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Geochemical analysis reveals temperature-dependent lithium-to-calcium ratios in fossil and modern brachiopod shells, suggesting major shifts in seawater lithium budgets across geologic eras.
Li/Ca ratios in modern brachiopod shells generally correlate inversely with growth temperature, ranging from ∼20 µmol/mol at 30°C to ∼50 µmol/mol at 0°C with no apparent interspecific offsets. Causes of the temperature effect on Li/Ca ratios are not yet understood. Cenozoic brachiopod Li/Ca ratios average ∼30 µmol/mol, similar to the average observed in modern brachiopods. Relatively constant Li/Ca ratios for Eocene to Pleistocene nonluminescent brachiopod shells, consistent with previous observations of Cenozoic planktonic foraminifera, support the conclusion of little variation in Cenozoic seawater Li/Ca. Nonluminescent portions of Permian and Carboniferous brachiopods have Li/Ca ratios substantially lower (generally <10 µmol/mol) than modern, Cenozoic, or Devonian samples. Mass balance considerations, constrained by δ 18 O of brachiopods, suggest that low Li concentrations in Permo‐Carboniferous seawater could be the result of a lower flux of dissolved Li from the continents and/or a higher flux of Li from seawater to clastic marine sediments. Nonluminescent Devonian brachiopods from a single hand specimen have Li/Ca ratios around 70% of the modern average. These Li/Ca ratios can be explained by either somewhat higher temperature with constant seawater Li/Ca, somewhat lower seawater Li/Ca at constant temperature, or a combination of slightly elevated temperature and slightly lower seawater Li/Ca.
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Delaney et al. (1989) studied this question.
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