Oxygen Isotope Analyses of Phosphate and Organophosphorus Compounds by Electrospray Ionization Orbitrap Mass Spectrometry
Year: 2025
Type: article
Abstract: High Resolution Image Download MS PowerPoint Slide Orbitrap mass spectrometry with electrospray ionization (ESI-Orbitrap MS) enables 18 O/ 16 O ratio measurements in phosphate and organophosphorus compounds, which offers promising avenues for the study of metabolic, biogeochemical, and environmental processes. While the instrumental feasibility of such 18 O/ 16 O ratio measurements has been shown, the applicability of such analyses in aqueous matrices on multipurpose mass spectrometers remains unaddressed. Here, we (i) evaluated the interplay between instrument parameters and the long-term accuracy and precision of ESI-Orbitrap MS for the determination of δ 18 O(PO 4 ) from H 2 PO 4 – vs PO 3 – fragments of phosphate, (ii) identified properties of methanolic sample solutions that are critical for accurate and precise measurements, and (iii) propose a sample purification procedure for the elimination of matrix-based interferences. In 10 measurement campaigns over two years, we observed a long-term reproducibility of δ 18 O(PO 4 ) within ±2.8‰. Results of in-source fragmentation experiments of H 2 PO 4 – to PO 3 – show excellent agreement of δ 18 O and offer promising opportunities to probe for 18 O/ 16 O ratios in organophosphorus compounds. By investigating the effect of the aqueous matrix and interfering anions on 18 O/ 16 O ratio measurements, we found that a water content exceeding 50 vol % and the presence of oxyanions such as nitrate and sulfate limit measurement accuracy due to interferences of matrix constituents in the ESI source. To overcome these challenges, we evaluated selective phosphate extraction with a zirconium-based metal–organic framework (MOF) as sorbent. The resulting purification procedure allowed for successful extraction and recovery of phosphate from nitrate- and sulfate-containing aqueous solutions, resulting in methanolic phosphate samples that enabled accurate analyses of δ 18 O(PO 4 ) by ESI-Orbitrap MS.
Source: Analytical Chemistry
Authors: Nora M. Bernet, Cleo Soldini, Timo M. O. Felder, Kristýna Lapčíková, Cajetan Neubauer, Wendy L. Queen, Ralf Kaegi, Federica Tamburini, Thomas B. Hofstetter
Language: English
Subfield: Spectroscopy
Field: Chemistry
Domain: Physical Sciences
Open Access status: hybrid
Estimated APC paid: $4,500
Awards: Unravelling new isotopic dimensions of oxyanions by ESI-Orbitrap, Wie Du mir - so ich Dir... Bedingungen und Grenzen egalitärer Rollenteilung in der Familie, Owen Jones' Grammar of Ornament. Building a theory of ornament in the middle of the nineteenth century, G5767762044, The training teacher as teacher trainer: Orientations and actions in the fulfillment of the dual professional mandate of teacher and trainer - a professional biographical longitudinal study including the perspective of school principals, Creating functional porosity for the rapid extraction of heavy metals and organics from complex aqueous mixtures, Collaborative Research: Innovative Resources: Into the ISOVERSE - open-source data tools for efficient, transparent, and reproducible processing of stable isotope data
OpenAlex ID: W4415029905