Molecular composition of dissolved organic matter from young organic‐rich hydrothermal deep‐sea sediments

Abstract Hydrothermal transformations of dissolved organic matter (DOM) are governed by temperature and sedimentary organic carbon content, resulting in the release of hydrothermal DOM containing bioavailable compounds fueling benthic microbes. However, the temperature‐dependent molecular changes in porewater DOM from organic‐rich hydrothermal sediments, and the extent to which these changes contribute to the marine recalcitrant DOM, remain largely unexplored. Here we investigated the DOM composition of hydrothermal porewater and bottom water samples from the Guaymas Basin, Gulf of California, where basaltic sill intrusions generate hydrothermal petroleum in organic‐rich sediments. Samples containing hydrothermal petroleum with in situ temperatures from 4°C to > 106°C were analyzed using Fourier‐transform ion cyclotron resonance mass spectrometry and parallel factor analysis of excitation‐emission matrices from fluorescent DOM (FDOM). We found that the porewater DOM composition was strongly influenced by temperature and petroleum dissolution, evidenced by the enrichment of hydrothermal DOM with highly unsaturated, oxygen‐depleted aromatic, sulfur‐containing molecular formulae and petroleum‐associated FDOM compared to a cold reference site. In bottom waters, hydrothermal DOM accounted for ~ 26% of the DOM molecular formulae, with 82% exhibiting hydrogen‐to‐carbon ratios < 1.5, indicating their recalcitrance. The remaining ~ 18% of the hydrothermal molecular formulae were aliphatic and saturated, representing the release of bioavailable DOM to the ocean. Our results show that hydrothermal sediments are a source of both bioavailable and recalcitrant DOM, releasing water‐soluble petroleum‐derived compounds to the deep ocean. Our study highlights the need for more quantitative research on the contribution of hydrothermal sediments to deep‐sea DOM cycling.