Past changes in the atmospheric concentration of carbon dioxide (Pco2) have had a major impact on earth system dynamics; yet, reconstructing secular trends of past Pco2 remains a prevalent challenge in paleoclimate studies. The current long-term Pco2 reconstructions rely largely on the compilation of many different proxies, often with discrepancies among proxies, particularly for periods older than 100 million years (Ma). Here, we reconstructed Phanerozoic Pco2 from a single proxy: the stable carbon isotopic fractionation associated with photosynthesis (Ɛp) that increases as Pco2 increases. This concept has been widely applied to alkenones, but here, we expand this concept both spatially and temporally by applying it to all marine phytoplankton via a diagenetic product of chlorophyll, phytane. We obtained data from 306 marine sediments and oils, which showed that Ɛp ranges from 11 to 24‰, agreeing with the observed range of maximum fractionation of Rubisco (i.e., 25 to 28‰). The observed secular Pco2) trend derived from phytane-basedƐp mirrors the available compilations of Pco2 over the past 420 Ma, except for two periods in which our higher estimates agree with the warm climate during those time periods. Our record currently provides the longest secular trend in Pco2) based on a single marine proxy, covering the past 500 Ma of Earth history.
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