Impacts of temperature and fluid seepage on organic matter composition in sediments of an active hydrothermal basin

• Published in: Organic geochemistry 2024-10, Vol.196, p.104829, Article 104829
• Main Authors: Gajendra, Niroshan, Deng, Longhui, Eglinton, Timothy I., Schubert, Carsten J., Lever, Mark A.
• Format: Article
• Language: English
• Subjects: Carbohydrates; Fluid Seepage; GC-FID; Macromolecules; Marine sediment; Organic Carbon; Organic matter degradation; Pyrolysis-Gas Chromatography/Mass Spectrometry (Py-GC/MS); Sediment Temperature Impact; Sequential Hydrolysis
• ISSN: 0146-6380
• DOI: 10.1016/j.orggeochem.2024.104829

•First comprehensive analysis of organic carbon compounds in Guaymas Basin sediment.•Contributions of major organic compound groups are stable up to ∼ 80 °C.•At > 80 °C, selective thermal degradation (loss) of carbohydrates and N compounds.•Structural changes imply thermochemical modifications of carbohydrates below 80 °C. Marine sediments are one of the largest organic carbon (OC) sinks on Earth. Yet, major knowledge gaps remain in our understanding of sedimentary OC cycling, particularly regarding temperature-induced alteration processes of OC from different sources. Here, we investigate OC-rich sediments of Guaymas Basin (Gulf of California) across two hydrothermal areas, one with only conductive geothermal heating and the other additionally experiencing seepage of hydrocarbon-rich fluids from deeper layers. We use Pyrolysis-Gas Chromatography/Mass Spectrometry (Py-GC/MS) to investigate diagenetic OC changes and show that cold control sites in both hydrothermal areas are dominated by similar contributions of lipid-derived compounds, nitrogenous (likely protein-derived) compounds, carbohydrates, and polyaromatic hydrocarbons (PAHs). These OC compound groups are largely derived from phytoplankton detritus from overlying water. Conductively heated sediments, which reach in situ temperatures of ∼ 80 °C, have similar general OC compositions and contents to these cold sites, but show evidence of diagenetic modifications of individual carbohydrate groups in deeper layers. By contrast, strong decreases in carbohydrate and nitrogenous compound abundances at the seep sites indicate that these compound groups are not only modified but also selectively degraded at the higher temperatures (>80 °C) of these sites. Increases in pyrolysis products of PAHs, prist-1-ene, and alkanes with depth, moreover, show that import of OC by deep hydrothermal fluids contributes significantly to sedimentary OC pools mainly in deeper layers of these sites. Our study provides the first comprehensive analysis of major OC compound groups in Guaymas Basin sediment and indicates that the supply of OC by hydrothermal fluid flow only has minor impacts on particulate organic matter compositions at the seafloor, even at active seep sites. We furthermore show that temperatures up to ∼ 80 °C already result in thermochemical modifications of organic matter (OM) that are potentially linked to the onset of kerogen formation. The sequence and time scales of chemical modifications and activations in