Separation of Protactinium Employing Sulfur-Based Extraction Chromatographic Resins

Mastren, Tara; Stein, Benjamin W.; Parker, T. Gannon; Radchenko, Valery; Copping, Roy; Owens, Allison; Wyant, Lance E.; Brugh, Mark; Kozimor, Stosh A.; Nortier, F. Meiring; Birnbaum, Eva R.; John, Kevin D.; Fassbender, Michael E.

doi:10.1021/acs.analchem.8b01380

Separation of Protactinium Employing Sulfur-Based Extraction Chromatographic Resins

Journal Article · Mon May 14 00:00:00 EDT 2018 · Analytical Chemistry

DOI:https://doi.org/10.1021/acs.analchem.8b01380· OSTI ID:1440455

Mastren, Tara ^[1]; Stein, Benjamin W. ^[1]; Parker, T. Gannon ^[1]; Radchenko, Valery ^[1]; Copping, Roy ^[2]; Owens, Allison ^[2]; Wyant, Lance E. ^[2]; Brugh, Mark ^[1]; Kozimor, Stosh A. ^[1]; Nortier, F. Meiring ^[1]; Birnbaum, Eva R. ^[1]; John, Kevin D. ^[1]; ^[1]

Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Nuclear Security and Isotope Technology Division

Protactinium-230 (t_1/2 = 17.4 d) is the parent isotope of ²³⁰U (t_1/2 = 20.8 d), a radionuclide of interest for targeted alpha therapy (TAT). Column chromatographic methods have been developed to separate no-carrier-added ²³⁰Pa from proton irradiated thorium targets and accompanying fission products. Results reported within this paper demonstrate the use of novel sulfur bearing chromatographic extraction resins for the selective separation of protactinium. The recovery yield of ²³⁰Pa was 93 ± 4% employing a R₃P=S type commercially available resin and 88 ± 4% employing a DGTA (diglycothioamide) containing custom synthesized extraction chromatographic resin. The radiochemical purity of the recovered ²³⁰Pa was measured via high purity germanium γ-ray spectroscopy to be >99.5% with the remaining radioactive contaminant being ⁹⁵Nb due to its similar chemistry to protactinium. Finally, measured equilibrium distribution coefficients for protactinium, thorium, uranium, niobium, radium, and actinium on both the R₃P=S type and the DGTA resin in hydrochloric acid media are reported, to the best of our knowledge, for the first time.

View Accepted Manuscript (DOE)

Research Organization:: Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Nuclear Physics (NP)

Grant/Contract Number:: AC52-06NA25396; AC05-00OR22725

OSTI ID:: 1440455

Report Number(s):: LA-UR--18-22616

Journal Information:: Analytical Chemistry, Journal Name: Analytical Chemistry Journal Issue: 11 Vol. 90; ISSN 0003-2700

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (52)

Characterization of an extraction chromatographic resin for the separation and determination of 36Cl and 129I Zulauf, Alexander; Happel, Steffen; Mokili, Marcel Bandombele Journal of Radioanalytical and Nuclear Chemistry, Vol. 286, Issue 2 https://doi.org/10.1007/s10967-010-0772-5	journal	August 2010
Sorption of protactinium(V) on extraction chromatographic resins from nitric and hydrochloric solutions Ostapenko, V.; Sinenko, I.; Arefyeva, E. Journal of Radioanalytical and Nuclear Chemistry, Vol. 311, Issue 2 https://doi.org/10.1007/s10967-016-4996-x	journal	September 2016
231Pa dating of deep-sea cores via 227Th counting Mangini, A.; Sonntag, C. Earth and Planetary Science Letters, Vol. 37, Issue 2 https://doi.org/10.1016/0012-821X(77)90170-4	journal	December 1977
Organic carbon decomposition rates in sediments of the pacific manganese nodule belt dated by 230Th and 231Pa Müller, P. J.; Mangini, A. Earth and Planetary Science Letters, Vol. 51, Issue 1 https://doi.org/10.1016/0012-821X(80)90259-9	journal	November 1980
Protactinium—I analytical separations Golden, J.; Maddock, A. G. Journal of Inorganic and Nuclear Chemistry, Vol. 2, Issue 1 https://doi.org/10.1016/0022-1902(56)80103-6	journal	January 1956
Association constants of anionic-protactinium (V) complexes Kolarich, R. T.; Ryan, V. A.; Schuman, R. P. Journal of Inorganic and Nuclear Chemistry, Vol. 29, Issue 3 https://doi.org/10.1016/0022-1902(67)80336-1	journal	March 1967
Extraction and separation of thorium(IV) and protactinium(V) by 2-carbethoxy-5-hydroxy-1-(4-tolyl)-4-pyridone Herak, M. J.; Janko, M. Journal of Inorganic and Nuclear Chemistry, Vol. 34, Issue 8 https://doi.org/10.1016/0022-1902(72)80211-2	journal	August 1972
Extraction of protactinium from mineral acid-alcohol media Alian, A. Talanta, Vol. 15, Issue 7 https://doi.org/10.1016/0039-9140(68)80149-3	journal	July 1968
and contamination at zero age: a possible limitation on U/Th series dating of speleothem material Whitehead, N. E.; Ditchburn, R. G.; Williams, P. W. Chemical Geology, Vol. 156, Issue 1-4 https://doi.org/10.1016/S0009-2541(98)00192-2	journal	April 1999
Observations of231Pa/235U disequilibrium in volcanic rocks Pickett, David A.; Murrell, Michael T. Earth and Planetary Science Letters, Vol. 148, Issue 1-2 https://doi.org/10.1016/S0012-821X(97)00037-X	journal	April 1997
Trivalent minor actinides/lanthanides separation, using organophosphinic acids Hill, C.; Madic, C.; Baron, P. Journal of Alloys and Compounds, Vol. 271-273 https://doi.org/10.1016/S0925-8388(98)00045-0	journal	June 1998
Determination of weight distribution ratios of Pa(V) and Np(V) with some extraction chromatography resins and the AG1-X8 resin Mendes, M.; Aupiais, J.; Jutier, C. Analytica Chimica Acta, Vol. 780 https://doi.org/10.1016/j.aca.2013.04.019	journal	May 2013
Chromatographic separation of the theranostic radionuclide 111Ag from a proton irradiated thorium matrix Mastren, Tara; Radchenko, Valery; Engle, Jonathan W. Analytica Chimica Acta, Vol. 998 https://doi.org/10.1016/j.aca.2017.10.020	journal	January 2018
Cross-sections of the reaction 232Th(p,3n)230Pa for production of 230U for targeted alpha therapy Morgenstern, Alfred; Apostolidis, Christos; Bruchertseifer, Frank Applied Radiation and Isotopes, Vol. 66, Issue 10 https://doi.org/10.1016/j.apradiso.2008.02.066	journal	October 2008
Large scale accelerator production of 225Ac: Effective cross sections for 78–192 MeV protons incident on 232Th targets Griswold, J. R.; Medvedev, D. G.; Engle, J. W. Applied Radiation and Isotopes, Vol. 118 https://doi.org/10.1016/j.apradiso.2016.09.026	journal	December 2016
Isolation and purification of protactinium-231 Jerome, S. M.; Collins, S. M.; Happel, S. Applied Radiation and Isotopes, Vol. 134 https://doi.org/10.1016/j.apradiso.2017.07.051	journal	April 2018
Covalency in f-element complexes Neidig, Michael L.; Clark, David L.; Martin, Richard L. Coordination Chemistry Reviews, Vol. 257, Issue 2 https://doi.org/10.1016/j.ccr.2012.04.029	journal	January 2013
Application of ion exchange and extraction chromatography to the separation of actinium from proton-irradiated thorium metal for analytical purposes Radchenko, V.; Engle, J. W.; Wilson, J. J. Journal of Chromatography A, Vol. 1380, p. 55-63 https://doi.org/10.1016/j.chroma.2014.12.045	journal	February 2015
Extraction of palladium(II) from nitric acid solutions with diglycolthioamide Huang, Huang; Huang, Chao; Wu, Yuxuan Hydrometallurgy, Vol. 156 https://doi.org/10.1016/j.hydromet.2015.05.002	journal	July 2015
Synthesis of symmetric dithiophosphinic acids for “minor actinide” extraction Klaehn, John R.; Peterman, Dean R.; Harrup, Mason K. Inorganica Chimica Acta, Vol. 361, Issue 8 https://doi.org/10.1016/j.ica.2008.01.007	journal	June 2008
A simple-rapid method to separate uranium, thorium, and protactinium for U-series age-dating of materials Knight, Andrew W.; Eitrheim, Eric S.; Nelson, Andrew W. Journal of Environmental Radioactivity, Vol. 134 https://doi.org/10.1016/j.jenvrad.2014.02.010	journal	August 2014
232Th(d,4n)230Pa cross-section measurements at ARRONAX facility for the production of 230U Duchemin, C.; Guertin, A.; Haddad, F. Nuclear Medicine and Biology, Vol. 41 https://doi.org/10.1016/j.nucmedbio.2013.12.011	journal	May 2014
Distribution coefficients of 60 elements on TODGA resin: Application to Ca, Lu, Hf, U and Th isotope geochemistry Pourmand, Ali; Dauphas, Nicolas Talanta, Vol. 81, Issue 3 https://doi.org/10.1016/j.talanta.2010.01.008	journal	May 2010
Metal ion extraction with a thiol hydrophilic resin Deratani, Andre.; Sebille, Bernard. Analytical Chemistry, Vol. 53, Issue 12 https://doi.org/10.1021/ac00235a007	journal	October 1981
Age Determination of Highly Enriched Uranium: Separation and Analysis of ²³¹ Pa Morgenstern, A.; Apostolidis, C.; Mayer, K. Analytical Chemistry, Vol. 74, Issue 21 https://doi.org/10.1021/ac0203948	journal	November 2002
Measurement of Attogram Quantities of ²³¹ Pa in Dissolved and Particulate Fractions of Seawater by Isotope Dilution Thermal Ionization Mass Spectroscopy Shen, Chuan-Chou; Cheng, Hai; Edwards, R. Lawrence Analytical Chemistry, Vol. 75, Issue 5 https://doi.org/10.1021/ac026247r	journal	March 2003
Quantitative Radiochemical Analysis by Ion Exchange. Anion Exchange Behavior of Several Metal Ions in Hydrochloric, Nitric, and Sulfuric Acid Solutions Bunney, L. R.; Ballou, N. E.; Pascual, Juan. Analytical Chemistry, Vol. 31, Issue 3 https://doi.org/10.1021/ac60147a001	journal	March 1959
Production of ²³⁰ U/ ²²⁶ Th for Targeted Alpha Therapy via Proton Irradiation of ²³¹ Pa Morgenstern, Alfred; Lebeda, Ondrej; Stursa, Jan Analytical Chemistry, Vol. 80, Issue 22 https://doi.org/10.1021/ac801304c	journal	November 2008
Elucidating Protactinium Hydrolysis: The Relative Stabilities of PaO ₂ (H ₂ O) ⁺ and PaO(OH) ₂ ⁺ Dau, Phuong D.; Wilson, Richard E.; Gibson, John K. Inorganic Chemistry, Vol. 54, Issue 15 https://doi.org/10.1021/acs.inorgchem.5b01078	journal	July 2015
Mercury(II) Adsorption from Wastewaters Using a Thiol Functional Adsorbent Nam, Kwan H.; Gomez-Salazar, Sergio; Tavlarides, Lawrence L. Industrial & Engineering Chemistry Research, Vol. 42, Issue 9 https://doi.org/10.1021/ie020834l	journal	April 2003
Anion-exchange Studies. XXI. Th(IV) and U(IV) in Hydrochloric Acid. Separation of Thorium, Protactinium and Uranium ^1,2 Kraus, Kurt A.; Moore, George E.; Nelson, Frederick Journal of the American Chemical Society, Vol. 78, Issue 12 https://doi.org/10.1021/ja01593a010	journal	June 1956
Spectroscopic and computational investigation of actinium coordination chemistry Ferrier, Maryline G.; Batista, Enrique R.; Berg, John M. Nature Communications, Vol. 7, Issue 1 https://doi.org/10.1038/ncomms12312	journal	August 2016
Antimicrobial activity of metals: mechanisms, molecular targets and applications Lemire, Joseph A.; Harrison, Joe J.; Turner, Raymond J. Nature Reviews Microbiology, Vol. 11, Issue 6 https://doi.org/10.1038/nrmicro3028	journal	May 2013
Investigation of para-sulfonatocalix[n]arenes [n = 6, 8] as potential chelates for ²³⁰ U Montavon, Gilles; Repinc, Urska; Apostolidis, Christos Dalton Trans., Vol. 39, Issue 5 https://doi.org/10.1039/B918426K	journal	January 2010
Synthesis and radiometric evaluation of diglycolamide functionalized mesoporous silica for the chromatographic separation of actinides Th, Pa and U Hopkins, Philip D.; Mastren, Tara; Florek, Justyna Dalton Transactions, Vol. 47, Issue 15 https://doi.org/10.1039/C8DT00404H	journal	January 2018
235U–231Pa age dating of uranium materials for nuclear forensic investigations Eppich, Gary R.; Williams, Ross W.; Gaffney, Amy M. Journal of Analytical Atomic Spectrometry, Vol. 28, Issue 5 https://doi.org/10.1039/c3ja50041a	journal	January 2013
Equilibrium core design methods for molten salt breeder reactor based on two-cell model Jeong, Yongjin; Park, Jinsu; Lee, Hyun Chul Journal of Nuclear Science and Technology, Vol. 53, Issue 4 https://doi.org/10.1080/00223131.2015.1062812	journal	July 2015
Comparative Studies on the Extraction of Protactinium Using Different Kinds of Organic Extractants El-Sweify, F. H.; Abdel Fattah, A. A.; Ali, S. M. Separation Science and Technology, Vol. 44, Issue 3 https://doi.org/10.1080/01496390802437016	journal	February 2009
EXTRACTION AND COEXTRACTION OF Tc(VII), Zr(IV), Np(IV.VI), Pa(V) AND Nb(V) WITH TRIBUTYL PHOSPHATE FROM NITRIC ACID SOLUTIONS Kolarik, Zdenek; Dressler, Paul Solvent Extraction and Ion Exchange, Vol. 7, Issue 4 https://doi.org/10.1080/07360298908962328	journal	January 1989
Sorption of Trace Heavy Metals by Thiol Containing Chelating Resins Saha, B.; Iglesias, M.; dimming, I. W. Solvent Extraction and Ion Exchange, Vol. 18, Issue 1 https://doi.org/10.1080/07366290008934676	journal	January 2000
Actinide Partitioning—A Review Mathur, J. N.; Murali, M. S.; Nash, K. L. Solvent Extraction and Ion Exchange, Vol. 19, Issue 3 https://doi.org/10.1081/SEI-100103276	journal	May 2001
Mechanism of Trivalent Actinide/Lanthanide Separation Using Bis(2,4,4-Trimethylpentyl) Dithiophosphinic acid (Cyanex 301) and Neutral O-Bearing Co-Extractant Synergistic Mixtures Ionova, G.; Ionov, S.; Rabbe, C. Solvent Extraction and Ion Exchange, Vol. 19, Issue 3 https://doi.org/10.1081/SEI-100103277	journal	May 2001
Extraction of Actinides(Iii), (Iv), (v), (Vi), and Lanthanides(Iii) by Structurally Tailored Diamides Sasaki, Yuji; Tachimori, Shoichi Solvent Extraction and Ion Exchange, Vol. 20, Issue 1 https://doi.org/10.1081/SEI-100108822	journal	February 2002
Novel Extraction of Chromatographic Resins Based on Tetraalkyldiglycolamides: Characterization and Potential Applications Horwitz, E. P.; McAlister, D. R.; Bond, A. H. Solvent Extraction and Ion Exchange, Vol. 23, Issue 3 https://doi.org/10.1081/SEI-200049898	journal	May 2005
Cross sections of the reaction Pa 231 ( d , 3 n ) U 230 for the production of U 230 / Th 226 for targeted α therapy Morgenstern, A.; Lebeda, O.; Stursa, J. Physical Review C, Vol. 80, Issue 5 https://doi.org/10.1103/PhysRevC.80.054612	journal	November 2009
The Solvent Extraction of Protactinium Goble, A.; Golden, J.; Maddock, A. G. Canadian Journal of Chemistry, Vol. 34, Issue 3 https://doi.org/10.1139/v56-042	journal	March 1956
Separation of Uranium and Protactinium from Thorium by Amine Extraction Ichikawa, Fujio; Uruno, Shinobu Bulletin of the Chemical Society of Japan, Vol. 33, Issue 5 https://doi.org/10.1246/bcsj.33.569	journal	May 1960
Possible Configurations for the Thorium Molten Salt Reactor and Advantages of the Fast Nonmoderated Version Mathieu, L.; Heuer, D.; Merle-Lucotte, E. Nuclear Science and Engineering, Vol. 161, Issue 1 https://doi.org/10.13182/NSE07-49	journal	January 2009
Liquid Fuel Molten Salt Reactors for Thorium Utilization Gehin, Jess C.; Powers, Jeffrey J. Nuclear Technology, Vol. 194, Issue 2 https://doi.org/10.13182/NT15-124	journal	May 2016
Molten-Salt Reactor Chemistry Grimes, W. R. Nuclear Applications and Technology, Vol. 8, Issue 2 https://doi.org/10.13182/NT70-A28621	journal	February 1970
Formation cross-sections and chromatographic separation of protactinium isotopes formed in proton-irradiated thorium metal Radchenko, Valery; Engle, Jonathan W.; Wilson, Justin J. Radiochimica Acta, Vol. 104, Issue 5 https://doi.org/10.1515/ract-2015-2486	journal	January 2016
Separation of Thorium, Protactinium and Uranium by Ion Exchange and Extraction Kluge, E.; Lieser, Κ. Η. ract, Vol. 27, Issue 3 https://doi.org/10.1524/ract.1980.27.3.161	journal	August 1980

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