Development of a fluorescence quenching assay to measure the fraction of organic carbon present in self-assembled gels in seawater

The dissolved organic carbon pool (DOC) is among the largest reservoir of reduced carbon on our planet. The demonstration that DOC polymers remain in assembly/dispersion equilibrium forming microscopic hydrogels has a broad range of critical implications. Previous studies estimate that  10% of DOC could be assembled as gels, yielding values of  7 × 10¹⁶ g of organic carbon present as microscopic hotspots of high substrate concentration. This huge mass of reduced carbon emphasizes the need to develop reliable methods to systematically investigate the budget of self-assembled marine gels (SAG), and their role in biogeochemical cycling. However, a quantitative method to measure SAG in seawater has not been available. Here we present the validation of a simple assay to measure the mass of organic carbon assembled as microgels in native seawater. This method is based on the ratio of Chlortetracycline (CTC) fluorescence quenching between Ca bound to non-assembled organic molecules and molecules assembled as microgels. This assay can be readily implemented on board using a low cost fluorometer and provisions to measure TOC.