『Abstract
　Silicon isotopes have been investigated for their potential to reveal both past and present patterns of silicic acid utilization, primarily by diatoms, in surface waters of the ocean. Interpretation of this proxy has thus far relied on characteristic tends in the isotope composition of the dissolved and particulate silicon pools in the upper ocean, as driven by biological fractionation during the production of biogenic silica (bSiO2, or opal) by diatoms. However, other factors which may influence the silicon isotope composition of diatom opal, particularly post-formational aging and maturation processes, remain largely uninvestigated. Here, we report a consistent fractionation of silicon isotopes during the physicochemical dissolution of diatom bSiO2 suspended in seawater under closed conditions. This fractionation acts counter to that occurring during bSiO2 production and at about half its absolute magnitude, with dissolution discriminating against the release of the heavier isotopes of silicon at an enrichment factor εDSi-BSi of -0.55‰, corresponding to a fractionation factor α30/28 of 0.99945. The enrichment factor did not vary with source material, indicating the lack of a significant species effect, or with temperature from 3 to 20℃. Thus, the dissolution of bSiO2 produces dissolved silicon with a δ³⁰Si value that is 0.55‰ more negative than its parent bSiO2, an effect that must be accounted for when interpreting oceanic δ³⁰Si distributions. The δ³⁰Si values of both the dissolved and particulate silicon pools increased linearly as dissolution progressed, implying a measurable (±0.1‰) change in the relative δ³⁰Si of opal samples whenever the difference in preservation efficiency between them is ＞20％. This effect could account for 〜10-30％ of the difference in diatom δ³⁰Si values observed between glacial and interglacial conditions. It is unlikely, however, that the inferred maximum possible change in δb³⁰SiO2 of +0.55‰ would be manifested in situ, as a high mean percentage of dissolution would include complete loss of the more soluble members of the diatom assemblage.』

1. Introduction
2. Materials and methods
　2.1. Source materials
　2.2. Closed system fractionation experiments and isotopic measurement
　2.3. Data analysis
3. Results
　3.1. Silica dissolution dynamics
　3.2. Isotopic fractionation
4. Discussion
　4.1. Magnitude and mechanism of fractionation
　4.2. Implications for modern applications of the δ³⁰Si proxy
　4.3. Implications for paleoceanographic applications of the δ³⁰Si proxy
5. Conclusions
Acknowledgments
References