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1.
Appl Radiat Isot ; 136: 10-17, 2018 Jun.
Article in English | MEDLINE | ID: mdl-29448060

ABSTRACT

A new sequential separation method for the determination of polonium and actinides (Pu, Am and U) in drinking water samples has been developed that can be used for emergency response or routine water analyses. For the first time, the application of TEVA chromatography column in the sequential separation of polonium and plutonium has been studied. This method utilizes a rapid Fe+3 co-precipitation step to remove matrix interferences, followed by plutonium oxidation state adjustment to Pu4+ and an incubation period of ~ 1 h at 50-60 °C to allow Po2+ to oxidize to Po4+. The polonium and plutonium were then separated on a TEVA column, while separation of americium from uranium was performed on a TRU column. After separation, polonium was micro-precipitated with copper sulfide (CuS), while actinides were micro co-precipitated using neodymium fluoride (NdF3) for counting by the alpha spectrometry. The method is simple, robust and can be performed quickly with excellent removal of interferences, high chemical recovery and very good alpha peak resolution. The efficiency and reliability of the procedures were tested by using spiked samples. The effect of several transition metals (Cu2+, Pb2+, Fe3+, Fe2+, and Ni2+) on the performance of this method were also assessed to evaluate the potential matrix effects. Studies indicate that presence of up to 25 mg of these cations in the samples had no adverse effect on the recovery or the resolution of polonium alpha peaks.


Subject(s)
Americium/isolation & purification , Chromatography, Liquid/methods , Drinking Water/chemistry , Plutonium/isolation & purification , Polonium/isolation & purification , Uranium/isolation & purification , Water Pollutants, Radioactive/isolation & purification , Reproducibility of Results , Spectrum Analysis/methods , Transition Elements/chemistry
2.
Appl Radiat Isot ; 134: 455-460, 2018 Apr.
Article in English | MEDLINE | ID: mdl-28735687

ABSTRACT

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.


Subject(s)
Americium/analysis , Neptunium/analysis , Plutonium/analysis , Radioactive Pollutants/analysis , Thorium/analysis , Uranium/analysis , Alpha Particles , Americium/isolation & purification , Americium/urine , Chromatography, Liquid/methods , Humans , Mass Spectrometry/methods , Neptunium/isolation & purification , Neptunium/urine , Plutonium/isolation & purification , Plutonium/urine , Radioactive Pollutants/isolation & purification , Radioactive Pollutants/urine , Spectrum Analysis/methods , Thorium/isolation & purification , Thorium/urine , Uranium/isolation & purification , Uranium/urine
3.
J Chromatogr A ; 1448: 58-66, 2016 May 27.
Article in English | MEDLINE | ID: mdl-27130582

ABSTRACT

Extraction chromatography resins, prepared by impregnating two multi-podant diglycolamide ligands, viz. diglycolamide-functionalized calix[4]arene (C4DGA) and tripodal diglycolamide (T-DGA) dissolved in the room temperature ionic liquid 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)amide (RTIL: C4mimTf2N) on Chromosorb-W (an inert solid support), gave excellent results for the removal of trivalent actinides from acidic waste solutions. Distribution coefficient measurements on several metal ions showed selective sorption of Am(III) over hexavalent uranyl ions and other fission product elements such as strontium and cesium. The sorbed metal ions could be efficiently desorbed with a complexing solution containing guanidine carbonate and EDTA buffer. The sorption of Am(III) on both resins followed pseudo-second order rate kinetics with rate constants of 1.37×10(-6) and 6.88×10(-7)g/cpmmin for T-DGA and C4DGA resins, respectively. The metal sorption on both resins indicated the Langmuir monolayer chemisorption phenomenon with Eu(III) sorption capacities of 4.83±0.21 and 0.52±0.05mg per g of T-DGA and C4DGA resins, respectively. The results of column studies show that these resins are of interest for a possible application for the recovery of hazardous trivalent actinides from dilute aqueous solutions.


Subject(s)
Americium/isolation & purification , Calixarenes/chemistry , Glycolates/chemistry , Ionic Liquids/chemistry , Cations , Cesium/isolation & purification , Chelating Agents/chemistry , Chromatography, Liquid , Kinetics , Ligands , Solutions , Strontium/isolation & purification , Temperature , Uranium/isolation & purification
4.
Radiat Res ; 185(6): 568-79, 2016 06.
Article in English | MEDLINE | ID: mdl-27195610

ABSTRACT

Diethylenetriaminepentaacetic acid (DTPA) is currently still the only known chelating drug that can be used for decorporation of internalized plutonium (Pu) and americium (Am). It is generally assumed that chelation occurs only in biological fluids, thus preventing Pu/Am deposition in target tissues. We postulate that actinide chelation may also occur inside cells by a mechanism called "intracellular chelation". To test this hypothesis, rats were given DTPA either prior to (termed "prophylactic" treatment) or belatedly after (termed "delayed" treatment) Pu/Am injection. DTPA decorporation efficacy was systematically tested for both plutonium and americium. Both prophylactic and delayed DTPA elicited marked decreases in liver Pu/Am. These results can be explained by chelation within subcellular compartments where DTPA efficacy increased as a function of a favorable intracellular DTPA-to-actinide molar ratio. The efficacy of intracellular chelation of liver actinides decreased with the delay of treatment. This is probably explained by progressive actinide binding to the high-affinity ligand ferritin followed by migration to lysosomes. Intracellular chelation was reduced as the gap between prophylactic treatment and contamination increased. This may be explained by the reduction of the intracellular DTPA pool, which declined exponentially with time. Skeletal Pu/Am was also reduced by prophylactic and delayed DTPA treatments. This decorporation of bone actinides may mainly result from extracellular chelation on bone surfaces. This work provides converging evidence for the involvement of an intracellular component of DTPA action in the decorporation process. These results may help to improve the interpretation of biological data from DTPA-treated contamination cases and could be useful to model DTPA therapy regimens.


Subject(s)
Americium/metabolism , Chelating Agents/metabolism , Intracellular Space/drug effects , Intracellular Space/metabolism , Pentetic Acid/metabolism , Plutonium/metabolism , Americium/isolation & purification , Americium/toxicity , Animals , Bone and Bones/drug effects , Bone and Bones/metabolism , Chelating Agents/pharmacology , Dose-Response Relationship, Drug , Kinetics , Liver/drug effects , Liver/metabolism , Male , Pentetic Acid/pharmacology , Plutonium/isolation & purification , Plutonium/toxicity , Rats , Rats, Sprague-Dawley
5.
Int J Radiat Biol ; 91(7): 568-75, 2015 Jul.
Article in English | MEDLINE | ID: mdl-25912343

ABSTRACT

PURPOSE: Currently two injectable products of diethylenetriaminepentaacetic acid (DTPA) are U.S. Food and Drug Administration (FDA)-approved for decorporation of (241)Am; however, an oral product is considered more amenable in a mass casualty situation. The di-ethyl ester of DTPA, named C2E2, is being developed as an oral drug for treatment of internal radionuclide contamination. MATERIALS AND METHODS: Single-dose decorporation efficacy of C2E2 administered 24-h post contamination was determined in beagle dogs using a (241)Am nitrate inhalation contamination model. Single and multiple dose toxicity studies in beagle dogs were performed as part of an initial safety assessment program. In addition, the genotoxic potential of C2E2 was evaluated by the in vitro bacterial reverse mutation Ames test, mammalian cell chromosome aberration cytogenetic assay and an in vivo micronucleus test. RESULTS: Oral administration of C2E2 significantly increased (241)Am elimination over untreated controls and significantly reduced the retention of (241)Am in tissues, especially liver, kidney, lung and bone. Daily dosing of 200 mg/kg/day for 10 days was well tolerated in dogs. C2E2 was found to be neither mutagenic or clastogenic. CONCLUSIONS: The di-ethyl ester of DTPA (C2E2) was shown to effectively enhance the elimination of (241)Am after oral administration in a dog inhalation-contamination model and was well tolerated in toxicity studies.


Subject(s)
Americium/chemistry , Inhalation , Pentetic Acid/adverse effects , Pentetic Acid/pharmacology , Safety , Administration, Oral , Americium/isolation & purification , Animals , CHO Cells , Cricetinae , Cricetulus , Dogs , Dose-Response Relationship, Drug , Female , Maximum Tolerated Dose , Models, Animal , Pentetic Acid/administration & dosage , Pentetic Acid/chemistry
6.
Dalton Trans ; 44(13): 6193-201, 2015 Apr 07.
Article in English | MEDLINE | ID: mdl-25736729

ABSTRACT

Mutual separation of trivalent actinide (An(3+)) and lanthanide (Ln(3+)) using several soft (N) donor ligands (bis(5,6-dialkyl-1,2,4-triazinyl)pyridine (R-BTP)) is attempted for the first time in room temperature ionic liquid (RTIL) medium. The results indicate a spectacular enhancement in the selectivity as compared to that in molecular diluents with a separation factor (S.F.) of >3000 for Am(3+) over Eu(3+) using the methyl derivative (Me-BTP) in RTIL medium using [C(n)mim]·[NTf2] as the diluents (where n = 2, 3, 4, 6 or 8). Such a high S.F. value has never been reported before with any of the R-BTP derivatives in molecular diluents. An opposite trend in the distribution ratio values of both Am(3+) and Eu(3+) with the increasing size of the alkyl (R) group is observed in RTIL medium when compared with that in molecular diluents. The differences in the extraction behaviour of R-BTPs in RTILs vis-à-vis molecular diluents are explained on the basis of the difference in the nature of complexes extracted in these two distinctly different media as supported by the time resolved fluorescence (TRFS) study. An unusually high extractability and selectivity for Am(3+) over Eu(3+) with Me-BTP was attributed to the formation of a 1 : 4 complex for Am(3+), which was never reported earlier with any of the R-BTP derivatives in molecular diluents. DFT studies indicated higher metal 'd' and 'f' orbital participation (covalence) in the bonding with R-BTP in the case of Am(3+) complexes as compared to that in the case of Eu(3+) complexes, which resulted in the selectivity of these classes of ligands. The observed results may have a great significance in the radioactive waste management involving the partitioning and transmutation strategy.


Subject(s)
Americium/isolation & purification , Coordination Complexes/chemistry , Europium/isolation & purification , Ionic Liquids/chemistry , Pyridines/chemistry , Solvents/chemistry , Triazines/chemistry , Americium/chemistry , Chemical Fractionation , Europium/chemistry , Ligands , Models, Molecular , Models, Theoretical , Molecular Structure
7.
Health Phys ; 108(4): 443-50, 2015 Apr.
Article in English | MEDLINE | ID: mdl-25706138

ABSTRACT

Diethylenetriaminepentaacetic acid (DTPA) is an FDA-approved chelating agent for enhancing the elimination of transuranic elements such as americium from the body. Early access to therapy minimizes deposition of these radionuclides in tissues such as the bone. Due to its poor oral bioavailability, DTPA is administered as an IV injection, delaying access. Therefore, a diethyl-ester analog of DTPA, named C2E2, was synthesized as a means to increase oral absorption. As a hexadentate ligand, it was hypothesized that C2E2 was capable of binding americium directly. Therefore, the protonation constants and americium stability constant for C2E2 were determined by potentiometric titration and a solvent extraction method, respectively. C2E2 was shown to bind americium with a log K of 19.6. The concentrations of C2E2, its metabolite C2E1, and DTPA required to achieve effective binding in rat, beagle, and human plasma were studied in vitro. Dose response curves for each ligand were established, and the 50% maximal effective concentrations were determined for each species. As expected, higher concentrations of C2E2 were required to achieve the same degree of binding as DTPA. The results indicated that chelation in beagle plasma is more representative of the human response than rats. Finally, the pharmacokinetics of C2E2 were investigated in beagles, and the data was fit to a two-compartment model with elimination from the central compartment, along with first-order absorption. Based on the in vitro data, a 100 mg kg dose of C2E2 can be expected to have an effective duration of action of 3.8 h in beagles.


Subject(s)
Americium/metabolism , Chelating Agents/administration & dosage , Pentetic Acid/analogs & derivatives , Americium/isolation & purification , Animals , Binding, Competitive , Biological Availability , Chelating Agents/pharmacokinetics , Dogs , Female , Humans , Injections, Intravenous , Male , Pentetic Acid/administration & dosage , Pentetic Acid/blood , Pentetic Acid/pharmacokinetics , Rats , Species Specificity , Tissue Distribution
8.
Environ Sci Technol ; 48(17): 10045-53, 2014 Sep 02.
Article in English | MEDLINE | ID: mdl-25126837

ABSTRACT

During the 1960s, radioactive waste containing small amounts of plutonium (Pu) and americium (Am) was disposed in shallow trenches at the Little Forest Burial Ground (LFBG), located near the southern suburbs of Sydney, Australia. Because of periodic saturation and overflowing of the former disposal trenches, Pu and Am have been transferred from the buried wastes into the surrounding surface soils. The presence of readily detected amounts of Pu and Am in the trench waters provides a unique opportunity to study their aqueous speciation under environmentally relevant conditions. This study aims to comprehensively investigate the chemical speciation of Pu and Am in the trench water by combining fluoride coprecipitation, solvent extraction, particle size fractionation, and thermochemical modeling. The predominant oxidation states of dissolved Pu and Am species were found to be Pu(IV) and Am(III), and large proportions of both actinides (Pu, 97.7%; Am, 86.8%) were associated with mobile colloids in the submicron size range. On the basis of this information, possible management options are assessed.


Subject(s)
Americium/chemistry , Americium/isolation & purification , Hazardous Waste Sites , Plutonium/chemistry , Plutonium/isolation & purification , Radioactive Waste/analysis , Water Pollutants, Radioactive/isolation & purification , Australia , Chemical Precipitation , Colloids/chemistry , Particle Size , Soil , Solutions , Water Pollutants, Radioactive/chemistry
9.
J Hazard Mater ; 280: 63-70, 2014 Sep 15.
Article in English | MEDLINE | ID: mdl-25128895

ABSTRACT

Cerium vanadate nanopowders were synthesized by a facile low temperature co-precipitation method. The product was characterized by X-ray diffraction and transmission electron microscopy and found to consist of ∼25 nm spherical nanoparticles. The efficiency of these nanopowders for uptake of alpha-emitting radionuclides (233)U (4.82 MeV α) and (241)Am (5.49 MeV α, 60 keV γ) has been investigated. Thermodynamically and kinetically favorable uptake of these radionuclides resulted in their complete removal within 3h from aqueous acidic feed solutions. The uptake capacity was observed to increase with increase in pH as the zeta potential value decreased with the increase in pH but effect of ionic strength was insignificant. Little influence of the ions like Sr(2+), Ru(3+), Fe(3+), etc., in the uptake process indicated CeVO4 nanopowders to be amenable for practical applications. The isotherms indicated predominant uptake of the radioactive metal ions in the solid phase of the exchanger at lower feed concentrations and linear Kielland plots with positive slopes indicated favorable exchange of the metal ions with the nanopowder. Performance comparison with the other sorbents reported indicated excellent potential of nano-cerium vanadate for removing americium and uranium from large volumes of aqueous acidic solutions.


Subject(s)
Americium/isolation & purification , Cerium/chemistry , Nanoparticles/chemistry , Uranium/isolation & purification , Vanadates/chemistry , Water Pollutants, Radioactive/isolation & purification , Adsorption , Kinetics , Microscopy, Electron, Transmission , X-Ray Diffraction
10.
Environ Sci Technol ; 48(12): 6874-81, 2014 Jun 17.
Article in English | MEDLINE | ID: mdl-24842652

ABSTRACT

Efficient capture of highly toxic radionuclides with long half-lives such as Americium-241 is crucial to prevent radionuclides from diffusing into the biosphere. To reach this purpose, three different types of mesoporous silicas functionalized with phosphonic acid ligands (SBA-POH, MCM-POH, and BPMO-POH) were synthesized via a facile procedure. The structure, surface chemistry, and micromorphology of the materials were fully characterized by (31)P/(13)C/(29)Si MAS NMR, XPS, and XRD analysis. Efficient adsorption of Am(III) was realized with a fast rate to reach equilibrium (within 10 min). Influences including structural parameters and functionalization degree on the adsorption behavior were investigated. Slope analysis of the equilibrium data suggested that the coordination with Am(III) involved the exchange of three protons. Moreover, extended X-ray absorption fine structure (EXAFS) analysis, in combination with XPS survey, was employed for an in-depth probe into the binding mechanism by using Eu(III) as a simulant due to its similar coordination behavior and benign property. The results showed three phosphonic acid ligands were coordinated to Eu(III) in bidentate fashion, and Eu(P(O)O)3(H2O) species were formed with the Eu-O coordination number of 7. These phosphonic acid-functionalized mesoporous silicas should be promising for the treatment of Am-containing radioactive liquid waste.


Subject(s)
Americium/isolation & purification , Phosphorous Acids/chemistry , Photoelectron Spectroscopy , Silicon Dioxide/chemistry , X-Ray Absorption Spectroscopy , Adsorption , Environment , Europium/isolation & purification , Hydrogen-Ion Concentration , Kinetics , Magnetic Resonance Spectroscopy , Microscopy, Electron, Transmission , Porosity , X-Ray Diffraction
11.
Acta Chim Slov ; 60(3): 695-700, 2013.
Article in English | MEDLINE | ID: mdl-24169726

ABSTRACT

Extraction of microamounts of europium and americium by a nitrobenzene solution of hydrogen dicarbollylcobaltate (H+B-) in the presence of dodecaethylene glycol (DDEG, L) has been investigated. The equilibrium data have been explained assuming that the species HL+, H2L2+, ML3+ and MH-1L2+ (M3+ = Eu3+, Am3+; L = DDEG) are extracted into the organic phase. The values of extraction and stability constants of the complex species in nitrobenzene saturated with water have been determined. It was found that in this nitrobenzene medium, the stability constant of the EuL3+ complex is comparable with that of AmL3+.


Subject(s)
Allyl Compounds/chemistry , Americium/isolation & purification , Cobalt/chemistry , Europium/isolation & purification , Hydrogen/chemistry , Nitrobenzenes/chemistry , Polyethylene Glycols/chemistry
12.
Health Phys ; 105(2): 208-14, 2013 Aug.
Article in English | MEDLINE | ID: mdl-23799506

ABSTRACT

Diethylenetriaminepentaacetic acid (DTPA) is a chelating agent that is used to facilitate the elimination of radionuclides such as americium from contaminated individuals. Its primary site of action is in the blood, where it competes with various biological ligands, including transferrin and albumin, for the binding of radioactive metals. To evaluate the chelation potential of DTPA under these conditions, the competitive binding of Am between DTPA and plasma proteins was studied in rat, beagle, and human plasma in vitro. Following incubation of DTPA and Am in plasma, the Am-bound ligands were fractionated by ultrafiltration and ion-exchange chromatography, and each fraction was assayed for Am content by gamma scintillation counting. Dose response curves of DTPA for Am binding were established, and these models were used to calculate the 90% maximal effective concentration, or EC90, of DTPA in each plasma system. The EC90 were determined to be 31.4, 15.9, and 10.0 µM in rat, beagle, and human plasma, respectively. These values correspond to plasma concentrations of DTPA that maximize Am chelation while minimizing excess DTPA. Based on the pharmacokinetic profile of DTPA in humans, after a standard 30 µmol kg intravenous bolus injection, the plasma concentration of DTPA remains above EC90 for approximately 5.6 h. Likewise, the effective duration of DTPA in rat and beagle were determined to be 0.67 and 1.7 h, respectively. These results suggest that species differences must be considered when translating DTPA efficacy data from animals to humans and offer further insights into improving the current DTPA treatment regimen.


Subject(s)
Americium/chemistry , Chelating Agents/chemistry , Pentetic Acid/blood , Pentetic Acid/chemistry , Americium/isolation & purification , Animals , Dogs , Humans , Rats , Species Specificity
13.
J Hazard Mater ; 243: 1-18, 2012 Dec.
Article in English | MEDLINE | ID: mdl-23141377

ABSTRACT

Pu, U, Np, Am and Tc are among the major risk drivers at nuclear waste management facilities throughout the world. Furthermore, uranium mining and milling operations have generated an enormous legacy of radioactively contaminated soils and groundwater. The sorption process of radionulcides onto ubiquitous Fe (hydr)oxides (FHOs; hematite, magnetite, goethite and ferrihydrite) is one of the most vital geochemical processes controlling the transport and fate of radionuclides and nuclear wastes in the subsurface zones. Meanwhile, understanding molecular-level chemical speciation of radionuclides onto FHOs is crucial to model their behavior in subsurface environments, and to develop new technologies for nuclear waste treatment and long-term remediation strategies for contaminated soils and groundwater. This review article aims (1) to provide risk or performance assessment modelers with macroscopic distribution coefficient (K(d)) data of Pu, U, Np, Am and Tc onto FHOs under different conditions (pH, radionuclide concentration, solution ion strength, sorbent loading, partial pressure of CO(2) (P CO(2)), equilibrium time) pertinent to environmental and engineered systems, and (2) to provide a microscopic or molecular-level understanding of the chemical speciation and sorption processes of these radionuclides to FHOs.


Subject(s)
Elements, Radioactive/chemistry , Ferric Compounds/chemistry , Iron/chemistry , Americium/chemistry , Americium/isolation & purification , Elements, Radioactive/isolation & purification , Ferric Compounds/isolation & purification , Hydroxides/chemistry , Hydroxides/isolation & purification , Neptunium/chemistry , Neptunium/isolation & purification , Plutonium/chemistry , Plutonium/isolation & purification , Radioactive Waste , Soil/analysis , Technetium/chemistry , Technetium/isolation & purification , Uranium/chemistry , Uranium/isolation & purification
14.
Dalton Trans ; 41(47): 14416-24, 2012 Dec 21.
Article in English | MEDLINE | ID: mdl-23104258

ABSTRACT

Theoretical studies were carried out on two pairs of americium and europium complexes formed by tetra-N-dentate lipophilic BTBP ligands, neutral [ML(NO(3))(3)] and cationic [ML(2)](3+) where M = Am(III) or Eu(III), and L = 6,6'-bis-(5,6-diethyl-1,2,4-triazin-3-yl)-2,2'-bipyridine (C2-BTBP). Molecular structures of the complexes have been optimized at the B3LYP/6-31G(d) level and total energies of the complexes in various media were estimated using single point calculations performed at the B3LYP/6-311G(d,p) and MP2/6-311G(d,p) levels of theory. In the calculations americium and europium ions were treated using pseudo-relativistic Stuttgart-Dresden effective core potentials and the accompanying basis sets. Selectivity in solvent extraction separation of two metal ions is a co-operative function of contributions from all extractable metal complexes, which depend on physico-chemical properties of each individual complex and on its relative amount in the system. Semi-quantitative analysis of BTBP selectivity in the Am/Eu separation process, based on the contributions from the two pairs of Am(III) and Eu(III) complexes, has been carried out. To calculate the energy of Am/Eu separation, a model of the extraction process was used, consisting of complex formation in water and transfer of the formed complex to the organic phase. Under the assumptions discussed in the paper, this simple two-step model results in reliable values of the calculated differences in the energy changes for each pair of the Am/Eu complexes in both steps of the process. The greater thermodynamic stability (in water) of the Am-BTBP complexes, as compared with the analogous Eu species, caused by greater covalency of the Am-N than Eu-N bonds, is most likely the main reason for BTBP selectivity in the separation of the two metal ions. The other potential reason, i.e. differences in lipophilic properties of the analogous complexes of Am and Eu, is less important with regard to this selectivity.


Subject(s)
2,2'-Dipyridyl/chemistry , Americium/isolation & purification , Coordination Complexes/chemistry , Europium/isolation & purification , Americium/chemistry , Chemical Fractionation , Europium/chemistry , Ligands , Models, Molecular , Solvents , Thermodynamics
15.
J Pharm Sci ; 101(8): 2844-53, 2012 Aug.
Article in English | MEDLINE | ID: mdl-22644947

ABSTRACT

Intravenously administered calcium and zinc complexes of diethylenetriaminepentaacetic acid (DTPA) are the agents of choice to treat individuals who have been contaminated with radioactive actinides. However, their use in a mass casualty scenario is hampered by the need for trained personnel to receive treatment. Because DTPA is a highly ionized molecule with permeability-limited bioavailability, the penta-ethyl ester prodrug of DTPA is under evaluation as an orally bioavailable radionuclide decorporation agent. In this work, the physicochemical properties of DTPA penta-ethyl ester were characterized to assess its potential for oral delivery. DTPA penta-ethyl ester was determined to be a low-viscosity liquid with Newtonian flow characteristics. Consistent with the measured pK(a) values, which range from 2.93 to 10.87, this prodrug exhibits pH-dependent solubility and lipophilicity properties that are representative of a weak base and favorable for oral absorption. It is miscible in solvents that are nonpolar to moderately polar and is sufficiently stable to avoid premature hydrolysis during gastrointestinal transit. Therapeutic effects were demonstrated in an initial efficacy study wherein oral treatments of the prodrug were given to rats contaminated with ²4¹Am, providing preliminary indications of successful oral delivery. The properties of the prodrug indicate that it is conducive to oral delivery and may offer therapeutic benefits over the standard DTPA therapy following radionuclide contamination.


Subject(s)
Americium/isolation & purification , Antidotes/chemistry , Antidotes/therapeutic use , Pentetic Acid/chemistry , Pentetic Acid/therapeutic use , Prodrugs/chemistry , Prodrugs/therapeutic use , Administration, Oral , Animals , Antidotes/administration & dosage , Antidotes/metabolism , Esters/administration & dosage , Esters/chemistry , Esters/metabolism , Esters/therapeutic use , Female , Hydrolysis , Pentetic Acid/administration & dosage , Pentetic Acid/metabolism , Prodrugs/administration & dosage , Prodrugs/metabolism , Rats , Rats, Sprague-Dawley , Solubility , Viscosity
16.
J Hazard Mater ; 221-222: 62-7, 2012 Jun 30.
Article in English | MEDLINE | ID: mdl-22541638

ABSTRACT

The extraction behavior of U(VI), Pu(IV) and Am(III) from nitric acid medium by a solution of N,N-dimethyl-N,N-dioctyl-2-(2-hexyloxyethyl)malonamide (DMDOHEMA) in the room temperature ionic liquid, 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide (C(4)mimNTf(2)), was studied. The distribution ratio of these actinides in DMDOHEMA/C(4)mimNTf(2) was measured as a function of various parameters such as the concentration of nitric acid, DMDOHEMA, NTf(2)(-), alkyl chain length of ionic liquid. The extraction of actinides in the absence of DMDOHEMA was insignificant and the distribution ratio achieved in conjunction with C(4)mimNTf(2), was remarkable. The separation factor of U(VI) and Pu(IV) achieved with the use of DMDOHEMA, ionic liquid was compared with Am(III) and other fission products. The stoichiometry of the metal-solvate was determined to be 1:2 for U(VI) and Pu(IV) and 1:3 for Am(III).


Subject(s)
Americium/isolation & purification , Liquid-Liquid Extraction/methods , Malonates/chemistry , Plutonium/isolation & purification , Uranium/isolation & purification , Ionic Liquids , Temperature
17.
J Hazard Mater ; 195: 238-44, 2011 Nov 15.
Article in English | MEDLINE | ID: mdl-21889846

ABSTRACT

Solvent extraction and supported liquid membrane transport studies for the preferential removal of Am(3+) from feeds containing a mixture of Am(3+) and Eu(3+) was carried out using 2,6-bis(5,6-dipropyl-1,2,4-triazin-3-yl)pyridine (n-Pr-BTP) as the extractant. Diluent plays an important role in these studies. It was observed that the distribution coefficients deteriorate significantly for both Am(3+) and Eu(3+) though the separation factors were affected only marginally. The transport studies were carried out at pH 2.0 in the presence of NaNO(3) to result in the preferential Am(3+) transport with high separation factors. Effect of different experimental parameters, viz. feed composition, stripping agents, diluents of the organic liquid membrane and membrane pore size was studied on the transport and separation behaviour of Am(3+) and Eu(3+). The supported liquid membrane studies indicated about 85% Am(3+) and 6% Eu(3+) transport in 6h using 0.03 M n-Pr-BTP in n-dodecane/1-octanol (7:3) diluent mixture for a feed containing 1M NaNO(3) at pH 2 and a receiver phase containing pH 2 solution as the strippant. Consequently, a permeability coefficient of (1.75 ± 0.21) × 10(-4)cms(-1) was determined for the Am(3+) transport. Stability of the n-Pr-BTP and its SLM was also studied by carrying out the distribution and transport experiment after different time intervals.


Subject(s)
Americium/isolation & purification , Europium/isolation & purification , Liquid-Liquid Extraction , Pyridines/chemistry , Triazines/chemistry , Magnetic Resonance Spectroscopy
18.
Health Phys ; 99(3): 413-9, 2010 Sep.
Article in English | MEDLINE | ID: mdl-20699706

ABSTRACT

Self-assembled monolayer on mesoporous supports (SAMMS) are hybrid materials created from attachment of organic moieties onto very high surface area mesoporous silica. SAMMS with surface chemistries including three isomers of hydroxypyridinone, diphosphonic acid, acetamide phosphonic acid, glycinyl urea, and diethylenetriamine pentaacetate (DTPA) analog were evaluated for chelation of actinides ((239)Pu, (241)Am, uranium, thorium) from blood. Direct blood decorporation using sorbents does not have the toxicity or renal challenges associated with traditional chelation therapy and may have potential applications for critical exposure cases, reduction of nonspecific dose during actinide radiotherapy, and for sorbent hemoperfusion in renal insufficient patients, whose kidneys clear radionuclides at a very slow rate. Sorption affinity (K(d)), sorption rate, selectivity, and stability of SAMMS were measured in batch contact experiments. An isomer of hydroxypyridinone (3,4-HOPO) on SAMMS demonstrated the highest affinity for all four actinides from blood and plasma and greatly outperformed the DTPA analog on SAMMS and commercial resins. In batch contact, a fifty percent reduction of actinides in blood was achieved within minutes, and there was no evidence of protein fouling or material leaching in blood after 24 h. The engineered form of SAMMS (bead format) was further evaluated in a 100-fold scaled-down hemoperfusion device and showed no blood clotting after 2 h. A 0.2 g quantity of SAMMS could reduce 50 wt.% of 100 ppb uranium in 50 mL of plasma in 18 min and that of 500 dpm mL(-1) in 24 min. 3,4-HOPO-SAMMS has a long shelf-life in air and at room temperature for at least 8 y, indicating its feasibility for stockpiling in preparedness for an emergency. The excellent efficacy and stability of SAMMS materials in complex biological matrices suggest that SAMMS can also be used as orally administered drugs and for wound decontamination. By changing the organic groups of SAMMS, they can be used not only for actinides but also for other radionuclides. By using the mixture of these SAMMS materials, broad spectrum decorporation of radionuclides is very feasible.


Subject(s)
Actinoid Series Elements/blood , Actinoid Series Elements/isolation & purification , Chelating Agents/chemistry , Decontamination/methods , Actinoid Series Elements/chemistry , Adsorption , Americium/blood , Americium/isolation & purification , Humans , Isomerism , Pentetic Acid/chemistry , Plutonium/blood , Plutonium/isolation & purification , Porosity , Pyridones/chemistry , Radiation Injuries/prevention & control , Radioactive Hazard Release , Terrorism , Thorium/blood , Thorium/isolation & purification , Time Factors , Uranium/blood , Uranium/isolation & purification
19.
Chemosphere ; 80(4): 433-7, 2010 Jun.
Article in English | MEDLINE | ID: mdl-20488505

ABSTRACT

A liquid surfactant membrane (LSMs) containing 2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester (H(2)A(2)) was tested for the extraction of americium(III) from aqueous nitrate solutions of different compositions. Span 80 a surface-active agent and 0.5M HNO(3) were used as emulsion stabilizer and internal phase respectively in the LSM system. Influence of some important experimental parameters such as pH of the exterior phase, ionic impurities in the exterior phase, concentration of H(2)A(2) and Span80 in liquid membrane phase on the LSM permeation process was systematically studied. The maximum efficiency of Am(III) extraction among group of experiments was 93+/-2% with modified permeability coefficient=1.21+/-0.02min(-1) and the corresponding concentration factor of Am(III) in the receiving phase was 10.5+/-0.2. Extraction of commonly associated fission product elements such as (137)Cs, (152,154)Eu, (90)Sr, (95)Zr, (144)Ce, (95)Nb and (103)Ru was also investigated from feed solution in the exterior phase adjusted at different pH. In a single batch of extraction, more than 90% removal and about 10 times concentration of Am(III) was obtained from uranium and plutonium depleted (process of Plutonium Uranium Recovery by Extraction) waste solution. A complete demulsification of metal loaded emulsion was obtained by chemical using 2-ethylhexanol and physical using freeze thaw method.


Subject(s)
Americium/chemistry , Nitrates/chemistry , Organophosphonates/chemistry , Surface-Active Agents/chemistry , Americium/isolation & purification , Emulsions/chemistry , Hexoses/chemistry , Hydrogen-Ion Concentration , Radioactive Waste/analysis
20.
Radiat Prot Dosimetry ; 141(2): 205-9, 2010 Sep.
Article in English | MEDLINE | ID: mdl-20494955

ABSTRACT

The selectivity of a rapid (90)Sr bioassay technique over (241)Am, (238/239)Pu, (210)Po, (137)Cs and (60)Co has been investigated. Similar to (90)Sr, these radionuclides are likely to be used in radiological dispersive devices. The purpose of this study was to demonstrate the degree to which the (90)Sr bioassay technique is free from interference by these radionuclides if present in a urine matrix. The interfering radionuclides were removed (from (90)Sr) by their retention on an anion exchange column. While, recovery of the target radionuclide ((90)Sr) was found to be >or= 90 %, contributions from (241)Am, (242)Pu and (208)Po were found to be

Subject(s)
Americium/urine , Biological Assay , Cesium Radioisotopes/urine , Cobalt Radioisotopes/urine , Plutonium/urine , Polonium/urine , Strontium Radioisotopes/urine , Urinalysis , Americium/isolation & purification , Cesium Radioisotopes/isolation & purification , Cobalt Radioisotopes/isolation & purification , Humans , Plutonium/isolation & purification , Polonium/isolation & purification , Radiation Monitoring , Strontium Radioisotopes/isolation & purification , Urine/chemistry
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