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Biosilicification has driven variation in the global Si cycle over geologic time. The evolution of different eukaryotic lineages that convert dissolved Si (DSi) into mineralized structures (higher plants, siliceous sponges, radiolarians, and diatoms) has driven a secular decrease in DSi in the global ocean leading to the low DSi concentrations seen today. Recent studies, however, have questioned the timing previously proposed for the DSi decreases and the concentration changes through deep time, which would have major implications for the cycling of carbon and other key nutrients in the ocean. Here, we combine relevant genomic data with geological data and present new hypotheses regarding the impact of the evolution of biosilicifying organisms on the DSi inventory of the oceans throughout deep time. Although there is no fossil evidence for true silica biomineralization until the late Precambrian, the timing of the evolution of silica transporter genes suggests that bacterial silicon-related metabolism has been present in the oceans since the Archean with eukaryotic silicon metabolism already occurring in the Neoproterozoic. We hypothesize that biological processes have influenced oceanic DSi concentrations since the beginning of oxygenic photosynthesis.

17The Ganges river system is responsible for the transportation of a large flux of 18 dissolved materials derived from Himalayan weathering to the oceans. Silicate 19 weathering-driven cooling resulting from uplift of the Himalayas has been 20 proposed to be a key player in Cenozoic climate variation. This study has 21analysed Li isotope (δ 7 Li) ratios from over 50 Ganges river waters and 22 sediments, in order to trace silicate weathering processes. Sediments have δ 7 Li of 23 ~0‰, identical to bulk continental crust, however suspended sediment depth 24 profiles do not display variations associated with grain size that have been 25

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Weathering of silicate minerals releases dissolved silicate (DSi) to the soil-vegetation system. Accumulation and recycling of this DSi by terrestrial ecosystems creates a pool of reactive Si on the continents that buffers DSi export to the ocean. Human perturbations to the functioning of the buffer have been a recent research focus, yet a common assumption is that the continental Si cycle is at steadystate. However, we have no good idea of the timescales of ecosystem Si pool equilibration with their environments. A review of modelling and geochemical considerations suggests the modern continental Si cycle is in fact characterised in the longterm by an active accumulation of reactive Si, at least partially attributable to lakes and reservoirs. These lentic systems accumulate Si via biological conversion of DSi to biogenic silica (BSi). An analysis of new and published data for nearly 700 systems is presented to assess their contribution to the accumulating continental pool. Surface sediment BSi concentrations (n = 692) vary between zero and [60 % SiO 2 by weight, apparently independently of lake size, location or water chemistry. Using sediment core BSi accumulation rates (n = 109), still no relationships are found with lake or catchment parameters. However, issues associated with single-core accumulation rates should in any case preclude their use in elemental accumulation calculations. Based on lake/reservoir mass-balances (n = 34), our best global-scale estimate of combined lake and reservoir Si retention is 1.53 TMol year -1 , or 21-27 % of river DSi export. Again, no scalable relationships are apparent, suggesting Si retention is a complex process that varies from catchment to catchment. The lake Si sink has implications for estimation of weathering flux generation from river chemistry. The size of the total continental Si pool is poorly constrained, as is its accumulation rate, but lakes clearly contribute substantially. A corollary to this emerging understanding is that the flux and isotopic composition of DSi delivered to the ocean has likely varied over time, partly mediated by a fluctuating continental pool, including in lakes.

The biogeochemical cycling of silicon (Si) along the land-to-ocean continuum is studied by a variety of research fields and for a variety of scientific reasons. However, there is an increasing need to refine the methodology and the underlying assumptions used to determine biogenic silica (BSi) concentrations. Recent evidence suggests that contributions of nonbiogenic sources of Si dissolving during alkaline extractions, not corrected by standard silicate mineral dissolution correction protocols, can be substantial. The ratio between dissolved Si and aluminum (Al) monitored continuously during the alkaline extraction can be used to infer the origin of the Si fractions present. In this study, we applied both a continuous analysis method (0.5 M NaOH) and a traditional 0.1 M Na 2 CO 3 extraction to a wide array of samples: (1) terrestrial vegetation, (2) soils from forest, cropland and pasture, (3) lake sediments, (4) suspended particulate matter and sediments from rivers, (5) sediments from estuaries and salt marshes and (6) ocean sediments. Our results indicate that the 0.1 M Na 2 CO 3 extraction protocol can overestimate the BSi content, by simultaneously dissolving Si fractions of nonbiogenic origin that may represent up to 100% of the Si traditionally considered as biogenic, hampering interpretation especially in some deeper soil horizons, rivers and coastal oceanic sediments. Moreover, although the term amorphous Si was coined to reflect a growing awareness of nonbiogenic phases we show it is actually inappropriate in samples where silicate minerals may account for a large part of the extracted Si even after linear mineral correction.

[1] Lentic water bodies (lakes and reservoirs) offer favorable conditions for silica (SiO 2 ) burial in sediments. Recent global estimates suggest that (1) lentic SiO 2 trapping is a globally important SiO 2 flux, and (2) through reservoir construction, humans have dramatically altered river dissolved SiO 2 (DSi) transport and coastal DSi delivery. However, regional to global scale patterns and controls of DSi removal in lentic systems are poorly constrained. Here we use 27 published lake and reservoir DSi budgets to develop insights into patterns and controls of lentic DSi retention and to develop a new, spatially explicit, global model of lentic DSi removal called SiRReLa (Silica Retention in Reservoirs and Lakes). In our analysis, lentic DSi removal (kg SiO 2 yr À1 ) was significantly and positively related to DSi loading (P < 0.0001; r 2 = 0.98), and DSi removal efficiency was significantly and positively related to water residence time (P < 0.0001; r 2 = 0.68). In addition, DSi settling rates were, on average, 6.5-fold higher in eutrophic systems than in non-eutrophic systems (median settling velocities: 11.1 and 1.7 m yr À1 for eutrophic and non-eutrophic systems, respectively; P < 0.01). SiRReLa, which incorporates these insights, performed quite well in predicting both total DSi removal (kg SiO 2 yr À1 ; Nash Sutcliffe Efficiency (N.S.E) = 0.88) and DSi removal efficiency (% Si removed; N.S.E. = 0.75), with no detectable bias in the model. Global application of SiRReLa confirms that lentic systems are important sinks for DSi, removing 89.1 Tg DSi yr À1 from watersheds globally, roughly 19-38% of all DSi inputs to surface waters. Small lakes and reservoirs (<50 km 2 ) were critical in the analysis, retaining 81% (72 Tg DSi yr À1 ) of the globally retained total. Furthermore, although reservoirs occupy just 6% of the global lentic surface area, they retained approximately 35% of the total DSi removed by lentic systems. Regional hot spots for lentic DSi removal were identified and imply that lentic systems can remove the vast majority of DSi across a large fraction of Earth's land surface. Finally, a sensitivity analysis indicates that future improvements in DSi trapping and transport models should focus on improving estimates of DSi input to surface waters.