Exploring the potential of electrospray-Orbitrap for stable isotope analysis using nitrate as a model
Analytical Chemistry
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Abstract
Widely used isotope ratio mass spectrometers have limited capabilities to measure metabolites, drugs, or small polyatomic ions without the loss of structural isotopic information. A new approach has recently been introduced that uses electrospray ionization Orbitrap to measure multidimensional isotope signatures of intact polar compounds. Using nitrate as a model compound, this study aims to establish performance metrics for comparisons with conventional IRMS at the natural abundance level. We present a framework on how to convert isotopolog intensities to δ values that are commonly used in the isotope geochemistry community. The quantification of seven nitrate isotopologs provides multiple pathways for obtaining the primary N and O δ values including non-mass-dependent O isotope variations, as well as opportunities to explore nonrandom isotopic distributions (i.e., clumping effects) within molecular nitrate. Using automation and the adaptation of measurement principles that are specific to isotope ratio analysis, nitrate δ15NAIR, δ18OVSMOW, and δ17OVSMOW were measured with a long-term precision of 0.4‰ or better for isotopic reference materials and purified nitrate from environmental samples. In addition, we demonstrate promising results for unpurified environmental samples in liquid form. With these new developments, this study connects the two largely disparate mass spectrometry fields of bioanalytical MS and isotope ratio MS, thus providing a route to measure new isotopic signatures in diverse organic and inorganic solutes.
Suggested Citation
Hilkert, A., Bohlke, J., Mroczkowski, S.J., Fort, K.L., Aizikov, K., Wang, X.T., Kopf, S.H., Neubauer, C., 2021, Exploring the potential of electrospray-Orbitrap for stable isotope analysis using nitrate as a model: Analytical Chemistry, v. 93, p. 9139-9148, https://doi.org/10.1021/acs.analchem.1c00944.
| Publication type | Article |
|---|---|
| Publication Subtype | Journal Article |
| Title | Exploring the potential of electrospray-Orbitrap for stable isotope analysis using nitrate as a model |
| Series title | Analytical Chemistry |
| DOI | 10.1021/acs.analchem.1c00944 |
| Volume | 93 |
| Publication Date | June 24, 2021 |
| Year Published | 2021 |
| Language | English |
| Publisher | American Chemical Society |
| Contributing office(s) | WMA - Earth System Processes Division |
| Description | 10 p. |
| First page | 9139 |
| Last page | 9148 |