for cesium uptake behaviour at 3 M acidity. The resin beads were irradiated to varying dose viz., 0 MRad, 10 MRad, 20 MRad, 50 MRad and 100 MRad. The time taken to attain equilibrium was rather long and about 2–5 h were found to be required for attaining equilibrium in batch studies. Batch Cs(I) uptake studies revealed no significant effect on the K d values in case of the PMMA resin while in case of the composite resin and ALIX resin, a decrease in the K d was observed as a function of irradiation dose. The resin capacity indicated contrasting behaviour with irradiation dose for the resins. Column runs have been carried out for the uptake of radio cesium using both unirradiated and irradiated resins using feed solutions containing 3 MHNO3. The loading capacities of the resins were found to be proportional to their Cs loading capacities observed in batch studies. Study revealed that the composite AMP had the maximum and PMMA has the least loading capacity. Results of these studies show that these AMP based resins can be used for cesium separation from acidic nuclear waste.

On the Radiation Stability of Crown Ethers in Ionic Liquids

Crown ethers (CEs) are macrocyclic ionophores used for the separation of strontium-90 from acidic nuclear waste streams. Room temperature ionic liquids (ILs) are presently being considered as replacements for traditional molecular solvents employed in such separations. It is desirable that the extraction efficacy obtained with such solvents should not deteriorate in the strong radiation fields generated by decaying radionuclides. This deterioration will depend on the extent of radiation damage to both the IL solvent and the CE solute. While radiation damage to ILs has been extensively studied, the issue of the radiation stability of crown ethers, particularly in an IL matrix, has not been adequately addressed. With this in mind, we have employed electron paramagnetic resonance (EPR) spectroscopy to study the formation of CE-related radicals in the radiolysis of selected CEs in ILs incorporating aromatic (imidazolium and pyridinium) cations. The crown ethers have been found to yield primarily hydrogen loss radicals, H atoms, and the formyl radical. In the low-dose regime, the relative yield of these radicals increases linearly with the mole fraction of the solute, suggesting negligible transfer of the excitation energy from the solvent to the solute; that is, the solvent has a "radioprotective" effect. The damage to the CE in the loading region of practical interest is relatively low. Under such conditions, the main chemical pathway leading to decreased extraction performance is protonation of the macrocycle. At high radiation doses, sufficient to increase the acidity of the IL solvent significantly, such proton complexes compete with the solvent cations as electron traps. In this regime, the CEs will rapidly degrade as the result of H abstraction from the CE ring by the released H atoms. Thus, the radiation dose to which a CE/IL system is exposed must be maintained at a level sufficiently low to avoid this regime.

An Inorganic Microsphere Composite for the Selective Removal of 137Cesium from Acidic Nuclear Waste Solutions. 1: Equilibrium Capacity and Kinetic Properties of the Sorbent

A new inorganic ion exchange composite consisting of ammonium molybdophosphate, (NH4)3P(Mo3O10)4·3H2O (AMP), synthesized within hollow aluminosilicate microspheres (AMP‐C) has been developed. Two different batches of the sorbent were produced resulting in 20% and 25% AMP loading for two and three loading cycles, respectively. The selective cesium exchange capacity of this inorganic composite was evaluated using simulated sodium bearing waste solution as a surrogate for the acidic tank waste currently stored at the Idaho National Laboratory (INL). Equilibrium isotherms obtained from these experiments were very favorable for cesium uptake and indicated maximum cesium loading of approximately 9% by weight of dry AMP. Batch kinetic experiments were also performed to obtain the necessary data to estimate the effective diffusion coefficient for cesium in the sorbent particle. These experiments resulted in effective intraparticle cesium diffusivity coefficients of 4.99 × 10−8 cm2/min and 4.72 × 10−8 cm2/min for the 20% and 25% AMP‐C material, respectively.

An Inorganic Microsphere Composite for the Selective Removal of 137Cesium from Acidic Nuclear Waste Solutions. 2: Bench‐Scale Column Experiments, Modeling, and Preliminary Process Design

A new inorganic ion exchange composite for removing radioactive cesium from acidic waste streams has been developed. The new material consists of ammonium molybdophosphate, (NH4)3P(Mo3O10)4·3H2O (AMP), synthesized within hollow aluminosilicate microspheres (AMP‐C), which are produced as a by‐product from coal combustion. The selective cesium exchange capacity of this inorganic composite was evaluated in bench‐scale column tests using simulated sodium bearing waste solution as a surrogate for the acidic tank waste currently stored at the Idaho National Laboratory (INL). Total cesium loading on the columns at saturation agreed very well with equilibrium values predicted from isotherm experiments performed previously. A numerical algorithm for solving the governing partial differential equations (PDE) for cesium uptake was developed using the intraparticle mass transfer coefficient obtained from previous batch kinetic experiments. Solutions to the governing equations were generated to obtain the cesium concentration at the column effluent as a function of throughput volume using the same conditions as those used for the actual column experiments. The numerical solutions of the PDE fit the column break through data quite well for all the experimental conditions in the study. The model should therefore provide a reliable prediction of column performance at larger scales.

Cobalt bis(dicarbollide) ions functionalized by CMPO-like groups attached to boron by short bonds; efficient extraction agents for separation of trivalent f-block elements from highly acidic nuclear waste

New boron substituted cobalta bis(dicarbollide)(1-) ion ( 1) derivatives of formula [(8,8′-(RPhP(O)(CH 2) nC(O)N) < (1,2-C 2B 9H 10) 2-3,3′-Co] − (R = Ph or C 8H 17, n = 1, 3a, 3b; R = Ph, n = 2, 3c), [(8-(Ph 2P(O)CH 2C(O)NR)(1,2-C 2B 9H 10))(1′,2′-C 2B 9H 11)-3,3′-Co] − (R = H, C 2H 5, CH 2C 6H 5, 5a–c) and [(8-( 2RPhP(O)CH 2C(O)N( 1R)CH 2-1,2-C 2B 9H 10))(8′-CH 3O-1′,2′-C 2B 9H 10)-3,3′-Co] − ( 1R = Benzyl, 2R = Ph or C 8H 17, 7a,b) were prepared with the aim to develop a new class of efficient extraction agents for partitioning of polyvalent f-block elements, i.e. lanthanides and actinides from high-level activity nuclear waste. The anionic ligands were characterized by multinuclear NMR spectroscopy and MS, the structures of Cs 3a and the calcium complex of 7a were determined by X-ray diffraction analysis. The crystallographic study of the Cs 3a proved a formation of linear chains in the structure, where the metal cation is coordinated by oxygen atoms of the CMPO terminal groups. The X-ray structure of the Ca 2+ complex of the ionic ligand 7a proved a 1:3 metal to ligand ratio. Presented also is the X-ray structure of the starting ammonium compound 6 used in the synthesis of 7a and 7b. With exception of 5c, these anionic ligands are of high extraction efficiency, the highest being found for 7a in low polar solvent mixture hexyl methyl ketone–dodecane 1:1. These properties qualify some of these derivatives for possible technological applications.

CMPO-Functionalized C3-Symmetric Tripodal Ligands in Liquid/Liquid Extractions: Efficient, Selective Recognition of Pu(IV) with Low Affinity for 3+ Metal Ions

Structural modifications of carbamoylmethylphosphine oxide (CPMO)-functionalized triphenoxymethane platforms are described, and the influence of these changes on the ability of the ligand to extract actinides from simulated acidic nuclear waste streams has been evaluated. The ligand system has been shown to have excellent binding efficiency and a selectivity for An(IV) in comparison to the a simple monomeric CMPO ligand under analogous conditions. Both the extraction efficiency and selectivity are strongly dependent on the flexibility and electronic properties of the ligating units in the triphenoxymethane construct. The Tb(III) and Bi(III) nitrate complexes of tris-CMPO derivatives have been isolated, and their structures were elucidated by NMR, ESI FT-ICR MS, and X-ray analysis, providing information on the interactions between metal ions and the tris-CMPO molecules.