LA-UR- J/ DOt/!. D/::7J Approved for public release; distribution is unlimited. Title: Molecular Forensic Science of Nuclear Materials Author(s): Marianne P. Wilkerson Intended for: LORD-DR Program Review 13 January 2011 Los Alamos, NM USA Los Alamos NATIONAL lABORATO'RY --- £5T.1943 --- Los Alamos National Laboratory, an affirmative action/equal opportunity employer, is operated by the Los Alamos National Security, LLC for the National Nuclear Security Administration of the U.S. Department of Energy under contract DE-AC52-06NA25396. By acceptance of this article, the publisher recognizes that the U.S. Government retains a nonexclusive, royalty-free license to publish or reproduce the published form of this contribution, or to allow others to do so, for U.S. Government purposes. Los Alamos National Laboratory requests that the publisher identify this article as work performed under the auspices of the U.S. Department of Energy. Los Alamos National Laboratory strongly supports academic freedom and a researcher's right to publish; as an institution, however, the Laboratory does not endorse the viewpoint of a publication or guarantee its technical correctness. Form 836 (7/06) Molecular Forensic Science of Nuclear Materials 20100048DR Marianne P. Wilkerson 13 January 2011 Laboratory Directed Research and Development - Directed Research Los Alamos National Laboratory NI~l'r(!;5~,6l,1l- "-AlfO'!tA.ITClItV UNCLASSIFIED Slide 1 ---- t.S>l,I,'4'J ---------------------------------------------------------------------------- Operated by Los Alamos iNational Security, LLC for the U.S. Department of Energy's NNSA ...' J~r;m ... V~~ Charge and Review Criteria for 12-15 month projects Assessment: Strengths and weakness of the project with respect to the standard OMS criteria for Federally supported R&D: Quality: Are the science and technology results of high quality compared to national and international peers? Performance (Project Execution): Is the project making good progress against its milestones? Is it well-conceived and executed? Leadership: Are the results of the project defining R&D directions for the broader community? Relevance: Is the project continuing to support the strategic directions of the Laboratory? Advice: Given the finite time remaining to the project, how might the project maximize its impact (both to its field and to the Los Alamos mission) at the end of 3 years? How should the project approach its transition to non-LORD funding? UNCLASSIFIED ~1.(\n6'",,1~!\. i!.ArO'~Alr~It'? _________________________________ Slide 2 ~~~;~;~~;~:;;~~~~;~~~~~~:~:~~;,::::::-;:;-;:;~~~~~=-:=- ~~~~ ____ rS·1f.l',.tl' Operated by Los Alamos National Security, LLC for the U.S. Department of Energy's NNSA -.'J~~ V~~'f. hat is the problem that Molecular Forensic Science of Nuclear Materials is addressing? . Increasingly varied and asymmetric threats are expanding the scope of nuclear forensics · Signatures are varied and can evolve, while any given sample may include multiple signatures LARGE · The scale of sample may be or tiny · Accurate, effective technical analysis depends on - identifying new signatures - understanding measurement limitations - evaluating complementary nature between traditional and new measurements - assessing the value of the information · Production, conversion and aging of actinide terials are chemical in nature, but chBmical Los Alamos signatures are not exploited r:J'Alr,'ONAII!. l.4:8-0~AIT"RY U N C LAS S I FIE D Slide 3 - ___ IS·T.i'fO' _ _______________________________ ____ _____________________ ------~~----- ~ ~ Operated by Los Alamos National Security, LLC for the U.S. Department of Energy's NNSA _ •••~ r:JI!fI VA.'f{~4 ium materia science is rich in information! denitration • Uranium pitchblend ores II t ~ must be separated from as precipitation many as 40 elements I I Ammonium Uranium Yellow Cake Uranyl Nitrahte diuranate trioxide 65-85% U30S ~ U02(N03 (NH4hU207 U03 · > 10 phases between U0 and 2 I calcination f U0 , in addition to hydrated forms & reduction 3 of U0 hydro 3 enrichment fluorination fluorination » » Green Salt Brown Oxide 0lIl( 0lIl( UF ~ U0 A 2 · Deceptively simple formula and cubic structure of U0 masks ~ reduction 2 incredibly complex speciation Uranium metal · Weathering initiates changes in speciation "The GomRlexily- of the system is awesome. U~O 11 Edelstein, N. M. et ai, Summary and Comparison of the Actinide and Transactinide Elements. In The Chemistry of the Actinide and Transactinide Elements, 2006; Chapter 15, pp. 1753-1835. - LoSAI1amos .. ~'AnOI5lIAl-t tABORAl-TOR,Y UNCLASSIFIED Slide 4 ---- fS>~~ ~9'«1 Operated by Los Alamos National Security, LLC for the U.S. Department of Energy's NNSA :.~~, V&;~itJ. owe ean by chemical speciation? Physical (or Phase) Speciation · Refers indirectly to the phase association: dissolved, or associated with various mineral or colloidal phases U(III) U(IIV) U(V) U(VI) Chemical Speciation · Refers to the chemical form and generally includes a knowledge of phase · Depending on the type of information, various levels exist U0 {OH)+ 2 · Identity of the element o 0 2+ <1 11 · Physical state H H Il oH 0 ",,.,,. 2 '... ... ......, . .. ,~ 2 idation state 0 • \ J x ~H'o ~ll, OH2 2 · tv-olacular formula II II H 0 H OH 2 2 · IVlolecular structure o 0 " J Los Alamos 1i1iAT"16NAL l-A!HiSIfA,,rOIfY UNCLASSIFIED Slide 5 £S~f9'r ~~~~~~~~~;:~~~~~~~~~~::~~::~~~::~~~~~ ~~~ ~~~ ------- ____ ______________________________________________________________ Operated by Los Alamos National Security. LLC for the U.S. Department of Energy's NNSA ••v&·.. ". S l /Ill ~~ nium oxidation is more complex than • • tty suggested . Plutonium metal coupon (1 g) J: 0::: o~ o H 0 N 2 J: 0::: o~ o U) Pu0 2 Traditional views of Pu corrosion: PU 0 2 3 Pu + 2H20 ~ Pu02+x + 2H2 Pu metal versus a new understanding of surface phase relationships Clark, D. L.; Hecker; S. 5.; Jarvinen, G. D.; Neu, M. P. Plutonium. In The Chemistry of the Actinide and Transactinide Elements, 3rd ed.; Morss, L. R., Edelstein, N. M., Fuger, J., Katz, J. J., Eds.; Springer: Dordrecht, The Netherlands, 2006; Chapter 15, pp. 1753-1835. UNCLASSIFIED NIA-,rr65'I'iIiA>~ r..1>i8'O'R',A'T~FfY Slide 6 ____ !S,r"f.9'4'1 ______________________________________________________ ------- ~----------- ~~~~ Operated by Los Alamos National Security, LLC for the U.S. Department of Energy's NNSA •.w ~~ VA."~"J · n't chemical speciation already applied to forensic alvses? Where is the innovation here? Morphology Elemental/isotopic Structural (lattice) . X-ray diffraction · Scanning Electron analysis · SEM-EDX Microscopy ·XANES ·XRF · EXAFS · TIMS/SIMS UNCLASSIFIED Slide 7 ------- --------------------------------------------____________________________________________________________________________________________ ~~':~f~1 ::~~~~:;~::; Operated by Los Alamos National Security, LLC for the U.S. Department of Energy's NNSA -·;,."~W V",'(~itj ar t:nvironmental Science ~ Molecular Forensic Science RFETS 1995 Molecular level information # revolutionized environmental science because speciation was a better determinant of future risk Clark, D. L.; Janecky, D. R.; Lane, L. J. "Science-based cleanup of Rocky Flats" Physics Today, 2006,59(9),34-40. · Developed a more defined scope with clear endpoint Molecular Molecular Forensic Environmental Establish: Science Actinide- Science Predict: age 0( I containing • dose history Back particle Forward risk source In time In time " We propose that chemical speciation can provide molecular level information source, production mode, age, b9!~lr!m~ intended use, and his~~~L ASS I FIE ---- r.S"F.1§"~3 Operated by Los Alamos National Security, LLC for the U.S. Department of Energy's NNSA NATIONAk LABORATORY --- nl.""l--- the tools used to determine chemical -ation in Molecular Environmental Science? ~ ~(j~ ~ ~e oCJ Q,-0 - 6'fOn\C e\eC" ~ ... Vibrational • ~ ,... .. " dime ~--------------------~~ LoS Alamos UNCLAS SIFIED NJAnO'N'~t lABOIM,OR'Y Slide 9 _______ ____________________________________________________________________________________________________________- ----------------------------------- 1~~lf.J Operated by Los Alamos National Security, LLC for the U.S. Department of Energy's NNSA ··,.,~9.'41 VA"~'l