Carbonate-associated organic matter: A form of “dissolvable” organic matter?

Carbonate-associated organic matter (CAOM) is the organic matter associated with carbonate minerals, and a survey of carbonate-rich surface sediments suggests that it is incorporated at a consistent amount scaling with the internal surface area of the carbonate grains. As the carbonate sediment is sensitive to changes in saturation state due to benthic biogeochemical processing, we predicted that CAOM could exhibit interesting biogeochemical cycling, based on its potential to bridge particulate and dissolved pools of organic matter. Here, we report on a study in a seagrass meadow in central Florida Bay, USA. We utilize a combination of inorganic stable isotope (C, S, O) and high resolution mass spectrometry (21T FT ICR-MS) techniques to explore the carbon and sulfur cycles here, with a particular emphasis on dissolved organic matter (DOM) characterization. CAOM is examined similar to standard solid phase extraction (SPE-DOM) methods, after first washing carbonate sediment and dissolving it incompletely under a mild hydrochloric acid treatment. The δ³⁴S and δ¹⁸O of sulfate, as well as the δ¹³C of dissolved inorganic carbon (DIC), suggest that the promotion of sulfide oxidation in the seagrass rhizosphere drives rapid carbonate dissolution and re-precipitation cycles. Sulfide oxidation, as well as elevated sulfide concentration, promotes sulfurization of CAOM, which is more sulfurized than porewater and surface water, as 42% of CAOM formulas vs 28% of surface water are sulfurized. Furthermore, a substantial quantity of molecular formulas present in the overlaying surface waters (90% of formulas, 97% by relative abundance) are also present in CAOM. Despite the CAOM sample containing nearly twice the number of formulas compared to surface water, due in part to its higher dissolved organic carbon concentration, these shared formulas make up 75% of the abundance of CAOM formulas. We argue that repeated coupled sulfur and inorganic carbon cycles, intensified by seagrasses, leads to increased sulfurization and release of CAOM, affecting DOM quality in the broader aquatic system. We estimate that approximately 9% of the particulate organic carbon (POC) stored in the sediments of this site are CAOM. Our results suggest that CAOM here is a form of “dissolvable” organic carbon which cycles much more rapidly than POC more broadly.