Direct analysis of cotton swipes for plutonium isotope determination by microextraction-ICP-MS

Manard, Benjamin T.; Metzger, Shalina C.; Rogers, Kayron T.; Ticknor, Brian W.; Zirakparvar, N. Alex; Roach, Benjamin D.; Bostick, Debra A.; Hexel, Cole R.

doi:10.1039/d1ja00255d

Direct analysis of cotton swipes for plutonium isotope determination by microextraction-ICP-MS

Journal Article · Fri Sep 10 00:00:00 EDT 2021 · Journal of Analytical Atomic Spectrometry

DOI:https://doi.org/10.1039/d1ja00255d· OSTI ID:1824979

^[1]; ^[1]; ^[1]; ^[1]; ^[1]; ^[1]; ^[1]; ^[1]

Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

This study demonstrates a method for determining the isotopic composition of low-level (sub-pg) plutonium (Pu) directly from a cotton swipe. Environmental sample (ES) swipes are routinely employed as a tool for monitoring activities in nuclear facilities. Traditional ES swipe analysis, as employed in nuclear safeguards, utilizes laborious ashing, digestion, and chemical separation procedures prior to mass spectrometric (MS) analysis. Here, an innovative sample introduction technique employing a microextraction probe to extract Pu directly from the swipe surface is described. The microextraction probe lowers onto the swipe surface, seals on a small area (8 mm²), and delivers solvent (2% HNO₃) to extract actinide material that may be present. The extracted analyte is subsequently directed into a sector field inductively coupled plasma (ICP)-MS for isotope ratio determination. This microextraction-ICP-MS method successfully determined the isotopic composition (²⁴⁰Pu/²³⁹Pu and ²⁴²Pu/²³⁹Pu) of three Pu certified reference materials (CRM 136, 137, and 138) that were deposited (1 pg) onto ES swipes. The percent relative difference from the certified value, uncorrected for instrumental fractionation, was <2% for the ²⁴⁰Pu/²³⁹Pu ratio on all three CRMs and <10% for the ²⁴²Pu/²³⁹Pu ratio on CRM 136 and 138. Here, the percent relative standard deviation, an estimate of the sample-to-sample isotopic precision, was <4% for the ²⁴⁰Pu/²³⁹Pu and <15% for the ²⁴²Pu/²³⁹Pu. Method limits of detection were determined, based on measurements of an enriched ²⁴⁴Pu material, to be ~7 fg. Additionally, a mixed uranium (U) and Pu deposition was made to determine the method's ability to simultaneously extract U and Pu and determine the isotopic composition of both analytes.

View Accepted Manuscript (DOE)

Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE National Nuclear Security Administration (NNSA)

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 1824979

Alternate ID(s):: OSTI ID: 1820479

Journal Information:: Journal of Analytical Atomic Spectrometry, Journal Name: Journal of Analytical Atomic Spectrometry Journal Issue: 10 Vol. 36; ISSN 0267-9477

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

References (37)

Rapid paper spray mass spectrometry characterization of uranium and exemplar molecular species Coopersmith, Kaitlin; Cody, Robert B.; Mannion, Joseph M. Rapid Communications in Mass Spectrometry, Vol. 33, Issue 22 https://doi.org/10.1002/rcm.8517	journal	October 2019
Ambient desorption/ionization mass spectrometry using a liquid sampling–atmospheric glow discharge (LS-APGD) ionization source Marcus, R. Kenneth; Burdette, Carolyn Q.; Manard, Benjamin T. Analytical and Bioanalytical Chemistry, Vol. 405, Issue 25 https://doi.org/10.1007/s00216-013-7216-3	journal	July 2013
Round-robins in the area of uranium and plutonium bulk analysis of environmental samples Pointurier, Fabien; Williams, Ross W.; LaMont, Stephen P. Journal of Radioanalytical and Nuclear Chemistry, Vol. 296, Issue 2 https://doi.org/10.1007/s10967-012-1985-6	journal	August 2012
Integration of a hyphenated HPIC-ICPMS protocol for the measurement of transplutonium isotopic mass distributions for 252Cf campaigns at Oak Ridge National Laboratory Roach, Benjamin D.; Giaquinto, Joseph M.; Keever, Tamara J. Journal of Radioanalytical and Nuclear Chemistry, Vol. 318, Issue 1 https://doi.org/10.1007/s10967-018-6072-1	journal	August 2018
Preparation and certification of the uranium nitrate solution reference materials series IRMM-2019 to IRMM-2029 for the isotopic composition Richter, S.; Venchiarutti, C.; Hennessy, C. Journal of Radioanalytical and Nuclear Chemistry, Vol. 318, Issue 2 https://doi.org/10.1007/s10967-018-6166-9	journal	September 2018
A highly-enriched 244Pu reference material for nuclear safeguards and nuclear forensics measurements Essex, Richard M.; Williams, Ross W.; Treinen, Kerri C. Journal of Radioanalytical and Nuclear Chemistry, Vol. 324, Issue 1 https://doi.org/10.1007/s10967-020-07075-y	journal	March 2020
Strengthening IAEA safeguards through environmental sampling and analysis Donohue, D. L. Journal of Alloys and Compounds, Vol. 271-273 https://doi.org/10.1016/S0925-8388(98)00015-2	journal	June 1998
Characterizing uranium oxide reference particles for isotopic abundances and uranium mass by single particle isotope dilution mass spectrometry Kraiem, M.; Richter, S.; Erdmann, N. Analytica Chimica Acta, Vol. 748 https://doi.org/10.1016/j.aca.2012.08.030	journal	October 2012
Feasibility study on evaluating uranium enrichment with the High Resolution Gamma-Ray Spectrometry and X-ray fluorescence Kim, Sung-Hwan; Song, Ji-Yeon; Jeon, Ju-Young Applied Radiation and Isotopes, Vol. 148 https://doi.org/10.1016/j.apradiso.2019.03.031	journal	June 2019
Development of a fast and efficient analytical technique for the isotopic analysis of fission and actinide elements in environmental matrices Roach, Benjamin D.; Fenske, Emilie K.; Ilgner, Ralph H. Journal of Chromatography A, Vol. 1587 https://doi.org/10.1016/j.chroma.2018.12.029	journal	February 2019
Direct uranium isotope ratio analysis of single micrometer-sized glass particles Kappel, Stefanie; Boulyga, Sergei F.; Prohaska, Thomas Journal of Environmental Radioactivity, Vol. 113 https://doi.org/10.1016/j.jenvrad.2012.03.017	journal	November 2012
Rapid determination of ultra-trace plutonium in large volume of urine samples by tandem quadrupole inductively coupled plasma-mass spectrometry Wu, Yang; Xu, Yihong; Xing, Shan Spectrochimica Acta Part B: Atomic Spectroscopy, Vol. 184 https://doi.org/10.1016/j.sab.2021.106259	journal	October 2021
Inductively coupled plasma-sector field mass spectrometry with a high-efficiency sample introduction system for the determination of Pu isotopes in settling particles at femtogram levels Zheng, Jian; Yamada, Masatoshi Talanta, Vol. 69, Issue 5 https://doi.org/10.1016/j.talanta.2005.12.047	journal	July 2006
Particle isolation for analysis of uranium minor isotopes in individual particles by secondary ion mass spectrometry Esaka, F.; Esaka, K. T.; Lee, C. G. Talanta, Vol. 71, Issue 3 https://doi.org/10.1016/j.talanta.2006.05.091	journal	February 2007
Optimization of uranium and plutonium separations using TEVA and UTEVA cartridges for MC-ICP-MS analysis of environmental swipe samples Metzger, Shalina C.; Rogers, Kayron T.; Bostick, Debra A. Talanta, Vol. 198 https://doi.org/10.1016/j.talanta.2019.02.034	journal	June 2019
Quantification of uranium, plutonium, neodymium and gadolinium for the characterization of spent nuclear fuel using isotope dilution HPIC-SF-ICP-MS Wanna, Nancy Nazem; Dobney, Andrew; Van Hoecke, Karen Talanta, Vol. 221 https://doi.org/10.1016/j.talanta.2020.121592	journal	January 2021
Peer Reviewed: Strengthened Nuclear Safeguards Donohue, David L. Analytical Chemistry, Vol. 74, Issue 1 https://doi.org/10.1021/ac021909y	journal	January 2002
Automation of a Surface Sampling Probe/Electrospray Mass Spectrometry System Kertesz, Vilmos; Ford, Michael J.; Van Berkel, Gary J. Analytical Chemistry, Vol. 77, Issue 22 https://doi.org/10.1021/ac0510742	journal	November 2005
Liquid Microjunction Surface Sampling Coupled with High-Pressure Liquid Chromatography−Electrospray Ionization-Mass Spectrometry for Analysis of Drugs and Metabolites in Whole-Body Thin Tissue Sections Kertesz, Vilmos; Van Berkel, Gary J. Analytical Chemistry, Vol. 82, Issue 14 https://doi.org/10.1021/ac100954p	journal	July 2010
Application of a Liquid Extraction Based Sealing Surface Sampling Probe for Mass Spectrometric Analysis of Dried Blood Spots and Mouse Whole-Body Thin Tissue Sections Van Berkel, Gary J.; Kertesz, Vilmos Analytical Chemistry, Vol. 81, Issue 21 https://doi.org/10.1021/ac901712b	journal	November 2009
Rapid Determination of Uranium Isotopic Abundance from Cotton Swipes: Direct Extraction via a Planar Surface Reader and Coupling to a Microplasma Ionization Source Paing, Htoo W.; Manard, Benjamin T.; Ticknor, Brian W. Analytical Chemistry, Vol. 92, Issue 12 https://doi.org/10.1021/acs.analchem.0c01606	journal	June 2020
Direct Uranium Isotopic Analysis of Swipe Surfaces by Microextraction-ICP-MS Manard, Benjamin T.; Rogers, Kayron T.; Ticknor, Brian W. Analytical Chemistry, Vol. 93, Issue 32 https://doi.org/10.1021/acs.analchem.1c01569	journal	July 2021
Automated Separation of Uranium and Plutonium from Environmental Swipe Samples for Multiple Collector Inductively Coupled Plasma Mass Spectrometry Metzger, Shalina C.; Ticknor, Brian W.; Rogers, Kayron T. Analytical Chemistry, Vol. 90, Issue 15 https://doi.org/10.1021/acs.analchem.8b02095	journal	June 2018
Intercomparison of the Radio-Chronometric Ages of Plutonium-Certified Reference Materials with Distinct Isotopic Compositions Mathew, Kattathu; Kayzar-Boggs, Theresa; Varga, Zsolt Analytical Chemistry, Vol. 91, Issue 18 https://doi.org/10.1021/acs.analchem.9b02156	journal	August 2019
A preliminary investigation into the use of molecular oxide and hydride secondary ion relationships for improvement of the 236U/238U determination on a NanoSIMS 50L Zirakparvar, N. Alex; Hexel, Cole R.; Smith, Julie B. Scientific Reports, Vol. 10, Issue 1 https://doi.org/10.1038/s41598-020-69121-9	journal	July 2020
Ultratrace determination of uranium and plutonium by nano-volume flow injection double-focusing sector field inductively coupled plasma mass spectrometry (nFI–ICP-SFMS) Schaumlöffel, Dirk; Giusti, Pierre; Zoriy, Myroslav V. J. Anal. At. Spectrom., Vol. 20, Issue 1 https://doi.org/10.1039/B411567H	journal	January 2005
Assessment of plutonium measurement in the femtogram range by ICP-MS; correction from interfering polyatomic species Pointurier, Fabien; Hémet, Philippe; Hubert, Amélie J. Anal. At. Spectrom., Vol. 23, Issue 1 https://doi.org/10.1039/B708568K	journal	January 2008
Mass spectrometric analysis for nuclear safeguards Boulyga, Sergei; Konegger-Kappel, Stefanie; Richter, Stephan Journal of Analytical Atomic Spectrometry, Vol. 30, Issue 7 https://doi.org/10.1039/C4JA00491D	journal	January 2015
Determination of the isotopic composition of micrometric uranium particles by UV femtosecond laser ablation coupled with sector-field single-collector ICP-MS Donard, A.; Pointurier, F.; Pottin, A. -C. Journal of Analytical Atomic Spectrometry, Vol. 32, Issue 1 https://doi.org/10.1039/C6JA00071A	journal	January 2017
Uranium isotope analysis by MC-ICP-MS in sub-ng sized samples Boulyga, Sergei F.; Koepf, Andreas; Konegger-Kappel, Stefanie Journal of Analytical Atomic Spectrometry, Vol. 31, Issue 11 https://doi.org/10.1039/C6JA00238B	journal	January 2016
Liquid sampling-atmospheric pressure glow discharge (LS-APGD) microplasmas for diverse spectrochemical analysis applications Marcus, R. Kenneth; Manard, Benjamin T.; Quarles, C. Derrick Journal of Analytical Atomic Spectrometry, Vol. 32, Issue 4 https://doi.org/10.1039/C7JA00008A	journal	January 2017
Laser ablation – inductively couple plasma – mass spectrometry/laser induced break down spectroscopy: a tandem technique for uranium particle characterization Manard, Benjamin T.; Derrick Quarles, C.; Wylie, E. Miller Journal of Analytical Atomic Spectrometry, Vol. 32, Issue 9 https://doi.org/10.1039/C7JA00102A	journal	January 2017
Determination of picogram amounts of uranium in micrometre-sized particles by isotope dilution mass spectrometry Venchiarutti, C.; Stadelmann, G.; Middendorp, R. Journal of Analytical Atomic Spectrometry, Vol. 36, Issue 3 https://doi.org/10.1039/D0JA00440E	journal	January 2021
Rapid determination of plutonium in urine using flow injection on-line preconcentration and inductively coupled plasma mass spectrometry Epov, Vladimir N.; Benkhedda, Karima; Cornett, R. Jack Journal of Analytical Atomic Spectrometry, Vol. 20, Issue 5 https://doi.org/10.1039/b501218j	journal	January 2005
241Am INGROWTH AND ITS EFFECT ON INTERNAL DOSE Konzen, Kevin Health Physics, Vol. 111, Issue 1 https://doi.org/10.1097/HP.0000000000000511	journal	January 2016
Application of Fission Track Technique for the Analysis of Individual Particles Containing Uranium in Safeguard Swipe Samples Esaka, Konomi T.; Esaka, Fumitaka; Inagawa, Jun Japanese Journal of Applied Physics, Vol. 43, Issue No. 7A https://doi.org/10.1143/JJAP.43.L915	journal	June 2004
Evaluation of a new sector-field ICP-MS with Jet Interface for ultra-trace determination of Pu isotopes: from femtogram to attogram levels Zheng, J. Journal of Nuclear and Radiochemical Sciences, Vol. 15, Issue 1 https://doi.org/10.14494/jnrs.15.1_7	journal	January 2015

Similar Records

Microextraction–TQ–ICP–MS for the Direct Analysis of U and Pu from Cotton Swipes

Journal Article · Fri Oct 06 00:00:00 EDT 2023 · Analytical Chemistry · OSTI ID:2205442

Assessment of Low-Level Pu Isotope Ratio Measurements Using Multicollector Inductively Coupled Plasma Mass Spectrometry (MC-ICP-MS/MS) Equipped with a Pre-Mass Filter

Journal Article · Fri Sep 12 00:00:00 EDT 2025 · Applied Spectroscopy Practica · OSTI ID:3002509

Direct Uranium Isotopic Analysis of Swipe Surfaces by Microextraction-ICP-MS

Journal Article · Thu Jul 08 00:00:00 EDT 2021 · Analytical Chemistry · OSTI ID:1817511

Related Subjects

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND TECHNOLOGY

Direct analysis of cotton swipes for plutonium isotope determination by microextraction-ICP-MS

Citation Formats

References (37)

Similar Records

Related Subjects