Early diagenetic processes in an iron-dominated marine depositional system

• Published in: Geochimica et cosmochimica acta Vol. 341; pp. 183 - 199
• Main Authors: Figueroa, Maria C., van de Velde, Sebastiaan J., Gregory, Daniel D., Lemieux, Sydnie, Drake, Jeana, Treude, Tina, Kemnitz, Nathaniel, Berelson, William, Choumiline, Konstantin, Bates, Steven, Kukkadapu, Ravi, Fogel, Marilyn, Riedinger, Natascha, Lyons, Timothy W.
• Format: Journal Article
• Language: English
• Published: Elsevier Ltd 15-01-2023
• Subjects: Early diagenesis; Iron sulfides; Marine sediments; Reactive iron; Redox cycling; Reactive iron; Early diagenesis; Marine sediments; Redox cycling; Iron sulfides
• ISSN: 0016-7037; 1872-9533
• DOI: 10.1016/j.gca.2022.11.026

The early diagenetic interplay between reactive iron, sulfur, and organic matter in the bathymetrically isolated Santa Monica Basin (SMB) sediments are investigated in this study. We explore solid-phase and porewater profiles from the basin, supplemented with a transect from 71 to 907 m water depth that includes oxygenated (>60 μM O2) bottom waters near the coast and oxygen-deficient waters (∼4 µM O2) in the basin. The geochemical data of the basin sediments are further scrutinized by means of reactive transport modeling.
The results show that the basin sediments do not follow the traditional geochemical signatures of oxygen-deficient settings. A lack of dissolved sulfide accumulation and sulfurized iron persists despite the sediments being deposited under reducing conditions (without bioturbation/bioirrigation), strong organic carbon input (TOC up to 5.0 wt%), and active dissimilatory sulfate reduction. Not only did we find an exceptional enrichment in highly reactive Fe in the surface sediments (∼45 % of total Fe), but the enrichment of reactive Fe, including ferrihydrite, persists downcore and coexists with high levels of dissolved Fe. The enhanced preservation of Fe oxides and lack of iron-sulfide precipitation is in part explained by detection via Mössbauer spectra of iron oxides bounded to organic matter (Fe[III]-OM coprecipitates).
The modeled Fe budget shows that most of the Fe oxides in the surface sediments are internally recycled by upward diffusion and subsequent oxidation of Fe2+. Sulfide oxidation coupled to Fe reduction effectively precludes sulfide accumulation while enhancing build-up of dissolved Fe, fueling the Fe cycle within the first 5 cm depth. Continuous reoxidation of Fe2+ enhances the formation of Fe(III)-OM coprecipitates, limiting the amount of reactive organic matter. In the unavailability of labile organic matter, other than within the uppermost layers, the organic-rich sediment profiles are dominated by Fe cycling that limits the production and preservation of sulfides and enhances the preservation of Fe oxides and organic carbon. This study highlights key local controls on Fe availability in marginal basins and describes an intricate biogeochemical C-Fe-S cycling in modern and possibly ancient marine systems with important implications for Fe availability in the marine realm.