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

Veronica C. Bradley; Brian W. Ticknor; Daniel R. Dunlap; N. Alex Zirakparvar; Shalina C. Metzger; Cole R. Hexel; Benjamin T. Manard

doi:10.1021/acs.analchem.3c01022

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

Veronica C. Bradley, Brian W. Ticknor, Daniel R. Dunlap, N. Alex Zirakparvar, Shalina C. Metzger, Cole R. Hexel, Benjamin T. Manard

Chemical & Isotopic Mass Spectrometry

Research output: Contribution to journal › Article › peer-review

1 Scopus citations

Abstract

The microextraction sampling technique was integrated with triple quadrupole─inductively coupled plasma-mass spectrometry (TQ-ICP-MS) to directly sample and measure the isotopic compositions of uranium (U) and plutonium (Pu) from cotton swipes. Once extracted, the U/Pu were directed into the TQ-ICP-MS instrument for isotopic determination. Carbon dioxide (CO₂) and helium (He) gases were delivered to a collision reaction cell within the ICP-MS system for ion separation. The CO₂ reacts with the U⁺ forming UO⁺ which is ultimately separated from the Pu⁺ ions of interest in the third quadrupole. This study demonstrates direct liquid extraction of U/Pu from a solid surface and subsequent measurement by TQ-ICP-MS in <60 s. Flow rates were optimized (0.3 mL min^-1 CO₂ and 5 mL min^-1 He) in the reaction cell of the ICP-MS system to maximize the Pu signal while minimizing U interferences (i.e., ²³⁸U⁺ tail and ²³⁸UH⁺) at m/z 239. Low levels of Pu (∼2 pg) were deposited on a cotton swipe along with U at concentrations ranging from 20 to 200 ng. The ²⁴⁰Pu/²³⁹Pu ratio was measured with <7% relative difference from the certified value at all U concentrations. Major and minor U isotope ratios were also measured with <4% relative difference. This highlights that the microextraction-TQ-ICP-MS method can extract a mixed U/Pu sample directly from a cotton swipe and measure both isotopic systems without chemical separation.

Original language	English
Pages (from-to)	15867-15874
Number of pages	8
Journal	Analytical Chemistry
Volume	95
Issue number	43
DOIs	https://doi.org/10.1021/acs.analchem.3c01022
State	Published - Oct 31 2023

Funding

This manuscript was authored in part by UT-Battelle, LLC, under contract DE-AC05-00OR22725 with the US Department of Energy (DOE). The US government retains and the publisher, by accepting the article for publication, acknowledges that the US government retains a nonexclusive, paid-up, irrevocable, worldwide license to publish or reproduce the published form of this manuscript, or allow others to do so, for US government purposes. DOE will provide public access to these results of federally sponsored research in accordance with the DOE Public Access Plan ( http://energy.gov/downloads/doe-public-access-plan ). This work was funded by the United States National Nuclear Security Administration’s Office of Defense Nuclear Nonproliferation Research & Development. The authors would like to acknowledge Adam Malin (ORNL) and Jacquelyn DeMink (ORNL) for assistance with graphics. This manuscript was authored in part by UT-Battelle, LLC, under contract DE-AC05-00OR22725 with the US Department of Energy (DOE). The US government retains and the publisher, by accepting the article for publication, acknowledges that the US government retains a nonexclusive, paid-up, irrevocable, worldwide license to publish or reproduce the published form of this manuscript, or allow others to do so, for US government purposes. DOE will provide public access to these results of federally sponsored research in accordance with the DOE Public Access Plan (http://energy.gov/downloads/doe-public-access-plan). This work was funded by the United States National Nuclear Security Administration’s Office of Defense Nuclear Nonproliferation Research & Development. The authors would like to acknowledge Adam Malin (ORNL) and Jacquelyn DeMink (ORNL) for assistance with graphics.

Funders	Funder number
Adam Malin
DOE Public Access Plan
United States National Nuclear Security Administration’s Office of Defense Nuclear Nonproliferation Research & Development
U.S. Department of Energy
Oak Ridge National Laboratory

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10.1021/acs.analchem.3c01022

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title = "Microextraction-TQ-ICP-MS for the Direct Analysis of U and Pu from Cotton Swipes",

abstract = "The microextraction sampling technique was integrated with triple quadrupole─inductively coupled plasma-mass spectrometry (TQ-ICP-MS) to directly sample and measure the isotopic compositions of uranium (U) and plutonium (Pu) from cotton swipes. Once extracted, the U/Pu were directed into the TQ-ICP-MS instrument for isotopic determination. Carbon dioxide (CO2) and helium (He) gases were delivered to a collision reaction cell within the ICP-MS system for ion separation. The CO2 reacts with the U+ forming UO+ which is ultimately separated from the Pu+ ions of interest in the third quadrupole. This study demonstrates direct liquid extraction of U/Pu from a solid surface and subsequent measurement by TQ-ICP-MS in <60 s. Flow rates were optimized (0.3 mL min-1 CO2 and 5 mL min-1 He) in the reaction cell of the ICP-MS system to maximize the Pu signal while minimizing U interferences (i.e., 238U+ tail and 238UH+) at m/z 239. Low levels of Pu (∼2 pg) were deposited on a cotton swipe along with U at concentrations ranging from 20 to 200 ng. The 240Pu/239Pu ratio was measured with <7% relative difference from the certified value at all U concentrations. Major and minor U isotope ratios were also measured with <4% relative difference. This highlights that the microextraction-TQ-ICP-MS method can extract a mixed U/Pu sample directly from a cotton swipe and measure both isotopic systems without chemical separation.",

author = "Bradley, {Veronica C.} and Ticknor, {Brian W.} and Dunlap, {Daniel R.} and Zirakparvar, {N. Alex} and Metzger, {Shalina C.} and Hexel, {Cole R.} and Manard, {Benjamin T.}",

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AU - Bradley, Veronica C.

AU - Ticknor, Brian W.

AU - Dunlap, Daniel R.

AU - Zirakparvar, N. Alex

AU - Metzger, Shalina C.

AU - Hexel, Cole R.

AU - Manard, Benjamin T.

PY - 2023/10/31

Y1 - 2023/10/31

N2 - The microextraction sampling technique was integrated with triple quadrupole─inductively coupled plasma-mass spectrometry (TQ-ICP-MS) to directly sample and measure the isotopic compositions of uranium (U) and plutonium (Pu) from cotton swipes. Once extracted, the U/Pu were directed into the TQ-ICP-MS instrument for isotopic determination. Carbon dioxide (CO2) and helium (He) gases were delivered to a collision reaction cell within the ICP-MS system for ion separation. The CO2 reacts with the U+ forming UO+ which is ultimately separated from the Pu+ ions of interest in the third quadrupole. This study demonstrates direct liquid extraction of U/Pu from a solid surface and subsequent measurement by TQ-ICP-MS in <60 s. Flow rates were optimized (0.3 mL min-1 CO2 and 5 mL min-1 He) in the reaction cell of the ICP-MS system to maximize the Pu signal while minimizing U interferences (i.e., 238U+ tail and 238UH+) at m/z 239. Low levels of Pu (∼2 pg) were deposited on a cotton swipe along with U at concentrations ranging from 20 to 200 ng. The 240Pu/239Pu ratio was measured with <7% relative difference from the certified value at all U concentrations. Major and minor U isotope ratios were also measured with <4% relative difference. This highlights that the microextraction-TQ-ICP-MS method can extract a mixed U/Pu sample directly from a cotton swipe and measure both isotopic systems without chemical separation.

AB - The microextraction sampling technique was integrated with triple quadrupole─inductively coupled plasma-mass spectrometry (TQ-ICP-MS) to directly sample and measure the isotopic compositions of uranium (U) and plutonium (Pu) from cotton swipes. Once extracted, the U/Pu were directed into the TQ-ICP-MS instrument for isotopic determination. Carbon dioxide (CO2) and helium (He) gases were delivered to a collision reaction cell within the ICP-MS system for ion separation. The CO2 reacts with the U+ forming UO+ which is ultimately separated from the Pu+ ions of interest in the third quadrupole. This study demonstrates direct liquid extraction of U/Pu from a solid surface and subsequent measurement by TQ-ICP-MS in <60 s. Flow rates were optimized (0.3 mL min-1 CO2 and 5 mL min-1 He) in the reaction cell of the ICP-MS system to maximize the Pu signal while minimizing U interferences (i.e., 238U+ tail and 238UH+) at m/z 239. Low levels of Pu (∼2 pg) were deposited on a cotton swipe along with U at concentrations ranging from 20 to 200 ng. The 240Pu/239Pu ratio was measured with <7% relative difference from the certified value at all U concentrations. Major and minor U isotope ratios were also measured with <4% relative difference. This highlights that the microextraction-TQ-ICP-MS method can extract a mixed U/Pu sample directly from a cotton swipe and measure both isotopic systems without chemical separation.

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JO - Analytical Chemistry

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ER -

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

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