Institute of Isotopes Hungarian Academy of Sciences Laboratory for nuclear forensics and environmental analysis Presented by: Éva Széles Seminar on R & D Activities at the Institute of Isotopes Related to Nuclear Security February 19, 2010, Vienna

Institute of Isotopes Hungarian Academy of Sciences Vienna, February 19, Laboratory for nuclear forensics and environmental analysis 2 Main Tasks of the Laboratory Analysis of confiscated nuclear materials – nuclear forensics characterization and identification of the found and confiscated samples with unknown origin destructive and non-destructive analysis analysis of U and Pu  e.g. precise isotope ratio measurements Analysis for safeguards purposes environmental and swipe samples single particle analysis by laser ablation ICP-MS (LA-ICP-MS) environmental monitoring for safeguards purposes before the decomissioning of nuclear facilities

Institute of Isotopes Hungarian Academy of Sciences Vienna, February 19, Laboratory for nuclear forensics and environmental analysis 3 Main Tasks of the Laboratory Analysis of environmental samples - other aspects Measurement of low-level actinides in environmental samples (soil, sediment, water, plant, etc.) Analysis of alternative nuclear materials (Am, Np, Cm) Direct analysis of solid samples by LA-ICP-MS technique (e.g. geological samples, uranium ore samples, metal samples, etc.)

Institute of Isotopes Hungarian Academy of Sciences Vienna, February 19, Laboratory for nuclear forensics and environmental analysis 4 Main instruments: High resolution inductively coupled plasma sector- field mass spectrometry (ICP-SFMS) High resolution gamma spectrometry (HRGS) Scanning electron microscope (SEM/EDX) Neutron coincidence counting (NCC) Additional techniques: X-ray diffraction analysis (XRD) Prompt-gamma activation analysis (PGAA) Applied Techniques

Institute of Isotopes Hungarian Academy of Sciences Vienna, February 19, Laboratory for nuclear forensics and environmental analysis 5 ELEMENT2 with single collector Installed in a clean room (Class ) Various sample introduction systems: Stable sample introduction Laser ablation system Sample preparation laboratory (Class ): With a Class 100 laminar flow hood Ultra-trace level measurements High-resolution inductively coupled plasma sector-field mass spectrometer (ICP-SFMS)

Institute of Isotopes Hungarian Academy of Sciences Vienna, February 19, Laboratory for nuclear forensics and environmental analysis 6 Quasi non-destructive measurement no chemical sample preparation needed short analysis time (typically <1 h/sample) Laser ablation (LA) unit for the mass spectrometer Laser ablation system: UP213 (New Wave) Laser ablation system: UP213 (New Wave)

Institute of Isotopes Hungarian Academy of Sciences Vienna, February 19, Laboratory for nuclear forensics and environmental analysis 7 Fully non-destructive measurement No sample preparation needed Low-background gamma spectrometer Iron chamber with 20 cm wall thickness 150 cm 3 coaxial HPGe detector 34% relative efficiency Sample cavity flushed with nitrogen Planned upgrades: Better detector Underground facility Low-energy planar HPGe detectors For U and Pu isotopics High-resolution gamma spectrometry (HRGS) N 2 flushing

Institute of Isotopes Hungarian Academy of Sciences Vienna, February 19, Laboratory for nuclear forensics and environmental analysis 8 Scanning Electron Microscope (SEM) Type JEOL JSM-5600LV Broad magnification range up to “Low vacuum” mode for observing nonconductive samples in their native state Elemental analysis Attached energy dispersive X-ray spectrometer (EDS)

Institute of Isotopes Hungarian Academy of Sciences Vienna, February 19, Laboratory for nuclear forensics and environmental analysis 9 Origin of nuclear forensics in Hungary Illicit trafficking in Hungary: since the early ’90s In the beginning: only planar HPGe used Since then: Low-background HPGe SEM ICP-MS NCC A possible site of illicit trafficking in Budapest

Institute of Isotopes Hungarian Academy of Sciences Vienna, February 19, Laboratory for nuclear forensics and environmental analysis 10 Tested with following nuclear materials: Powder (U compounds) DA & NDA Pellets (U oxide) DA & NDA Fuel rods (U oxide) NDA Fuel assemblies NDA Sealed sources (eg. Pu) NDA … Nuclear forensic applications at IKI Non-destructive techniques (NDA) are still needed though very accurate destructive methods (DA) are available

Institute of Isotopes Hungarian Academy of Sciences Vienna, February 19, Laboratory for nuclear forensics and environmental analysis 11 Selected nuclear forensic applications developed at the Institute of Isotopes

Institute of Isotopes Hungarian Academy of Sciences Vienna, February 19, Laboratory for nuclear forensics and environmental analysis 12 Uranium age dating by destructive ICP-MS Digestion of the uranium-oxide sample Determination of 234 U-content by isotope dilution ICP-MS analysis Determination of 230 Th-content by isotope dilution ICP-MS analysis after extraction-chromatographic separation Production of 229 Th tracer: from 233 U-solution („milking”) Uranium age dating by quasi-non destructive LA-ICP-MS Determination of production date of nuclear materials

Institute of Isotopes Hungarian Academy of Sciences Vienna, February 19, Laboratory for nuclear forensics and environmental analysis 13 Two measurements: 234 U/ 238 U by planar HPGe 214 Bi/ 238 U by coaxial HPGe in low background Activity ratios determined by relative (“intrinsic”) efficiency calibration Independent of measurement geometry Uranium age dating by fully non-destructive HRGS

Institute of Isotopes Hungarian Academy of Sciences Vienna, February 19, Laboratory for nuclear forensics and environmental analysis 14 Detecting the presence of reprocessed uranium 232 U content indicates reprocessed uranium  232 U analysis by HRGS  236 U and Pu isotopes can be measured by ICP-MS 232 U content determined by HRGS as a function of 235 U enrichment 232 U content determined by HRGS as a function of 235 U enrichment

Institute of Isotopes Hungarian Academy of Sciences Vienna, February 19, Laboratory for nuclear forensics and environmental analysis 15 Rare-earth elements in uranium-bearing materials determined by ICP-SFMS – Origin assessment Three uranium ore concentrates originating from different mills in order to compare their REE profiles after digestion of the samples and separation of the matrix (U)

Institute of Isotopes Hungarian Academy of Sciences Vienna, February 19, Laboratory for nuclear forensics and environmental analysis 16 Trace elements in uranium-oxide determined by ICP-SFMS – Origin assessment Samples:  590: Natural (HU-NAT)  642: LEU (HU-LEU)  643: DU (HU-DEP) Trace element analysis in 3 confiscated uranium-oxid pellets  Joint analysis with Institute for Transuranium Elements (ITU) sample 590

Institute of Isotopes Hungarian Academy of Sciences Vienna, February 19, Laboratory for nuclear forensics and environmental analysis 17 Quality assurance ISO 9001:2000 ISO/IEC – accreditation of the ICP-MS laboratory is in progress Participation in interlaboratory comparisons and proficiency tests ITWG - HEU REIMEP, NUSIMEP, IAEA-PT Joint analysis with JRC ITU, Karlsruhe

Institute of Isotopes Hungarian Academy of Sciences Vienna, February 19, Laboratory for nuclear forensics and environmental analysis 18 Inter-laboratory comparison (Round Robin) organised by the ITWG (2001) 232 U 234 U 235 U 236 U 238 U Average of RR0.964 ± ± ± ± 1.22 HRGS(7.50±0.55)* ± ± ± ± 0.5 LA-ICP-SFMS0.965 ± ± ± ± 0.25 Production date by HRGS Production date by LA-ICP-SFMS Production date from Round-Robin 1978 ± 3 yearsAugust, 1979 ± 6 monthsFeb-July 1979 Isotopic composition Production date More than 10 nuclear forensic laboratories participated ~1 g HEU sample/lab.

Institute of Isotopes Hungarian Academy of Sciences Vienna, February 19, Laboratory for nuclear forensics and environmental analysis 19 Joint analysis with Institute for Transuranium Elements (ITU) 3 uranium oxide pellets from 3 different batches were analysed at IKI by HRGS and LA-ICP-SFMS The pellets were sent to ITU for further investigation using DA methods MC-ICP-MS TIMSIDMSHRGS LA-ICP- SFMS 232 U 3.2(9)  U (5)0.0347(21)0.0345(33)0.025(20)0.0362(24)0.0358(9) 235 U (14)2.5121(14)2.5119(30)2.51(12)2.562(34)2.529(19) 236 U 0.451(22)0.47(44)0.47(86)-0.38(24)0.474(24) 238 U (21) (20) (12)97.47(12)97.021(34)96.961(20) IKIITU

Institute of Isotopes Hungarian Academy of Sciences Vienna, February 19, Laboratory for nuclear forensics and environmental analysis 20 Safeguards analysis of environmental samples

Institute of Isotopes Hungarian Academy of Sciences Vienna, February 19, Laboratory for nuclear forensics and environmental analysis 21 Analysis of swipe samples – bulk analysis The laboratory is capable of determining ultra-trace amounts of uranium and plutonium isotopes and their precise isotope ratios in environmental swipe samples Analytical procedures developed for bulk analysis: Screening by gamma spectrometry Microwave digestion instead of ashing Extraction chromatographic separation with TRU ® column process ICP-SFMS measurement Detection limits achieved: Uranium: 0.01 – 5 ng (IAEA SAL req.: ng) Plutonium: 1 – 7 fg (IAEA SAL req.: 10 fg) Special developments: reduction of procedure background Clean room facilities Optimized procedure Sub-boiled acids and minimal chemical consumption Method was tested by analysis of real swipe samples

Institute of Isotopes Hungarian Academy of Sciences Vienna, February 19, Laboratory for nuclear forensics and environmental analysis 22 Analytical performance parameters achieved

Institute of Isotopes Hungarian Academy of Sciences Vienna, February 19, Laboratory for nuclear forensics and environmental analysis 23 Analysis of single particles by LA-ICP-MS technique Development of a novel methodology for the isotopic composition measurement of single particles Current results: Isotopic analysis of individual uranium particles by laser ablation ICP-SFMS Tested for uranium-oxide particles with different enrichment, lateral dimensions: down to 10 micron Applicable also for low-abundant isotopes ( 234 U, 236 U) Typical precision achieved: 0.2-5% RSD for 235 U/ 238 U Testing for sub-micron particles (JRC IRMM, NUSIMEP) Particle location : fission track and SEM/EDS  Further aim: adaptation of the method for swipe samples

Institute of Isotopes Hungarian Academy of Sciences Vienna, February 19, Laboratory for nuclear forensics and environmental analysis 24 Analysis of single particles by LA-ICP-MS technique LEU particle (40 x 38 um) LA-ICP-MS measurement SEM/EDS

Institute of Isotopes Hungarian Academy of Sciences Vienna, February 19, Laboratory for nuclear forensics and environmental analysis 25 Provision for decommissioning of nuclear facilities - environmental monitoring Objectives: determination of the environmental contamination baseline/level as a reference database in the vicinity of Hungarian nuclear facilities comprehensive environmental monitoring and analysis before decommissioning for safeguards purposes Test measurements at the KFKI site near the research reactor: plutonium and uranium concentrations and isotopic ratios in soil and wood-moss were determined Results: Pu: ~fg/g, U: ~ng/g

Institute of Isotopes Hungarian Academy of Sciences Vienna, February 19, Laboratory for nuclear forensics and environmental analysis 26 Conclusion IKI is capable of a complete nuclear-forensic characterization of most types of nuclear material Combined use of DA and NDA instrumentation HRGS, ICP-SFMS, SEM, NCC Note on Pu: handling only sealed sources Only NDA can be applied Environmental measurements at ultra-trace level

Institute of Isotopes Hungarian Academy of Sciences Vienna, February 19, Laboratory for nuclear forensics and environmental analysis 27 Conclusion Planned developments : Particle analysis with laser ablation ICP-MS Upgrading the low-background HRGS facilities Possible future application: In-field age dating of shielded HEU (e.g. of an Improvised Nuclear Device)?

Institute of Isotopes Hungarian Academy of Sciences Vienna, February 19, Laboratory for nuclear forensics and environmental analysis 28 Thank You for Your attention! Section Head: Dr. András Kovács Staff:Staff on-leave: ICP-MS: Dr. Tamás Bíró Dr. Zsolt Stefánka (HAEA) Dr. Éva SzélesDr. Zsolt Varga (ITU) Mr. Róbert Katona Ms. Zsuzsanna Mácsik HRGS: Dr. László Lakosi Dr. József Zsigrai (ITU) Dr. Nguyen Cong Tam Mr. János Bagi (JRC Ispra) Mr. István Almási Mr. Péter Nagy SEM: Dr. Péter Hargittai