Single-Particle Isotopic Analysis Using the Liquid Sampling-Atmospheric Pressure Glow Discharge Microplasma Coupled to an Orbitrap Mass Spectrometer

Shrestha, Suraj [Clemson Univ., SC (United States)]; Szakas, Sarah E. [Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)] (ORCID:0000000241332197); Andrews, Hunter B. [Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)] (ORCID:0000000220919415); Manard, Benjamin T. [Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)] (ORCID:0000000207400627); Marcus, R. Kenneth [Clemson Univ., SC (United States)] (ORCID:0000000342765805)

doi:10.1021/acs.analchem.6c02718

DOE OSTI · 3395408

Single-Particle Isotopic Analysis Using the Liquid Sampling-Atmospheric Pressure Glow Discharge Microplasma Coupled to an Orbitrap Mass Spectrometer

Shrestha, Suraj [Clemson Univ., SC (United States)]·Szakas, Sarah E. [Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)] (ORCID:0000000241332197)·Andrews, Hunter B. [Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)] (ORCID:0000000220919415)·Manard, Benjamin T. [Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)] (ORCID:0000000207400627)·Marcus, R. Kenneth [Clemson Univ., SC (United States)] (ORCID:0000000342765805)

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Abstract

Isotope ratio (IR) determinations on individual particles can provide valuable information relative to the sample, including processing and dating, which could be valuable to geological and nuclear material analysis communities. In comparison to “bulk” measurements, in which all particle information is lost and homogenized within a sample, “particle” measurements allow for fingerprinting and can provide unique insights related to the sample’s nano- and micro- compositions. Furthermore, the complex nature of particles, with potential isobaric interferences from either the matrix or other elements within the same particle, poses a significant analytical challenge for conventional mass spectrometry platforms employed for elemental analysis due to their limited mass resolution. Presented here is the first demonstration of an ultrahigh resolution method for single particle (SP) isotopic analysis using the liquid sampling-atmospheric pressure glow discharge (LS-APGD) microplasma ionization source coupled to an Orbitrap mass spectrometer and FTMS Booster X2T acquisition/processing system. For proof of concept, well-characterized CeO 2 microparticles with a nominal diameter of 1.0 μm were analyzed at a mass resolution of ∼330,000. Important instrumental parameters were optimized to enable the detection of single particles. The 142 Ce/ 140 Ce ratio of individual particles and the population average were determined and compared to an SP inductively coupled plasma time-of-flight mass spectrometry (ICP-TOF-MS) analysis. The isotopic accuracy and precision were determined by two methods and found to be in good agreement with the SP-ICP-TOF-MS method, with the linear regression slope method providing a more accurate ratio, showing a ∼1.4% relative difference from the ratio determined from a particle digest. The encouraging performance of the method was further supported by a determined detection limit of 2.9 fg ( 142 Ce). The developed method is anticipated to overcome many of the challenges posed by isobaric interferences encountered in conventional mass spectrometry techniques when analyzing real-world samples for particle isotopic composition.

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY Ions Isotopes Mass spectrometry Nanoparticles Plasma

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Shrestha, Suraj [Clemson Univ., SC (United States)], Szakas, Sarah E. [Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)] (ORCID:0000000241332197), Andrews, Hunter B. [Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)] (ORCID:0000000220919415), Manard, Benjamin T. [Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)] (ORCID:0000000207400627), Marcus, R. Kenneth [Clemson Univ., SC (United States)] (ORCID:0000000342765805). 2026-06-25. Single-Particle Isotopic Analysis Using the Liquid Sampling-Atmospheric Pressure Glow Discharge Microplasma Coupled to an Orbitrap Mass Spectrometer. https://doi.org/10.1021/acs.analchem.6c02718

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