Continuous sterane and phytane δ13C record reveals a substantial pCO2 decline since the mid-Miocene.

Constraining the relationship between temperature and atmospheric concentrations of carbon dioxide (pCO2) is essential to model near-future climate. Here, we reconstruct pCO2 values over the past 15 million years (Myr), providing a series of analogues for possible near-future temperatures and pCO2, from a single continuous site (DSDP Site 467, California coast). We reconstruct pCO2 values using sterane and phytane, compounds that many phytoplankton produce and then become fossilised in sediment. From 15.0-0.3 Myr ago, our reconstructed pCO2 values steadily decline from 650 ± 150 to 280 ± 75 ppmv, mirroring global temperature decline. Using our new range of pCO2 values, we calculate average Earth system sensitivity and equilibrium climate sensitivity, resulting in 13.9 °C and 7.2 °C per doubling of pCO2, respectively. These values are significantly higher than IPCC global warming estimations, consistent or higher than some recent state-of-the-art climate models, and consistent with other proxy-based estimates.

Toward a Cenozoic history of atmospheric CO2.

The geological record encodes the relationship between climate and atmospheric carbon dioxide (CO2) over long and short timescales, as well as potential drivers of evolutionary transitions. However, reconstructing CO2 beyond direct measurements requires the use of paleoproxies and herein lies the challenge, as proxies differ in their assumptions, degree of understanding, and even reconstructed values. In this study, we critically evaluated, categorized, and integrated available proxies to create a high-fidelity and transparently constructed atmospheric CO2 record spanning the past 66 million years. This newly constructed record provides clearer evidence for higher Earth system sensitivity in the past and for the role of CO2 thresholds in biological and cryosphere evolution.

Testing algal-based pCO2 proxies at a modern CO2 seep (Vulcano, Italy).

Understanding long-term trends in atmospheric concentrations of carbon dioxide (pCO2) has become increasingly relevant as modern concentrations surpass recent historic trends. One method for estimating past pCO2, the stable carbon isotopic fractionation associated with photosynthesis (Ɛp) has shown promise over the past several decades, in particular using species-specific biomarker lipids such as alkenones. Recently, the Ɛp of more general biomarker lipids, organic compounds derived from a multitude of species, have been applied to generate longer-spanning, more ubiquitous records than those of alkenones but the sensitivity of this proxy to changes in pCO2 has not been constrained in modern settings. Here, we test Ɛp using a variety of general biomarkers along a transect taken from a naturally occurring marine CO2 seep in Levante Bay of the Aeolian island of Vulcano in Italy. The studied general biomarkers, loliolide, cholesterol, and phytol, all show increasing depletion in 13C over the transect from the control site towards the seep, suggesting that CO2 exerts a strong control on isotopic fractionation in natural phytoplankton communities. The strongest shift in fractionation was seen in phytol, and pCO2 estimates derived from phytol confirm the utility of this biomarker as a proxy for pCO2 reconstruction.

Molecular fossils from phytoplankton reveal secular Pco2 trend over the Phanerozoic.

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-based Ɛp 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.