Formation of non-evaporitic gypsum in gas hydrate-bearing sediments at Håkon Mosby mud volcano, SW Barents sea

Abstract

Authigenic minerals such as carbonate and iron sulfide are known features at cold seeps worldwide and form as a result of the anaerobic oxidation of methane in the sulfate-methane transition zone (SMTZ). Recent findings of seep-related non-evaporitic gypsum raise questions regarding its distribution, formation mechanisms, and relationships with the other proxies for confident paleo-seep reconstructions. Here, we report new findings of gypsum in the seep-impacted sediments of the hydrate-bearing Håkon Mosby mud volcano, SW Barents Sea. We combined sediment core logging (XRF, X-Ray) with optical microscopy and scanning electron microscopy - electron dispersive energy to characterize the authigenic mineral fraction of the sediment. Three paleo-SMTZs marked by the co-occurrence of pyrite and gypsum accumulations were found at 7–10 cm, 13–18 cm and 19–21 cm, above the modern one (at ∼50 cm) and match with carbonate-poor and foraminifera-free sediment intervals. Our results indicate that gypsum formation required a descending SMTZ (decreasing methane flux), triggering the oxidation of previously-formed pyrite which supplied extra SO42− to the pore water. Acidic conditions caused by pyrite oxidation would have promoted the dissolution of carbonate particles, thus releasing Ca2+ that is available for gypsum formation. As seen in other studies, the presence of shallow gas hydrates seems to play an important role as a calcium source for gypsum precipitation, via ion exclusion during hydrate formation. HMMV represents an optimal natural laboratory to investigate the interplay between different processes in gypsum biogeochemistry and its potential use as a proxy for methane seeps in modern and ancient settings.