Coccolithophores are marine algae that use carbon for calcification and photosynthesis. The long term adaptation of these and other marine algae to decreasing carbon dioxide levels during the Cenozoic era 1 has resulted in modern algae capable of actively enhancing carbon dioxide at the site of photosynthesis. This enhancement occurs through the transport of dissolved bicarbonate (HCO 3-) and with the help of enzymes whose expression can be modulated by variable aqueous carbon dioxide concentration, [CO 2 ], in laboratory cultures 2,3. Coccolithophores preserve the geological history of this adaptation because the stable carbon and oxygen isotopic compositions of their calcite plates (coccoliths), which are preserved in the fossil record, are sensitive to active carbon uptake and transport by the cell. Here we use a model of cellular carbon fluxes and show that at low [CO 2 ], the increased demand for HCO 3 at the site of photosynthesis results in a diminished allocation of HCO 3 to calcification, which is most pronounced in larger cells. This results in a large divergence between the carbon isotopic compositions of small versus large coccoliths only at low [CO 2 ]. Our evaluation of the oxygen and carbon isotope record of size-separated fossil coccoliths reveals that this isotopic divergence first arose during the late Miocene to the earliest Pliocene epoch (about 7-5 million years ago). We interpret this to be a threshold

Marine algae are instrumental in carbon cycling and atmospheric carbon dioxide (CO2) regulation. One group, coccolithophores, uses carbon to photosynthesize and to calcify, covering their cells with chalk platelets (coccoliths). How ocean acidification influences coccolithophore calcification is strongly debated, and the effects of carbonate chemistry changes in the geological past are poorly understood. This paper relates degree of coccolith calcification to cellular calcification, and presents the first records of size-normalized coccolith thickness spanning the last 14 Myr from tropical oceans. Degree of calcification was highest in the low-pH, high-CO2 Miocene ocean, but decreased significantly between 6 and 4 Myr ago. Based on this and concurrent trends in a new alkenone ɛp record, we propose that decreasing CO2 partly drove the observed trend via reduced cellular bicarbonate allocation to calcification. This trend reversed in the late Pleistocene despite low CO2, suggesting an additional regulator of calcification such as alkalinity.

Published alkenone  p records spanning known glacial pCO 2 cycles show considerably less variability than predicted by the diffusive model for cellular carbon acquisition and isotope fractionation. We suggest this pattern is consistent with a systematic cellular enhancement of the carbon supply to photosynthesis via carbon concentrating mechanisms under the case of carbon limitation during low pCO 2 glacial time periods, an effect also manifest under carbon limitation in experimental cultures of coccolithophores as well as diatoms. While the low-amplitude  p signal over glacial pCO 2 cycles has led some to question the reliability of  p for reconstructing long-term pCO 2 , the [CO 2 ] aq in the tropical oceans during glacial pCO 2 minima represents the most extreme low CO 2 conditions likely experienced by phytoplankton in the Cenozoic, and the strongest upregulation of carbon concentrating mechanisms. Using a statistical multilinear regression model, we quantitatively parse out the factors (namely light, growth rate, and [CO 2 ] aq ), that contribute to variation in  p in alkenone-producing algae, which confirms a much smaller dependence of  p on [CO 2 ] aq in the low [CO 2 ] aq range, than inferred from the hyperbolic form of the diffusive model. Application of the new statistical model to two published tropical  p records spanning the late Neogene produces much more dynamic pCO 2 estimates than the conventional diffusive model and reveals a significant pCO 2 decline over the last 15 Ma, which is broadly consistent with recent results from boron isotopes of foraminifera. The stable isotopic fractionation between coccolith calcite and seawater dissolved inorganic carbon (here ∆ coccolith-DIC ) also shows systematic variations over glacial-interglacial cycles which may, following future experimental constraints, help estimate the degree of upregulation of parts of the algal carbon concentrating mechanism over glacial cycles.This simplified formulation clarifies the dependence of b on variation in the cellular C content and surface area, which scale with cell size; as well as variation in the growth rate and the effective permeability to CO 2 . When the effects of these factors are considered in aggregate, e.g. by empirical derivations of b from photic zone or culture samples, it must be remembered that the covariation and relative weight of each of these factors spatially in the modern ocean, or in culture experiments, may differ from past temporal significance and covariation of these factors. In practice, however, most previous work has interpreted variation in b to reflect either changes only in the growth rate parameter (Bidigare et al., 1997;Seki et al., 2010), or over long timescales also changes in the cell size and consequently in /S (Henderiks and Pagani, 2008;Seki et al., 2010). Potential variations in P have not been evaluated for glacial samples or the full range of published experiments with  p determinations in experimental culture, although some previous studies have acknowledged that the b...

The Miocene epoch (23.03-5.33 Ma) was a time interval of global warmth, relative to today.Continental configurations and mountain topography transitioned toward modern conditions, and many flora and fauna evolved into the same taxa that exist today. Miocene climate was dynamic: long periods of early and late glaciation bracketed a ∼2 Myr greenhouse interval-the Miocene Climatic Optimum (MCO). Floras, faunas, ice sheets, precipitation, pCO 2 , and ocean and atmospheric circulation mostly (but not ubiquitously) covaried with these large changes in climate. With higher temperatures and moderately higher pCO 2 (∼400-600 ppm), the MCO has been suggested as a particularly appropriate analog for future climate scenarios, and for assessing the predictive accuracy of numerical climate models-the same models that are used to simulate future climate. Yet, Miocene conditions have proved difficult to reconcile with models. This implies either missing positive feedbacks in the models, a lack of knowledge of past climate forcings, or the need for re-interpretation of proxies, which might mitigate the model-data discrepancy. Our understanding of Miocene climatic, biogeochemical, and oceanic changes on broad spatial and temporal scales is still developing. New records documenting the physical, chemical, and biotic aspects of the Earth system are emerging, and together provide a more comprehensive understanding of this important time interval. Here, we review the state-of-the-art in Miocene climate, ocean circulation, biogeochemical cycling, ice sheet dynamics, and biotic adaptation research as inferred through proxy observations and modeling studies. Plain Language Summary During the Miocene time period (∼23-5 million years ago),Planet Earth looked similar to today, with some important differences: the climate was generally warmer and highly variable, while atmospheric CO 2 was not much higher. Continental-sized ice sheets were only present on Antarctica, but not in the northern hemisphere. The continents drifted to near their modernday positions, and plants and animals evolved into the many (near) modern species. Scientists study the Miocene because present-day and projected future CO 2 levels are in the same range as those reconstructed for the Miocene. Therefore, if we can understand climate changes and their biotic responses from the Miocene past, we are able to better predict current and future global changes. By comparing Miocene climate reconstructions from fossil and chemical data to climate simulations produced by computer models, scientists are able to test their understanding of the Earth system under higher CO 2 and warmer conditions than those of today. This helps in constraining future warming scenarios for the coming STEINTHORSDOTTIR ET AL.

Throughout Earth's history, CO2 is thought to have exerted a fundamental control on environmental change. Here we review and revise CO2 reconstructions from boron isotopes in carbonates and carbon isotopes in organic matter over the major climate transition of the past 66 million years. We find close coupling between CO2 and climate throughout the Cenozoic, with peak CO2 levels of ∼1,500 ppm in the Eocene greenhouse, decreasing to ∼550 ppm in the Miocene, and falling further into ice age world of the Plio–Pleistocene. Around two-thirds of Cenozoic CO2 drawdown is explained by an increase in the ratio of alkalinity to dissolved inorganic carbon, likely linked to a change in the balance of weathering to outgassing, with the remaining one-third due to changing ocean temperature and major ion composition. Earth system climate sensitivity is explored and may vary between different time intervals. The Cenozoic CO2 record highlights the truly geological scale of anthropogenic CO2 change: Current CO2 levels were last seen around 3 million years ago, and major cuts in emissions are required to prevent a return to the CO2 levels of the Miocene or Eocene in the coming century. ▪ CO2 reconstructions over the past 66 Myr from boron isotopes and alkenones are reviewed and re-evaluated. ▪ CO2 estimates from the different proxies show close agreement, yielding a consistent picture of the evolution of the ocean-atmosphere CO2 system over the Cenozoic. ▪ CO2 and climate are coupled throughout the past 66 Myr, providing broad constraints on Earth system climate sensitivity. ▪ Twenty-first-century carbon emissions have the potential to return CO2 to levels not seen since the much warmer climates of Earth's distant past. Expected final online publication date for the Annual Review of Earth and Planetary Sciences, Volume 49 is May 2021. Please see http://www.annualreviews.org/page/journal/pubdates for revised estimates.

Keywords: speleothems northern Iberian Peninsula Marine Isotope Stage 2 last deglaciation stable isotopes trace elements rapid climate change Low and high frequency climatic fluctuations in northern Iberian Peninsula during the last glacial maximum (LGM) and deglaciation are documented in a stalagmite using δ 18 O and δ 13 C and hydrologically sensitive trace metal ratios Mg/Ca and Ba/Ca. U/Th dating indicates speleothem growth commenced at 25 kyr BP (Present = year 1950) and extended to 11.6 kyr BP making this one of few European speleothem growing during the last glacial period. Rapid climatic fluctuations as Heinrich event 2 (H2) and Greenland Interstadial (GI-) 2 are well characterized in this record by more arid and cold conditions and by more humid conditions, respectively. Speleothem growth ceased from 18.2 to 15.4 kyr BP (the so-called Mystery Interval) likely reflecting the driest and potentially coldest conditions of this record, coincident with the 2 kyr duration shutdown of the North Atlantic Meridional Overturning Circulation (MOC). A major gradual increase in humidity and possibly in temperature occurred from 15.5 to 13.5 kyr BP, beginning in the Bølling and culminating in the Allerød period. This gradual humidity change contrasts with more abrupt humidity shifts in the Mediterranean, suggesting a different climate threshold for Mediterranean vs. Atlantic margin precipitation.

Summary RuBisCO‐catalyzed CO2 fixation is the main source of organic carbon in the biosphere. This enzyme is present in all domains of life in different forms (III, II, and I) and its origin goes back to 3500 Mya, when the atmosphere was anoxygenic. However, the RuBisCO active site also catalyzes oxygenation of ribulose 1,5‐bisphosphate, therefore, the development of oxygenic photosynthesis and the subsequent oxygen‐rich atmosphere promoted the appearance of CO2 concentrating mechanisms (CCMs) and/or the evolution of a more CO2‐specific RuBisCO enzyme. The wide variability in RuBisCO kinetic traits of extant organisms reveals a history of adaptation to the prevailing CO2/O2 concentrations and the thermal environment throughout evolution. Notable differences in the kinetic parameters are found among the different forms of RuBisCO, but the differences are also associated with the presence and type of CCMs within each form, indicative of co‐evolution of RuBisCO and CCMs. Trade‐offs between RuBisCO kinetic traits vary among the RuBisCO forms and also among phylogenetic groups within the same form. These results suggest that different biochemical and structural constraints have operated on each type of RuBisCO during evolution, probably reflecting different environmental selective pressures. In a similar way, variations in carbon isotopic fractionation of the enzyme point to significant differences in its relationship to the CO2 specificity among different RuBisCO forms. A deeper knowledge of the natural variability of RuBisCO catalytic traits and the chemical mechanism of RuBisCO carboxylation and oxygenation reactions raises the possibility of finding unrevealed landscapes in RuBisCO evolution.

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