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The Phanerozoic Eon marked a major transition from marine silica deposition exclusively via abiotic pathways to a system dominated by biogenic silica sedimentation. For decades, prevailing ideas predicted this abiotic‐to‐biogenic transition were marked by a significant decrease in the concentration of dissolved silica in seawater; however, due to the lower perceived abundance and uptake affinity of sponges and radiolarians relative to diatoms, marine dissolved silica is thought to have remained elevated above modern values until the Cenozoic radiation of diatoms. Studies of modern marine silica biomineralizers demonstrated that the Si isotope ratios (δ30Si) of sponge spicules and planktonic silica biominerals produced by diatoms or radiolarians can be applied as quantitative proxies for past seawater dissolved silica concentrations due to differences in Si isotope fractionations among these organisms. We undertook 446 ion microprobe analyses of δ30Si and δ18O of sponge spicules and radiolarians from Ordovician–Silurian chert deposits of the Mount Hare Formation in Yukon, Canada. These isotopic data showed that sponges living in marine slope and basinal environments displayed small Si isotope fractionations relative to coeval radiolarians. By constructing a mathematical model of the major fluxes and reservoirs in the marine silica cycle and the physiology of silica biomineralization, we found that the concentration of dissolved silica in seawater was less than ~150 μM during early Paleozoic time—a value that is significantly lower than previous estimates. We posit that the topology of the early Paleozoic marine silica cycle resembled that of modern oceans much more closely than previously assumed. [ABSTRACT FROM AUTHOR]

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 steady-state. 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 long-term 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 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, 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. [ABSTRACT FROM AUTHOR]

• Neoarchean silicified volcanic rocks from the Abitibi greenstone belt that range in composition from rhyolitic to basaltic overlap in silicon and oxygen isotope values with similar Paleoarchean silicified basalts from the Barberton greenstone belt. • Silicon isotope values measured from Neoarchean iron formation samples in the Deloro assemblage change with stratigraphic position, possibly due to a shift in the silicon isotope value of the reservoir, or silicification, which is more prevalent at the top of the section. • The Temagami greenstone belt iron formation silicon isotope data overlap with values measured from the upper Deloro iron formation, and could reflect local, basinal changes in the isotopic composition of the silicon isotope reservoir on short time scales. Silica-rich Precambrian rocks often preserve geochemical information and microfossil remnants from the early biosphere and could play a critical role in the formation of early crust. Because these rocks are important geochemical and paleontological archives, we need to better constrain their geochemical and isotopic attributes and generate a refined picture of the evolving Archean silica cycle. Here, we investigate a series of sub- to greenschist facies Si-rich Archean rocks from the ~ 2.7 Ga Abitibi greenstone belt, Canada, that represent chemical sedimentary rocks and rocks formed via silica-addition through the process of silicification. We report data for major and trace element geochemistry, multi-crystal silicon and oxygen isotopes of quartz using isotope ratio mass spectrometry, and texture-specific silicon isotope values measured using secondary ion mass spectrometry on Neoarchean chemical sedimentary rocks, their silicified equivalents, and associated silicified volcanic rocks. We find that in such a well-preserved terrane we can utilize petrographic textures and geochemical attributes to establish rock origin, distinguishing siliceous rocks that form via chemical sedimentation from those that form via silicification. Chemical sedimentary rocks display a wide range of 30Si-depleted silicon isotopes values that vary with stratigraphy similar to other Archean iron formation. Silicified volcanic rocks possess 30Si-enriched values, similar to Archean silicified basalts. We conclude that because silicon isotope values of iron formation shift toward 30Si-enriched values up stratigraphy, basinal changes in the composition of the silicon isotope reservoir may be preserved. Silicon isotope values of silicified volcanic rocks by contrast, likely represent precipitation from an isotopically heavy silicon reservoir, influenced by downward percolating seawater and upward moving convecting fluids interacting with host volcanic rock (basalt or andesite). Overall, we confirm that Neoarchean silicified rocks are 30Si-enriched like their Paleoarchean counterparts. [ABSTRACT FROM AUTHOR]