Post‐mortem oxygen isotope exchange within cultured diatom silica. (14th September 2017)

• Record Type: Journal Article
• Authors: Tyler, Jonathan J.; Sloane, Hilary J.; Rickaby, Rosalind E.M.; Cox, Eileen J.; Leng, Melanie J.
• Is Part Of: Rapid communications in mass spectrometry. Volume 31:Number 20(2017)
• Page Start: 1749
• Page End: 1760
• Publication Date: 2017-09-14
• Subjects: Mass spectrometry -- Periodicals; 543.65
• DOI: 10.1002/rcm.7954
• Languages: English
• ISSNs: 0951-4198

Abstract

Abstract : Rationale: Potential post‐mortem alteration to the oxygen isotope composition of biogenic silica is critical to the validity of palaeoclimate reconstructions based on oxygen isotope ratios (δ 18 O values) from sedimentary silica. We calculate the degree of oxygen isotope alteration within freshly cultured diatom biogenic silica in response to heating and storing in the laboratory. Methods: The experiments used freshly cultured diatom silica. Silica samples were either stored in water or dried at temperatures between 20 °C and 80 °C. The mass of affected oxygen and the associated silica‐water isotope fractionation during alteration were calculated by conducting parallel experiments using endmember waters with δ 18 O values of −6.3 to −5.9 ‰ and −36.3 to −35.0 ‰. Dehydroxylation and subsequent oxygen liberation were achieved by stepwise fluorination with BrF5 . The 18 O/ 16 O ratios were measured using a ThermoFinnigan MAT 253 isotope ratio mass spectrometer. Results: Significant alterations in silica δ 18 O values were observed, most notably an increase in the δ 18 O values following drying at 40–80 °C. Storage in water for 7 days between 20 and 80 °C also led to significant alteration in δ 18 O values. Mass balance calculations suggest that the amount of affected oxygen is positively correlated with temperature. The estimated oxygen isotope fractionation during alteration is an inverse function of temperature, consistent with the extrapolation of models for high‐temperature silica‐water oxygen isotope fractionation. Conclusions: Routinely used preparatory methods may impart significant alterations to the δ 18 O values of biogenic silica, particularly when dealing with modern cultured or field‐collected material. The significance of such processes within natural aquatic environments is uncertain; however, there is potential that similar processes also affect sedimentary diatoms, with implications for the interpretation of biogenic silica‐hosted δ 18 O palaeoclimate records.