Exploring sediment porewater dissolved organic matter (DOM) in a mud volcano: Clues of a thermogenic DOM source from fluorescence spectroscopy

Mud volcanoes (MVs) are potential conduit migration pathways for deep thermogenic DOM. In this study, we investigated the dissolved organic matter (DOM) of porewater in a MV in the Canadian Beaufort Sea and compared dissolved organic carbon (DOC) and fluorescent DOM (FDOM) between the MV and a reference site (RS). The chemical and isotopic compositions (Cl−, δ18O and δD) of porewater from the MVs indicated that these fluids are derived from a mixture of seawater, meteoric water, and clay dehydration, causing a freshening of the porewaters. Interestingly, the porewaters in the MV exhibited DOC concentrations up to 14 times higher than those in the RS. This high DOC concentration was attributed to a higher concentration in the deep fluid moving upwards through the MV, and in minor part to processes such as particulate organic matter sulfate reduction, anaerobic oxidation of methane and higher biological activity in the MV sediments. The fluorescence results showed the presence of four components in both MV and RS sites, which included two humic-like, one microbial humic-like, and a protein-like component. All the four fluorescent components increased with depth, showing a good linear relationship with DOC. However, the DOC-normalized fluorescence in the porewater DOM was on average 3 to 7 times lower in the MV, suggesting that the DOM molecules have undergone thermogenic processes in the deep sediments, and that shallow processes do not affect significantly the FDOM composition. Our results highlight that fluids migrating from the deep sediment through the MV can be an important source of thermogenically altered DOM to the shallow sediments and overlaying water column.