Long chain glycolipids with pentose head groups as biomarkers for marine endosymbiotic heterocystous cyanobacteria

•We developed a mass spectrometry method for analysis of long chain C5 HGs.•C5 HGs were detected in marine SPM and surface sediments, suggesting a biomarker potential.•They were not detected in SPM or surface sediment from freshwater settings in the Amazon basin.•C5 HGs are suitable biomarkers for marine endosymbiotic heterocystous cyanobacteria. Marine endosymbiotic heterocystous cyanobacteria make unique heterocyst glycolipids (HGs) containing pentose (C5) moieties. Functionally similar HGs with hexose (C6) moieties found in free-living cyanobacteria occur in the sedimentary record, but C5 HGs have not been documented in the natural environment. Here we developed a high performance liquid chromatography multiple reaction monitoring (MRM) mass spectrometry (HPLC–MS2) method specific for trace analysis of long chain C5 HGs and applied it to cultures of Rhizosolenia clevei Ostenfeld and its symbiont Richelia intracellularis which were found to contain C5 HGs and no C6 HGs. The method was then applied to suspended particulate matter (SPM) and surface sediment from the Amazon plume region known to harbor marine diatoms carrying heterocystous cyanobacteria as endosymbionts. C5 HGs were detected in both marine SPM and surface sediments, but not in SPM or surface sediment from freshwater settings in the Amazon basin. Rather, the latter contained C6 HGs, established biomarkers for free-living heterocystous cyanobacteria. Our results indicate that the C5 HGs may be potential biomarkers for marine endosymbiotic heterocystous cyanobacteria.