A n~ajorpurposecxfthe Techni- ixiiiinformation Center iii”to provide IhQ broadest dissemination possi- informationcontained in industry, the and federal, stateand kxxil governments= Although a small portionof this report is not reproducible, it is being made available to expedite the avai!abitity ofinformationcmthe research discussed herein. ‘L.,,... T’dEMDmQnmIsIRY OF UM3m!’R,~ MD ~ - AR UmA%mc RwS-IW--3O63 DE$6 007600 by Richard A. Roberts Xallinckrodt Medical Products 675 HcDmmell Boulevard St. k@UiS, HO 63134 GregoryR. *pPin Department of C2mmistxy Florids State University Tallahassee, Florida ~OhXS F. Wild Nuclear bistry Division kence IA-more R8t ional IAor8tory Liverm3re, Califormi8 Prepared for bittee on Ruclear and Rsdiockdstxy Eoard on ChemicalSciemces and Techmolo~ _ission on Fhysical Sciences, Ha-tics, and ResourcPs ?IathrbslAca~ of Schhces--htioml Reaeuch Cowhcil Feb- 19S6 Pubuiedby Edward S. Macias, Chairmau Committee on Wuclear”and Radiochemistry —~Preface some procedures used in the radiochemical, isolation, purification an~or an~lysis of uranium, neptuiliuxt and plutenium. The original makgraphs were: The Radiochemistry of Uranium, J. 1%.Gindler, NAS-HS-3050 { 1962) , 350 pp. , 18 procedures. The Radiochemistry of Neptunium, G. A. Burney and R. M. HarbourP NAS-??S-3060 (1974)P 229 pp.g 25 procedures. The Radiochemistry of Elutonium, G. H. Coleman; ~AS-lE’-3O58 [1965), 18”4pp., 25 procedures. In addition to the description of the procedures, these earlier monographs list the isotopes and their nuclear properties for each element. They also discuss the chemistry of the separation processes af these elements with primary emphasis m precipitation, ion exchange and solvent extraction techniques. In this update of the procedures, we have net attempted to discuss the developments in the chemistry of U, Up and Pu but have restricted the monograph to the newer procedures, most of which have resulted from the increased emphasis in environmental concern which requires analysis of extremely small amounts of the actinide element in quite complex matrices. The final section of this monograph describes several scheqes “for isolation of actinides by oxidation state. The “individual procedures fran the earlie”r monographs are listed by title to provide a more complete view of available separation techniques. The new procedures in this monograph are included for each element following the list from the earlier publications. R. A. Roberts G. R. Choppin J. F. Wild ~. .... ...~i~ . ~." ....................................."...... ............iv 1. of PreVio-l?:~. ...............-....--..~ 11. .....................“2.. Iii. of PreviousPht*um Proce~ .......................& IV. ~ .........................................6 Introduction........... .........................................6 Discussion of Proce&es. .......... ............................6 Procedures: 1. Smd-Quantitative Determinationof Urani= ( aSpectroscopy)..........................................IL 2. Concentration of Uranitm by”,Coprecipitathn with Iron-Potassi~ Ferrocyanophospkmates................16 3. Extraction of Uraniti with TQh and Spectro- photometric Determinationwith Arsenazo 111...............17 4. Detemi=tion of Uranium (and ?lutonim) Isotopes in Soil Samples by a-Spectroscopy................19 5. Aniti Exchange Separation of U in Halmic and Ascorbic Acid Hedia...................................21 6. Separation of Uraniua from Heavy 14ecalsby Chromatography Using snksonic kid ~sin ................23 7 Chr-togrsphic Separation and a-Spectr&cric Detemination of Uraniun. ...........2& 8. Determinationof Ikanlum in NaturalMaters Afte=Aaion-Exchange Sepa.ration...........................26 9. Uranium kalyais by Liquid Scfnttl18tlonCounting.........28 “lo. Detamimaeion of ‘fraceUrani= in Biological Ma~rlals by Reutron Activation ~yais and Solmimtetraction...............................:........31 11. Datarmimtian @f Zrace Uranium by hse~ntal neutron Activation @alysis ...............................33 ,. v. Nemt- Ikoce- .......................................36 Introduction. ....................................................34 Procedures: 1. Cl&matographic Separation of Heptuniua Using Quaternary *nitm Hitrate =tractant ....................33 2. A SpectrophotomatricMethod for the Determination of Rleptuni- in Proces,sSolutions.........................36 VI. ~ . 38 Introduction.............................‘h....... ....”...........28 “’.\ Discussionoft heProcedures. ..................................38 Procedures: 1. Liquid-Liquid Extraction Separation and Detemination of Plutonium................................~dll ,2. Determinationof Plutoniumin Sedimentsby SolventExtraction............................... ...42 3. Ratiochemical Determinationof Plutonium in Marine Samples by Extraction.Chrmatography:.............”.44 4. The Determinationof Plutonim in EnVir~ntal Samples by Extraction with Tridodecylamine.................46 5. SolventExtractionHetlwd for Determination of Plutonim in Soft Tissue...............................48 6. Determinationof Plutonium in Tissue by Aliquat-336 Extraction~...................................50 7. Deterninathnof Trace ~ts of Plutonium in Urine..................................................52 8. Extractive PhotometricDeterminationof Plumniqs(IV) with Al@wt-336 and Xylenol fJrange.........54 9. Si.mu.ltsneousDeterminations of Plutoni- Alpha- and Bata+ctivfq in LiquidEffiwnts and Bnwir=sn=l ~lom . ........55 VSI. ~.. --’”...”...-..-.”-””....”.’.......--57 htroductsosl. ... .. .. .. .. .. .. .. .. .. .. .. .57 1. SUr!EEuyof Fretimkg Uraaim Fz=ocedurea J. E. Gindh?r 1. .D’etemhaticm of uranium -237 2. Purification of Uranium -240 3. Purification of Irradiated Uranium’-236 4. Uranium and Plutonium Analysis 5. Spectmphotmetric Extraction l%etbd~~$pecific for Uranium 6. Determination of Uranium in Urani’umConcentrates 7. Carrier Free Determination of ?Jraniuai-237 8. ~adioassay of uranium and PLutoniu in Vegetation, SoilP and Water 9. Separation of Uranium by Sclvent Extraction with TOW 10. Radiochemical Eeterminakion of Uranium -23? 12. Isolation and Measurement of Uranium at the Microgram Level 13. The Determination of Uranium by Solvent Extraction 14* Uranium Radiochemical Procedure l’sed at the U.S. Radiation Laboratory at Liwermore 15. Use of Ion Exchange Resins for the Dete-inatiOn of Uranium in Ores and Solutions 16. The Use of a Compound Column of Alumina and Cellulose for the Determination of Uranim in Minerals and Ore= Containing Arsenic and F301ybdemm 17. Determination of Uranium -235 in Mixtures of Naturally occurring Uranium Isotopes by Radioactivation ib . Determination of Microgram and SubmicrogEam Quantities of Uranium by Neutron Activation Analysis Roberts/Chopp18/UiM p~ 2 II. Skliav of Prwious Meptamim Procqdums G. A. Burriey and R. H. Harbour N#kS-BK-3060 (1974) ., 1. Separation of Np by TTA Extractim 2.” Separation of Np by TTA Extraction . 3. Determination of 23?NP in Samples Containing U~ put and Fission Pralucts \ ●.‘. “+..,. 4. Determination. of Np 5. Determination of Small Amounts of Np in Pu Metal 6.” Determination of ?Up in Samples Containing Fission Products, U, and Other Actinides 7. ~-.eterminationof Np in Samples of U and Fission Products 8. ::xtraction Chromatographic Separation of 29%p from Fission +nd Activation Products in the Deteminatio”n of PSicrcy anti 3ub-F!icrogram Quantities... of U 9. Separation”of U, Np, Pu, and Am by Reversed Phase Partition Chromatography 10 ● An Analytical Method for 237Np Using Anion Exchange 11. Separation of Ut Np~ and Pu Using Anion Exchange 12. Separation of Zr, Np, and Nb Using Anion Exchange 13 ● Separation of Np ati Pu by Anim Bx,change 14 ● Separation of BP a- Pu by Cation Exchange 15. Separation and Radiochzmical Determination “of U and Transuranim Elements Using Barium Sulfate 16-” The L8+Level. Radiochemical Determinations of 23‘Np in Environmental Sa9ples 17. Radiochedcal PrOCedu~ for the Separation of Trace Amounts =f 2q4p from Reactor Effluent Uater 18. Determination of Np in Urine . Roberts/ChOppin/f?iH W& 3 . Sualsmyof Previous %epmaim Procedures. coatinued 19. Determination of 23 ‘Np by Gamma my Spectrometry 20. Spectrophotometric Determination of Np 21 ● Microvolumetric Complexometric Hethod for Np with EDTA 22. Photometric Determination of Np as the Peroxide Complex 23 ● Separation of ??p for Spectrographic ~alysis of Impurities 24. Photometric Mtermination of Np as ti>’-Xylenol Orange Complex 25. Analysis for Np by Controlled Potential Coukmetry Roberts!ChoppinlWild page 4 . XII. S~ry nf Pretious Pluemlm Procedure ,,: G. El.Coleman NAS-NS-3058 (196,5) 1. Determination of W in Solutions Containing Large Amounts of Fe and Cr” 2. Separation and Determination of Pu by TTA Extraction 3. Separation ati.Determination of Pu h,.U-Fission Product Mixtures \ ., 49 Plutonium 5. Plutonium 6. Separation of Plutonium from Uranium and Fission Products in Irradiated Reactor Targets 7. Determination of Pu 8. Uranium an@ Plutonium Analysis . 9am Separation”of ,Plutonimn frm Irradiated Uranium 9b. Separation of Plutonium frcan Uranium Metal 10. Purification of Plutotiium frm Uranium and Fission Products 11. Uranium and Plutonium from Environmental Samples of Soil, Vegetation, and Water 12. Plutonium from Environmental water Samples 13. Plutonium from Environmental water Samples 14 ● Separation of Plutonium in Uranium-Plutonium Fission Element Alloys by TBP Extraction from Chloride Solutions 15. Separation of Pu before Spectrographic Analysis of Impurities