Radiochemical studies in chemical separation and spectrographic determination of rare earths in thorium oxide matrix (Preprint No. RA.06)

International Nuclear Information System (INIS)

Adya, V.C.; Dhawale, B.A.; Rajeshwari, B.; Bangia, T.R.; Sastry, M.D.

1989-01-01

A chemical separation procedure was standardised for the separation of traces of rare earths from ThO 2 matrix using HDEHP (Di 2-ethyl hexyl phosphoric acid). The studies were carried out using both nitric acid and hydrochloric acid medium in different concentrations. The extraction studies were also carried out using radioactive isotopes of rare earths viz. 141 Ce, 152-154 Eu, 153 Gd, 170 Tm etc. The extraction was effective in both media. In 0.1 M HDEHP/xylene and 3 M HNO 3 , Ce was partially extracted into organic phase. So HCl/xylene medium was chosen for extraction purposes. The recovery was confirmed by both gamma counting and emission spectropgraphic method. It was found to be quantitative within experimental error. The separation procedure development here was used for determination of rare earths in thorium oxide matrix by emission spectrographic method. (author)

Extraction Chromatography for Am and Cm Recovery in Engineering Scale

International Nuclear Information System (INIS)

Koma, Y.; Watanabe, S.; Sano, Y.; Asakura, T.; Morita, Y.

2008-01-01

The Japan Atomic Energy Agency (JAEA) has been developing the extraction chromatography for Am and Cm (An(III)) recovery from HLLW aiming at an engineering scale application. For process development, we started to assess the characteristics of adsorbents with some extractants by laboratory scale experiments. The experimental results with HDEHP/SiO 2 -P adsorbent suggested that An(III) is separated from other fission products by adjusting the pH of a feed solution and/or an eluent containing DTPA to be an appropriate value. The durability of CMPO/SiO 2 -P and HDEHP/SiO 2 -P adsorbents for gamma-ray irradiation were estimated to be 1 and 0.5 MGy, respectively. In the system development, system experiments for fluid flow, safety and durability using engineering scale column as well as studies on remote control/maintenance are now under progress. (authors)

Synergistic solvent extraction investigation of Am (III), Eu (III), Zn(II), and Cs(I), using 2-heptyl-2-methyl-nonanoic acid mixed with different organophosphorus compounds from nitrate media. Vol. 3

Energy Technology Data Exchange (ETDEWEB)

El-Naggar, H A; Ramadan, A; Abdel-Fattah, A [Nuclear Chemistry Department, Hot Laboratories Center, Atomic Energy Authority, Cairo (Egypt)

1996-03-01

Extraction studies for investigating the effect of mixing 2-heptyl-2-methyl nonanoic acid (HA) with a number of organophosphorus compounds; namely tributyl phosphate (TBP), terphenyl phosphate oxide (TPPO); tri octyl phosphine oxide (TOPO) or bis-2-(ethyl hexyl) phosphoric acid (HDEHP) in benzene on the extraction of trace elements Am(III), Eu(III), Zn(II), and Cs(I) from nitrate media of ionic strength, I=0.1 M were carried out. The effect of adding different organophosphorus compounds to HA was tested to account for the presence or absence of the phenomenon of synergism. It was found that TBP, TPPO, and TOPO causing some antagonistic effects for the elements studied. Extraction enhancement was only observed with bis- (2-ethyl-hexyl) -phosphoric acid (HDEHP) for all the elements investigated. The extraction mechanisms as well as the thermodynamic parameters for the mixed extracted species are discussed. 19 figs.

Synergistic solvent extraction investigation of Am (III), Eu (III), Zn(II), and Cs(I), using 2-heptyl-2-methyl-nonanoic acid mixed with different organophosphorus compounds from nitrate media. Vol. 3

International Nuclear Information System (INIS)

El-Naggar, H.A.; Ramadan, A.; Abdel-Fattah, A.

1996-01-01

Extraction studies for investigating the effect of mixing 2-heptyl-2-methyl nonanoic acid (HA) with a number of organophosphorus compounds; namely tributyl phosphate (TBP), terphenyl phosphate oxide (TPPO); tri octyl phosphine oxide (TOPO) or bis-2-(ethyl hexyl) phosphoric acid (HDEHP) in benzene on the extraction of trace elements Am(III), Eu(III), Zn(II), and Cs(I) from nitrate media of ionic strength, I=0.1 M were carried out. The effect of adding different organophosphorus compounds to HA was tested to account for the presence or absence of the phenomenon of synergism. It was found that TBP, TPPO, and TOPO causing some antagonistic effects for the elements studied. Extraction enhancement was only observed with bis- (2-ethyl-hexyl) -phosphoric acid (HDEHP) for all the elements investigated. The extraction mechanisms as well as the thermodynamic parameters for the mixed extracted species are discussed. 19 figs

Comprehension of synergistic mechanisms for uranium extraction from phosphate ores

International Nuclear Information System (INIS)

Pecheur, Olivia

2014-01-01

Uranium VI is commonly extracted from phosphoric ores by a well-known process exploiting the synergistic mixture of two extractant molecules: HDEHP and TOPO. In the field of liquid-liquid extraction, synergistic combinations are common but the mechanisms at the origin of the synergy are not well understood. A multi-scale approach has been used to describe these mechanisms, combining two different descriptions: the molecular scale focuses on the ion point of view, while the supramolecular scale focuses on extractants' aggregation. These two approaches have been rationalized by molecular dynamics computations. The results allow describing the synergy through the structure of the complexes and aggregates. With the same approach, some bifunctional compounds, combining the two extracting sites in one molecule, have been studied and compared to the HDEHP/TOPO system in order to identify the origin of their increased capacities in extraction and selectivity. (author) [fr

A contribution to the study of mass transfer: uranium extraction from phosphoric acid

International Nuclear Information System (INIS)

Maher, A.

1985-12-01

Liquid-liquid extraction of uranium (VI) contained in phosphoric acid is examined. Synergism and thermodynamical equilibria are studied. Influence of drop size, extractant concentration and temperature on reaction kinetics are determined. The experimental study concerns extraction by HDEHP, TOPO and the mixture of both. Reaction mechanisms are interpreted [fr

Extraction chromatogrpahy of actinides, ch. 7

International Nuclear Information System (INIS)

Mueller, W.

1975-01-01

This review on extraction chromatography of actinides emphasizes the important usage of neutral (Tributylphosphate), basic (substituted ammonium salts), and acidic (HDEHP) extractants, and their application to separations of actinides in the di-to hexavalent oxidation state. Furthermore, the actinide extraction by ketones, ethers, alcohols and β-diketones is discussed

Supercritical fluid extraction of uranium and thorium from nitric acid medium using organophosphorous compounds

Energy Technology Data Exchange (ETDEWEB)

Pitchaiah, K.C.; Sujatha, K.; Rao, C.V.S. Brahmmananda; Subramaniam, S.; Sivaraman, N.; Rao, P.R. Vasudeva [Indira Gandhi Centre for Atomic Research, Kalpakkam (India). Chemistry Group

2015-06-01

In recent years, Supercritical Fluid Extraction (SFE) technique has been widely used for the extraction of metal ions. In the present study, extraction of uranium from nitric acid medium was investigated using supercritical carbon dioxide (Sc-CO{sub 2}) containing various organophosphorous compounds such as trialkyl phosphates e.g. tri-iso-amyl phosphate (TiAP), tri-sec-butyl phosphate (TsBP) and tri-n-butyl phosphate (TBP), dialkylalkyl phosphonates, e.g. diamylamyl phosphonate (DAAP) and dibutyl butyl phosphonate (DBBP), dialkyl hydrogen phosphonates, e.g. dioctyl hydrogen phosphonate (DOHP), dioctylphosphineoxide (DOPO), trioctyl phosphine oxide (TOPO), n-octylphenyl N,N-diisobutyl carbamoylmethylphosphine oxide (CMPO) and di-2-ethyl-hexyl phosphoric acid (HDEHP). Some of these ligands have been investigated for the first time in the supercritical phase for the extraction of uranium. The extraction efficiency of uranium was studied with TiAP, DAAP and DBBP as a function of nitric acid concentration; the kinetics of the equilibration period (static extraction) and transportation of the metal complex (dynamic extraction) was investigated. The influence of pressure and temperature on the extraction behaviour of uranium with DAAP was studied from 4 N HNO{sub 3}. The extraction efficiency of uranium from 4 N nitric acid medium was found to increase in the order of phosphates < phosphonates < HDEHP < TOPO < CMPO. In the case of phosphates and phosphonates, the maximum extraction of uranium was found to be from 4 N HNO{sub 3} medium. The acidic extractants, HDEHP and DOHP showed relatively higher extraction at lower acidities. The relative extraction of uranium and thorium from their mixture was also examined using Sc-CO{sub 2} containing phosphates, phosphonates and TOPO. The ligand, TsBP provided better fractionation between uranium and thorium compared to trialkyl phosphates, dialkyl alkyl phosphonates and TOPO.

Simplified method of analysis of Strontium-90 in milk

International Nuclear Information System (INIS)

Suomela, J.

1987-06-01

The milk sample is freeze-dried and the milk powder ignited. The ash is dissolved in hydrochloric acid and yttrium is extracted from the solution by 5% HDEHP (dioctyl phosforic acid). After re-extraction in nitric acid the Cherenkov radiation of yttrium 90 is measured in a low beta liquid scintillation counter. (O.S.)

Extraction of niobium and tantalum isotopes using organophosphorus compounds. Pt. 1. Extraction of 'carrier-free' metal concentrations from HCl solutions

International Nuclear Information System (INIS)

Gates, J.M.; California Univ., Berkeley, CA; Sudowe, R.; Stavsetra, L.

2009-01-01

The extraction of niobium (Nb) and tantalum (Ta) from hydrochloric acid media by bis(2-ethylhexyl) hydrogen phosphate (HDEHP) and bis(2-ethylhexyl) hydrogen phosphite (BEHP) was studied. The goal of the experiments is to find a system that demonstrates selectivity between the members of group five of the Periodic Table and is also suitable for the study of dubnium (Db, Z=105). Experiments were performed at the trace level (10 -16 M Nb or Ta) using hydrochloric acid with concentrations ranging from 1-11 M and short-lived isotopes of Nb and Ta produced in nuclear reactions. When HDEHP was used as the extractant, the Nb extraction yield decreased with increasing acid concentrations above 6 M, while the amount of Ta extracted remained over 75% for all acid concentrations studied. Tantalum was found to be extracted by BEHP at acid concentrations above 6 M, while niobium was not significantly extracted. The data obtained are used as the basis to discuss the speciation of Nb and Ta under the conditions studied and to evaluate possible extraction mechanisms. (orig.)

Determination of /sup 90/Sr in milk by solvent extraction of /sup 90/Y

Energy Technology Data Exchange (ETDEWEB)

Mitsuhashi, T [National Inst. of Animal Industry, Chiba (Japan); Sakanoue, M

1977-10-01

In order to replace the conventional method using violent fuming nitric acid, a new method for the determination of /sup 90/Sr in milk has been developed by using the solvent extraction with bis (2-ethylhexyl) phosphoric acid (HDEHP). The daughter nuclide /sup 90/Y in a radiochemical equilibrium with its parent /sup 90/Sr was extracted with 2:1 HDEHP-toluene from the acid solution (1M HCl) of milk ash sample prepared by dry-ashing. After stripping with 8M HCl, /sup 90/Y, together with stable yttrium added as carrier, was precipitated as oxalate to prepare ..beta..-counting source. The radiochemical purity was confirmed by decay curve. The decontamination of strontium was checked by applying non-dispersive fluorescence x-ray analysis using /sup 133/Ba as irradiating source. Bone samples of cow were also analyzed by the same method and the results were compared with those obtained by other methods. The duplicate crosschecking analyses of finely ground bone samples were carried out to examine the effectiveness of this method. This simple new method was found to be very effective for the routine analysis of /sup 90/Sr in these samples.

Determination of 90Sr in milk by solvent extraction of 90Y

International Nuclear Information System (INIS)

Mitsuhashi, Toshihiko; Sakanoue, Masanobu.

1977-01-01

In order to replace the conventional method using violent fuming nitric acid, a new method for the determination of 90 Sr in milk has been developed by using the solvent extraction with bis (2-ethylhexyl) phosphoric acid (HDEHP). The daughter nuclide 90 Y in a radiochemical equilibrium with its parent 90 Sr was extracted with 2:1 HDEHP-toluene from the acid solution (1M HCl) of milk ash sample prepared by dry-ashing. After stripping with 8M HCl, 90 Y, together with stable yttrium added as carrier, was precipitated as oxalate to prepare β-counting source. The radiochemical purity was confirmed by decay curve. The decontamination of strontium was checked by applying non-dispersive fluorescence x-ray analysis using 133 Ba as irradiating source. Bone samples of cow were also analyzed by the same method and the results were compared with those obtained by other methods. The duplicate crosschecking analyses of finely ground bone samples were carried out to examine the effectiveness of this method. This simple new method was found to be very effective for the routine analysis of 90 Sr in these samples. (auth.)

quality control

International Nuclear Information System (INIS)

Skujina, A.; Purina, S.; Riekstina, D.

1999-01-01

The optimal objects: soils, spruce needles and bracken ferns were found for the environmental monitoring in the regions of possible radioactive contamination - near SalaspiIs nuclear reactor and Ignalina nuclear power plant. The determination of Sr-90 was based on the radiochemical separation of Sr-90 (=Y-90) by HDEHP extraction and counting the Cerenkov radiation. The quality control of the results was carried out. (authors)

Separation of carrier-free 181Re produced in 16O-irradiated thulium target

International Nuclear Information System (INIS)

Lahiri, Susanta; Mukhopadhyay, Krishnendu; Banerjee, Kakoli; Ramaswami, A.; Manohar, S.B.

2001-01-01

Heavy ion activation of natural Tm 2 O 3 with 90 MeV 16 O beam results in the formation of carrier-free short-lived 181 Ir and 181 Os which ultimately decay out to 181 Re in the matrix. The liquid cation exchanger, HDEHP, has effectively been utilized as an extractant for quantitative separation of bulk thulium target matrix from carrier-free rhenium radionuclide

Determination of uranium, plutonium and transplutonium elements in urine

International Nuclear Information System (INIS)

Zablotskaya, I.D.; Vorob'ev, G.V.; Golutvina, M.M.

1983-01-01

An extraction-coprecipitation method is proposed for determining enriched U, Pu and transplutonium elements (Am, Cm, Cf) in urine of people having contact with these substances. The nuclides were extracted from HDEHP sulfuri.c acid solutions with a subsequent reextraction by ammonium carbonate and HCl. The reliability of the developed method is confirmed by semiconductor α-spectrometry. The nuclide yields are shown to equal 70-90%

Radiochemical neutron activation analysis of zirconium and zirconium-niobium alloys

International Nuclear Information System (INIS)

Tashimova, F.A.; Sadikov, I.I.; Salimov, M.

2004-01-01

Full text: Zirconium and zirconium-niobium alloys are used on nuclear technology, as fuel cladding of nuclear reactors. Their nuclear-physical, mechanical and thermophysical properties are influenced them matrix and impurity composition, therefore determination of matrix and impurity content of these materials is a very important task. Neutron activation analysis is one from multielemental and high sensible techniques that are widely applied in analysis of high purity materials. Investigation of nuclear-physical characteristics of zirconium has shown that instrumental variant NAA is unusable for analysis due to high radioactivity of a matrix. Therefore it is necessary carrying out radiochemical separation of impurity radionuclides from matrix. Study of the literature datum have shown, that zirconium and niobium are very well extracted from muriatic solution with 5% tributyl phosphineoxide (TBPO) solution in toluene and 0,75 M solution of di-2-ethyl hexyl phosphoric acid (HDEHP) in cyclohexanone. Investigation of these elements extraction in these systems has shown that more effective and selective separation of matrix radionuclides is achieved in HDEHP-3M HCI system. This system is also extracted and hafnium, witch is an accompanying element of zirconium and its high content prevented determination of other impurity elements in sample. Therefore we used extraction system HDEHP-3M HCl for analysis of zirconium and zirconium-niobium alloys in chromatographic variant. By measurement of distribution profile of a matrix and of elution curve of determined elements is established, that for effective separation of impurity and matrix radionuclides there is enough chromatographic column with diameter 1 cm and height of a sorbent layer 7 cm, thus volume of elute, necessary for complete elution of determinate elements is 35-40 ml. On the basis of the carried out researches the technique of radiochemical NAA of high purity zirconium and zirconium-niobium alloy, which allows to

Effect of pKa on the extraction behavior of Am(III) in organo phosphorus acid and diglycolamide solvent system

International Nuclear Information System (INIS)

Swami, K. Rama; Antony, M.P.; Homi Bhabha National Institute, Mumbai; Kumaresan, R.; Nayak, P.K.; Venkatesan, K.A.

2018-01-01

A combination of neutral and acidic extractant has been proposed for the single-cycle separation of trivalent actinides from high-level liquid waste (HLLW). The nature of acidic extractant in the combined solvent formulation plays a profound role in deciding the extraction and stripping of trivalent actinides. Therefore, the extraction behavior of Am(III) in a solution of tetra-bis(2-ethylhexyl)-diglycolamide (TEHDGA) and acidic extractant (HA) was studied from nitric acid medium. The acidic extractants chosen were bis(2-ethylhexyl)phosphoric acid (HDEHP), bis(2-ethylhexyl)phosphonic acid (PC88A) and bis(2,4,4-trimethylpentyl)phosphinic acid (CYANEX-272) whose pKa values were 3.24, 4.51 and 6.37, respectively. The distribution ratio of Am(III) was measured as a function of various parameters such as concentration of nitric acid, TEHDGA, HA etc. The data were compared with those obtained in individual solvent systems namely 0.1 M TEHDGA/n-DD and HA/n-DD. Slope analysis of the extraction data indicated the synergic participation of both TEHDGA and HDEHP in the extraction of Am(III) at all acidities. However, antagonistic effect was observed at lower acidity when TEHDGA was mixed to PC88A or CYANEX-272 present in n-DD. Accordingly, a suitable mechanism has been proposed for the extraction of Am(III) at all acidities using these combined solvent formulation. Studies with fast reactor simulated high level liquid waste indicated that extraction of Am(III) was accompanied by co-extraction of lanthanides and unwanted metal ions such as Zr(IV), Mo(VI), Y(III) and Pd(II). However, addition of trans-1,2-diaminocyclohexane-N,N,N,N ' -tetraaceticacid (CyDTA) reduced the extraction of unwanted metal ions. Batch extraction and stripping studies indicated the possibility of using 0.1 M TEHDGA+0.25 M HDEHP in n-dodecane for the single cycle separation of Am(III) from FR-SHLLW.

Preparation of polymeric fibers immobilizing inorganic compounds, enzymes, and extractants designed for radionuclide decontamination, ultrapure water production, and rare-earth metal purification

International Nuclear Information System (INIS)

Saito, Kyoichi

2014-01-01

To remove and recover targeted ions and molecules at a high rate, inorganic compounds, enzymes, and extractants were immobilized onto a commercially available 6-nylon fiber by radiation-induced graft polymerization and subsequent chemical modifications. Fibrous supports with a smaller diameter provide a larger external interface area with liquids. Modified fibers are fabricated into various shapes such as wound filter and braid according to application sites. First, insoluble cobalt ferrocyanide-impregnated fiber was prepared via precipitation by immersing ferrocyanide ion-bound anion-exchange fiber in cobalt chloride solution. Cobalt ferrocyanide impregnated onto the polymer chain grafted onto the fiber specifically captured cesium ions in seawater. Similarly, sodium titanate impregnated onto a cation-exchange fiber selectively captured strontium ions in seawater. Second, urease was bound by an anion-exchange graft chain, followed by enzymatic cross-linking among urease molecules with transglutaminase. The bed charged with the urease-immobilized fiber exhibited a quantitative hydrolysis of urea at a high space velocity of urea solution. Third, an acidic extractant (HDEHP, bis(2-ethylhexyl) phosphate) was impregnated onto a dodecylamino-group-containing polymer chain grafted onto the 6-nylon fiber. Distribution coefficients of the HDEHP-impregnated fiber for neodymium and dysprosium agreed well with those in n-dodecane. (author)

FY-2011 Status Report for Thermodynamics and Kinetics of Advanced Separations Systems

Energy Technology Data Exchange (ETDEWEB)

Leigh R. Martin; Peter R. Zalupski; Travis S. Grimes

2011-09-01

This report presents a summary of the work performed in the area of thermodynamics and kinetics of advanced separations systems under the Fuel Cycle Research and Development (FCR&D) program during FY 2011 at the INL. On the thermodynamic front, investigations of liquid-liquid distribution of lanthanides at TALSPEAK-related conditions continued in FY11. It has been determined that a classical ion-exchanging phase transfer mechanism, where three HDEHP dimers solvate the metal ion in the organic phase, dominates metal extraction for systems that contain up to 0.1 M free lactate in solution. The correct graphical interpretation of the observed data in those regions relied on incorporating corrections for non-ideal behavior of HDEHP dimer in aliphatic diluents as well as sodium extraction equilibria. When aqueous conditions enter the complex regions of high lactate concentrations, slope analysis is no longer possible. When normalized metal distribution ratios were studied along the increasing concentration of free lactate, a slope of -1 was apparent. Such dependency either indicates aqueous complexing competition from lactate, or, a more likely scenario, a participation of lactate in the extracted metal complex. This finding agrees with our initial assessment of postulated changes in the extraction mechanism as a source of the lactate-mediated loss of extraction efficiency. The observed shape in the lanthanide distribution curve in our studies of TALSPEAK systems was the same for solutions containing no lactate or 2.3 M lactate. As such we may conclude that the mechanism of phase transfer is not altered dramatically and remains similarly sensitive to effective charge density of the metal ion. In addition to these thermodynamics studies, this report also summarizes the first calorimetric determination of heat of extraction of 248Cm in a bi-phasic system. The heat of extraction measured by isothermal titration calorimetry is compared to that determined using van

Enrichment and determination of small amounts of 90Sr/90Y in water samples

International Nuclear Information System (INIS)

Mundschenk, H.

1979-01-01

Small amounts of 90 Sr/ 90 Y can be concentrated from large volumes of surface water (100 l) by precipitation of the phosphates, using bentonite as adsorber matrix. In the case of samples containing no or nearly no suspended matter (tap water, ground water, sea water), the daughter 90 Y can be extracted directly by using filter beds impregnated with HDEHP. The applicability of both techniques is demonstrated under realistic conditions. (orig.) 891 HP/orig. 892 MKO [de

Dialkyldithiophosphoric acids - chemical properties and 5f and 4f elements ions extraction

International Nuclear Information System (INIS)

Pattee, D.

1987-09-01

This work is a contribution to the study of the properties of the dialkyldithiophosphoric acids and of the extraction of the 4f and 5f ions from weakly acidic nitrate and phosphate media. Following a complete bibliographic study, synthesis and purification of the di-2-ethylhexyl-dithiophosphoric acid (HDEHDTP) is studied. It is identified with chemical methods and spectroscopic methods (I.R., N.M.R., V.P.C.); its by products, the di-2-ethylhexyl (monothio) phosphoric acids (HDEHTP, HDEHP) are also identified and characterized. Stability against hydrolysis and radiolysis is determined. The extractive properties are studied for the 4f and 5f ions. The presence of a sulfur donor atom in HDEHDTP makes it inefficient for the extraction of trivalent lanthanides and actinides but brings out a certain selectivity for americium. For HDEHTP, the presence of an oxygen donor atom rubs out any selectivity and the extraction constants are greater. Selectivity of HDEHDTP is increased by TBP (tri-n-butylphosphate) in synergistic mixtures. The mechanism of extraction of hexavalent uranium from phosphoric medium is elucidated. A model is developed by NMR for the micellisation of the sodium salts of HDEHDTP, HDEHTP and HDEHP, and extrapolated it to the trivalent rare earth salts of the acids. The structures are verified by light scattering and low angle X-ray diffraction [fr

Transport of Eu3+ through a Bis(2-ethylhexyl)-phosphoric acid, n-dodecane solid supported liquid membrane

International Nuclear Information System (INIS)

Danesi, P.R.; Horwitz, E.P.; Rickert, P.

1982-01-01

The coupled transpot of Eu 3 + and H + ions througn a solid supported liquid membrane consisting of a porous polypropylene film immobilizing an HDEHP solution in n-dodecane has been studied as a function of the membrane area, stirring speed of the aqueous solutions, membrane composition, and acidity of the feed solution. The experimental results are in agreement with predictions derived from a theoretical permeability coefficient equation which assumes that membrane diffusion and aqueous film diffusion are the only rate-controlling factors

Equilibrium Speciation of Select Lanthanides in the Presence of Acidic Ligands in Homo- and Heterogeneous Solutions

Energy Technology Data Exchange (ETDEWEB)

Robinson, Troy A [Univ. of Nevada, Las Vegas, NV (United States)

2011-08-01

This dissertation explores lanthanide speciation in liquid solution systems related to separation schemes involving the acidic ligands: bis(2-ethylhexyl) phosphoric acid (HDEHP), lactate, and 8-hydroxyquinoline. Equilibrium speciation of neodymium (Nd³⁺), sodium (Na+), HDEHP, water, and lactate in the TALSPEAK liquid-liquid extraction system was explored under varied Nd³⁺ loading of HDEHP in the organic phase and through extraction from aqueous HCl and lactate media. System speciation was probed through vapor pressure osmometry, visible and Fourier Transform Infrared (FTIR) spectroscopy, ²²Na and ¹³C labeled lactate radiotracer distribution measurements, Karl Fischer titrations, and equilibrium pH measurements. Distribution of Nd³⁺, Na⁺, lactate, and equilibrium pH were modeled using the SXLSQI software to obtain logKNd and logKNa extraction constants under selected conditions. Results showed that high Nd³⁺ loading of the HDEHP led to Nd³⁺ speciation that departs from the ion exchange mechanism and includes formation of highly aggregated, polynuclear [NdLactate(DEHP)₂]_x; (with x > 1). By substituting lanthanum (La³⁺) for Nd³⁺ in this system, NMR scoping experiments using ²³Na, ³¹P nuclei and ¹³C labeled lactate were performed. Results indicated that this technique is sensitive to changes in system speciation, and that further experiments are warranted. In a homogeneous system representing the TALSPEAK aqueous phase, Lactate protonation behavior at various temperatures was characterized using a combination of potentiometric titration and modeling with the Hyperquad computer program. The temperature dependent deprotonation behavior of lactate showed little change with temperature at 2.0 M NaCl ionic strength. Cloud point extraction is a non-traditional separation technique that starts with a homogeneous

Sigma Team for Minor Actinide Separation: PNNL FY 2011 Status Report

Energy Technology Data Exchange (ETDEWEB)

Lumetta, Gregg J.; Braley, Jenifer C.; Sinkov, Sergey I.; Levitskaia, Tatiana G.; Carter, Jennifer C.; Warner, Marvin G.; Pittman, Jonathan W.

2011-08-13

This report summarizes work conducted in FY 2011 at PNNL to investigate new methods of separating the minor actinide elements (Am and Cm) from the trivalent lanthanide elements, and separation of Am from Cm. For the former, work focused on a solvent extraction system combining an acidic extractant (HDEHP) with a neutral extractant (CMPO) to form a hybrid solvent extraction system referred to as TRUSPEAK (combining the TRUEX and TALSPEAK processes). For the latter, ligands that strongly bing uranyl ion were investigated for stabilizing corresponding americyl ion.

Kinetics of americium(VI) mass transfer through solid supported liquid membrane with HDEHP

International Nuclear Information System (INIS)

Mikheeva, M.N.; Novicoov, P.; Myasoedov, B.F.; Tikhomirov, S.V.

1994-01-01

The main regularities of membrane extraction of americium under conditions of different redox potentials in aqueous phases have been studied. The physico-chemical model of the process including steps of americium oxidation in feed solution, extraction by membrane, partial reduction on membrane surface, trans-membrane diffusion and reextraction to strip solution has been developed. The calculation of reduction rate constant on membrane surface has been carried out. (author) 9 refs.; 4 figs.; 3 tabs

Hypersensitive transition spectrum of f-element and coordination structure

International Nuclear Information System (INIS)

Cao Xuan; Song Chongli; Zhu Youngjun

1992-10-01

Some f-f transitions of Ln(An) metallic ions have particular super-sensitivity to the change of coordination environments. This is called super-sensitive transitions. Based on the irreducible tensor operator method, a computation model and corresponding computer program for calculating the hypersensitive transition spectrum of f-element were developed. By comparing the theoretical spectra of all possible coordination structures with experimental one, the possible coordination structures of complex can be determined. The coordination structures of Nd 3+ , Er 3 + hydrate and their extraction complex with H(DEHP) were successfully determined by this method, and the experimental spectra were also assigned

Solvent extraction studies on cadmium Part 3

International Nuclear Information System (INIS)

Alian, A.; El-Kot, A.

1976-01-01

An extraction study was performed on various concentrations of cadmium, zinc and cobalt halides in the presence of sulphuric acid. A long chain amine (Amberlite LA-2) and an organophosphorus solvent (TBP) were used. In most cases the value of the distribution ratio decreases with the increase of metal concentration in the aqueous phase. The various possibilities of chemical and radiochemical separations of cadmium from accompanying metal species are reported: separation of (sup109m)Ag from irradiated Cd targets, separation of (sup115m)In using HDEHP, separation of Cd and Zn from their mixtures. (T.G.)

The determination of small amounts of fluoride in uranium compounds by use of an ion-selective electrode

International Nuclear Information System (INIS)

Shelton, B.M.

1975-01-01

A method is presented for the determination of fluoride in uranium metal and oxide at levels from 16 p.p.m. upwards. Uranium is separated from fluoride by extraction into a solution of di(2-ethylhexyl)-phosphoric acid (HDEHP) in carbon tetrachloride. The fluoride remaining in the aqueous phase is determined by potentiometric measurement with an ion-selective electrode. A correction is made for the fluoride lost during the dissolution or extraction step, or both, which is based on a determination of the apparent loss of fluoride on spiked samples that are taken through the whole procedure [af

Removal of Radioactive Pollutants by Liquid Emulsion Membrane From Liquid Waste

International Nuclear Information System (INIS)

Yossef, Y.A.A.

2013-01-01

Radioactive liquid waste should be safely managed because it is potentially hazardous to human health and the environment. Several methods were used for treatment of liquid waste, such as liquid emulsion membrane (LEM). In this work, liquid emulsion membrane using Tri-butyl phosphate (TBP) plus Bis (2-ethylhexyl) phosphate (HDEHP) as mobile carriers, hydrochloric acid (HCl) as stripping agents and an emulsifying agent (span 80) was used for the extraction of uranium ions from radioactive liquid waste. Various parameters influencing the permeation of uranium ions through the membrane have been optimized to separate uranium ions from radioactive liquid waste such as: the effects of membrane material, carrier concentration, operating conditions, etc. were examined; moreover, the transport mechanism of this uranium was also studied. The internal mass transfer in the water/oil (W/O) emulsion drop, the external mass transfer around the drop, the rates of formation, and the decomposition of the complex at the external aqueous-organic interface were considered. The results show that, the liquid emulsion membrane which consists of (25% by volume HDEHP, 0.005 M + 75% by volume TBP, 0.01 M) as extractant (carrier), span 80, 4% (v/v) (sorbitan monooleate) as surfactant agent, hydrochloric acid (HCl), (1.0 M) as stripping agent. From the results, the maximum extraction percent of uranium ions (nearly about of 100%) occurred at the operating conditions: stirring speed =500 rpm, the ratio between LEM and feed phase (liquid waste) = 20 ml: 100 ml, the ratio between organic phase (membrane phase) to internal aqueous phase (stripping phase) = 1.0 and the ph value of the external aqueous phase equal to 5.0.

Studies on removal of plutonium from oxalic acid containing hydrochloric acid solutions

Energy Technology Data Exchange (ETDEWEB)

Ghadse, D R; Noronha, D M; Joshi, A R [Fuel Chemistry Division, Bhabha Atomic Research Centre, Mumbai (India)

1994-06-01

Solution containing hydrochloric acid, oxalic acid and considerable quantities of plutonium may be generated while recycling of scrap produced during the metallic fuel fabrication. Plutonium from such waste is normally recovered by anion exchange method after the destruction of oxalic acid using suitable oxidising agent. Solvent extraction and ion exchange methods are being explored in this laboratory for recovery of Pu from oxalic acid containing HCl solutions without prior destruction of oxalic acid. This paper describes the results on the determination of distribution ratios for extraction of Pu(IV) from hydrochloric acid using Aliquot-336 or HDEHP under varying experimental conditions. (author). 5 refs., 5 tabs.

Distribution equilibria of Eu(III) in the system: bis(2-ethylhexyl)phosphoric acid organic diluent-NaCl, lactic acid, polyaminocarboxylic acid, water

International Nuclear Information System (INIS)

Danesi, P.R.; Cianetti, C.; Horwitz, E.P.

1982-01-01

The distribution equilibria of Eu 3+ between aqueous phases containing lactic acid and N'-(2hydroxyethyl)ethylenediamine-N,N,N'-triacetic acid (HEDTA) or diethylenetriamine-N,N,N',N',N''-penetaacetic acid (DTPA) at constant ionic strength (μ = 1.0), and n-dodecane solutions of HDEHP have been studied. The formation constants of the simple Eu-lactate complexes and Eu-lactate-HEDTA mixed complex were evaluated from the k/sub d/ data. The conclusion is reached that no lactic acid is coextracted into the organic phase at tracer metal concentrations. The separation factors between Eu 3+ , Pm 3+ , and Am 3+ have been evaluated in the presence of HEDTA

Thin-layer chromatography - liquid chromatography, an ideal supplement demonstrated by the separation of lanthanoids

International Nuclear Information System (INIS)

Specker, H.; Hufnagel, A.

1984-01-01

All lanthanoids have been separated by thin-layer chromatography (TLC) with short retention times by using a mixture of ether/tetrahydrofurane (THF)/bis-(2-ethylhexyl)-phosphate (HDEHP)/nitric acid. The eluent was empirically tested by synergistic effects. The results have been transferred to high-performance liquid chromatography /HPLC). It was possible to use the same eluent in TLC and HPLC both for the analytical separation of all lanthanoids and for the separation of fission products. The experimental experience gained in HPLC could be applied to the pre-concentration of isotopes in TLC. Both methods excellently supplemented each other in the separation of lanthanoids. (orig.) [de

Preparation of extraction resin for radio lanthanides separation; Preparacion de resina de extraccion para separacion de radiolantanidos

Energy Technology Data Exchange (ETDEWEB)

Cruz B, C.C. de la; Monroy G, F. [ININ, 52750 La Marquesa, Estado de Mexico (Mexico)]. e-mail: delacruzbc@hotmail.com

2008-07-01

The present work presents the methodology that was developed for the preparation of one extractant resin with the aim of HDEHP, to separate radio lanthanides with serial atomic numbers. In this case it is exemplified with the separation of the following elements: Gadolinium-161 and the Terbium-161; this last radioisotope it is a beta emitting ({beta}{sup -}) that has a great potential to be used in therapy, also in nuclear medicine and in oncology, this is due to the high penetration power of their {beta}{sup -} particles that can kill to the cancerous cells and to inhibit the growth of the same ones. To be able to separate them it is necessary to appeal to extremely selective separation techniques, since the chemical properties of these elements are very similar. The chromatography is one of the more used analytical tools, this is due to its great sensibility and the selectivity in the compounds separation, in particular the use of the extractive chromatography has shown the feasibility of carrying out this type of separations for this type of elements. The resin with base of HDEHP was absorbed in an inert support under diverse preparation conditions. The extractant properties of the resin, in relation to the elements Gd and Tb (distribution coefficients), its were determined by means of the dynamic method, using as eluent solutions of nitric acid. The Gd-159 was prepared by irradiation of Gd-168 with thermal neutrons and the Tb-161 it is the result of the radioactive decay of the Gd-161 that is produced in turn with the irradiation with neutrons of Gd-160. The coefficients of distribution of Gd and Tb, using the prepared resin under diverse conditions are presented. (Author)

Determination of uranium and thorium in complex matrices by two solvent extraction separation techniques and photon electron rejecting alpha liquid spectrometry

International Nuclear Information System (INIS)

Ayranov, M.; Wacker, L.; Kraehenbuehl, U.

2001-01-01

The separation of uranium and thorium from complex matrixes such as marine sediments using solvent extraction and determination by means of photon-electron rejecting liquid alpha spectrometry (PERALS trademark) has successfully been performed. Two extraction schemes, using TOPO and HDEHP, respectively, were compared for the separation of uranium and thorium from the matrix components. The results show recoveries between 73 and 92% for 234 U, 238 U, 232 Th, 230 Th and 238 Th with an accuracy of the methods ±12%. Minimum detectable activities for counting time up to 500 000 seconds for 0.5 g sample material were between 0.34-1.15 Bq/kg for uranium and 0.31-1.66 Bq/kg for thorium. (orig.)

Behaviour of solvent extraction of niobium in nitric acid

International Nuclear Information System (INIS)

Lin Cansheng; Huang Meixin; Zhang Xianzi; Zhang Chonghai

1988-01-01

The behaviour of solvent extraction of niobium is discussed. The expractants, includding TBP, HDBP, H 2 MBP, TBP irradiated, HDEHP, TTA and Aliquat-7402, are used. The special influence of molybdenum and zirconium on solvent extraction of niobium and the extraction behaviur of niobium with TBP irradiated are described. The effect of fluorine and uranium in aqueous phase on extraction of niobium is mentioned. It is observed that the interfacial crud has not relevance to D Nb , but niobium-95 can be absorbed on it. The species of extractable niobium, extraction mechanism, and the reason brought niobum into organic phase are discussed. Finally, the idea of increasing decontamination factor for niobium is suggested

Recovering phosphorus and uranium values from phosphate rock

International Nuclear Information System (INIS)

Sze, M.C.Y.; Long, R.H.

1981-01-01

Phosphate rock is acidulated with aqueous nitric acid to produce an aqueous solution containing phosphate values, calcium and uranium values. The aqueous solution is contacted with an extraction solvent for the uranium values: the extraction solvent comprising a water immiscible organic diluent, a dialkyl phosphoric acid having at least 10 carbon atoms, and an organic phosphorus compound having the formula R 1 R 2 R 3 P = O where R 1 , R 2 and R 3 are each either alkyl or alkoxy, the organic phosphorus compound having at least 10 carbon atoms. The uranium values are then recovered from the extraction solvent. In an example the extraction solvent is HDEHP and TOPO in kerosene. (author)

Thermodynamics and Kinetics of Advanced Separations Systems – FY 2010 Summary Report

Energy Technology Data Exchange (ETDEWEB)

Leigh R. Martin; Peter R. Zalupski

2010-09-01

This report presents a summary of the work performed in the area of thermodynamics and kinetics of advanced separations systems under the Fuel Cycle Research and Development (FCR&D) program during FY 2010. Thermodynamic investigations into metal extraction dependencies on lactate and HDEHP have been performed. These metal distribution studies indicate a substantial deviation from the expected behavior at conditions that are typical of TALSPEAK process operational platform. These studies also identify that no thermodynamically stable mixed complexes exist in the aqueous solutions and increasing the complexity of the organic medium appears to influence the observed deviations. Following on from this, the first calorimetric measurement of the heat of extraction of americium across a liquid-liquid boundary was performed.

Burn-up measurements on nuclear reactor fuels using high performance liquid chromatography

International Nuclear Information System (INIS)

Sivaraman, N.; Subramaniam, S.; Srinivasan, T.G.; Vasudeva Rao, P.R.

2002-01-01

Burn-up measurements on thermal as well as fast reactor fuels were carried out using high performance liquid chromatography (HPLC). A column chromatographic technique using di-(2-ethylhexyl) phosphoric acid (HDEHP) coated column was employed for the isolation of lanthanides from uranium, plutonium and other fission products. Ion-pair HPLC was used for the separation of individual lanthanides. The atom percent fissions were calculated from the concentrations of the lanthanide (neodymium in the case of thermal reactor and lanthanum for the fast reactor fuels) and from uranium and plutonium contents of the dissolver solutions. The HPLC method was also used for determining the fractional fissions from uranium and plutonium for the thermal reactor fuel. (author)

Recovering phosphorus and uranium values from phosphate rock

Energy Technology Data Exchange (ETDEWEB)

Sze, M C.Y.; Long, R H

1981-02-11

Phosphate rock is acidulated with aqueous nitric acid to produce an aqueous solution containing phosphate values, calcium and uranium values. The aqueous solution is contacted with an extraction solvent for the uranium values: the extraction solvent comprising a water immiscible organic diluent, a dialkyl phosphoric acid having at least 10 carbon atoms, and an organic phosphorus compound having the formula R/sub 1/ R/sub 2/ R/sub 3/ P = O where R/sub 1/, R/sub 2/ and R/sub 3/ are each either alkyl or alkoxy, the organic phosphorus compound having at least 10 carbon atoms. The uranium values are then recovered from the extraction solvent. In an example the extraction solvent is HDEHP and TOPO in kerosene.

Hot test of a TALSPEAK procedure for separation of actinides and lanthanides using recirculating DTPA-lactic acid solution

International Nuclear Information System (INIS)

Persson, G.; Svantesson, I.; Wingefors, S.; Liljenzin, J.O.

1984-01-01

Results are reported from a hot test of a TALSPEAK type process for separation of higher actinides (Am, Cm) from lanthanides. Actinides and lanthanides are extracted by 1 M HDEHP and separated by selective strip of the actinides, using a mixture of DTPA and lactic acid (reversed TALSPEAK process). In order to minimize the generation of secondary waste, a procedure using recirculating DTPA-Lactic acid solution has been developed. A separation factor between Am and Eu of 132 was achieved. In regard to separations of Am and Cm from commercial HLLW (high level liquid wastes), the factor corresponds to 1.5% of the lanthanide group remaining with the actinides. The loss of Am was about 0.2%. 9 figures, 3 tables

The solvent extraction of ytterbium from a molten eutectic

International Nuclear Information System (INIS)

Lengyel, T.

1977-01-01

The paper summarizes the results which were obtained in measurements performed with different binary mixtures of solvents being capable of effectively extracting ytterbium from the molten eutectic lithium nitrate--ammonium nitrate. In the course of elaborating the possible ways of extractive separation of rare earths systematic investigations regarding the individual members of the group are required. The binary solvent mixtures consisted of thenoyl-trifluoracetone (TTA), β-isopropil-tropolone (IPT), tributyl phosphate (TBP), di-2-ethylhexyl phosphoric acid (HDEHP), 2,2'-bipyridyl (bipy), dibutyl phtalate (DBP) and Amberlite LA-2 (LA-2). The concentration of the central ion was kept at 5x10 -6 M by using Yb-169 of high specific activity as a tracer for the radiometric assay. (T.I.)

Thermodynamics and Kinetics of Advanced Separations Systems - FY 2010 Summary Report

International Nuclear Information System (INIS)

Martin, Leigh R.; Zalupski, Peter R.

2010-01-01

This report presents a summary of the work performed in the area of thermodynamics and kinetics of advanced separations systems under the Fuel Cycle Research and Development (FCR and D) program during FY 2010. Thermodynamic investigations into metal extraction dependencies on lactate and HDEHP have been performed. These metal distribution studies indicate a substantial deviation from the expected behavior at conditions that are typical of TALSPEAK process operational platform. These studies also identify that no thermodynamically stable mixed complexes exist in the aqueous solutions and increasing the complexity of the organic medium appears to influence the observed deviations. Following on from this, the first calorimetric measurement of the heat of extraction of americium across a liquid-liquid boundary was performed.

Intercomparison of methods for determining 90Sr and 137Cs in plant samples

International Nuclear Information System (INIS)

Sha Lianmao; Zhao Min; Tian Guizhi

1986-01-01

The results of intercomparison of methods for determining 90 Sr and 137 Cs in plant samples are reported. Nine laboratories participated in the intercomparison. The samples used in intercomparison were reed and tea powders. The analytical results of 90 Sr in reed and 137 Cs in tea from different laboratories show good comparability and follow the normal-distribution. Some results reported of 137 Cs in reed are apparently lower than others. The results of 90 Sr in tea from different laboratories have poor comparability. The results obtained by HDEHP rapid extraction chromatograph appear to be too high, and it's cause is discussed. The 95% confidence intervals of content of 90 Sr and 137 Cs in reed and tea samples are given

On the determination of Zr(IV), Ce((III), Th(IV) and U(VI) in organic phase using arsenazo-I and arsenazo-III

International Nuclear Information System (INIS)

El-Sweify, F.H.; Kamel, M.M.; Shabana, R.

1997-01-01

Some organic extractants of different types, namely tridodecylamine (TDA), tricapryl methyl ammonium chloride (TCMA), di(2-ethylhexyl) phosphoric acid (HDEHP) and 1-[thenoyl-(2)]-3,3,3-trifluoroacetone (HTTA) in xylene have been used to study the extraction behaviour of coloured complexes of Zr(IV), Ce(III), Th(IV) and U(VI) from slightly acidic aqueous solutions of arsenazo-III. Spectrophotometric study for the determination of the aforementioned elements, as well as the colouring agents arsenazo-I and arsenazo-III in the organic phase has been carried out. Some factors affecting the spectrophotometric determination of these elements were studied. These factors were hydrogen ion concentration, concentration of the colouring agents in the aqueous phase and diluent type. Absorption spectra and standard curves are given. The molar extinction coefficients have been calculated. 10 figs

Carrier effect on separation efficiency of the column in reversed-phase partition chromatography

International Nuclear Information System (INIS)

Pszonicka, M.; Siekierski, S.

1972-01-01

Chromatographic columns were filled with carriers of diatomaceous earth type (Hyflo Super Cell, and Celite 545) of large pores, and two microporous silica gels respectively. These columns were used for the separation of europium and gadolinium by reversed-phase partition chromatography in the system: stationary phase-diethylhexylphosphoric acid (HDEHP) mobile phase-0.4 N nitric acid. In each case the separation of the above mentioned elements was achieved. The plate height that characterizes separation efficiency of the column, decreases with the decrease of particle diameter of the carrier. Best columns were obtained from carriers of large pores (Hyflo Super Cell and Celite 545) for which plate hights below 0.1 mm could be achieved. Columns filled with microporous silica gels showed plate heights of 0.2-0.3 mm. (author)

Development of a rapid procedure for the measurement of uranium in drinking water by PERALSR spectrometry

International Nuclear Information System (INIS)

Duffey, J.M.; Case, F.I.; Metzger, R.L.; Jessop, B.J.; Schweitzer, G.K.

1997-01-01

A new method has been developed for the measurement of U in water samples by selective and quantitative extraction from DTPA solution into an extractive scintillator containing HDEHP and alpha-counting by PERALS R spectrometry. Because this method offers several advantages over the current EPA and ASTM standard test methods for U in drinking water, including speed, simplicity and isotopic information, it has been proposed as a new ASTM standard test method. Sample preparation requires from 1-4 h. Less than 0.5% of Am, Pu, Po, Ra and Th were found to extract under the prescribed conditions. Typical backgrounds are ≤ 0.01 cpm. A comparison of this method with EPA standard method 908.0 and the results of two interlaboratory test of this method are reported. (author)

Isotope separation by chemical exchange process: Final technical report

International Nuclear Information System (INIS)

Schneider, A.

1987-02-01

The feasibility of a chemical exchange method for the separation of the isotopes of europium was demonstrated in the system EuCl 2 -EuCl 3 . The single stage separation factor, α, in this system is 1.001 or 1.0005 per mass unit. This value of α is comparable to the separation factors reported for the U 4+ - U 6 and U 3+ - Y 4+ systems. The separation of the ionic species was done by precipitation of the Eu 2+ ions or by extraction of the Eu 3+ ions with HDEHP. Conceptual schemes were developed for a countercurrent reflux cascades consisting of solvent extraction contractors. A regenerative electrocel, combining simultaneous europium reduction, europium oxidation with energy generation, and europium stripping from the organic phase is described. 32 refs., 22 figs., 6 tabs

Production of no-carrier-added {sup 123}I via heavy-ion activation of natural antimony oxide

Energy Technology Data Exchange (ETDEWEB)

Maji, S. [The Univ. of Burdwan (India). Dept. of Chemistry; Lahiri, S. [Saha Institute of Nuclear Physics, Kolkata (India). Chemical Sciences Div.

2007-07-01

Activation of natural Sb{sub 2}O{sub 3} with 48 MeV {sup 7}Li{sup 3+} beam results in the formation of no-carrier-added {sup 123}I in the matrix along with the radionuclides {sup 123,125}Xe and {sup 122}Sb. The {sup 123}I yield amounts to about 400 kBq/{mu}Ah and the radionuclidic impurity of {sup 124}I to {proportional_to}1.2% of {sup 123}I. Attempts to separate no-carrier-added iodine from bulk antimony target involved liquid-liquid extraction with TOA and HDEHP as well as precipitation of Sb{sub 2}S{sub 3} with thioacetamide. The precipitation technique was found to be the most effective for quantitative separation of {sup 123}I from the bulk antimony oxide target. (orig.)

A contribution to the study of thorium and neptunium (IV) complexes in acidic phosphoric media; Contribution a l`etude des complexes de thorium et de neptunium (IV) en milieux phosphoriques acides

Energy Technology Data Exchange (ETDEWEB)

Ghafar, M

1995-11-30

The thorium and neptunium (IV) phosphate complexes formation in acidic media has been investigated, essentially at the indicator`s level with {sup 227} Th, {sup 234} Th, {sup 235} Np and {sup 239} Np. Solvent extraction, a commonly used method for determining stability constants in solutions, was used with HDEHP in toluene. In order to get a better understanding of inorganic transparent gels formation in phosphoric aqueous solutions, the effect of the thorium concentration is also studied. Specific experimental conditions have been chosen in order to avoid the formation of chelate and hydrolysis in the aqueous solution. The equilibrium constants and stability constants are calculated, and the results are compared with literature. The results show that increasing the thorium concentration does not lead to polymer forms. refs., 42 figs., 19 tabs.

The sequential separation of strontium-90, yttrium-90, promethium-147, and cerium-144 from urine and their subsequent estimation

International Nuclear Information System (INIS)

Kramer, G.H.; Davies, J.M.

1981-04-01

A method has been developed for separating low-level activities of the beta-emitting isotopes strontium-90, yttrium-90, promethium-147 and cerium-144 from urine and aqueous solutions. They are subsequently estimated by planchet or liquid scintillation counting. The radionuclides are separated from each other and from interfering elements by solvent extraction with HDEHP (di-2-ethylhexyl phosphoric acid) in n-heptane. It is possible to separate the elements with a minimum of cross-contamination by selecting appropriate pH's and solvent concentrations. Percentage recoveries for the radionuclides are: 90 Sr, 100 +- 12; 90 Y, 65 +- 4; 147 Pm, 90 +- 8; 144 Ce, 87 +- 11. The limits of detection are: 90 Sr, 0.6 pCi; 90 Y, 0.7 pCi; 147 Pm, 1.0 pCi; 144 Ce, 0.8 pCi. (author)

Low-level detection and quantification of Plutonium(III, IV, V,and VI) using a liquid core waveguide

International Nuclear Information System (INIS)

Wilson, Richard E.; Hu, Yung-Jin; Nitsche, Heino

2003-01-01

Understanding the aqueous chemistry of plutonium, in particular in environmental conditions, is often complicated by plutonium's complex redox chemistry. Because plutonium possesses four oxidation states, all of which can coexist in solution, a reliable method for the identification of these oxidation states is needed. The identification of plutonium oxidation states at low levels in aqueous solution is often accomplished through an indirect determination using series of liquid-liquid extraction procedures using oxidation state specific reagents such as HDEHP and TTA. While these methods, coupled with radioactive counting techniques provide superior limits of detection they may influence the plutonium redox equilibrium, are time consuming, waste intensive and costly. Other analytical methods such as mass spectrometry and radioactive counting as stand alone methods provide excellent detection limits but lack the ability to discriminate between the oxidation states of the plutonium ions in solution

Contribution to the study of the behavior of tetravalent technetium at tracer amounts in aqueous media

International Nuclear Information System (INIS)

Guennec, J.Y.

The behavior of /sup 99m/Tc was studied first in perchloric media. Reduction of TcO 4 - by BH 4 - at pH 7 in perchloric medium leads to Tc(IV) as a radiocolloid (20 percent) and soluble TcO 2 (50 percent). Acidification of the medium oxidizes the soluble Tc(IV) fraction. Acid solutions containing only the IV species and free of radiocolloids can be studied using back extraction. Tc(IV) is extracted by the organic phases, containing or not containing TTA or HDEHP from solutions of Tc(VII) reduced by BH 4 - at pH 7. These organic phases are then contacted with aqueous phases 5 x 10 -2 to 3 M HClO 4 , and the variation of the distribution coefficient was studied as a function of the chelating agent content and of the pH. In the absence of a chelating agent, the extracted species is TcO 2 . In the presence of chelating agents, the cation TcO(OH) + is extracted in the forms TcO(OH)A and TcO(OH)A 2 H respectively with TTA and HDEHP. Hydrolysis of this cation leads to TcO 2 . Study of the reduction of Tc(VII) in hydrochloric medium is complicated by the oxychlorinated forms of Tc(IV). The hexachlorotechnetate ion, TcCl 6 , exists in HCl 12 M down to 1 M and is very inert. Addition of chloride ions to solutions containing only TcO 2 and TcO(OH) + , when [Cl - ] is less than 1 M, leads to a neutral extractable species, which could be TcOCl 2 . When the Cl - concentration is greater than 1 M, there is formation of a species with one more chlorine atoms; this could be TcOCl 3 . The behavior of technetium during the formation of the complex ''Tc-Iron-Ascorbic Acid'' used in medical scintigraphy was also studied. Ascorbic acid alone or divalent iron alone slightly reduce the pertechnetate. Addition of Fe 2+ (or BH 4 - ) to Tc(VII) and ascorbic acid produces a high percentage of Tc(IV). So it is the ascorbate of iron which reduces the Tc(VII) and the excess ascorbic acid maintains the technetium in its reduced state by formation of a weak complex

Trace recovery of uranium and rare earth contained in phosphates by liquid-liquid extraction in sulfuric attack liquor

International Nuclear Information System (INIS)

Bousquet, F.; Foraison, D.; Leveque, A.; Sabot, J.L.

1980-06-01

Uranium and rare earths can be recovered in sedimentary phosphates during the wet processing of the ore by sulfuric acid giving raw phosphoric acid at 30 per cent of P 2 O 5 . Practically all the uranium contained and only part of rare earths are put into solution in this treatment. Separation of these elements in the phosphoric solution is obtained by liquid-liquid extraction with alkylphosphoric acids and especially with their mono and di esters. Partition isotherms are determined and counter-current tests are effected. Uranium and rare earths reextraction from these solvents can be simultaneous or separate with aqueous solutions alkaline or containing HF or by antisynergism. Pros and cons of each reextraction process are discussed. In conclusion HDEHP or OPPA are recommended because of availability, stability and hydrodynamic, OPPA less selective with rare earths allows the recovery with uranium of ceric earths, yttrium and yttric earths [fr

Solvent extraction separations of trivalent lanthanide and actinide ions using an aqueous aminomethanediphosphonic acid

International Nuclear Information System (INIS)

Jensen, M. P.

1998-01-01

The possibility of separating the trivalent lanthanides, represented by EU 3+ , and actinides, represented by Cf 3+ , using HDEHP in toluene and an aqueous phase containing N-piperidinomethane-1,1-diphosphotic acid, PMDPA, has been investigated. This modified aqueous phase offers potential advantages over the diethylenetriaminepentaacetic acid based TALSPEAK process because of the improved complexation properties of PMDPA in acidic solutions, and the ability to decompose PMDPA before disposal. Extraction experiments were conducted at 25 C in 2 M NaClO 4 between -log [H + ] 1 and 2. The studies enabled us to derive the aqueous phase speciation, the stability constants of the aqueous complexes, and the Cf/Eu separation factors. Despite the presence of an amino group in PMDPA that should favor the retention of the actinides in the aqueous phase, the Cf/Eu separation factors are near unity under the conditions studied

Determination of Np, Pu and Am in high level radioactive waste with extraction-liquid scintillation counting

International Nuclear Information System (INIS)

Yang Dazhu; Zhu Yongjun; Jiao Rongzhou

1994-01-01

A new method for the determination of transuranium elements, Np, Pu and Am with extraction-liquid scintillation counting has been studied systematically. Procedures for the separation of Pu and Am by HDEHP-TRPO extraction and for the separation of Np by TTA-TiOA extraction have been developed, by which the recovery of Np, Pu and Am is 97%, 99% and 99%, respectively, and the decontamination factors for the major fission products ( 90 Sr, 137 Cs etc.) are 10 4 -10 6 . Pulse shape discrimination (PSD) technique has been introduced to liquid scintillation counting, by which the counting efficiency of α-activity is >99% and the rejection of β-counts is >99.95%. This new method, combining extraction and pulse shape discrimination with liquid scintillation technique, has been successfully applied to the assay of Np, Pu and Am in high level radioactive waste. (author) 7 refs.; 7 figs.; 4 tabs

Poisoning of liquid membrane carriers in extraction of metal ions

International Nuclear Information System (INIS)

Wang, Yuchun; Wang, Dexian

1992-01-01

As means of effective separation and preconcentration, emulsion liquid membranes (ELMs) have found application in many fields including biochemical separation, wastewater treatment, hydrometallurgy, and preconcentration in analytical chemistry. In the extraction of desired metal (scandium, mixed rare earths) ions using chelating extractants (TTA, HDEHP) as liquid membrane carriers, the carriers will become poisoned owing to the presence of even minute quantity of certain high ionic potential ions in the feed solution. The reason for the poisoning of carriers is that those ions have so much greater affinity than the desired ions for the membrane carrier that the ion-carrier coordination compound cannot be stripped at the interior interface of the membrane and gradually no more free carrier transports any metal ions across the membrane. The calculated results are in agreement with the experiments, and methods to avoid the poisoning are given in the paper

Cleanex process: a versatile solvent extraction process for recovery and purification of lanthanides, americium, and curium

International Nuclear Information System (INIS)

Bigelow, J.E.; Collins, E.D.; King, L.J.

1979-01-01

At a concentration of 1 M in straight-chain hydrocarbon diluent, HDEHP will extract americium, curium, and other trivalent actinide and lanthanide elements from dilute acid or salt solutions. The solute is back-extracted with more concentrated acid, either nitric or hydrochloric. The process has been used in the continuous, countercurrent mode, but its greatest advantage arises in batch extractions where the excess acid can be titrated with NaOH to produce a final acidity of about 0.03 M. Under these conditions, 99% recovery can be achieved, usually in one stage. Cleanex was used on the 50-liter scale at the Transuranium Processing Plant at Oak Ridge for 12 years to provide a broad spectrum cleanup to transuranium elements before applying more sophisticated techniques for separating individual products. The process is also used routinely to recover excessive losses of curium and/or californium from plant waste streams. The solvent system is relatively resistant to radiation damage, being usable up to 200 W-h/liter

41Ca standardization by the CIEMAT/NIST LSC method

International Nuclear Information System (INIS)

Rodriguez Barquero, L.; Los Arcos, J.M.

1996-01-01

A procedure for the liquid scintillation counting standardization of the electron-capture nuclide 41 Ca has been successfully developed and applied with 41 CaCl 2 and 41 Ca-(HDEHP) n samples synthesized in the laboratory from 41 CaCO 3 supplied by Oak Ridge National Laboratory. Six scintillators were tested: the organic samples were stable in toluene-alcohol, Ultima-Gold TM and HiSafe III TM for 30 d, whereas the inorganic samples were only stable in toluene-alcohol and HiSafe III TM for the same period of time. Despite of the low counting efficiencies (1%-13%) due to the very low-energy of less than 3.6 keV of the X-rays and Auger electrons of 41 Ca, the stable samples were standardized by the CIEMAT/NIST method to a combined uncertainty of 2.4% over a range of figures of merit of 1.75 to 7.25 ( 3 H equivalent efficiency of 40% to 7%). (orig.)

Rapid determination of strontium-89 and strontium-90 in food and environmental samples by Cerenkov counting

International Nuclear Information System (INIS)

Melin, Judith; Suomela, Jorma

1995-01-01

The method has been developed for emergency situations. Minimum detectable concentrations of 5 Bq/liter, kilogram of strontium-89 and strontium-90 respectively is achievable in the presence of nuclides considered to be released under accidental conditions. Result on the strontium-89 and strontium-90 content in a sample can be obtained within 12 hours. One technician can easily handle 8-10 samples during a working day of eight hours. The determination of the strontium isotopes is accomplished by monitoring the Cerenkov radiation from strontium-89 and yttrium-90 in a liquid scintillation counter. The latter is the daughter product of strontium-90. Prior to the Cerenkov counting the sample is separated from interfering nuclides by oxalate precipitation, chromate precipitation and HDEHP-extraction. The method has to be further improved and evaluated with respect to different soil types such as forest mineral soil layers, agricultural soils and pastures. Furthermore, the decontamination procedure should be evaluated for a sample containing freshly irradiated uranium. (author)

A Rapid Method for Measuring Strontium-90 Activity in Crops in China

Science.gov (United States)

Pan, Lingjing Pan; Yu, Guobing; Wen, Deyun; Chen, Zhi; Sheng, Liusi; Liu, Chung-King; Xu, X. George

2017-09-01

A rapid method for measuring Sr-90 activity in crop ashes is presented. Liquid scintillation counting, combined with ion exchange columns 4`, 4"(5")-di-t-butylcyclohexane-18-crown-6, is used to determine the activity of Sr-90 in crops. The yields of chemical procedure are quantified using gravimetric analysis. The conventional method that uses ion-exchange resin with HDEHP could not completely remove all the bismuth when comparatively large lead and bismuth exist in the samples. This is overcome by the rapid method. The chemical yield of this method is about 60% and the MDA for Sr-90 is found to be 2:32 Bq/kg. The whole procedure together with using spectrum analysis to determine the activity only takes about one day, which is really a large improvement compared with the conventional method. A modified conventional method is also described here to verify the value of the rapid one. These two methods can meet di_erent needs of daily monitoring and emergency situation.

Recovery of Tungsten and Molybdenum from Low-Grade Scheelite

Science.gov (United States)

Li, Yongli; Yang, Jinhong; Zhao, Zhongwei

2017-10-01

With most high-quality tungsten ores being exhausted, the enhancement of low-grade scheelite concentrates processing has attracted a great deal of attention. The objective of this study is to develop a method to maximize the recovery tungsten and molybdenum from a low-grade scheelite via a new acid leaching process followed by solvent extraction. Under optimal conditions (350 g/L H2SO4, 95°C, and 2 h), approximately 99.8% of tungsten and 98% of molybdenum were leached out. In the subsequent solvent extraction process, more than 99% of the tungsten and molybdenum were extracted with a co-extraction system (50% TBP, 30% HDEHP, and 10% 2-octanol in kerosene) using a three-stage cross-flow extraction. The raffinate can be recycled for the next leaching process after replenishing the H2SO4 to the initial value (approximately 350 g/L). Based on these results, a conceptual flowsheet is presented to recover tungsten and molybdenum from the low-grade scheelite.

Application of the radiochemical - and the direct gamma ray spectrometry method to the burnup determination of irradiated uranium oxide

International Nuclear Information System (INIS)

Cunha, I.I.L.

1979-01-01

The burn up of natural U 3 O 8 that occurs by the action of thermal neutrons was determined, using the radioisotopes 144 Ce, 137 Cs, 103 Ru, 106 Ru and 95 Zr as monitors. The determination of the burn up was made using both destructive and non-destructive methods. In the non-destructive method, the technique of direct gamma-ray spectrometry was used and the radioisotopes mentioned were simultaneously counted in a Ge-Li detector. In the radiochemical method the same radioisotopes were isolated one from the other and from all other fission products before counting. The solvent extraction technique was used for the radiochemical separation of uranium, cerium, cesium and ruthenium. To separate zirconium and niobium, adsorption in silica-gel was used. The extraction agent employed to isolate cesium was dipycrilamine and for the separation of the other radioisotopes Di-(2-Ethyl Hexyl) Phosphoric acid (HDEHP) was used. (Author) [pt

Sequential separation of transuranic elements and fission products from uranium metal ingots in electrolytic reduction process of spent PWR fuels

International Nuclear Information System (INIS)

Chang Heon Lee; Kih Soo Joe; Won Ho Kim; Euo Chang Jung; Kwang Yong Jee

2009-01-01

A sequential separation procedure has been developed for the determination of transuranic elements and fission products in uranium metal ingot samples from an electrolytic reduction process for a metallization of uranium dioxide to uranium metal in a medium of LiCl-Li 2 O molten salt at 650 deg C. Pu, Np and U were separated using anion-exchange and tri-n-butylphosphate (TBP) extraction chromatography. Cs, Sr, Ba, Ce, Pr, Nd, Sm, Eu, Gd, Zr and Mo were separated in several groups from Am and Cm using TBP and di(2-ethylhexyl)phosphoric acid (HDEHP) extraction chromatography. Effect of Fe, Ni, Cr and Mg, which were corrosion products formed through the process, on the separation of the analytes was investigated in detail. The validity of the separation procedure was evaluated by measuring the recovery of the stable metals and 239 Pu, 237 Np, 241 Am and 244 Cm added to a synthetic uranium metal ingot dissolved solution. (author)

Cold Fusion Production and Decay of Neutron-Deficient Isotopes of Dubnium and Development of Extraction Systems for Group V Elements

Energy Technology Data Exchange (ETDEWEB)

Gates, Jacklyn M. [Univ. of California, Berkeley, CA (United States)

2008-07-31

Excitation functions for the 1n and 2n exit channels of the ²⁰⁸Pb(⁵¹V,xn)^259-xDb reaction were measured. A maximum cross section of the 1n exit channel of 2070$+1100\\atop{-760}$ pb was measured at an excitation energy of 16.0 ± 1.8 MeV. For the 2n exit channel, a maximum cross section of 1660$+450\\atop{-370}$ pb was measured at 22.0 ± 1.8 MeV excitation energy. The 1n excitation function for the 209Bi(50Ti,n)258Db reaction was remeasured, resulting in a cross section of 5480$+1730\\atop{-1370}$ pb at an excitation energy of 16.0 ± 1.6 MeV. Differences in cross section maxima are discussed in terms of the fusion probability below the barrier. The extraction of niobium (Nb) and tantalum (Ta) from hydrochloric acid and mixed hydrochloric acid/lithium chloride media by bis(2-ethylhexyl) hydrogen phosphate (HDEHP) and bis(2-ethylhexyl) hydrogen phosphite (BEHP) was studied. The goal of the experiments was to find a system that demonstrates selectivity among the members of group five of the Periodic Table and is also suitable for the study of dubnium (Db, Z = 105). Experiments with niobium and tantalum were performed with carrier (10^-6 M), carrier free (10^-10 M) and trace (10^-16 M) concentrations of metal using hydrochloric acid solution with concentrations ranging from 1 - 11 M. The extraction of niobium and tantalum from mixed hydrochloric acid/lithium chloride media by HDEHP and BEHP as a function of hydrogen ion (H⁺) concentration was also investigated. The data obtained are used as the basis to discuss the speciation of niobium and tantalum under the conditions studied and to evaluate possible extraction mechanisms. The ⁷⁴Se(¹⁸O,p3n)^88gNb excitation function was measured to determine the best energy for producing the ⁸⁸Nb used in chemistry experiments. A maximum cross section of 495 +- 5 mb was observed at an ¹⁸O energy of 74.0 Me

Transuranium analysis methodologies for biological and environmental samples

International Nuclear Information System (INIS)

Wessman, R.A.; Lee, K.D.; Curry, B.; Leventhal, L.

1978-01-01

Analytical procedures for the most abundant transuranium nuclides in the environment (i.e., plutonium and, to a lesser extent, americium) are available. There is a lack of procedures for doing sequential analysis for Np, Pu, Am, and Cm in environmental samples, primarily because of current emphasis on Pu and Am. Reprocessing requirements and waste disposal connected with the fuel cycle indicate that neptunium and curium must be considered in environmental radioactive assessments. Therefore it was necessary to develop procedures that determine all four of these radionuclides in the environment. The state of the art of transuranium analysis methodology as applied to environmental samples is discussed relative to different sample sources, such as soil, vegetation, air, water, and animals. Isotope-dilution analysis with 243 Am ( 239 Np) and 236 Pu or 242 Pu radionuclide tracers is used. Americium and curium are analyzed as a group, with 243 Am as the tracer. Sequential extraction procedures employing bis(2-ethyl-hexyl)orthophosphoric acid (HDEHP) were found to result in lower yields and higher Am--Cm fractionation than ion-exchange methods

Transplutonium elements production program: extraction chromatographic process for plutonium irradiated targets

International Nuclear Information System (INIS)

Bourges, J.; Madic, C.; Koehly, G.

1980-01-01

The treatment of irradiated plutonium targets by extraction chromatography allowed the purification of the isotopes 243 Am and 244 Cm on the scale of few tens of grams. This process proved to be extremely simple and flexible, and yielded results which are reproducible in time. The chief advantage of the TBP process over the HDEHP process in high and medium activity conditions lies in the rapid absorption/desorption kinetics of the elements to be purified and in the separation of americium from curium, which largely offsets its lower selectivity for lanthanide elements. it is certainly possible to improve the performance of this process by: a) optimization of the characteristics of the stationary phase, b) improvement in the filling technique and in hydraulic operation of the columns, c) on-line analysis of americium (the key element in actinide/lanthanide separation) in the eluate. The application of extraction chromatography with HD(DiBM)P to the purification of 243 Am of the end of treatment makes the process more consistent, eliminates the delicate stages implemented in hot cell, and considerably improves final product quality

Thermodynamic and structural of the water - dodecane - bis(ethyl-2-hexyl) phosphoric acid and its sodium salt

International Nuclear Information System (INIS)

Lovera, Jacqueline

1985-01-01

This research thesis reports the study of the appearance and disappearance of the 'third phase' obtained during the salification of the bis(ethyl-2 hexyl) phosphoric acid (HDEHP) diluted in dodecane, by sodium aqueous solutions. After a large bibliographical study on the properties of the intervening compounds (extraction of metallic cation by the acid, parameters influencing the 'third phase' appearance, surfactant properties, direct and inverse micelles, formation of para-crystalline phases), the author presents chemical experimental methods: liquid-liquid extraction tests, tests by the synthetic way, preparation of reactants, dosing method, methods of chemical analysis). Then, she reports and discusses experimental results in terms of determination of phase diagrams at 25 C, of composition by weight of the third phase, of influence of the apolar diluent, and of influence of the electrolyte. Physical experimental methods are then presented (differential calorimetric analysis, NMR, small angle X-ray scattering, light scattering, polarised light microscopy, constrained phase microscopy, photography, infrared spectroscopy, conductometry, transmission electron micrography, volumetric mass measurements, surface and interface tension measurements, viscoelasticity measurements) and their results are discussed and interpreted [fr

Silicate complexation of NpO2+ ion in perchlorate media

International Nuclear Information System (INIS)

Pathak, P.N.; Choppin, G.R.

2007-01-01

Complexation behavior of NpO 2 + with ortho-silicic acid (o-SA) has been studied using solvent extraction at ionic strengths varying from 0.10 to 1.00M (NaClO 4 ) at pcH 3.68±0.08 and 25 deg C with bis-(2-ethylhexyl) phosphoric acid (HDEHP) as the extractant. The stability constant value (log β 1 ) for the 1:1 complex, NpO 2 (OSi(OH) 3 ), was found to decrease with increase in ionic strength of the aqueous phase [6.83±0.01 at I = 0.10M to 6.51±0.02 at I = 1.00M]. These values have been fitted in the SIT model expression and compared with similar values of complexation of the metal ions Am 3+ , Eu 3+ , UO 2 2+ , PuO 2 2+ , Np 4+ , Ni 2+ and Co 2+ . The speciation of NpO 2 + -o-silicate/carbonate system has been calculated as a function of pcH under ground water conditions. (author)

Preparation of 45Ca(HDEHP)n and (CaH1502)2 samples for liquid scintillation counting, compared to 45caCl2 results

International Nuclear Information System (INIS)

Rodriguez, L.; Arcos, J. M. los; Grau Malonda, A.

1994-01-01

A procedure for preparation of liquid scintillation counting organic samples of the Di-2-ethylhexyl phosphate calcium complex and the 2-ethylhexanoate calcium salt, labelled with 45Ca, is described. The chemical quench, the counting stability and spectral evolution of both compounds is studied in six scintillators,Toluene-alcohol, Dioxane-naphtalene, Hi safe II, Ultimate-Gold and Instagel, and compared to results obtained from a commercial solution of 4 5CaCl2. (Author) 7 refs

Use of Electro-spray Ionization Mass Spectrometry (ESI-MS) for the characterization of complexes 'ligand - metallic cations' in solution

Energy Technology Data Exchange (ETDEWEB)

Berthon, Laurence; Zorz, Nicole; Lagrave, Stephanie; Gannaz, Benoit; Hill, Clement [CEA-Marcoule DEN-DRCP-SCPS-LCSE, BP 17171, 30207 Bagnols sur Ceze cedex (France)

2008-07-01

In the framework of nuclear waste reprocessing, separation processes of minor actinides from fission products are developed by Cea. In order to understand the mechanisms involved in the extraction processes, the 'ligand/metallic cation' complexes, formed in the organic phases are characterized by electro-spray-mass-spectrometry (ESI-MS). This paper deals with the extraction of lanthanides (III) and americium (III) cations by an organic phase composed of a malonamide or / and a dialkyl phosphoric acid, diluted in an aliphatic diluent. For the dialkyl phosphoric acid, Ln(DEHP){sub 3}(HDEHP){sub 3} complexes are observed and in the presence of a large excess of Ln(NO{sub 3}){sub 3}, dinuclear species are also observed. For the malonamide extractant, it appears that the complexes formed in the organic phase are of the Nd(NO{sub 3}){sub 3}D{sub x} type, with 2 {<=} x {<=} 4: their distributions depend on the ratio [Ln]/[DMDOHEMA]. When the two extractants are present in the organic phase, mixed 'Ln-malonamide-dialkyl phosphoric acid' species are observed. The influence of several parameters, such as extractant concentration, solute concentration, aqueous acidity and the nature of the cations (lanthanides or americium) are studied. (authors)

Non-Ideal Behavior in Solvent Extraction

International Nuclear Information System (INIS)

Zalupski, Peter

2011-01-01

This report presents a summary of the work performed to meet FCR and D level 3 milestone M31SW050801, 'Complete the year-end report summarizing FY11 experimental and modeling activities.' This work was carried out under the auspices of the Non-Ideality in Solvent Extraction Systems FCR and D work package. The report summarizes our initial considerations of potential influences that non-ideal chemistry may impose on computational prediction of outcomes in solvent extraction systems. The report is packaged into three separate test cases where a robustness of the prediction by SXFIT program is under scrutiny. The computational exercises presented here emphasize the importance of accurate representation of both an aqueous and organic mixtures when modeling liquid-liquid distribution systems. Case No.1 demonstrates that non-ideal behavior of HDEHP in aliphatic diluents, such as n-dodecane, interferes with the computation. Cases No.2 and No.3 focus on the chemical complexity of aqueous electrolyte mixtures. Both exercises stress the need for an improved thermodynamic model of an aqueous environment present in the europium distribution experiments. Our efforts for year 2 of this project will focus on the improvements of aqueous and non-aqueous solution models using fundamental physical properties of mixtures acquired experimentally in our laboratories.

Interfacial chemistry in solvent extraction systems: Progress report for period April 1, 1986-March 31, 1987

International Nuclear Information System (INIS)

Neuman, R.D.

1986-11-01

Proton magnetic resonance spectroscopic, vapor pressure osmometric and Karl Fischer titrimetric measurements have provided support for our earlier findings obtained from interfacial tension and mass transfer experiments that reversed micelles are formed, under certain conditions, in the system HDEHP/n-hexane/CaCl 2 solution. These studies were further extended to include different organophosphorus acid (PC 88A), diluent (benzene), and metal ions (Co 2+ , Ni 2+ , and Zn 2+ ) to determine whether reversed micellization is a general phenomenon occurring in solvent extraction systems which employ organophosphorus acids. The data obtained so far, suggest that reversed micellization indeed is a general phenomenon operative in organophosphorus acid extractant systems. A new mass transfer cell has been constructed in order to investigate the metal distribution equilibria and extraction kinetics of Co, Ni and Zn using atomic absorption spectrophotometric technique. A quasi-elastic light-scattering apparatus has been installed to investigate aggregation phenomena in solvent extraction systems. Preliminary drop-interface coalescence studies were performed, and the results were correlated with those obtained from interfacial tension measurements. The laser heterodyne light-scattering apparatus for measurement of interfacial viscoelastic properties also has been set-up and is being optimized for high resolution measurements. 21 refs., 16 figs

Studies on iron absorption and retention in malnourished Indian subjects, using Fe-59 and whole-body counting

International Nuclear Information System (INIS)

Gopalan, C.; Srikantia, S.G.

1975-12-01

The gastrointestinal absorption of iron under various conditions in representatives of the Indian population, and several related matters, have been investigated. Percentage absorption was determined by whole-body counting of 59Fe, or by measuring the concentration of 55Fe in the blood, at about two weeks after administration of the respective tracer. It was confirmed or established that: (1) food or supplemental iron, if available at all, tends to be absorbed from the intestines as if present there in one of two alternative pools: heme and non heme; (2) 30%-50% of iron measured chemically in Indian foods appears to be in an unavailable form, for example as a contaminant in adventitiously present dust; (3) fortification of the diet with iron may be feasible by adding FePO 4 + 2 molar NaHSO 4 to common salt under suitable conditions; (4) monkeys appear to be sufficiently similar to humans in their iron absorption characteristics that they may be the best available non-human model for preliminary experimental investigations of iron absorption; and (5) a promising preparative method for liquid scintillation counting of 55Fe present in blood is to extract it into toluene in the presence of di (2-ethyl-hexyl) phosphate (HDEHP)

Non-Ideal Behavior in Solvent Extraction

Energy Technology Data Exchange (ETDEWEB)

Peter Zalupski

2011-09-01

This report presents a summary of the work performed to meet FCR&D level 3 milestone M31SW050801, 'Complete the year-end report summarizing FY11 experimental and modeling activities.' This work was carried out under the auspices of the Non-Ideality in Solvent Extraction Systems FCR&D work package. The report summarizes our initial considerations of potential influences that non-ideal chemistry may impose on computational prediction of outcomes in solvent extraction systems. The report is packaged into three separate test cases where a robustness of the prediction by SXFIT program is under scrutiny. The computational exercises presented here emphasize the importance of accurate representation of both an aqueous and organic mixtures when modeling liquid-liquid distribution systems. Case No.1 demonstrates that non-ideal behavior of HDEHP in aliphatic diluents, such as n-dodecane, interferes with the computation. Cases No.2 and No.3 focus on the chemical complexity of aqueous electrolyte mixtures. Both exercises stress the need for an improved thermodynamic model of an aqueous environment present in the europium distribution experiments. Our efforts for year 2 of this project will focus on the improvements of aqueous and non-aqueous solution models using fundamental physical properties of mixtures acquired experimentally in our laboratories.

Features of the Thermodynamics of Trivalent Lanthanide/Actinide Distribution Reactions by Tri-n-Octylphosphine Oxide and Bis(2-EthylHexyl) Phosphoric Acid

Energy Technology Data Exchange (ETDEWEB)

Travis S. Grimes; Peter R. Zalupski

2014-11-01

A new methodology has been developed to study the thermochemical features of the biphasic transfer reactions of trisnitrato complexes of lanthanides and americium by a mono-functional solvating ligand (tri-n-octyl phosphine oxide - TOPO). Stability constants for successive nitrato complexes (M(NO3)x3-x (aq) where M is Eu3+, Am3+ or Cm3+) were determined to assist in the calculation of the extraction constant, Kex, for the metal ions under study. Enthalpies of extraction (?Hextr) for the lanthanide series (excluding Pm3+) and Am3+ by TOPO have been measured using isothermal titration calorimetry. The observed ?Hextr were found to be constant at ~29 kJ mol-1across the series from La3+-Er3+, with a slight decrease observed from Tm3+-Lu3+. These heats were found to be consistent with enthalpies determined using van ’t Hoff analysis of temperature dependent extraction studies. A complete set of thermodynamic parameters (?G, ?H, ?S) was calculated for Eu(NO3)3, Am(NO3)3 and Cm(NO3)3 extraction by TOPO and Am3+ and Cm3+ extraction by bis(2-ethylhexyl) phosphoric acid (HDEHP). A discussion comparing the energetics of these systems is offered. The measured biphasic extraction heats for the transplutonium elements, ?Hextr, presented in these studies are the first ever direct measurements offered using two-phase calorimetric techniques.

TALSPEAK Chemistry in Advanced Nuclear Fuel Cycles

International Nuclear Information System (INIS)

Nilsson, Mikael; Nash, Kenneth L.

2008-01-01

The separation of trivalent transplutonium actinides from fission product lanthanide ions represents a challenging aspect of advanced nuclear fuel partitioning schemes. The challenge of this separation could be amplified in the context of the AFCI-UREX+1a process, as Np and Pu will accompany the minor actinides to this stage of separation. At present, the baseline lanthanide-actinide separation method is the TALSPEAK (Trivalent Actinide - Lanthanide Separation by Phosphorus reagent Extraction from Aqueous complexes) process. TALSPEAK was developed in the late 1960's at Oak Ridge National Laboratory and has been demonstrated at pilot scale. This process relies on the complex interaction between an organic and an aqueous phase both containing complexants for selectively separating the trivalent actinide. The 3 complexing components are: the di(2-ethylhexyl) phosphoric acid (HDEHP), the lactic acid (HL) and the diethylenetriamine-N,N,N',N'',N''-pentaacetic acid (DTPA). In this report we discuss observations on kinetic and thermodynamic features described in the prior literature and describe some results of our ongoing research on basic chemical features of this system. The information presented indicates that the lactic acid buffer participates in the net operation of the TALSPEAK process in a manner that is not explained by existing information on the thermodynamic features if the known Eu(III)-lactate species. (authors)

Preparation of 45 Ca (HDEHP)n and (C8H15O2)2 samples for liquid scintillation counting, compared to 45CaCl2 results

International Nuclear Information System (INIS)

Rodriguez Barquero, L.; Los Arcos Merino, J.M.; Grau Malonda, A.

1994-01-01

A procedure for preparation of liquid scintillation counting organic samples of the Di-2-ethylhexyl phosphate calcium complex and the 2-ethyhexanoate calcium salt, labelled with ''45 Ca, is described. The chemical quench, the counting stability and spectral evolution of both compounds is studied in six scintillators, Toluene, Toluene-alcohol, Dioxane-napthalhene, Hisafe II, Ultima-Gold and Instagel, and compared to results obtained from a commercial solution of ''45 CaCl 2

Features of the thermodynamics of trivalent lanthanide/actinide distribution reactions by tri-n-octylphosphine oxide and bis(2-ethylhexyl) phosphoric acid.

Science.gov (United States)

Grimes, Travis S; Zalupski, Peter R; Martin, Leigh R

2014-11-06

A new methodology has been developed to study the thermochemical features of the biphasic transfer reactions of trisnitrato complexes of lanthanides and americium by a monofunctional solvating ligand (tri-n-octylphosphine oxide, TOPO). Stability constants for successive nitrato complexes (M(NO3)x(3-x)(aq) where M is Eu(3+), Am(3+), or Cm(3+)) were determined to assist in the calculation of the extraction constant, K(ex), for the metal ions under study. Enthalpies of extraction (ΔH(extr)) for the lanthanide series (excluding Pm(3+)) and Am(3+) by TOPO have been measured using isothermal titration calorimetry. The observed ΔH(extr) were found to be constant at ~29 kJ mol(-1) across the series from La(3+) to Er(3+), with a slight decrease observed from Tm(3+) to Lu(3+). These heats were found to be consistent with enthalpies determined using van't Hoff analysis of temperature dependent extraction studies. A complete set of thermodynamic parameters (ΔG, ΔH, ΔS) was calculated for Eu(NO3)3, Am(NO3)3, and Cm(NO3)3 extraction by TOPO and Am(3+) and Cm(3+) extraction by bis(2-ethylhexyl) phosphoric acid (HDEHP). A discussion comparing the energetics of these systems is offered. The measured biphasic extraction heats for the transplutonium elements, ΔH(extr), presented in these studies are the first ever direct measurements offered using two-phase calorimetric techniques.

Improvement of the cloud point extraction of uranyl ions by the addition of ionic liquids.

Science.gov (United States)

Gao, Song; Sun, Taoxiang; Chen, Qingde; Shen, Xinghai

2013-12-15

The cloud point extraction (CPE) of uranyl ions by different kinds of extractants in Triton X-114 (TX-114) micellar solution was investigated upon the addition of ionic liquids (ILs) with various anions, i.e., bromide (Br(-)), tetrafluoroborate (BF4(-)), hexafluorophosphate (PF6(-)) and bis[(trifluoromethyl)sulfonyl]imide (NTf2(-)). A significant increase of the extraction efficiency was found on the addition of NTf2(-) based ILs when using neutral extractant tri-octylphosphine oxide (TOPO), and the extraction efficiency kept high at both nearly neutral and high acidity. However, the CPE with acidic extractants, e.g., bis(2-ethylhexyl) phosphoric acid (HDEHP) and 8-hydroxyquinoline (8-HQ) which are only effective at nearly neutral condition, was not improved by ILs. The results of zeta potential and (19)F NMR measurements indicated that the anion NTf2(-) penetrated into the TX-114 micelles and was enriched in the surfactant-rich phase during the CPE process. Meanwhile, NTf2(-) may act as a counterion in the CPE of UO2(2+) by TOPO. Furthermore, the addition of IL increased the separation factor of UO2(2+) and La(3+), which implied that in the micelle TOPO, NTf2(-) and NO3(-) established a soft template for UO2(2+). Therefore, the combination of CPE and IL provided a supramolecular recognition to concentrate UO2(2+) efficiently and selectively. Copyright © 2013 Elsevier B.V. All rights reserved.

Preparation of 45Ca(HDEHP)n and (CaH{sub 1}50{sub 2})2 samples for liquid scintillation counting, compared to 45caCl{sub 2} results; Preparacion de Ca (HDEHP)n y (C{sub 8}H{sub 1}50{sub 2})2 marcados con 45Ca y estudio comparativo con 4 5ca Cl2 en medidas por centelleo liquido

Energy Technology Data Exchange (ETDEWEB)

Rodriguez, L.; Arcos, J. M. los; Grau Malonda, A.

1994-07-01

A procedure for preparation of liquid scintillation counting organic samples of the Di-2-ethylhexyl phosphate calcium complex and the 2-ethylhexanoate calcium salt, labelled with 45Ca, is described. The chemical quench, the counting stability and spectral evolution of both compounds is studied in six scintillators,Toluene-alcohol, Dioxane-naphtalene, Hi safe II, Ultimate-Gold and Instagel, and compared to results obtained from a commercial solution of 4 5CaCl2. (Author) 7 refs.

The determination of plutonium isotopes in environmental samples

International Nuclear Information System (INIS)

Siripirom, Lopchai.

1983-01-01

The concentration of plutonium in environmental samples such as soil, water, and surface air in the middle part of Thailand were studied. The surface air were collected only at the fifth floor of the Office of Atomic Energy for Peace (OAEP). Plutonium-242 was used as a tracer. Soil and air samples were dissolved by pyrosulphate fusion, and plutonium was co-precipitated with barium sulfate. Then dissolved the precipitate in perchloric acid. Plutonium was extracted out by using solvent bis-(2-ethylhexyl) phosphoric acid (HDEHP). Plutonium in water samples were coprecipitated with iron (III) hydroxide and were dissolved in 8 M. nitric acid. Then the plutonium was separated out by using anion exchange resin, Dowex 1x4. After the solvent extraction or the anion exchange, plutonium was coprecipitated with cerous hydroxide. The activities of plutonium were measured by a surface barrier detector for about 24 hours. Lower limit of detection for 1,440 minutes is 0.012 pCi. These studies showed that only plutonium-239, 240 was observed. The range of activities of plutonium-239, 240 in soil were 0.002-0.157 pCi/g (dry), in water were 0.1-81 f Ci/l, and in air were 7-330 a Ci/m 3 . However, the plutonium concentrations in these studies are far below the maximum permissible concentration (MPC) recommended by International Commission on Radiological Protection (ICRP) for general population which is equal to 3x10 8 f Ci/l of water and 5x10 6 a Ci/m 3 of air

Spectrophotometric determination of trace amount of uranium (VI) in different aqueous and organic streams of nuclear fuel processing using 2-(5-bromo-2-pyridylazo-5-diethylaminophenol)

International Nuclear Information System (INIS)

Das, S.K.; Kedari, C.S.; Tripathi, S.C.

2010-01-01

Present investigation describes the development of a spectrophotometric method for trace level determination of U(VI) encountered during the process of nuclear fuel fabrication and reprocessing industries. A chromogenic reagent, 2-(5-bromo-2-pyridylazo-5-diethylaminophenol) (Br-PADAP) is used to complex with U(VI) under optimized solution conditions. The absorption maxima of the uranyl Br-PADAP complex at 578 nm is computed to be 73540 ± 1438 for U-Br-PADAP solution containing 20% ethanol (in aqueous sample media) and 58216 ± 1208 for U-Br-PADAP solution containing 80% ethanol (for organic sample media). Employing suitable sample treatment methods, the scope of analytical method has been widened to permit accurate determination of U(VI) in the samples with variation in the relative compositions of Th(IV), Pu(IV) and Fe(III). The method is applicable to samples matrices with, acidic, alkaline highly salted media. Effect of commonly associated ionic species on the optical density of U-Br-PADAP is determined. Depending on the extent of the interfering impurities present, the method permits estimation of U(VI) either direct or after its selective extraction into tri-octyl phosphine oxide dissolved in cyclohexane. The method is precise with <5% standard error and can be used for the estimation of uranium in organic as well as in aqueous samples. The method has been validated for quantitative determination of uranium extracted in the organic phase comprising of heavy metal extractants like TBP, HDEHP, PC-88A and Aliquot 336. (author)

Removal of americium and curium from high-level wastes

International Nuclear Information System (INIS)

Bond, W.D.; Leuze, R.E.

1979-01-01

The DHDECMP process was demonstrated to give a 99.5% removal of actinides from actual HLLW in small-scale, batch extraction tests. Results from cold tests indicate that it may be possible to carry out the oxalate precipitation step of the OPIX process continuously. About 90% recovery of the trivalent actinides and lanthanides can be achieved in the continuous precipitation. the presence of zirconium impurity in feed solutions to Talspeak process at concentrations of 10 -4 M (0.5% of the Zr in the original waste) affected phase separations but equipment could be operated satisfactory in cold tests. Zirconium concentrations of 10 -3 M seriously affected phase separations and substantial quantities of interfacial cruds were formed. Modest concentrations (0.006 M or less) of H 2 MEHP, a suspected degradation product of HDEHP, did not effect separation factors. The presence of impurities derived from the thermal degradation of DHDECMP did not inhibit the loading of the trivalent actinide and lanthanide elements in the cation exchange chromatographic process for their separation. It appears that the biodentate (DHDECMP) solvent extraction process and the OPIX process are the leading candidate process for the co-removal of trivalent actinide and lanthanide elements from HLLW. The cation exchange chromatography and the Talspeak processes, are the leading candidate processes for the subsequent separation of actinides and lanthanides. The bidentate and cation exchange processes are further along in their development than the other processes and are currently considered the reference processes for the partitioning of Am-Cm from HLLW. 4 figures, 4 tables

Synergism studies on some radionuclides of nuclear and environmental importance using phosphonate compounds mixed with oxygen and phosphorous containing neutral compounds

International Nuclear Information System (INIS)

EL-Zahhar, A.Abd El Wahed M.

1998-01-01

As solvent extraction is a technique which has been highly developed within various national energy programs because of its suitability as selective separation process for fission products, actinides and other radioactive substances. It is very important to look for to be used as extractants and to study the optimum condition under which these compounds can be used as such. This work aims at studying the use of the carbamoyl phosphonate as an extractant in the extraction of certain elements. Also studying the effect of mixed extraction (possibility of enhancing extraction or synergism) as will as temperature effect on the extraction process and calculating the thermodynamic parameters of the proposed extraction reactions. To compare the extraction behavior of the phosphonate compound with other chelating agents as HTTA and HDEHP , studying the extraction of the same elements with these cheating agents under the same conditions is also one of the objectives of this work. This work also aims at studying the extraction of certain elements in comparable oxidation states. The selected elements; uranium which represents the main pert in the nuclear fuel, cobalt which is produced in the nuclear fission products, europium which is also produced as a fission product and is analog of the trivalent actinides series and chromium which is a corrosion product in the nuclear fuel cycle and is an analogue of transition elements. The work also aims at studying the extraction of the selected elements from different aqueous media of low acidic nature to classify the effect of the aqueous phase on the extraction systems handled

Determination of minor-and trace elements in magnesite samples, by activation analysis

International Nuclear Information System (INIS)

Sepulveda Munita, C.J.A.

1979-01-01

A method employing activation analysis with thermal neutron was developed for the determination of minor and trace elements in magnesite samples from the states of Ceara and Bahia (Brazil). Ten samples were analyzed. A qualitative analysis of the samples indicated the presence of Mn, Fe, Sc, Ca, Cu, Co and some of the lanthanides. The experimental part includes a non-destructive analysis of manganese and analysis with chemical separation of the other elements, individually or in groups, after sample dissolution, The dissolutions were made with concentrated HCl and the further separations were carried out in 8 N HCl medium. Iron was separated by means of an extraction of HFeCl 4 with isopropyl ether. Scandium and calcium were determined by retention of scandium with di-(2-ehylhexyl) phosphoric acid (HDEHP). The activities of 46 Sc and 47 Sc (a 47 Ca descendant) were employed for the analysis of scandium and calcium in the sample. In the effluent of the kieselguhr column copper and cobalt were determined, after retention in an anionic resin of the CuCl - 3 and CoCl - 3 complexes. Finally, in the effluent of the resin, the lanthanide group was separated by oxalate precipitation. In the gamma-ray spectrum of this precipitate the elements europium, cerium, samarium and lanthanum were determined. A detailed study of the possible interferences in the neutron activation analysis of the elements analysed was also made. The precision and accuracy of the results obtained and the sensitivity of the method are discussed. (Author) [pt

Recovery and Separation of Valuable Metals from Spent Nickel-Metal Hydride Batteries using some Organophosphorus Extractants

International Nuclear Information System (INIS)

Aly, M.I.; Daoud, J.A.; ALy, H.F.

2012-01-01

The separation of cobalt, nickel, and rare earth elements from NiMH battery residues is evaluated in this paper. A hydrometallurgical process is developed for the recovery of metals from spent batteries and a selective separation of RE by precipitation of sodium RE double sulfate is performed. The methodology used benefits the solubility of the battery electrode materials in sulfuric or hydrochloric acids. The results obtained show that sulfuric acid is slightly less powerful in leaching (NiMH) compared to HCl acid. However, sulfuric acid was used on economic basis. Leaching solution was obtained by using 3 M H 2 SO 4 at 70 +1 degree C + 3% wt. H 2 O 2 for 5 hours. It has been shown that it is possible to recover about 98 % of the RE contained in spent NiMH batteries. The maximum recovery of nickel and cobalt metals was 99.9% and 99.4%, respectively. The effects of the main operating variables of both leaching and solvent extraction steps of nickel (II) and cobalt (II) from the leach solution using HDEHP (di-2-ethylhexyl phosphoric acid) and CYANEX 272 (di-(2,4,4 trimethyl pentyl) phosphinic acid) in kerosene were investigated aiming to maximize metal separation for recycling purposes. The developed process for the recovery and separation of nickel (II) , cobalt (II), and rare earth from spent NiMH batteries is tested and the obtained sulfate salts CoSO 4 and NiSO 4 have a high purity, suggesting that these recovered products could be used as chemical materials without further purification

Development of Novel Method for Rapid Extract of Radionuclides from Solution Using Polymer Ligand Film

Science.gov (United States)

Rim, Jung H.

Accurate and fast determination of the activity of radionuclides in a sample is critical for nuclear forensics and emergency response. Radioanalytical techniques are well established for radionuclides measurement, however, they are slow and labor intensive, requiring extensive radiochemical separations and purification prior to analysis. With these limitations of current methods, there is great interest for a new technique to rapidly process samples. This dissertation describes a new analyte extraction medium called Polymer Ligand Film (PLF) developed to rapidly extract radionuclides. Polymer Ligand Film is a polymer medium with ligands incorporated in its matrix that selectively and rapidly extract analytes from a solution. The main focus of the new technique is to shorten and simplify the procedure necessary to chemically isolate radionuclides for determination by alpha spectrometry or beta counting. Five different ligands were tested for plutonium extraction: bis(2-ethylhexyl) methanediphosphonic acid (H2DEH[MDP]), di(2-ethyl hexyl) phosphoric acid (HDEHP), trialkyl methylammonium chloride (Aliquat-336), 4,4'(5')-di-t-butylcyclohexano 18-crown-6 (DtBuCH18C6), and 2-ethylhexyl 2-ethylhexylphosphonic acid (HEH[EHP]). The ligands that were effective for plutonium extraction further studied for uranium extraction. The plutonium recovery by PLFs has shown dependency on nitric acid concentration and ligand to total mass ratio. H2DEH[MDP] PLFs performed best with 1:10 and 1:20 ratio PLFs. 50.44% and 47.61% of plutonium were extracted on the surface of PLFs with 1M nitric acid for 1:10 and 1:20 PLF, respectively. HDEHP PLF provided the best combination of alpha spectroscopy resolution and plutonium recovery with 1:5 PLF when used with 0.1M nitric acid. The overall analyte recovery was lower than electrodeposited samples, which typically has recovery above 80%. However, PLF is designed to be a rapid field deployable screening technique and consistency is more important

Evaluate the role of organic acids in the protection of ligands from radiolytic degradation

Energy Technology Data Exchange (ETDEWEB)

Miller, Anneka [Idaho National Lab. (INL), Idaho Falls, ID (United States); Mezyk, Stehpen [Idaho National Lab. (INL), Idaho Falls, ID (United States); Peterman, Dean [Idaho National Lab. (INL), Idaho Falls, ID (United States)

2016-08-01

In the Advanced TALSPEAK process, the bis(2-ethylhexyl)phosphoric acid (HDEHP) extractant used in the traditional TALSPEAK process is replaced by the extractant 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester (HEH[EHP]). In addition, the aqueous phase complexant and buffer used in traditional TALSPEAK is replaced with the combination of N-(2-hydroxyethyl)ethylenediamine-N,N’,N’-triacetic acid (HEDTA) and citric acid. In order to evaluate the possible impacts of gamma radiolysis upon the efficacy of the Advanced TALSPEAK flowsheet, aqueous and organic phases corresponding to the extraction section of the proposed flowsheet were irradiated in the INL test loop under an ambient atmosphere. The results of these studies conducted at INL, led INL researchers to conclude that the scarcity of values of rate constants for the reaction of hydroxyl radical with the components of the Advanced TALSPEAK process chemistry was severely limiting the interpretation of the results of radiolysis studies performed at the INL. In this work, the rate of reaction of hydroxyl radical with citric acid at several pH values was measured using a competitive pulse radiolysis technique. This report describes those results and is written in completion of milestone M3FT-16IN030102028, the goal of which was to evaluate the role of organic acids in the protection of ligands from radiolytic degradation. The results reported here demonstrate the importance of obtaining hydroxyl radical reaction rate data for the conditions that closely resemble actual solution conditions expected to be used in an actual solvent extraction process. This report describes those results and is written in completion of milestone M3FT-16IN030102028, the goal of which was to evaluate the role of organic acids in the protection of ligands from radiolytic degradation.

Molecular and supramolecular speciations of solvent extraction systems based on malonamide and/or dialkyl-phosphoric acids for An(III)/Ln(III); Speciations moleculaire et supramoleculaire de systemes d'extraction liquide-liquide a base de malonamide et/ou d'acides dialkylphosphoriques pour la separation An(III)/Ln(III)

Energy Technology Data Exchange (ETDEWEB)

Gannaz, B

2006-06-15

The solvent extraction system used in the DIAMEX-SANEX process, developed for the actinide(III)/lanthanide(III) separation, is based on the use of mixtures of the malonamide DMDOHEMA and a dialkyl-phosphoric acid (HDEHP or HDHP), in hydrogenated tetra-propylene. The complexity of these systems urges on a novel approach to improve the conventional methods (thermodynamics, solvent extraction) which hardly explain the macroscopic behaviors observed (3. phase, over-stoichiometry). This approach combines studies on both supramolecular (VPO, SANS, SAXS) and molecular (liquid-liquid extraction, ESI-MS, IR, EXAFS) speciations of single extractant systems (DMDOHEMA or HDHP in in n-dodecane) and their mixture. In spite of safety constraints due to the handling of radio-material, they were used in the studies as much as possible, like for SAXS measurements on americium-containing samples, a worldwide first-time. In each of the investigated systems, actinides(III) and lanthanides(III) are extracted to the organic phase in polar cores of reversed micelles, the inner and outer-sphere compositions of which are proposed. Thus, the 4f and 5f cations are extracted by reversed micelles such as [(DMDOHEMA){sub 2}M(NO{sub 3}){sub 3}]{sub inn} (DMDOHEMA){sub x}(HNO{sub 3}){sub z}(H{sub 2}O){sub w}]{sub out} and M(DHP){sub 3}(HDHP){sub y-3}(H{sub 2}O){sub w} with y = 3 to 6, for the single extractant systems. In the case of the two extractants system, the less concentrated one acts like a co-surfactant regarding the mixed aggregate formation [(DMDOHEMA){sub 2}M(NO{sub 3}){sub 3-v}(DHP){sub v}]{sub inn} [(DMDOFIEMA){sub x}(HDHP){sub y}(HNO{sub 3})z(H{sub 2}O){sub w}]{sub out}. (author)

Radioactivity monitoring of Irish dairy produce

International Nuclear Information System (INIS)

Kelleher, K.

2010-01-01

Full text: The RPII has been carrying out monitoring of milk and dairy produce since 1986. Milk samples are routinely analysed for radiocaesium and strontium-90 as part of the RPII's environmental monitoring programme to determine the doses received to the Irish population from milk consumption. The method the RPII utilises for determining the Sr-90 activity in milk is by measuring the Cerenkov radiation produced by its daughter 90 Y isolated from interfering nuclides such as uranium, thorium, radium and their decay products as well as isotopes of caesium, potassium and strontium by extraction with 10% di-(2-ethylhexyl)phosphate (HDEHP) in toluene. The chemical yield of 90 Y is determined by the acidmetric titration of yttrium nitrate carrier with titriplex III. The levels of Sr-90 and dose to the Irish population from milk consumption have been negligible when compared to other radioactive sources in the Irish environment. Other dairy products are analysed for radiocaesium on a routine basis for commercial customers to ensure the levels of radioactivity in the dairy products fall within EC regulations governing the export/import of dairy produce. The export of milk and milk produce from Ireland is a very important industry, 80% of dairy products produced in Ireland are exported and these exports are worth Euro 2.2 billion annually to the Irish economy. The dairy products are analysed by gamma spectroscopy and include full and skim milk powders, butter, casein, cheese, cream, whey and lactose. The levels of radiocaesium in these products are typically below 5 Bk/kg and fall well within the limit of 370 Bq/kg laid down by the European Community in Council Regulation 737/90. Although the levels of these radionuclides are relatively low the RPII recognises the importance of analysing these samples for radioactivity to inform the public, ensure consumer confidence and, more importantly, to maintain a level of expertise in the RPII in these analytical techniques so that

Determination of 236U and transuranium elements in depleted uranium ammunition by α-spectrometry and ICP-MS

International Nuclear Information System (INIS)

Desideri, D.; Meli, M.A.; Roselli, C.; Testa, C.; Boulyga, S.F.; Becker, J.S.

2002-01-01

It is well known that ammunition containing depleted uranium (DU) was used by NATO during the Balkan conflict. To evaluate the origin of DU (the enrichment of natural uranium or the reprocessing of spent nuclear fuel) it is necessary to directly detect the presence of activation products ( 236 U, 239 Pu, 240 Pu, 241 Am, and 237 Np) in the ammunition. In this work the analysis of actinides by α-spectrometry was compared with that by inductively coupled plasma mass spectrometry (ICP-MS) after selective separation of ultratraces of transuranium elements from the uranium matrix. 242 Pu and 243 Am were added to calculate the chemical yield. Plutonium was separated from uranium by extraction chromatography, using tri-n-octylamine (TNOA), with a decontamination factor higher than 10 6 ; after elution plutonium was determined by ICP-MS ( 239 Pu and 240 Pu) and α-spectrometry ( 239+240 Pu) after electroplating. The concentration of Pu in two DU penetrator samples was 7 x 10 -12 g g -1 and 2 x 10 -11 g g -1 . The 240 Pu/ 239 Pu isotope ratio in one penetrator sample (0.12±0.04) was significantly lower than the 240 Pu/ 239 Pu ratios found in two soil samples from Kosovo (0.35±0.10 and 0.27±0.07). 241 Am was separated by extraction chromatography, using di(2-ethylhexyl)phosphoric acid (HDEHP), with a decontamination factor as high as 10 7 . The concentration of 241 Am in the penetrator samples was 2.7 x 10 -14 g g -1 and -15 g g -1 . In addition 237 Np was detected at ultratrace levels. In general, ICP-MS and α-spectrometry results were in good agreement.The presence of anthropogenic radionuclides ( 236 U, 239 Pu, 240 Pu, 241 Am, and 237 Np) in the penetrators indicates that at least part of the uranium originated from the reprocessing of nuclear fuel. Because the concentrations of radionuclides are very low, their radiotoxicological effect is negligible. (orig.)

Determination of (236)U and transuranium elements in depleted uranium ammunition by alpha-spectrometry and ICP-MS.

Science.gov (United States)

Desideri, D; Meli, M A; Roselli, C; Testa, C; Boulyga, S F; Becker, J S

2002-11-01

It is well known that ammunition containing depleted uranium (DU) was used by NATO during the Balkan conflict. To evaluate the origin of DU (the enrichment of natural uranium or the reprocessing of spent nuclear fuel) it is necessary to directly detect the presence of activation products ((236)U, (239)Pu, (240)Pu, (241)Am, and (237)Np) in the ammunition. In this work the analysis of actinides by alpha-spectrometry was compared with that by inductively coupled plasma mass spectrometry (ICP-MS) after selective separation of ultratraces of transuranium elements from the uranium matrix. (242)Pu and (243)Am were added to calculate the chemical yield. Plutonium was separated from uranium by extraction chromatography, using tri- n-octylamine (TNOA), with a decontamination factor higher than 10(6); after elution plutonium was determined by ICP-MS ((239)Pu and (240)Pu) and alpha-spectrometry ((239+240)Pu) after electroplating. The concentration of Pu in two DU penetrator samples was 7 x 10(-12) g g(-1) and 2 x 10(-11) g g(-1). The (240)Pu/(239)Pu isotope ratio in one penetrator sample (0.12+/-0.04) was significantly lower than the (240)Pu/(239)Pu ratios found in two soil samples from Kosovo (0.35+/-0.10 and 0.27+/-0.07). (241)Am was separated by extraction chromatography, using di(2-ethylhexyl)phosphoric acid (HDEHP), with a decontamination factor as high as 10(7). The concentration of (241)Am in the penetrator samples was 2.7 x 10(-14) g g(-1) and <9.4 x 10(-15) g g(-1). In addition (237)Np was detected at ultratrace levels. In general, ICP-MS and alpha-spectrometry results were in good agreement. The presence of anthropogenic radionuclides ((236)U, (239)Pu,(240)Pu, (241)Am, and (237)Np) in the penetrators indicates that at least part of the uranium originated from the reprocessing of nuclear fuel. Because the concentrations of radionuclides are very low, their radiotoxicological effect is negligible.

Radioactivity monitoring of Irish dairy produce

Energy Technology Data Exchange (ETDEWEB)

Kelleher, K. (Radiological Protection Institute of Ireland. Radiation Monitoring, Dublin (Ireland))

2010-03-15

Full text: The RPII has been carrying out monitoring of milk and dairy produce since 1986. Milk samples are routinely analysed for radiocaesium and strontium-90 as part of the RPII's environmental monitoring programme to determine the doses received to the Irish population from milk consumption. The method the RPII utilises for determining the Sr-90 activity in milk is by measuring the Cerenkov radiation produced by its daughter 90Y isolated from interfering nuclides such as uranium, thorium, radium and their decay products as well as isotopes of caesium, potassium and strontium by extraction with 10% di-(2-ethylhexyl)phosphate (HDEHP) in toluene. The chemical yield of 90Y is determined by the acidmetric titration of yttrium nitrate carrier with titriplex III. The levels of Sr-90 and dose to the Irish population from milk consumption have been negligible when compared to other radioactive sources in the Irish environment. Other dairy products are analysed for radiocaesium on a routine basis for commercial customers to ensure the levels of radioactivity in the dairy products fall within EC regulations governing the export/import of dairy produce. The export of milk and milk produce from Ireland is a very important industry, 80% of dairy products produced in Ireland are exported and these exports are worth Euro 2.2 billion annually to the Irish economy. The dairy products are analysed by gamma spectroscopy and include full and skim milk powders, butter, casein, cheese, cream, whey and lactose. The levels of radiocaesium in these products are typically below 5 Bk/kg and fall well within the limit of 370 Bq/kg laid down by the European Community in Council Regulation 737/90. Although the levels of these radionuclides are relatively low the RPII recognises the importance of analysing these samples for radioactivity to inform the public, ensure consumer confidence and, more importantly, to maintain a level of expertise in the RPII in these analytical techniques so

New method for large scale production of medically applicable Actinium-225 and Radium-223

International Nuclear Information System (INIS)

Aliev, R.A.; Vasilyev, A.N.; Ostapenko, V.; Kalmykov, S.N.; Zhuikov, B.L.; Ermolaev, S.V.; Lapshina, E.V.

2014-01-01

Alpha-emitters ( 211 At, 212 Bi, 213 Bi, 223 Ra, 225 Ac) are promising for targeted radiotherapy of cancer. Only two alpha decays near a cell membrane result in 50% death of cancer cell and only a single decay inside the cell is required for this. 225 Ac may be used either directly or as a mother radionuclide in 213 Bi isotope generator. Production of 225 Ac is provided by three main suppliers - Institute for Transuranium Elements in Germany, Oak Ridge National Laboratory in USA and Institute of Physics and Power Engineering in Obninsk, Russia. The current worldwide production of 225 Ac is approximately 1.7 Ci per year that corresponds to only 100-200 patients that could be treated annually. The common approach for 225 Ac production is separation from mother 229 Th or irradiation of 226 Ra with protons in a cyclotron. Both the methods have some practical limitations to be applied routinely. 225 Ac can be also produced by irradiation of natural thorium with medium energy protons . Cumulative cross sections of 225 Ac, 227 Ac, 227 Th, 228 Th formations have been obtained recently. Thorium targets (1-9 g) were irradiated by 114-91 MeV proton beam (1-50 μA) at INR linear accelerator. After dissolution in 8 M HNO 3 + 0.004 M HF thorium was removed by double LLX by HDEHP in toluene (1:1). Ac and REE were pre-concentrated and separated from Ra and most fission products by DGA-Resin (Triskem). After washing out by 0.01 M HNO 3 Ac was separated from REE by TRU Resin (Triskem) in 3 M HNO 3 media. About 6 mCi 225 Ac were separated in hot cell with chemical yield 85%. The method may be upscaled for production of Ci amounts of the radionuclide. The main impurity is 227 Ac (0.1% at the EOB) but it does not hinder 225 Ac from being used for medical 225 Ac/ 213 Bi generators. (author)

Microsystems for liquid-liquid extraction of radionuclides in the analytical protocols

International Nuclear Information System (INIS)

Helle, Gwendolyne

2014-01-01

Radiochemical analyses are necessary to numerous steps for nuclear wastes management and for the control of the environment. An analytical protocol generally includes different steps of chemical separations which are lengthy, manual and complicated to implement because of their confinement in glove boxes and because of the hostile chemical and radiochemical media. Thus there is a huge importance to propose innovative and robust solutions to automate these steps but also to reduce the volumes of the radioactive and chemical wastes at the end of the analytical cycle. One solution consists in the miniaturization of the analyses through the use of lab-on-chip. The objective of this thesis work was to propose a rational approach to the conception of separative microsystems for the liquid-liquid extraction of radionuclides. To achieve this, the hydrodynamic behavior as well as the extraction performances have been investigated in one chip for three different chemical systems: Eu(III)-HNO 3 /DMDBTDMA, Eu(III)-AcO(H,Na)-HNO 3 /HDEHP and U(VI)-HCl/Aliquat336. A methodology has been developed for the implementation of the liquid-liquid extraction in micro-system for each chemical system. The influence of various geometric parameters such as channel length or specific interfacial area has been studied and the comparison of the liquid-liquid extraction performances has led to highlight the influence of the phases viscosities ratio on the flows. Thanks to the modeling of both hydrodynamics and mass transfer in micro-system, the criteria related to physical and kinetic properties of the chemical systems have been distinguished to propose a rational conception of tailor-made chips. Finally, several examples of the liquid-liquid extraction implementation in micro-system have been described for analytical applications in the nuclear field: U/Co separation by Aliquat336, Eu/Sm separation by DMDBTDMA or even the coupling between a liquid-liquid extraction chip and the system of

Consolidation of the EXAm process: towards the reprocessing of a concentrated PUREX raffinate

Energy Technology Data Exchange (ETDEWEB)

Vanel, V.; Bollesteros, M.J.; Marie, C.; Montuir, M.; Pacary, V.; Antegnard, F.; Costenoble, S.; Boyer-Deslys, V. [CEA Marcoule, Nuclear Energy Division, Radiochemistry and Processes Department, Bagnols-sur-Ceze, F-30207 (France)

2016-07-01

Recycling americium alone from the spent fuel is an important issue currently studied for the future nuclear cycle (Generation IV systems) as Am is one of the main contributors to the long-term radiotoxicity and heat power of final waste. The solvent extraction process called EXAm has been developed by the CEA to enable the recovery of Am alone from a PUREX raffinate (with U, Np and Pu already removed). A mixture of DMDOHEMA and HDEHP diluted in TPH is used as the solvent and the Am/Cm selectivity is improved using TEDGA as a selective complexing agent to maintain Cm and the heavier lanthanides in the acidic aqueous phase (HNO{sub 3} 5-6 M). Americium is then selectively stripped from the light lanthanides at low acidity (pH 2.5-3) with a poly-aminocarboxylic acid (DTPA). An additional step is necessary before Am recovery, in order to strip molybdenum which would otherwise be complexed by DTPA and contaminate the Am raffinate. In order to make the process and its associated future plant more compact, the objective is now to adapt the EXAm process to a concentrated raffinate. With a concentrated PUREX raffinate, the process operates under conditions close to saturation both for the solvent and complexing agent TEDGA during the Am extraction step. Consequently, some changes were needed to adapt the flowsheet to higher concentrations of cations. Before the test on a real PUREX raffinate in the CBP shielded line at ATALANTE (at the end of 2015), the EXAm flowsheet had to be consolidated and achievable target performances ensured. A series of experiments and tests was performed: on laboratory scale (batch experiments), to identify the good operating conditions and to simulate the main phenomena involved (2010-2014); first on an inactive surrogate feed solution at G1 facility (2011-2013), and then on a surrogate feed solution with trace amounts of americium and curium (spiked test) in the C17 shielded line at ATALANTE (2014). (authors)

Separation of americium by liquid-liquid extraction using diglycol-amides water-soluble complexing agents

Energy Technology Data Exchange (ETDEWEB)

Chapron, S.; Marie, C.; Pacary, V.; Duchesne, M.T.; Miguirditchian, M. [CEA, Centre de Marcoule, Nuclear Energy Division, RadioChemistry and Processses Departement, 30207 Bagnols-sur-Ceze (France); Arrachart, G.; Pellet-Rostaing, S. [Institut de Chimie Separative de Marcoule, LTSM, Bat 426, F-30207 Bagnols-sur- Ceze (France)

2016-07-01

Recycling americium (Am) alone from spent nuclear fuels is an important option studied for the future nuclear cycle (Generation IV systems) since Am belongs to the main contributors of the long-term radiotoxicity and heat power of final waste. Since 2008, a liquid-liquid extraction process called EXAm has been developed by the CEA to allow the recovery of Am alone from a PUREX raffinate (a dissolution solution already cleared from U, Np and Pu). A mixture of DMDOHEMA (N,N'-dimethyl-N,N'-dioctyl-2-(2-(hexyloxy)ethyl)-malonamide) and HDEHP (di-2-ethylhexylphosphoric acid) in TPH is used as the solvent and the Am/Cm selectivity is improved using TEDGA (N,N,N',N'-tetraethyl-diglycolamide) as a selective complexing agent to maintain Cm and heavier lanthanides in the acidic aqueous phase (5 M HNO{sub 3}). Americium is then stripped selectively from light lanthanides at low acidity (pH=3) with a poly-aminocarboxylic acid. The feasibility of sole Am recovery was already demonstrated during hot tests in ATALANTE facility and the EXAm process was adapted to a concentrated raffinate to optimize the process compactness. The speciation of TEDGA complexes formed in the aqueous phase with Am, Cm and lanthanides was studied to better understand and model the behavior of TEDGA in the process. Some Ln-TEDGA species are extracted into the organic phase and this specific chemistry might play a role in the Am/Cm selectivity improvement. Hence the hydrophilicity-lipophilicity balance of the complexing agent is an important parameter. In this comprehensive study, new analogues of TEDGA were synthesized and tested in the EXAm process conditions to understand the relationship between their structure and selectivity. New derivatives of TEDGA with different N-alkyl chain lengths and ramifications were synthesized. The impact of lipophilicity on ligand partitioning and Am/Cm selectivity was investigated. (authors)

Treatment of aqueous outflows by complexation in micellar media and precipitation with a sol-gel process

International Nuclear Information System (INIS)

Lavaud, Cyril

2013-01-01

Being able to deal with aqueous outflows from treatment sites in the Hague is a major environmental issue. These outflows are contaminated with organic substances and elements with residual radioactivity. This work deals with the development and optimization of the process of de-polluting, and we aim at removing all pollution from the outflow, and produce a final waste compatible with traditional conditioning matrices in the nuclear area. The separation process consists of two steps: dissolving the pollution in the surfactants micelles, and precipitating a mineral phase via sol-gel transition. Within this thesis, only pollution originating from radionuclides is studied. During the first step, our strategy is to use complexing molecules able to interact with ions and to form mainly solvable complexes at the core of surfactant micelles. Thereafter, the second step consisted to add silica precursor which, after hydrolyse and polycondensation, makes it possible to aggregate those micelles that contain complexes together, and to form a silica phase which precipitates in an in-situ fashion. The goal to de-pollute the outflow was achieved, and the final waste thus produced is a silica powder that contains the micelles and the pollution which, after calcination, is compatible with conditioning matrices such as glass or concrete. A reference system for which the separation process is optimal was defined throughout various studies. This system contains a non-ionic surfactant (P123), an ion that surrogates radionuclides (neodymium), a complexing agent (HDEHP) and a silica precursor (TEOS). Hence, this system was further studied in order to broaden the application scope of the separation process, as well as to understand the mechanisms involved, during the complexation of the ions and the micellar solubilization and during the formation of the silica powder. This study was performed using diffusion, imaging and spectrometry techniques.To conclude, the alternative de

Radiation chemistry in solvent extraction: FY2010 Research

International Nuclear Information System (INIS)

Mincher, Bruce J.; Martin, Leigh R.; Mezyk, Stephen P.

2010-01-01

This report summarizes work accomplished under the Fuel Cycle Research and Development (FCR and D) program in the area of radiation chemistry during FY 2010. The tasks assigned during FY 2010 included: (1) Development of techniques to measure free radical reaction kinetics in the organic phase. (2) Initiation of an alpha-radiolysis program; (3) Initiation of an effort to understand dose rate effects in radiation chemistry; (4) Continued work to characterize TALSPEAK radiation chemistry Progress made on each of these tasks is reported here. Briefly, a method was developed and used to measure the kinetics of the reactions of the NO3 radical with solvent extraction ligands in organic solution, and the method to measure OH radical reactions under the same conditions has been designed. Rate constants for the CMPO and DMDOHEMA reaction with NO3 radical in organic solution are reported. Alpha-radiolysis was initiated on samples of DMDOHEMA in alkane solution using He ion beam irradiation and 211At isotope irradiation. The samples are currently being analyzed for comparison to DMDOHEMA ?-irradiations using a custom-developed mass spectrometric method. Results are also reported for the radiolytic generation of nitrous acid, in ?-irradiated nitric acid. It is shown that the yield of nitrous acid is unaffected by an order-of-magnitude change in dose rate. Finally, recent results for TALSPEAK radiolysis are reported, summarizing the effects on solvent extraction efficiency due to HDEHP irradiation, and the stable products of lactic acid and DTPA irradiation. In addition, results representing increased scope are presented for the radiation chemistry program. These include an investigation of the effect of metal complexation on radical reaction kinetics using DTPA as an example, and the production of a manuscript reporting the mechanism of Cs-7SB radiolysis. The Cs-7SB work takes advantage of recent results from a current LDRD program to understand the fundamental chemistry of

Managing Zirconium Chemistry and Phase Compatibility in Combined Process Separations for Minor Actinide Partitioning

Energy Technology Data Exchange (ETDEWEB)

Wall, Nathalie [Washington State Univ., Pullman, WA (United States); Nash, Ken [Washington State Univ., Pullman, WA (United States); Martin, Leigh [Washington State Univ., Pullman, WA (United States)

2017-03-17

In response to the NEUP Program Supporting Fuel Cycle R&D Separations and Waste Forms call DEFOA- 0000799, this report describes the results of an R&D project focusing on streamlining separation processes for advanced fuel cycles. An example of such a process relevant to the U.S. DOE FCR&D program would be one combining the functions of the TRUEX process for partitioning of lanthanides and minor actinides from PUREX(UREX) raffinates with that of the TALSPEAK process for separating transplutonium actinides from fission product lanthanides. A fully-developed PUREX(UREX)/TRUEX/TALSPEAK suite would generate actinides as product(s) for reuse (or transmutation) and fission products as waste. As standalone, consecutive unit-operations, TRUEX and TALSPEAK employ different extractant solutions (solvating (CMPO, octyl(phenyl)-N,Ndiisobutylcarbamoylmethylphosphine oxide) vs. cation exchanging (HDEHP, di-2(ethyl)hexylphosphoric acid) extractants), and distinct aqueous phases (2-4 M HNO₃ vs. concentrated pH 3.5 carboxylic acid buffers containing actinide selective chelating agents). The separate processes may also operate with different phase transfer kinetic constraints. Experience teaches (and it has been demonstrated at the lab scale) that, with proper control, multiple process separation systems can operate successfully. However, it is also recognized that considerable economies of scale could be achieved if multiple operations could be merged into a single process based on a combined extractant solvent. The task of accountability of nuclear materials through the process(es) also becomes more robust with fewer steps, providing that the processes can be accurately modeled. Work is underway in the U.S. and Europe on developing several new options for combined processes (TRUSPEAK, ALSEP, SANEX, GANEX, ExAm are examples). There are unique challenges associated with the operation of such processes, some relating to organic phase chemistry, others arising from the

Determination of {sup 236}U and transuranium elements in depleted uranium ammunition by {alpha}-spectrometry and ICP-MS

Energy Technology Data Exchange (ETDEWEB)

Desideri, D.; Meli, M.A.; Roselli, C.; Testa, C. [General Chemistry Institute, Urbino University, Urbino (Italy); Boulyga, S.F.; Becker, J.S. [Central Department of Analytical Chemistry, Research Centre Juelich, Juelich (Germany)

2002-11-01

It is well known that ammunition containing depleted uranium (DU) was used by NATO during the Balkan conflict. To evaluate the origin of DU (the enrichment of natural uranium or the reprocessing of spent nuclear fuel) it is necessary to directly detect the presence of activation products ({sup 236}U, {sup 239}Pu, {sup 240}Pu, {sup 241}Am, and {sup 237}Np) in the ammunition. In this work the analysis of actinides by {alpha}-spectrometry was compared with that by inductively coupled plasma mass spectrometry (ICP-MS) after selective separation of ultratraces of transuranium elements from the uranium matrix. {sup 242}Pu and {sup 243}Am were added to calculate the chemical yield. Plutonium was separated from uranium by extraction chromatography, using tri-n-octylamine (TNOA), with a decontamination factor higher than 10{sup 6}; after elution plutonium was determined by ICP-MS ({sup 239}Pu and {sup 240}Pu) and {alpha}-spectrometry ({sup 239+240}Pu) after electroplating. The concentration of Pu in two DU penetrator samples was 7 x 10{sup -12} g g{sup -1} and 2 x 10{sup -11} g g{sup -1}. The {sup 240}Pu/{sup 239}Pu isotope ratio in one penetrator sample (0.12{+-}0.04) was significantly lower than the {sup 240}Pu/{sup 239}Pu ratios found in two soil samples from Kosovo (0.35{+-}0.10 and 0.27{+-}0.07). {sup 241}Am was separated by extraction chromatography, using di(2-ethylhexyl)phosphoric acid (HDEHP), with a decontamination factor as high as 10{sup 7}. The concentration of {sup 241}Am in the penetrator samples was 2.7 x 10{sup -14} g g{sup -1} and <9.4 x 10{sup -15} g g{sup -1}. In addition {sup 237}Np was detected at ultratrace levels. In general, ICP-MS and {alpha}-spectrometry results were in good agreement.The presence of anthropogenic radionuclides ({sup 236}U, {sup 239}Pu,{sup 240}Pu, {sup 241}Am, and {sup 237}Np) in the penetrators indicates that at least part of the uranium originated from the reprocessing of nuclear fuel. Because the concentrations of

Radiation chemistry in solvent extraction: FY2010 Research

Energy Technology Data Exchange (ETDEWEB)

Bruce J. Mincher; Leigh R. Martin; Stephen P. Mezyk

2010-09-01

This report summarizes work accomplished under the Fuel Cycle Research and Development (FCR&D) program in the area of radiation chemistry during FY 2010. The tasks assigned during FY 2010 included: • Development of techniques to measure free radical reaction kinetics in the organic phase. • Initiation of an alpha-radiolysis program • Initiation of an effort to understand dose rate effects in radiation chemistry • Continued work to characterize TALSPEAK radiation chemistry Progress made on each of these tasks is reported here. Briefly, a method was developed and used to measure the kinetics of the reactions of the •NO3 radical with solvent extraction ligands in organic solution, and the method to measure •OH radical reactions under the same conditions has been designed. Rate constants for the CMPO and DMDOHEMA reaction with •NO3 radical in organic solution are reported. Alpha-radiolysis was initiated on samples of DMDOHEMA in alkane solution using He ion beam irradiation and 211At isotope irradiation. The samples are currently being analyzed for comparison to DMDOHEMA ?-irradiations using a custom-developed mass spectrometric method. Results are also reported for the radiolytic generation of nitrous acid, in ?-irradiated nitric acid. It is shown that the yield of nitrous acid is unaffected by an order-of-magnitude change in dose rate. Finally, recent results for TALSPEAK radiolysis are reported, summarizing the effects on solvent extraction efficiency due to HDEHP irradiation, and the stable products of lactic acid and DTPA irradiation. In addition, results representing increased scope are presented for the radiation chemistry program. These include an investigation of the effect of metal complexation on radical reaction kinetics using DTPA as an example, and the production of a manuscript reporting the mechanism of Cs-7SB radiolysis. The Cs-7SB work takes advantage of recent results from a current LDRD program to understand the fundamental chemistry

Actinides and rare earths complexation with adenosine phosphate nucleotides

International Nuclear Information System (INIS)

Mostapha, Sarah

2013-01-01

Organophosphorus compounds are important molecules in both nuclear industry and living systems fields. Indeed, several extractants of organophosphorus compounds (such as TBP, HDEHP) are used in the nuclear fuel cycle reprocessing and in the biological field. For instance, the nucleotides are organophosphates which play a very important role in various metabolic processes. Although the literature on the interactions of actinides with inorganic phosphate is abundant, published studies with organophosphate compounds are generally limited to macroscopic and / or physiological approaches. The objective of this thesis is to study the structure of several organophosphorus compounds with actinides to reach a better understanding and develop new specific buildings blocks. The family of the chosen molecules for this procedure consists of three adenine nucleotides mono, bi and triphosphate (AMP, adenosine monophosphate - ADP, adenosine diphosphate - ATP, adenosine triphosphate) and an amino-alkylphosphate (AEP O-phosphoryl-ethanolamine). Complexes synthesis was conducted in aqueous and weakly acidic medium (2.8-4) for several lanthanides (III) (Lu, Yb, Eu) and actinides (U (VI), Th (IV) and Am (III)). Several analytical and spectroscopic techniques have been used to describe the organization of the synthesized complexes: spectrometric analysis performed by FTIR and NMR were used to identify the functional groups involved in the complexation, analysis by ESI-MS and pH-metric titration were used to determine the solution speciation and EXAFS analyzes were performed on Mars beamline of the SOLEIL synchrotron, have described the local cation environment, for both solution and solid compounds. Some theoretical approaches of DFT were conducted to identify stable structures in purpose of completing the experimental studies. All solid complexes (AMP, ADP, ATP and AEP) have polynuclear structures, while soluble ATP complexes are mononuclear. For all synthesized complexes, it has been

Advanced Aqueous Separation Systems for Actinide Partitioning

Energy Technology Data Exchange (ETDEWEB)

Nash, Ken [Washington State Univ., Pullman, WA (United States); Martin, Leigh [Idaho National Lab. (INL), Idaho Falls, ID (United States); Lumetta, Gregg [Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

2015-04-02

necessary for commercial fuel processing supporting transmutation of transplutonium elements. This research project continued basic themes investigated by this research group during the past decade. In the Fuel Cycle Research and Development program at DOE, the current favorite process for accomplishing the separation of trivalent actinides from fission product lanthanides is the TALSPEAK process. TALSPEAK is a solvent extraction method (developed at Oak Ridge National Lab in the 1960s) based on the combination of a cation exchanging extractant (e.g., HDEHP), an actinide-selective aminopolycarboxylate complexing agent (e.g., DTPA), and a carboxylic acid buffer to control pH in the range of 3-4. Considerable effort has been expended in this research group during the past 8 years to elaborate the details of TALSPEAK in the interest of developing improved approaches to the operation of TALSPEAK-like systems. In this project we focused on defining aggregation phenomena in conventional TALSPEAK separations, on supporting the development of Advanced TALSPEAK processes, on profiling the aqueous complexation kinetics of lanthanides in TALSPEAK relevant aqueous media, on the design of new diglycolamide and N-donor extractants, and on characterizing cation-cation complexes of pentavalent actinides.

An Overview of the Production, Quality Control and Feasibility of Using 90Y as a Therapeutic Radionuclide

International Nuclear Information System (INIS)

Venkatesh, M.

2009-01-01

90 Y is increasingly accepted world wide as a radionuclide for in-vivo therapy owing to attractive decay features (T1/2 2.67 d; Eβ max 2.28 MeV) and viable production feasibility in high specific activities. 90 Y is most often recommended for treatment of large tumour lesions as the hard β rays are effective in delivering therapeutic dose to large volume. However, possibility of high radiation dose to the critical organs such as bone marrow and kidneys is an important concern that is given due weightage while designing therapy using 90 Y. The best route to avail 90 Y for therapy applications is from 90 Sr, though neutron actiation of natural 89 Y(100% abundance) is feasible. The absorption cross section σ is barely 1.38 b, resulting in low specific activity 90 Y which is useful for limited applications. The possibility of obtaining 90Y through a radionuclide generator as the daughter of a long lived parent 90 Sr (T1/2 28.9 y) is a major advantage that enables access to high specific activity 90 Y. Transporting the 90Y activity to a user institution from a centralized production facility is reasonably feasible and this facilitates its wide spread use. Several generator designs have been developed and reported to access 90 Y. Solvent extraction using a chelating molecule in an organic solvent (0.3M HDEHP/n-dodecane), column chromatography using ion exchange resins (cationic as well as anionic; Dowex-50x8; AG 50x16; Aminex-A5) or inorganic exchanger, membrane based separation using chelating ligand impregnated membranes (CMPO in electrochemical separation are some of the methods reported. Limitations such as elution of 90 Y after initial elution of 90 Sr, availability of 90 Y as a chelated complex which then has to be treated to enable labeling the molecule of interest, possibility of obtaining small quantities of 90 Y owing to radiolytic damages to the separation system components, paucity of special automation gadgets for handling the high activities remotely