Item

Abstract

Shallow submarine hydrothermal systems are extreme environments with unique biogeochemical conditions, originating from the interaction of hot, reduced fluids and cold, oxygenated seawater. Hydrothermal fluids represent one of the marine sources of essential trace elements like iron, the flux of which is controlled by dissolved organic matter (DOM) in and between terrestrial and marine ecosystems. However, the selectivity of the DOM with iron in marine environments is not well understood. Here we characterized at a molecular level the marine hydrothermal iron–DOM interaction using Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS). Our study site was a shallow-water hydrothermal system off Dominica Island (Lesser Antilles, Caribbean Sea), where reduced fluids were strongly enriched in dissolved Fe and Si as compared to surface seawater. The dissolved organic carbon (DOC) concentration was lower in the hydrothermal fluids, most likely due to low-DOC meteoric water influence, but also suggesting biotic or abiotic processes consuming or depleting DOC when seawater is re-circulated through the sediment. The formation of hydrous ferric oxides upon aeration of the hydrothermal fluids for 10 h leads to an 8% decrease in DOC, indicating co-precipitation of iron and DOM. Re-solubilization of iron precipitates revealed increased relative abundance of aromatic compounds in co-precipitated DOM, which is in accordance with iron-coagulation observed in terrestrial environments. In conclusion, we provide evidence of co-precipitation of DOM with iron at hydrothermal systems as a selective process, which characteristically alters the molecular composition of DOM released with hydrothermal fluids.