Abstract. Phosphorus is often invoked as the ultimate limiting nutrient, modulating primary productivity on geological timescales. Consequently, along with nitrogen, phosphorus bioavailability exerts a fundamental control on organic carbon production, linking all the biogeochemical cycles across the Earth system. Unlike nitrogen that can be microbially fixed from an essentially infinite atmospheric reservoir, phosphorus availability is dictated by the interplay between its sources and sinks. While authigenic apatite formation has received considerable attention as the dominant sedimentary phosphorus sink, the quantitative importance of reduced iron-phosphate minerals, such as vivianite, has only recently been acknowledged and their importance remains under-explored. Combining microscopic and spectroscopic analyses of handpicked mineral aggregates with sediment geochemical profiles we characterize the distribution and mineralogy of iron-phosphate minerals present in methane-rich sediments recovered from the northern South China Sea. Here, we demonstrate that vivianite authigenesis is pervasive in the iron oxide-rich sediments below the sulfate-methane transition zone (SMTZ). We hypothesize that the downward migration of the SMTZ concentrated vivianite formation below the current SMTZ. Our observations support recent findings from non-steady state post-glacial coastal sedimentary successions, suggesting that iron reduction below the SMTZ, probably driven by iron-mediated anaerobic oxidation of methane (Fe-AOM), is coupled to phosphorus cycling on a much greater spatial scale than previously assumed. Calculations reveal that vivianite acts as an important burial phase for both iron and phosphorus below the SMTZ, sequestering approximately half of the total reactive iron pool. By extension, sedimentary vivianite formation could serve as a mineralogical marker of Fe-AOM, signalling a low-sulfate availability against methanogenic and ferruginous backdrop. Given that similar conditions were likely present throughout vast swaths of Earth history, it is possible that Fe-AOM may have modulated phosphorus and methane availability on the early Earth.
Anaerobic oxidation of methane in coastal sediment from Guishan Island (Pearl River Estuary), South China Sea