Biologically driven isotopic fractionations in bivalves: from palaeoenvironmental problem to palaeophysiological proxy.

Traditional bulk stable isotope (δ 18 O and δ 13 C) and clumped isotope (Δ 47 ) records from bivalve shells provide invaluable histories of Earth's local and global climate change. However, biologically driven isotopic fractionations (BioDIFs) can overprint primary environmental signals in the shell. Here, we explore how conventional measurements of δ 18 O, δ 13 C, and Δ 47 in bivalve shells can be re-interpreted to investigate these physiological processes deliberately. Using intrashell Δ 47 and δ 18 O alignment as a proxy for equilibrium state, we separately examine fractionations and/or disequilibrium occurring in the two major stages of the biomineralisation process: the secretion of the extrapallial fluid (EPF) and the precipitation of shell material from the EPF. We measured δ 18 O, δ 13 C, and Δ 47 in fossil shells representing five genera (Lahillia, Dozyia, Eselaevitrigonia, Nordenskjoldia, and Cucullaea) from the Maastrichtian age [66-69 million years ago (Ma)] López de Bertodano Formation on Seymour Island, Antarctica. Material was sampled from both the outer and inner shell layers (OSL and ISL, respectively), which precipitate from separate EPF reservoirs. We find consistent δ 18 O values across the five taxa, indicating that the composition of the OSL can be a reliable palaeoclimate proxy. However, relative to the OSL baseline, ISLs of all taxa show BioDIFs in one or more isotopic parameters. We discuss/hypothesise potential origins of these BioDIFs by synthesising isotope systematics with the physiological processes underlying shell biomineralisation. We propose a generalised analytical and interpretive framework that maximises the amount of palaeoenvironmental and palaeobiological information that can be derived from the isotopic composition of fossil shell material, even in the presence of previously confounding 'vital effects'. Applying this framework in deep time can expand the utility of δ 18 O, δ 13 C, and Δ 47 measurements from proxies of past environments to proxies for certain biomineralisation strategies across space, time, and phylogeny among Bivalvia and other calcifying organisms.