An Evaluation of Actinide Reactivity with CO2, O2, and O2/He Gases using Inductively Coupled Plasma Tandem Mass Spectrometry: Application to Simultaneous Measurement of 241Am/241Pu Ratios in Unseparated Complex Matrices

Schlieder, Tyler D.; Hobbs, Kirby P.; French, Amanda D.; Hughes, Lee H.; Arnquist, Isaac J.; Beck, Chelsie

doi:10.1021/acs.analchem.5c01397

An Evaluation of Actinide Reactivity with CO₂, O₂, and O₂/He Gases using Inductively Coupled Plasma Tandem Mass Spectrometry: Application to Simultaneous Measurement of ²⁴¹Am/²⁴¹Pu Ratios in Unseparated Complex Matrices

Journal Article · Wed Jun 04 00:00:00 EDT 2025 · Analytical Chemistry

DOI:https://doi.org/10.1021/acs.analchem.5c01397· OSTI ID:2569732

^[1]; ^[1]; ^[1]; Hughes, Lee H. ^[1]; Arnquist, Isaac J. ^[1]; ^[1]

Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)

Accurate actinide measurements are critical within the field of nuclear science. Traditional methods for actinide quantification require time-consuming sample processing prior to analysis. There is a need for rapid analytical techniques that still maintain a high degree of accuracy. In this work, actinide reactivity was assessed for multiple oxygen-containing reaction gases using quadrupole inductively coupled plasma tandem mass spectrometry (Q-ICP-MS/MS) to evaluate actinide analysis in complex sample matrices without analyte-matrix separation. A novel method was developed to measure ²⁴¹Am/²⁴¹Pu in complex sample matrices using O₂/He reaction gas with no matrix removal or analyte pre-concentration. This inline method reduces matrix-derived polyatomic interferences that complicate traditional ICP-MS analyses by mass-shifting to ²⁴¹Am¹⁶O⁺ and ²⁴¹Pu¹⁶O₂⁺, allowing Am and Pu to be mass separated for simultaneous analysis. While mass shifting is efficient, a small portion of Am⁺ (<1.3%) and Pu⁺ (<1.4%) react to from AmO₂⁺ and PuO⁺, respectively. Therefore, a mass balance approach was used, in combination with reactivity determined from ²⁴²Pu and ²⁴³Am standard solutions, to correct for residual ²⁴¹PuO⁺ and ²⁴¹AmO₂⁺. The method was validated by measuring ²⁴¹Am/²⁴¹Pu in Pu isotope standards CRM-136 and CRM-137 (separated in March/April 1970 and February 2022, respectively) in both neat solutions and complex matrices containing diluted soil (NIST SRM 2711a, >1000 µg·g^-1). Method detection limits of 15.9 and 9.6 fg·g^-1 were determined for ²⁴¹Am and ²⁴¹Pu, respectively, and ²⁴¹Am/²⁴¹Pu ratios were measured with accuracies within <3.5%. In conclusion, this work presents the first direct analysis of ²⁴¹Am/²⁴¹Pu in unseparated complex matrices, advancing capabilities for rapid actinide measurements.

View Accepted Manuscript (DOE)

Research Organization:: Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)

Sponsoring Organization:: USDOE Laboratory Directed Research and Development (LDRD) Program; USDOE National Nuclear Security Administration (NNSA), Office of Defense Nuclear Nonproliferation

Grant/Contract Number:: AC05-76RL01830

OSTI ID:: 2569732

Report Number(s):: PNNL-SA--209135

Journal Information:: Analytical Chemistry, Journal Name: Analytical Chemistry Journal Issue: 23 Vol. 97; ISSN 0003-2700; ISSN 1520-6882

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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An Evaluation of Actinide Reactivity with CO2, O2, and O2/He Gases using Inductively Coupled Plasma Tandem Mass Spectrometry: Application to Simultaneous Measurement of 241Am/241Pu Ratios in Unseparated Complex Matrices

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An Evaluation of Actinide Reactivity with CO₂, O₂, and O₂/He Gases using Inductively Coupled Plasma Tandem Mass Spectrometry: Application to Simultaneous Measurement of ²⁴¹Am/²⁴¹Pu Ratios in Unseparated Complex Matrices