Transformation of Mackinawite to Interlayered Greigite-Pyrrhotite and Pyrite in the Gaoping Submarine Canyon Sediments off Southwestern Taiwan

Iron monosulfides and neoformed pyrite below the sulfate–methane transition zone (SMTZ) of rapidly accumulating turbiditic sediments from the Gaoping submarine canyon off southwestern Taiwan were examined by SEM-EDS-EBSD, HRTEM, and HAADF STEM to investigate their microstructural characteristics and processes of formation and transformation. Within a few meters below the SMTZ, mackinawite (Mkw) is largely replaced by interlayered greigite-pyrrhotite (Grg-Po) with {111}Grg//{001}Po and ⟨110⟩Grg//⟨110⟩Po, followed by pyrite neoformation in clusters of disseminated matrix grains consisting of coalescing pyrite microcrystals, arrays of polycrystalline interlayer pyrite grains between the cleavage planes of layer silicates, with each grain’s core having inclusions of interlayered Grg-Po locally containing relict Mkw, and amassed pyrite microcrystals on the surface of porous interlayered Grg-Po micronodules. In the deeper sediments, neoformed pyrite is absent and Mkw is largely preserved, with partial replacement by interlayered Grg-Po having an overall topotactic relationship of ⟨110⟩Grg//⟨110 ⟩Po//⟨100⟩Mkw and {111}Grg//(001)Po//~{011}Mkw and a sharp reaction front without transitional profiles. The mineral grain boundaries and structural discontinuities with Mkw resulting from extensive interlayering between Grg {111} cubic close-packed segments and Po {001} hexagonal close-packed layers could serve as conduits for fluid flow and mass transport to drive the replacement reaction. The conversion of Mkw to metastable interlayered Grg-Po is inferred to occur through interface-coupled dissolution–reprecipitation processes associated with partial oxidation while the partial replacement of interlayered Grg-Po ± minor relict Mkw by pyrite microcrystals with irregular grain boundaries and orientations probably occurred via a dissolution–precipitation mechanism. Mkw could be initially formed by sulfate reduction driven by anaerobic oxidation of methane in reactive iron-rich sediments in paleo-SMTZs and subsequently transformed into interlayered Grg-Po followed by pyrite neoformation in the sulfidization front below the SMTZ or recent SMTZs in the Gaoping submarine canyon sediments.