Silicon (Si) released as H4SiO4 by weathering of Si-containing solid phases is partly recycled through vegetation before its land-to-rivers transfer. By accumulating in terrestrial plants to a similar extent as some major macronutrients (0.1–10% Si dry weight), Si becomes largely mobile in the soil-plant system. Litter-fall leads to a substantial reactive biogenic silica pool in soil, which contributes to the release of dissolved Si (DSi) in soil solution. Understanding the biogeochemical cycle of silicon in surface environments and the DSi export from soils into rivers is crucial given that the marine primary bio-productivity depends on the availability of H4SiO4 for phytoplankton that requires Si. Continental fluxes of DSi seem to be deeply influenced by climate (temperature and runoff) as well as soil-vegetation systems. Therefore, continental areas can be characterized by various abilities to transfer DSi from soil-plant systems towards rivers. Here we pay special attention to those processes taking place in soil-plant systems and controlling the Si transfer towards rivers. We aim at identifying relevant geochemical tracers of Si pathways within the soil-plant system to obtain a better understanding of the origin of DSi exported towards rivers. In this review, we compare different soil-plant systems (weathering-unlimited and weathering-limited environments) and the variations of the geochemical tracers (Ge/Si ratios and δ30Si) in DSi outputs. We recommend the use of biogeochemical tracers in combination with Si mass-balances and detailed physico-chemical characterization of soil-plant systems to allow better insight in the sources and fate of Si in these biogeochemical systems.

Three Si isotope materials have been used for an inter-laboratory comparison exercise to ensure reproducibility between international laboratories investigating natural Si isotope variations using a variety of chemical preparation methods and mass spectrometric techniques. These proposed standard reference materials are (i) IRMM-018 (a SiO₂ standard), (ii) Big-Batch (a fractionated SiO₂ material prepared at the University of California Santa Barbara), and (iii) Diatomite (a natural diatomite sample originally deposited as marine biogenic opal). All analyses are compared with the international Si standard NBS28 (RM8546) and are in reasonable agreement (<±0.22‰ 1σ_SDδ³⁰Si) given the different measurement techniques involved. These methods include both acid and alkaline dissolution/fusion, Si separation using cation exchange, selective co-precipitation, and gas-source versus plasma-ionization (high and low resolution) mass-spectrometric techniques. The average δ³⁰Si for Diatomite, IRMM-018, and Big-Batch are +1.26‰, −1.65‰ and −10.48‰, respectively, with corresponding δ²⁹Si values of +0.64‰, −0.85‰ and −5.35‰ for the same standards, respectively. For the most fractionated standard (Big-Batch), results demonstrate a kinetic mass-dependent fractionation effect for atomic Si (i.e., δ²⁹Si ∼ 0.51 × δ³⁰Si). There is almost no statistical difference between the mean values obtained by each participating laboratory, with the notable exception of the IRMM-018 standard. This effect could be caused by heterogeneity or contamination of this standard. The results for the other two standards indicate that data sets produced using any of the methods employed in this study will have similar precision and differences are limited to 0.2‰ in mean δ³⁰Si values for a given sample between laboratories, or differences of 0.13‰ in mean δ²⁹Si values.