Authigenesis of vivianite as influenced by methane-induced sulfidization in cold-seep sediments off southwestern Taiwan

• Vivianite occurs below a sulfidization zone in cold-seep sediments off SW Taiwan.
• Sulfide scavenging in overlying sediments favored the mineralization of vivianite.
• Precipitations of vivianite and AVS could take place by turns in the transition.
• A significant but varied Mg content is characteristic of the nodular vivianite.
• Vivianite influences P burial in iron-rich sediments with high sedimentation rates.

Authigenesis of iron-rich phosphate nodules occurs in iron-rich cold-seep sediments (MD052911 core) at Yung-An Ridge offshore southwestern Taiwan. Raman, FTIR, and quantitative X-ray energy-dispersive spectroscopic analyses indicate that the phosphate mineral is vivianite (or barićite) and shows Fe/Mg molar ratios spanning from ca. 0.6 to 4.0 and a general down core trend of increasing Fe/Mg ratios. The formation of vivianite is limited to a depth interval of 13–17 mbsf (meters below seafloor) and is most prominent at ∼16 mbsf in association with high dissolved iron concentrations and depleted dissolved sulfide below a peak sulfidization zone (enriched in mackinawite and greigite). Alternate growths of vivianite and iron monosulfides and compositional zoning with Mg enriched towards the peripheries of individual nodules occur in the transition from the zone of vivianite mineralization to the sulfidization zone. The crystallization of vivianite below the sulfidization front could have been favored by scavenging of downward diffusive dissolved sulfide from pore waters in the sulfidization zone. Alternate growths and overlapping of the zones of iron monosulfides and vivianite can be attributed to fluctuations of the sulfidization front and methane flux. The discovery of vivianite in the Yung-An Ridge sediments implies that authigenic vivianite can be an important sink for phosphorus burial in cold-seep sediments that have high reactive-iron contents and high sedimentation rates.