Authigenic Gypsum Precipitation in the ARAON Mounds, East Siberian Sea

Abstract

Authigenic gypsum has been observed in marine methane hydrate-bearing sediments throughout the last decade. However, changes in mineral composition and gypsum precipitation in methane emission environments have not yet been reported in the Arctic. Expeditions aboard R/V ARAON revealed several mound structures described as active seeps, which were given the name ARAON Mounds (AMs). Core sediments from the AMs provide an excellent opportunity to research authigenic mineral production in the Arctic methane environment. We identified sedimentary units and investigated the mineral composition of gravity cores from the AMs and a background site. The background core ARA09C-St13, obtained between the mound structures, contains five sedimentary units that extend from the Chukchi Rise to Chukchi Basin, and core sediments from the AMs contain three sedimentary units in the same order. The fundamental difference between AMs and the background site is the lack of dolomite and abundance of gypsum in AMs. This gypsum precipitated authigenically in situ based on its morphological features. Precipitation was more closely associated with the absence of dolomite than the location of the sulfate-methane transition according to the vertical distribution of gypsum in the sediment. Chemical weathering and gypsum overgrowth were confirmed on dolomite surfaces recovered from the AMs, suggesting that dolomite dissolution is the primary source of Ca for gypsum precipitation. Dissolution of biological carbonates and ion exclusion may provide Ca for gypsum precipitation, but this mechanism appears to be secondary, as gypsum is present only in sedimentary units containing dolomite. The main sources of sulfate were inferred to be oxidation of H2S and disproportionation of sulfide, as no sulfide other than gypsum was observed. Our findings reveal that gypsum precipitation linked to methane emission in the Arctic Ocean occurs mainly in dolomite-rich sediments, suggesting that gypsum is a suitable proxy for identifying methane hydrate zones in the Arctic Ocean.