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Many studies use sedimentary biogenic silica (bSiO2) stable isotopes (e.g., δ30Si) as paleoproxies but neglect signals from other sedimentary reactive SiO2 phases. We quantified δ30Si for multiple reactive Si pools in coastal river‐plume sediments, revealing up to −5‰ difference between acid‐leachable and alkaline‐digestible amorphous SiO2. Thus, previous studies have missed valuable information on early diagenetic products and, in cases where sediments were not cleaned, potentially biased bSiO2 δ30Si values. Acid‐leachable δ30Si, that is, from authigenic products, are the result of either multistep fractionation from a bSiO2 source or an ~2‰ fractionation (consistent with metal hydroxide formation) from slowly dissolving lithogenic SiO2. This analysis also suggests that sedimentary diatom bSiO2, which has increased regionally in the last half‐century, is the critical substrate of early authigenic Si precipitates. Regional eutrophication, which has stimulated sedimentary bSiO2 accumulation, may have facilitated additional sequestration of both sedimentary Si and cations from early diagenetic products.

<p><strong>Abstract.</strong> The silicon isotope composition of deep-sea sponges skeletal element – spicules – reflects the silicic acid (DSi) concentration of their surrounding water, and can be used as natural archives of bottom water nutrients. In order to reconstruct the past silica cycle robustly, it is essential to better constrain the mechanisms of biosilicification, which are not yet well understood. Here, we show that the apparent isotopic fractionation (∆<sup>30</sup>Si) during spicule formation in deep–sea sponges from the equatorial Atlantic range from −6.74 ‰ to −1.50 ‰ in relatively low DSi concentrations (15 to 35 μM). The wide range in isotopic composition highlights the potential difference in silicification mechanism between the two major classes, Demospongiae and Hexactinellida. We find the anomalies in the isotopic fractionation correlates with skeletal morphology, whereby fused framework structures, characterised by secondary silicification, exhibit extremely light δ<sup>30</sup>Si signatures. Our results provide insights into the process involved during silica deposition, and indicate that reliable reconstructions of past DSi can only be obtained using silicon isotopes ratios derived from sponges with certain spicule types.</p>

Reconstruction of silica cycling in the oceans is key to a thorough understanding of past climates because of the inherent links between the biogeochemistry of silicifiers and sequestration of organic carbon. Diatoms are one of the most important phytoplankton groups in determining export production from surface waters, and rely largely on upwelling deeper waters as a source of dissolved silicon, an essential nutrient for their growth. Quantification of changes in deep water dissolved silicon concentrations in the past allows a more robust understanding of changes in surface nutrient supply and whole-ocean silicon cycling, but cannot be achieved using surfacederived geochemical archives. In the last few years, there has been increasing focus on the use of geochemical archives in siliceous skeletal elements, or spicules, from seafloor-dwelling sponges to fill this gap. The stable silicon isotopic composition of spicules has been shown to be a function of ambient dissolved silicon, providing a potential archive for past changes in bottom water nutrients. However, biomineralisation processes impact silicon isotope fractionation and silica formed by atypical processes (derived from carnivorous sponges, hypersilicified spicules, and giant basal spicules) result in anomalous geochemical signatures. Furthermore, there is considerable scatter in the calibration between spicule silicon isotopes and dissolved silicon in seawater, even when the atypical groups have been removed. Here, we explore this variability further, by examining aggregation and assemblage-level differences in isotopic fractionation, using silicon isotopic measurements of specimens from two monospecific sponge groups (Pheronema carpenteri and Vazella pourtalesi), and one mixed-species population (genus Geodia) from the North Atlantic. Our new data reveal that variability within the monospecific aggregations is less than mixed-species assemblage, pointing towards a genetic control in isotopic fractionation. However, there is still variability within the monospecific aggregations, which cannot be explained by macroscale environmental differences: such variability is likely a reflection of the physiological health of the individuals, or highly localised heterogeneities in sponge habitats. Other challenges remain in the interpretation of spicule silicon isotopes as proxies for dissolved silicon changes through time, especially when investigating periods of Earth history that extend back considerably further than the residence time of dissolved silicon in the oceans. Despite all the questions still surrounding the use of sponge silicon isotopes in palaeoceanographic applications, they are still the only known archive of bottom water dissolved silicon. Continued efforts to understanding sponge biomineralisation and to incorporate silicon isotopes into oceanic models will help to improve further the reliability of the archive.

00000International audienceThe silicon isotope composition (δ30Si) of dissolved silicon (DSi) and biogenic silica (BSi) provides information about the silicon cycle and its role in oceanic carbon uptake in the modern ocean and in the past. However, there are still questions outstanding regarding the impact of processes such as oceanic mixing, export and dissolution on the isotopic signature of seawater, and the impacts on sedimentary BSi. This study reports the δ30Si of DSi from surface waters at the Rothera Time Series (RaTS) site, Ryder Bay, in a coastal region of the West Antarctic Peninsula (WAP). The samples were collected at the end of austral spring through the end of austral summer/beginning of autumn over two field seasons, 2004/5 and 2005/6. Broadly, for both field seasons, DSi diminished and δ30Si of DSi increased through the summer, but this was accomplished during only a few short periods of net nutrient drawdown. During these periods, the δ30Si of DSi was negatively correlated with DSi concentrations. The Si isotope fractionation factor determined for the net nutrient drawdown periods, ɛuptake, was in the range of −2.26 to −1.80‰ when calculated using an open system model and −1.93 to −1.33‰ when using a closed system model. These estimates of ɛ are somewhat higher than previous studies that relied on snapshots in time rather than following changes in δ30Si and DSi over time, which therefore were more likely to include the effects of mixing of dissolved silicon up into the mixed layer. Results highlight also that, even at the same station and within a single growing season, the apparent fractionation factor may exhibit significant temporal variability because of changes in the extent of biological removal of DSi, nutrient source, siliceous species, and mixing events.ăăPaleoceanographic studies using silicon isotopes need careful consideration in the light of our new results