Rapid Commun Mass Spectrom
March 2024
Rationale: The efficiency of selected ion monitoring (SIM) and selected reaction monitoring (SRM) analyses for the quantification of three mono-, di- and tri-unsaturated highly branched isoprenoid (HBI) alkenes (IP , IPSO and HBI III, respectively), often used as proxies for the occurrence of Arctic and Antarctic sea ice or the adjacent open waters, was compared.
Methods: Gas chromatography (GC)-mass spectrometry (MS)/SIM and GC/MS/MS/SRM analyses were carried out on dilute solutions made from purified standards of these three HBIs, and then on hydrocarbon fractions of several sediment and sea ice sample extracts. More efficient and specific SRM transitions were selected after collision-induced dissociation of each precursor ion at different collision energies.
The variability of Arctic sea-ice during abrupt stadial-interstadial shifts in the last glacial period remain poorly understood. Here, we investigated the millennial-scale relationship, with a focus on Heinrich Stadials (HS), between sea-ice cover and bottom water temperature (BWT) during Marine Isotope Stages (MIS) 3 and 2 (64-13 ka) in the Fram Strait using new molecular sea ice biomarker data and published benthic foraminiferal BWT records. Widespread spring sea-ice cover (SpSIC) dominated the studied interval, especially in mid-late MIS 3 (45-29 ka).
View Article and Find Full Text PDFThe Southern Ocean paleoceanography provides key insights into how iron fertilization and oceanic productivity developed through Pleistocene ice-ages and their role in influencing the carbon cycle. We report a high-resolution record of dust deposition and ocean productivity for the Antarctic Zone, close to the main dust source, Patagonia. Our deep-ocean records cover the last 1.
View Article and Find Full Text PDFComparison of Type II photosensitized oxidation of lipids (the photodynamic effect) and photodegradation of chlorophyll (sensitizer photobleaching) in samples of particulate matter collected previously from locations representing a diverse range of latitudes reveals an enhancement of the photooxidation of lipids at the expense of chlorophyll photodegradation in the polar regions. The efficiency of the photodynamic effect appears to be particularly high in sinking particles collected under sea ice and is attributed to the rapid settling of highly aggregated sympagic algae to depths of low light transmission favouring the photodynamic effect at the expense of photobleaching of the sensitizer. Paradoxically, the low efficiency of Type II photosensitized oxidation of lipids observed in temperate and equatorial regions is associated with high solar irradiances in these regions.
View Article and Find Full Text PDFRationale: Some highly branched isoprenoid (HBI) alkenes are commonly used as proxies for palaeoceanographic reconstructions. However, there is a need to identify compounds that are sufficiently stable and abundant to be used as tracers of HBI oxidation in sediments. 2,6,10,14-Tetramethyl-7-(3-methylpent-4-enyl)-pentadec-5(Z/E)-en-4-ols resulting from 2,6,10,14-tetramethyl-7-(3-methylpent-4-enyl)-pentadec-5-ene appear to be useful for this purpose.
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