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Diatoms are important primary producers in lake ecosystems and, as a sink for dissolved (DSi) and biogenic silica (BSi) originating from land, can significantly impact the global Si cycle. After burial in lake sediments, resistant diatom frustules can also be used for reconstructions of past ecosystem change. The BSi content of lake sediments is thus often used as a proxy for past diatom productivity, and measured using a time-step analysis of Si extracted in 0.1 M NaCO. However, studies in soils and ocean sediments have shown that also certain non-biogenic Si fractions are prone to dissolve in alkaline solutions, contributing to a potential overestimate of sedimentary BSi concentration. In lakes, volcanic and terrestrial Si compounds reactive at high pH are likely to interfere with the analysis. In this study we used a continuous analysis of Si and Al extracted in 0.5 M NaOH and a new mathematical model improved from Koning et al. (Aquat Geochem 8:37-67, ) to distinguish between biogenic and non-biogenic Si fractions in lake-sediment extracts. We tested this approach in 43 samples of a 19,000-year sediment sequence recovered from Lake Rutundu, a volcanic crater lake on Mt. Kenya. Our results show that a significant fraction of the extractable Si is of non-biogenic origin, especially in the part of the sequence deposited during the glacial period. We conclude that this technique is essential for the characterization of different Si phases, and in particular the diatom-derived BSi, in the sediment of lakes situated in volcanic catchments. It allows calculating a correction, based on the distinct Si:Al ratio of each of those Si phases, that eliminates the contribution from non-BSi fractions. [ABSTRACT FROM AUTHOR]

While the importance of grasslands in terrestrial silicon (Si) cycling and fluxes to rivers is established, the influence of large grazers has not been considered. Here, we show that hippopotamuses are key actors in the savannah biogeochemical Si cycle. Through a detailed analysis of Si concentrations and stable isotope compositions in multiple ecosystem compartments of a savannah-river continuum, we constrain the processes influencing the Si flux. Hippos transport 0.4 metric tons of Si day -1 by foraging grass on land and directly egesting in the water. As such, they bypass complex retention processes in secondary soil Si pools. By balancing internal processes of dissolution and precipitation in the river sediment, we calculate that hippos affect up to 76% of the total Si flux. This can have a large impact on downstream lake ecosystems, where Si availability directly affects primary production in the diatom-dominated phytoplankton communities.