Post column infusion of an internal standard into LC-FT-ICR MS enables semi-quantitative comparison of dissolved organic matter in original samples.
Rebecca Rodrigues MatosElaine K JenningsJan KaeslerThorsten ReemtsmaBoris P KochOliver Jens LechtenfeldPublished in: The Analyst (2024)
Ultrahigh resolution mass spectrometry hyphenated with liquid chromatography (LC) is an emerging tool to explore the isomeric composition of dissolved organic matter (DOM). However, matrix effects limit the potential for semi-quantitative comparison of DOM molecule abundances across samples. We introduce a post-column infused internal standard (PCI-IS) for reversed-phase LC-FT-ICR MS measurements of DOM and systematically evaluate matrix effects, detector linearity and the precision of mass peak intensities. Matrix effects for model compounds spiked into freshwater DOM samples ranging from a headwater stream to a major river were reduced by 5-10% for PCI-IS corrected mass peak intensities as compared to raw ( i.e. , untransformed) intensities. A linear regression of PCI-IS corrected DOM mass peak intensities across a typical DOM concentration range (2-15 mg dissolved organic carbon L -1 ) in original, non-extracted freshwater samples demonstrates excellent linearity of the detector response ( r 2 > 0.9 for 98% of detected molecular formulas across retention times). Importantly, PCI-IS could compensate for 80% of matrix effects across an environmental gradient of DOM composition from groundwater to surface water. This enabled studying the ionization efficiency of DOM isomers and linking the observed differences to the biogeochemical sources. With PCI-IS original, non-extracted DOM samples can be analysed by LC-FT-ICR MS without carbon load adjustment, and mass peak intensities can be reliably used to semi-quantitatively compare isomer abundances between compositionally similar DOM samples.
Keyphrases
- organic matter
- mass spectrometry
- liquid chromatography
- high resolution mass spectrometry
- coronary artery disease
- acute myocardial infarction
- acute coronary syndrome
- percutaneous coronary intervention
- tandem mass spectrometry
- simultaneous determination
- high resolution
- antiplatelet therapy
- gas chromatography
- st segment elevation myocardial infarction
- st elevation myocardial infarction
- solid phase extraction
- high performance liquid chromatography
- heart failure
- low dose
- capillary electrophoresis
- human health
- magnetic resonance imaging
- water quality
- monte carlo