Articles | Volume 20, issue 9
https://doi.org/10.5194/cp-20-2081-2024
© Author(s) 2024. This work is distributed under
the Creative Commons Attribution 4.0 License.
the Creative Commons Attribution 4.0 License.
https://doi.org/10.5194/cp-20-2081-2024
© Author(s) 2024. This work is distributed under
the Creative Commons Attribution 4.0 License.
the Creative Commons Attribution 4.0 License.
A clumped isotope calibration of coccoliths at well-constrained culture temperatures for marine temperature reconstructions
Department of Earth Sciences, ETH Zürich, Zurich, Switzerland
Ismael Torres-Romero
Department of Earth Sciences, ETH Zürich, Zurich, Switzerland
Madalina Jaggi
Department of Earth Sciences, ETH Zürich, Zurich, Switzerland
Stefano M. Bernasconi
Department of Earth Sciences, ETH Zürich, Zurich, Switzerland
Heather M. Stoll
Department of Earth Sciences, ETH Zürich, Zurich, Switzerland
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Nikita Kaushal, Carlos Pérez-Mejías, and Heather M. Stoll
Clim. Past, 21, 1633–1660, https://doi.org/10.5194/cp-21-1633-2025, https://doi.org/10.5194/cp-21-1633-2025, 2025
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Terminations are large-magnitude rapid events triggered in the North Atlantic region that manifest across the global climate system. They provide key examples of climatic teleconnections and dynamics. In this study, we use the SISAL global speleothem database and find that there are sufficient climatic records from key locations to make speleothems a valuable archive for studying terminations and provide instances for more targeted work on speleothem research.
Laura Endres, Carlos Pérez-Mejías, Ruza Ivanovic, Lauren Gregoire, Anna L. C. Hughes, Hai Cheng, and Heather Stoll
EGUsphere, https://doi.org/10.5194/egusphere-2025-3911, https://doi.org/10.5194/egusphere-2025-3911, 2025
This preprint is open for discussion and under review for Climate of the Past (CP).
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Stable isotope data of a precisely dated stalagmite from northwestern Iberia indicate gradual North Atlantic meltwater input during the last glacial maximum, followed by abrupt surges early in the last deglaciation. The first abrupt surge was followed by cooling about 850 years later – unlike later events – which reveals that the Atlantic circulation’s sensitivity to meltwater is variable and related to the evolving background climate boundary conditions.
Heather Stoll, Clara Bolton, Madalina Jaggi, Alfredo Martinez-Garcia, and Stefano Bernasconi
EGUsphere, https://doi.org/10.5194/egusphere-2025-2449, https://doi.org/10.5194/egusphere-2025-2449, 2025
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In periods of high atmospheric CO2 many proxies suggest more extreme past polar warming than is simulated by current coupled climate models. Providing new data on high latitude temperatures in the South Atlantic over the last 15 million years using clumped isotope thermometry, we show that absolute temperatures may not have been as warm as indicated by some biomarker based proxy climate records.
Nicolas Tapia, Laura Endres, Madalina Jaggi, and Heather Stoll
EGUsphere, https://doi.org/10.5194/egusphere-2025-1000, https://doi.org/10.5194/egusphere-2025-1000, 2025
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We use stalagmites to study past changes in the terrestrial P cycle. Our P records from multiple, coeval stalagmites from NW Spain, show that past abrupt cooling events are characterized by multi-century reproducible peaks in stalagmite P which reflect higher groundwater P/Ca concentrations and enhanced P export, potentially resulting from increased freeze-thaw frequency and more intense infiltration from snowmelt.
Judit Torner, Isabel Cacho, Heather Stoll, Ana Moreno, Joan O. Grimalt, Francisco J. Sierro, Joan J. Fornós, Hai Cheng, and R. Lawrence Edwards
Clim. Past, 21, 465–487, https://doi.org/10.5194/cp-21-465-2025, https://doi.org/10.5194/cp-21-465-2025, 2025
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We offer a clearer view of the timing of three relevant past glacial terminations. By analyzing the climatic signal recorded in stalagmite and linking it with marine records, we revealed differences in the intensity and duration of the ice melting associated with these three key deglaciations. This study shows that some deglaciations began earlier than previously thought; this improves our understanding of natural climate processes, helping us to contextualize current climate change.
José Guitián, Samuel R. Phelps, Reto S. Wijker, Pratigya J. Polissar, Laura Arnold, and Heather M. Stoll
Clim. Past Discuss., https://doi.org/10.5194/cp-2024-65, https://doi.org/10.5194/cp-2024-65, 2024
Preprint under review for CP
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We reconstructed from sediments of different ocean sites phytoplankton carbon isotopic fractionation (εp), mainly linked to CO2 variations, during the Oligocene to early Miocene. Records confirm long-term trends but show contrasting relationships with the sea surface temperatures evolution. We evaluate the role of non-CO2 physiological factors such as temperature and nutrients at each site εp, highlighting the complexity of interpreting climate dynamics and CO2 reconstructions.
Nikita Kaushal, Franziska A. Lechleitner, Micah Wilhelm, Khalil Azennoud, Janica C. Bühler, Kerstin Braun, Yassine Ait Brahim, Andy Baker, Yuval Burstyn, Laia Comas-Bru, Jens Fohlmeister, Yonaton Goldsmith, Sandy P. Harrison, István G. Hatvani, Kira Rehfeld, Magdalena Ritzau, Vanessa Skiba, Heather M. Stoll, József G. Szűcs, Péter Tanos, Pauline C. Treble, Vitor Azevedo, Jonathan L. Baker, Andrea Borsato, Sakonvan Chawchai, Andrea Columbu, Laura Endres, Jun Hu, Zoltán Kern, Alena Kimbrough, Koray Koç, Monika Markowska, Belen Martrat, Syed Masood Ahmad, Carole Nehme, Valdir Felipe Novello, Carlos Pérez-Mejías, Jiaoyang Ruan, Natasha Sekhon, Nitesh Sinha, Carol V. Tadros, Benjamin H. Tiger, Sophie Warken, Annabel Wolf, Haiwei Zhang, and SISAL Working Group members
Earth Syst. Sci. Data, 16, 1933–1963, https://doi.org/10.5194/essd-16-1933-2024, https://doi.org/10.5194/essd-16-1933-2024, 2024
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Speleothems are a popular, multi-proxy climate archive that provide regional to global insights into past hydroclimate trends with precise chronologies. We present an update to the SISAL (Speleothem Isotopes
Synthesis and AnaLysis) database, SISALv3, which, for the first time, contains speleothem trace element records, in addition to an update to the stable isotope records available in previous versions of the database, cumulatively providing data from 365 globally distributed sites.
Synthesis and AnaLysis) database, SISALv3, which, for the first time, contains speleothem trace element records, in addition to an update to the stable isotope records available in previous versions of the database, cumulatively providing data from 365 globally distributed sites.
Miguel Bartolomé, Ana Moreno, Carlos Sancho, Isabel Cacho, Heather Stoll, Negar Haghipour, Ánchel Belmonte, Christoph Spötl, John Hellstrom, R. Lawrence Edwards, and Hai Cheng
Clim. Past, 20, 467–494, https://doi.org/10.5194/cp-20-467-2024, https://doi.org/10.5194/cp-20-467-2024, 2024
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Reconstructing past temperatures at regional scales during the Common Era is necessary to place the current warming in the context of natural climate variability. We present a climate reconstruction based on eight stalagmites from four caves in the Pyrenees, NE Spain. These stalagmites were dated precisely and analysed for their oxygen isotopes, which appear dominated by temperature changes. Solar variability and major volcanic eruptions are the two main drivers of observed climate variability.
Heather M. Stoll, Leopoldo D. Pena, Ivan Hernandez-Almeida, José Guitián, Thomas Tanner, and Heiko Pälike
Clim. Past, 20, 25–36, https://doi.org/10.5194/cp-20-25-2024, https://doi.org/10.5194/cp-20-25-2024, 2024
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The Oligocene and early Miocene periods featured dynamic glacial cycles on Antarctica. In this paper, we use Sr isotopes in marine carbonate sediments to document a change in the location and intensity of continental weathering during short periods of very intense Antarctic glaciation. Potentially, the weathering intensity of old continental rocks on Antarctica was reduced during glaciation. We also show improved age models for correlation of Southern Ocean and North Atlantic sediments.
Heather M. Stoll, Chris Day, Franziska Lechleitner, Oliver Kost, Laura Endres, Jakub Sliwinski, Carlos Pérez-Mejías, Hai Cheng, and Denis Scholz
Clim. Past, 19, 2423–2444, https://doi.org/10.5194/cp-19-2423-2023, https://doi.org/10.5194/cp-19-2423-2023, 2023
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Stalagmites formed in caves provide valuable information about past changes in climate and vegetation conditions. In this contribution, we present a new method to better estimate past changes in soil and vegetation productivity using carbon isotopes and trace elements measured in stalagmites. Applying this method to other stalagmites should provide a better indication of past vegetation feedbacks to climate change.
Jasmine S. Berg, Paula C. Rodriguez, Cara Magnabosco, Longhui Deng, Stefano M. Bernasconi, Hendrik Vogel, Marina Morlock, and Mark A. Lever
EGUsphere, https://doi.org/10.5194/egusphere-2023-2102, https://doi.org/10.5194/egusphere-2023-2102, 2023
Preprint archived
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The addition of sulfur to organic matter is generally thought to protect it from microbial degradation. We analyzed buried sulfur compounds in a 10-m sediment core representing the entire ~13,500 year history of an alpine lake. Surprisingly, organic sulfur and pyrite formed very rapidly and were characterized by very light isotope signatures that suggest active microbial sulfur cycling in the deep subsurface.
Oliver Kost, Saúl González-Lemos, Laura Rodríguez-Rodríguez, Jakub Sliwinski, Laura Endres, Negar Haghipour, and Heather Stoll
Hydrol. Earth Syst. Sci., 27, 2227–2255, https://doi.org/10.5194/hess-27-2227-2023, https://doi.org/10.5194/hess-27-2227-2023, 2023
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Cave monitoring studies including cave drip water are unique opportunities to sample water which has percolated through the soil and rock. The change in drip water chemistry is resolved over the course of 16 months, inferring seasonal and hydrological variations in soil and karst processes at the water–air and water–rock interface. Such data sets improve the understanding of hydrological and hydrochemical processes and ultimately advance the interpretation of geochemical stalagmite records.
Amanda Gerotto, Hongrui Zhang, Renata Hanae Nagai, Heather M. Stoll, Rubens César Lopes Figueira, Chuanlian Liu, and Iván Hernández-Almeida
Biogeosciences, 20, 1725–1739, https://doi.org/10.5194/bg-20-1725-2023, https://doi.org/10.5194/bg-20-1725-2023, 2023
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Based on the analysis of the response of coccolithophores’ morphological attributes in a laboratory dissolution experiment and surface sediment samples from the South China Sea, we proposed that the thickness shape (ks) factor of fossil coccoliths together with the normalized ks variation, which is the ratio of the standard deviation of ks (σ) over the mean ks (σ/ks), is a robust and novel proxy to reconstruct past changes in deep ocean carbon chemistry.
Jessica G. M. Crumpton-Banks, Thomas Tanner, Ivan Hernández Almeida, James W. B. Rae, and Heather Stoll
Biogeosciences, 19, 5633–5644, https://doi.org/10.5194/bg-19-5633-2022, https://doi.org/10.5194/bg-19-5633-2022, 2022
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Past ocean carbon is reconstructed using proxies, but it is unknown whether preparing ocean sediment for one proxy might damage the data given by another. We have tested whether the extraction of an organic proxy archive from sediment samples impacts the geochemistry of tiny shells also within the sediment. We find no difference in shell geochemistry between samples which come from treated and untreated sediment. This will help us to maximize scientific return from valuable sediment samples.
José Guitián, Miguel Ángel Fuertes, José-Abel Flores, Iván Hernández-Almeida, and Heather Stoll
Biogeosciences, 19, 5007–5019, https://doi.org/10.5194/bg-19-5007-2022, https://doi.org/10.5194/bg-19-5007-2022, 2022
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The effect of environmental conditions on the degree of calcification of marine phytoplankton remains unclear. This study implements a new microscopic approach to quantify the calcification of ancient coccolithophores, using North Atlantic sediments. Results show significant differences in the thickness and shape factor of coccoliths for samples with minimum dissolution, providing the first evaluation of phytoplankton physiology adaptation to million-year-scale variable environmental conditions.
Cinthya Esther Nava Fernandez, Tobias Braun, Bethany Fox, Adam Hartland, Ola Kwiecien, Chelsea Pederson, Sebastian Hoepker, Stefano Bernasconi, Madalina Jaggi, John Hellstrom, Fernando Gázquez, Amanda French, Norbert Marwan, Adrian Immenhauser, and Sebastian Franz Martin Breitenbach
Clim. Past Discuss., https://doi.org/10.5194/cp-2021-172, https://doi.org/10.5194/cp-2021-172, 2022
Manuscript not accepted for further review
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We provide a ca. 1000 year long (6.4–5.4 ka BP) stalagmite-based reconstruction of mid-Holocene rainfall variability in the tropical western Pacific. The annually laminated multi-proxy (δ13C, δ18O, X/Ca, gray values) record comes from Niue island and informs on El Nino-Southern Oscillation and South Pacific Convergence Zone dynamics. Our data suggest that ENSO was active and influenced rainfall seasonality over the covered time interval. Rainfall seasonality was subdued during active ENSO phases
Luca Smeraglia, Nathan Looser, Olivier Fabbri, Flavien Choulet, Marcel Guillong, and Stefano M. Bernasconi
Solid Earth, 12, 2539–2551, https://doi.org/10.5194/se-12-2539-2021, https://doi.org/10.5194/se-12-2539-2021, 2021
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In this paper, we dated fault movements at geological timescales which uplifted the sedimentary successions of the Jura Mountains from below the sea level up to Earth's surface. To do so, we applied the novel technique of U–Pb geochronology on calcite mineralizations that precipitated on fault surfaces during times of tectonic activity. Our results document a time frame of the tectonic evolution of the Jura Mountains and provide new insight into the broad geological history of the Western Alps.
Thomas J. Leutert, Sevasti Modestou, Stefano M. Bernasconi, and A. Nele Meckler
Clim. Past, 17, 2255–2271, https://doi.org/10.5194/cp-17-2255-2021, https://doi.org/10.5194/cp-17-2255-2021, 2021
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The Miocene climatic optimum associated with high atmospheric CO2 levels (~17–14 Ma) was followed by a period of dramatic climate change. We present a clumped isotope-based bottom-water temperature record from the Southern Ocean covering this key climate transition. Our record reveals warm conditions and a substantial cooling preceding the main ice volume increase, possibly caused by thresholds involved in ice growth and/or regional effects at our study site.
Andre Baldermann, Oliver Wasser, Elshan Abdullayev, Stefano Bernasconi, Stefan Löhr, Klaus Wemmer, Werner E. Piller, Maxim Rudmin, and Sylvain Richoz
Clim. Past, 17, 1955–1972, https://doi.org/10.5194/cp-17-1955-2021, https://doi.org/10.5194/cp-17-1955-2021, 2021
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We identified the provenance, (post)depositional history, weathering conditions and hydroclimate that formed the detrital and authigenic silicates and soil carbonates of the Valley of Lakes sediments in Central Asia during the Cenozoic (~34 to 21 Ma). Aridification pulses in continental Central Asia coincide with marine glaciation events and are caused by Cenozoic climate forcing and the exhumation of the Tian Shan, Hangay and Altai mountains, which reduced the moisture influx by westerly winds.
Franziska A. Lechleitner, Christopher C. Day, Oliver Kost, Micah Wilhelm, Negar Haghipour, Gideon M. Henderson, and Heather M. Stoll
Clim. Past, 17, 1903–1918, https://doi.org/10.5194/cp-17-1903-2021, https://doi.org/10.5194/cp-17-1903-2021, 2021
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Soil respiration is a critical but poorly constrained component of the global carbon cycle. We analyse the effect of changing soil respiration rates on the stable carbon isotope ratio of speleothems from northern Spain covering the last deglaciation. Using geochemical analysis and forward modelling we quantify the processes affecting speleothem stable carbon isotope ratios and extract a signature of increasing soil respiration synchronous with deglacial warming.
Annika Fiskal, Eva Anthamatten, Longhui Deng, Xingguo Han, Lorenzo Lagostina, Anja Michel, Rong Zhu, Nathalie Dubois, Carsten J. Schubert, Stefano M. Bernasconi, and Mark A. Lever
Biogeosciences, 18, 4369–4388, https://doi.org/10.5194/bg-18-4369-2021, https://doi.org/10.5194/bg-18-4369-2021, 2021
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Microbially produced methane can serve as a carbon source for freshwater macrofauna most likely through grazing on methane-oxidizing bacteria. This study investigates the contributions of different carbon sources to macrofaunal biomass. Our data suggest that the average contribution of methane-derived carbon is similar between different fauna but overall remains low. This is further supported by the low abundance of methane-cycling microorganisms.
Ana Moreno, Miguel Iglesias, Cesar Azorin-Molina, Carlos Pérez-Mejías, Miguel Bartolomé, Carlos Sancho, Heather Stoll, Isabel Cacho, Jaime Frigola, Cinta Osácar, Arsenio Muñoz, Antonio Delgado-Huertas, Ileana Bladé, and Françoise Vimeux
Atmos. Chem. Phys., 21, 10159–10177, https://doi.org/10.5194/acp-21-10159-2021, https://doi.org/10.5194/acp-21-10159-2021, 2021
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We present a large and unique dataset of the rainfall isotopic composition at seven sites from northern Iberia to characterize their variability at daily and monthly timescales and to assess the role of climate and geographic factors in the modulation of δ18O values. We found that the origin, moisture uptake along the trajectory and type of precipitation play a key role. These results will help to improve the interpretation of δ18O paleorecords from lacustrine carbonates or speleothems.
Hongrui Zhang, Chuanlian Liu, Luz María Mejía, and Heather Stoll
Biogeosciences, 18, 1909–1916, https://doi.org/10.5194/bg-18-1909-2021, https://doi.org/10.5194/bg-18-1909-2021, 2021
Alba Zappone, Antonio Pio Rinaldi, Melchior Grab, Quinn C. Wenning, Clément Roques, Claudio Madonna, Anne C. Obermann, Stefano M. Bernasconi, Matthias S. Brennwald, Rolf Kipfer, Florian Soom, Paul Cook, Yves Guglielmi, Christophe Nussbaum, Domenico Giardini, Marco Mazzotti, and Stefan Wiemer
Solid Earth, 12, 319–343, https://doi.org/10.5194/se-12-319-2021, https://doi.org/10.5194/se-12-319-2021, 2021
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The success of the geological storage of carbon dioxide is linked to the availability at depth of a capable reservoir and an impermeable caprock. The sealing capacity of the caprock is a key parameter for long-term CO2 containment. Faults crosscutting the caprock might represent preferential pathways for CO2 to escape. A decameter-scale experiment on injection in a fault, monitored by an integrated network of multiparamerter sensors, sheds light on the mobility of fluids within the fault.
Catarina Cavaleiro, Antje H. L. Voelker, Heather Stoll, Karl-Heinz Baumann, and Michal Kucera
Clim. Past, 16, 2017–2037, https://doi.org/10.5194/cp-16-2017-2020, https://doi.org/10.5194/cp-16-2017-2020, 2020
Cited articles
Anderson, N., Kelson, J., Kele, S., Daëron, M., Bonifacie, M., Horita, J., Mackey, T., John, C., Kluge, T., Petschnig, P., Jost, A., Huntington, K., Bernasconi, S., and Bergmann, K.: A Unified Clumped Isotope Thermometer Calibration (0.5–1,100 °C) Using Carbonate-Based Standardization, Geophys. Res. Lett., 48, e2020GL092069, https://doi.org/10.1029/2020GL092069, 2021.
Bajnai, D., Fiebig, J., Tomašových, A., Milner Garcia, S., Rollion-Bard, C., Raddatz, J., Löffler, N., Primo-Ramos, C., and Brand, U.: Assessing kinetic fractionation in brachiopod calcite using clumped isotopes, Sci. Rep., 8, 533, https://doi.org/10.1038/s41598-017-17353-7, 2018.
Barry, J., Hall-Spencer, J., and Tyrrell, T.: In situ perturbation experiments: natural venting sites, spatial/temporal gradients in ocean pH, manipulative in situ pCO2 perturbations, in: Guide to best practices for ocean acidification research and data reporting, edited by: Riebesell, U., Fabry, V., Hansson, L., and Gattuso, J.-P., Office for Official Publications of the European Communities, Luxembourg, 123–136, https://doi.org/10.2777/66906, 2012.
Berger, W.: Deep-sea carbonates: evidence for a coccolith lysocline, Deep-Sea Res., 20, 917–921, 1973.
Berman, A., Hanson, J., Leiserowitz, L., Koetzle, T., Weiner, S., and Addadi, B.: Biological Control of Crystal Texture: A Widespread Strategy for Adapting Crysta Properties to Function, Science, 259, 776–779, https://doi.org/10.1126/science.259.5096.776, 1993.
Bernasconi, S., Hu, B., Wacker, U., Fiebig, J., Breitenbach, S., and Rutz, T.: Background effects on Faraday collectors in gas-source mass spectrometry and implications for clumped isotope measurements, Rapid Commun. Mass Sp., 27, 603–612, https://doi.org/10.1002/rcm.6490, 2013.
Bernasconi, S., Müller, I., Bergmann, K., Breitenbach, S., Fernandez, A., Hodell, D., Jaggi, M., Meckler, A., Millan, I., and Ziegler, M.: Reducing Uncertainties in Carbonate Clumped Isotope Analysis Through Consistent Carbonate-Based Standardization, Geochem. Geophy. Geosy., 19, 2895–2914, https://doi.org/10.1029/2017GC007385, 2018.
Bernasconi, S., Daëron, M., Bergmann, K., Bonifacie, M., Meckler, A., Affek, H., Anderson, N, Bajnai, D., Barkan, E., Beverly, E., Blamart, D., Burgener, L., Calmels, D., Chaduteau, C., Clog, M., Davidheiser-Kroll, B., Davies, A., Dux, F., Eiler, J., Elliott, B., Fetrow, A., Fiebig, J., Goldberg, S., Hermoso, M., Huntington, K., Hyland, E., Ingalls, M., Jaggi, M., John, C., Jost, A., Katz, S., Kelson, J., Kluge, T., Kocken, I., Laskar, A., Leutert, T., Liang, D., Lucarelli, J., Mackey, T., Mangenot, X., Meinicke, N., Modestou, S., Muller, I., Murray, S., Neary, A., Packard, N., Passey, B., Pelletier, E., Petersen, S., Piasecki, A., Schauer, A., Snell, K.E., Swart, P., Tripati, A., Upadhyay, D., Vennemann, T., Winkelstern, I., Yarian, D., Yoshida, N., Zhang, N., and Ziegler, M.: InterCarb: A Community Effort to Improve Interlaboratory Standardization of the Carbonate Clumped Isotope Thermometer Using Carbonate Standards, Geochem. Geophy. Geosy. 22, e2020GC009588, https://doi.org/10.1029/2020GC009588, 2021.
Blanco-Ameijeiras, S., Stoll, H., Zhang, H., and Hopkinson, B.: Influence of temperature and CO2 on plasma-membrane permeability to CO2 and HCO in the marine haptophytes Emiliania huxleyi and Calcidiscus leptoporus (Prymnesiophyceaea), J. Phycol., 56, 1283–1294, https://doi.org/10.1111/jpy.13017, 2020.
Bolton, C. and Stoll, H.: Late Miocene threshold response of marine algae to carbon dioxide limitation, Nature, 500, 558–562, https://doi.org/10.1038/nature12448, 2013.
Bonifacie, M., Calmels, D., Eiler, J., Horita, J., Chaduteau, C., Vasconcelos, C., Agrinier, P., Katz, A., Passey, B., Ferry, J., and Bourrand, J.: Calibration of the dolomite clumped isotope thermometer from 25 to 350 °C, and implications for a universal calibration for all (Ca, Mg, Fe)CO3 carbonates, Geochim. Cosmochim. Ac., 200, 255–279, https://doi.org/10.1016/j.gca.2016.11.028, 2017.
Brownlee, C., Wheeler, G., and Taylor, A.: Coccolithophore biomineralization: New questions, new answers, Semin. Cell Dev. Biol., 46, 11–16, https://doi.org/10.1016/j.semcdb.2015.10.027, 2015.
Caldarescu, D., Sadatzki, H., Andersson, C., Schafer, P., Fortunato, H., and Meckler, A.: Clumped isotope thermometry in bivalve shells: A tool for reconstructing seasonal upwelling, Geochim. Cosmochim. Ac., 294, 174–191, https://doi.org/10.1016/j.gca.2020.11.019, 2021.
Candelier, Y., Minoletti, F., Probert, I., and Hermoso, M.: Temperature dependence of oxygen isotope fractionation in coccolith calcite: A culture and core top calibration of the genus Calcidiscus, Geochim. Cosmochim. Ac., 100, 264–281, 2013.
Cantrell, C. A.: Technical Note: Review of methods for linear least-squares fitting of data and application to atmospheric chemistry problems, Atmos. Chem. Phys., 8, 5477–5487, https://doi.org/10.5194/acp-8-5477-2008, 2008.
Clark, A., Jaggi, M., Bernasconi, S., and Stoll, H.: Do coccolith clumped isotopes record sea surface temperatures? A sediment trap perspective, EGU General Assembly 2024, Vienna, Austria, 14–19 Apr 2024, EGU24-15587, https://doi.org/10.5194/egusphere-egu24-15587, 2024a.
Clark, A., Torres-Romero, I., Jaggi, M., Bernasconi, S., and Stoll, H.: Coccolith specific clumped isotope calibration data, Version 1.0, Interdisciplinary Earth Data Alliance (IEDA), EarthChem [data set], https://doi.org/10.60520/IEDA/113247, 2024b.
Clark, I., Fontes, J., and Fritz, P.: Stable isotope disequilibria in travertine from high pH waters: Laboratory investigations and field observations from Oman, Geochim. Cosmochim. Ac., 56, 2041–2050, https://doi.org/10.1016/0016-7037(92)90328-G, 1992.
Coplen, T.: Calibration of the calcite-water oxygen-isotope geothermometer at Devils Hole, Nevada, a natural laboratory, Geochim. Cosmochim. Ac., 71, 3948–3957, https://doi.org/10.1016/j.gca.2007.05.028, 2007.
Daëron, M.: Full Propagation of Analytical Uncertainties in Δ47 Measurements, Geochem. Geophy. Geosy., 22, e2020GC009592, https://doi.org/10.1029/2020GC009592, 2021.
Daëron, M. and Gray, W.: Revisiting oxygen-18 and clumped isotopes in planktic and benthic foraminifera, Paleoceanography and Paleoclimatology, 38, 2023–2032, https://doi.org/10.1029/2023PA004660, 2023.
Daëron, M. and Vermeesch, P.: Omnivariant Generalized Least Squares regression: Theory, geochronological applications, and making the case for reconciled Δ47 calibrations, Chem. Geol., 647, 121881, https://doi.org/10.1016/j.chemgeo.2023.121881, 2024.
Daëron, M., Blamart, D., Peral, M., and Affek, H.: Absolute isotopic abundance ratios and the accuracy of Δ47 measurements, Chem. Geol., 442, 83–96, https://doi.org/10.1016/j.chemgeo.2016.08.014, 2016.
Daëron, M., Drysdale, R., Peral, M., Huyghe, D., Blamart, D., Coplen, T., Lartaud, F., and Zanchetta, G.: Most Earth-surface calcites precipitate out of isotopic equilibrium, Nat. Commun., 10, 429, 10.1038/s41467-019-08336-5, 2019.
Davies, A., Guo, W., Bernecker, M., Tagliavento, M., Raddatz, J., Gischler, E., Flögel, S., and Fiebig, J.: Dual clumped isotope thermometry of coral carbonate, Geochim. Cosmochim. Ac., 338, 66–78, https://doi.org/10.1016/j.gca.2022.10.015, 2022.
Davies, A., Brand, U., Tagliavento, M., Bitner, M., Bajnai, D., Staudigel, P., Bernecker, M., and Fiebig, J.: Isotopic disequilibrium in brachiopods disentangled with dual clumped isotope thermometry, Geochim. Cosmochim. Ac., 359, 135–147, https://doi.org/10.1016/j.gca.2023.08.005, 2023.
de Winter, N., Witbaard, R., Kocken, I., Müller, I., Guo, J., Goudsmit, B., and Ziegler, M.: Temperature Dependence of Clumped Isotopes (Δ47) in Aragonite, Geophys. Res. Lett., 49, e2022GL099479, https://doi.org/10.1029/2022GL099479, 2022.
Defliese, W. and Lohmann, K.: Non-linear mixing effects on mass-47 CO2 clumped isotope thermometry: Patterns and implications, Rapid Commun. Mass Sp., 29, 901–909, https://doi.org/10.1002/rcm.7175, 2015.
Deng, X., Li, Q., Su, J., Liu, C., Atekwana, E., and Cai, W.: Performance evaluations and applications of a δ13C-DIC analyzer in seawater and estuarine waters, Sci. Total Environ., 833, 155013, https://doi.org/10.1016/j.scitotenv.2022.155013, 2022.
Dennis, K. and Schrag, D.: Clumped isotope thermometry of carbonatites as an indicator of diagenetic alteration, Geochim. Cosmochim. Ac., 74, 4110–4122, https://doi.org/10.1016/j.gca.2010.04.005, 2010.
Devriendt, L., Watkins, J., and McGregor, H.: Oxygen isotope fractionation in the CaCO3-DIC-H2O system, Geochim. Cosmochim. Ac., 214, 115–142, https://doi.org/10.1016/j.gca.2017.06.022, 2017.
Dickson, A.: Standard potential of the reaction: AgCl(s) + 1/2H2(g) = Ag(s) + HCl(aq), and the standard acidity constant of the ion HSO in synthetic sea water from 273.15 to 318.15 K, J. Chem. Thermodyn., 22, 113–127, https://doi.org/10.1016/0021-9614(90)90074-Z, 1990.
Dietzel, M., Usdowski, E., and Hoefst, J.: Chemical and C- and O-isotope evolution of alkaline drainage waters and the precipitation of calcite, Appl. Geochem., 7, 177–184, https://doi.org/10.1016/0883-2927(92)90035-2, 1992.
Drury, A. and John, C.: Exploring the potential of clumped isotope thermometry on coccolith-rich sediments as a sea surface temperature proxy, Geochem. Geophy. Geosy., 17, 4092–4104, https://doi.org/10.1002/2016GC006459, 2016.
Eiler, J.: “Clumped-isotope” geochemistry-The study of naturally-occurring, multiply-substituted isotopologues, Earth Planet. Sc. Lett., 262, 309–327, https://doi.org/10.1016/j.epsl.2007.08.020, 2007.
Eiler, J., and Schauble, E.: 18O13C16O in Earth's atmosphere, Geochim. Cosmochim. Ac., 68, 4767–4777, https://doi.org/10.1016/j.gca.2004.05.035, 2004.
Elzenga, J., Prins, H., and Stefels, J.: The role of extracellular carbonic anhydrase activity in inorganic carbon utilization of Phaeocystis globosa (Prymnesiophyceae): A comparison with other marine algae using the isotopic disequilibrium technique, Limnol. Oceanogr., 45, 372–380, https://doi.org/10.4319/lo.2000.45.2.0372, 2000.
Falster, G., Delean, S., and Tyler, J.: Hydrogen Peroxide Treatment of Natural Lake Sediment Prior to Carbon and Oxygen Stable Isotope Analysis of Calcium Carbonate, Geochem. Geophy. Geosy., 19, 3583–3595, https://doi.org/10.1029/2018GC007575, 2018.
Fernandez, A., Müller, I., Rodríguez-Sanz, L., van Dijk, J., Looser, N., and Bernasconi, S.: A Reassessment of the Precision of Carbonate Clumped Isotope Measurements: Implications for Calibrations and Paleoclimate Reconstructions, Geochem. Geophy. Geosy., 18, 4375–4386, https://doi.org/10.1002/2017GC007106, 2017.
Fiebig, J., Daëron, M., Bernecker, M., Guo, W., Schneider, G., Boch, R., Bernasconi, S., Jautzy. J., and Dietzel, M.: Calibration of the dual clumped isotope thermometer for carbonates, Geochim. Cosmochim. Ac., 312, 235–256, https://doi.org/10.1016/j.gca.2021.07.012, 2021.
Frølich, S., Sørensen, H., Hakim, S., Marin, F., Stipp, S., and Birkedal, H.: Smaller calcite lattice deformation caused by occluded organic material in coccoliths than in mollusk shell, Cryst. Growth Des., 15, 2761–2767, https://doi.org/10.1021/acs.cgd.5b00118, 2015.
Gal, A., Wirth, R., Kopka, J., Fratzl, P., Faivre, D., and Scheffel, A.: Macromolecular recognition directs calcium ions to coccolith mineralization sites, Science, 353, 590–593, https://doi.org/10.1126/science.aaf7889, 2016.
Gal, A., Sviben, S., Wirth, R., Schreiber, A., Lasalle-Kaiser, B., Faivre, D., and Scheffel, A.: Trace-Element Incorporation into Intracellular Pools Uncovers Calcium-Pathways in a Coccolithophore, Adv. Sci., 4, 1700088, https://doi.org/10.1002/advs.201700088, 2017.
Ghosh, P., Adkins, J., Affek, H., Balta, B., Guo, W., Schauble, E., Schrag, D., and Eiler, J.: 13C–18O bonds in carbonate minerals: A new kind of paleothermometer, Geochim. Cosmochim. Ac., 70, 1439–1456, https://doi.org/10.1016/j.gca.2005.11.014, 2006.
Guo, W.: Kinetic clumped isotope fractionation in the DIC-H2O-CO2 system: Patterns, controls, and implications, Geochim. Cosmochim. Ac., 268, 230–257, https://doi.org/10.1016/j.gca.2019.07.055, 2020.
Guo, W. and Zhou, C.: Patterns and controls of disequilibrium isotope effects in speleothems: Insights from an isotope-enabled diffusion-reaction model and implications for quantitative thermometry, Geochim. Cosmochim. Ac., 267, 196–226, https://doi.org/10.1016/j.gca.2019.07.028, 2019.
Gupta, P., Noone, D., Galewsky, J., Sweeney, C., and Vaughn, B.: Demonstration of high-precision continuous measurements of water vapor isotopologues in laboratory and remote field deployments using wavelength-scanned cavity ring-down spectroscopy (WS-CRDS) technology, Rapid Commun. Mass Sp., 23, 2534–2542, https://doi.org/10.1002/rcm.4100, 2009.
Henriksen, K., Young, J., Brown, P., and Stipp, S.: Coccolith biomineralisation studied with atomic force microscopy, Palaeontology, 47, 725–743, https://doi.org/10.1111/j.0031-0239.2004.00385.x, 2004.
Herfort, L., Thake, B., and Roberts, J.: Acquisition and use of bicarbonate by Emiliania huxleyi, New Phytol., 156, 427–436, https://doi.org/10.1046/j.1469-8137.2002.00523.x, 2002.
Hermoso, M.: Coccolith-derived isotopic proxies in palaeoceanography: Where geologists need biologists, Cryptogamie, Algol, 35, 323–351, https://doi.org/10.7872/crya.v35.iss4.2014.323, 2014.
Hermoso, M., Horner, T., Minoletti, F., and Rickaby, R.: Constraints on the vital effect in coccolithophore and dinoflagellate calcite by oxygen isotopic modification of seawater, Geochim. Cosmochim. Ac., 141, 612–627, https://doi.org/10.1016/j.gca.2014.05.002, 2014.
Hermoso, M., Minoletti, F., Aloisi, G., Bonifacie, M., McClelland, H., Labourdette, N., Renforth, P., Chaduteau, C., and Rickaby, R.: An explanation for the 18O excess in Noelaerhabdaceae coccolith calcite, Geochim. Cosmochim. Ac., 189, 132–142, https://doi.org/10.1016/j.gca.2016.06.016, 2016.
Hill, P., Tripati, A., and Schauble, E.: Theoretical constraints on the effects of pH, salinity, and temperature on clumped isotope signatures of dissolved inorganic carbon species and precipitating carbonate minerals, Geochim. Cosmochim. Ac., 125, 610–652, https://doi.org/10.1016/j.gca.2013.06.018, 2014.
Holtz, L., Wolf-Gladrow, D., and Thoms, S.: Simulating the effects of light intensity and carbonate system composition on particulate organic and inorganic carbon production in Emiliania huxleyi, J. Theor. Biol., 372, 192–204, https://doi.org/10.1016/j.jtbi.2017.01.030, 2015.
Holtz, L., Wolf-Gladrow, D., and Thoms, S.: Stable carbon isotope signals in particulate organic and inorganic carbon of coccolithophores – A numerical model study for Emiliania huxleyi, J. Theor. Biol., 420, 117–127, https://doi.org/10.1016/j.jtbi.2015.02.024, 2017.
Houdan, A., Probert, I., Zatylny, C., Véron, B., and Billard, C.: Ecology of oceanic coccolithophores. I. Nutritional preferences of the two stages in the life cycle of Coccolithus braarudii and Calcidiscus leptoporus, Aquat. Microb. Ecol., 44, 291–301, https://doi.org/10.3354/ame044291, 2006.
Hu, B., Radke, J., Schlüter, H., Heine, F., Zhou, L., and Bernasconi, S.: A modified procedure for gas-source isotope ratio mass spectrometry: The long-integration dual-inlet (LIDI) methodology and implications for clumped isotope measurements, Rapid Commun. Mass Sp., 28, 1413–1425, https://doi.org/10.1002/rcm.6909, 2014.
Huntington, K. and Petersen, S.: Frontiers of Carbonate Clumped Isotope Thermometry, Annu. Rev. Earth Pl. Sc., 51, 611–641, https://doi.org/10.1146/annurev-earth-031621-085949, 2023.
Huyghe, D., Daëron, M., de Rafelis, M., Blamart, D., Sébilo, M., Paulet, Y., and Lartaud, F.: Clumped isotopes in modern marine bivalves, Geochim. Cosmochim. Ac., 316, 41–58, https://doi.org/10.1016/j.gca.2021.09.019, 2022.
Jautzy, J., Savard, M., Dhillon, R., Bernasconi, S., and Smirnoff, A.: Clumped isotope temperature calibration for calcite: Bridging theory and experimentation, Geochem. Perspect. Lett., 14, 36–41, https://doi.org/10.7185/geochemlet.2021, 2020.
John, C. and Bowen, D.: Community software for challenging isotope analysis: First applications of `Easotope' to clumped isotopes, Rapid Commun. Mass Sp., 30, 2285–2300, https://doi.org/10.1002/rcm.7720, 2016.
Katz, A., Bonifacie, M., Hermoso, M., Cartigny, P., and Calmels, D.: Laboratory-grown coccoliths exhibit no vital effect in clumped isotope (Δ47) composition on a range of geologically relevant temperatures, Geochim. Cosmochim. Ac., 208, 335–353, https://doi.org/10.1016/j.gca.2017.02.025, 2017.
Kele, S., Breitenbach, S., Capezzuoli, E., Meckler, A., Ziegler, M., Millan, I., Kluge, T., Deak, J., Hanselmann, K., John, C., Yan, H., Liu, Z., and Bernasconi, S.: Temperature dependence of oxygen- and clumped isotope fractionation in carbonates: A study of travertines and tufas in the 6–95 °C temperature range, Geochim. Cosmochim. Ac., 168, 172–192, https://doi.org/10.1016/j.gca.2015.06.032, 2015.
Keller, M., Seluin, R., Claus, W., and Guillard, R.: Media for the culture of oceanic ultraphytoplankton, J. Phycol., 23, 633–638, https://doi.org/10.1111/j.1529-8817.1987.tb04217.x, 1987.
Kelson, J., Huntington, K., Schauer, A., Saenger, C., and Lechler, A.: Toward a universal carbonate clumped isotope calibration: Diverse synthesis and preparatory methods suggest a single temperature relationship, Geochim. Cosmochim. Ac., 197, 104–131, https://doi.org/10.1016/j.gca.2016.10.010, 2017.
Kester, D., Duedall, I., Connors, D., and Pytkowicz, R.: Preparation of Artificial Seawater, Limnol. Oceanogr., 12, 176–179, https://doi.org/10.4319/lo.1967.12.1.0176, 1967.
Kim, S. and O'Neil, J.: Equilibrium and nonequilibrium oxygen isotope effects in synthetic carbonates, Geochim. Cosmochim. Ac., 61, 3461–3475, https://doi.org/10.1016/S0016-7037(97)00169-5, 1997.
Langer, G., Geisen, M., Baumann, K.-H., Kläs, J., Riebesell, U., Thoms, S., and Young, J. R.: Species-specific responses of calcifying algae to changing seawater carbonate chemistry, Geochem. Geophy. Geosy., 7, Q09006, https://doi.org/10.1029/2005GC001227, 2006.
Langer, G., Oetjen, K., and Brenneis, T.: Calcification of Calcidiscus leptoporus under nitrogen and phosphorus limitation, J. Exp. Mar. Biol. Ecol., 413, 131–137, 10.1016/j.jembe.2011.11.028, 2012.
Lee, K., Kim, T., Byrne, R., Millero, F., Feely, R., and Liu, Y.: The universal ratio of boron to chlorinity for the North Pacific and North Atlantic oceans, Geochim. Cosmochim. Ac., 74, 1801–1811, https://doi.org/10.1038/ncomms13144, 2010.
Lee, R., Mavridou, D., Papadakos, G., McClelland, H., and Rickaby, R.: The uronic acid content of coccolith-associated polysaccharides provides insight into coccolithogenesis and past climate, Nat. Commun., 7, 1801–1811, https://doi.org/10.1016/j.gca.2009.12.027, 2016.
Letulle, T., Gaspard, D., Daëron, M., Arnaud-Godet, F., Vinçon-Laugier, A., Suan, G., and Lécuyer, C.: Multi-proxy assessment of brachiopod shell calcite as a potential archive of seawater temperature and oxygen isotope composition, Biogeosciences, 20, 1381–1403, https://doi.org/10.5194/bg-20-1381-2023, 2023.
Leuker, T., Dickson, A., and Keeling, C.: Ocean pCO2 calculated from dissolved inorganic carbon, alkalinity, and equations for K1 and K2: validation based on laboratory measurements of CO2 in gas and seawater at equilibrium, Mar. Chem., 70, 105–119, https://doi.org/10.1016/S0304-4203(00)00022-0, 2000.
Leutert, T., Sexton, P., Tripati, A., Piasecki, A., Ho, S., and Meckler, A.: Sensitivity of clumped isotope temperatures in fossil benthic and planktic foraminifera to diagenetic alteration, Geochim. Cosmochim. Ac., 257, 354–372, https://doi.org/10.1016/j.gca.2019.05.005, 2019.
Levitt, N., Eiler, J., Romanek, C., Beard, B., Xu, H., and Johnson, C.: Near Equilibrium 13C–18O Bonding During Inorganic Calcite Precipitation Under Chemo-Stat Conditions, Geochem. Geophy. Geosy., 19, 901–920, https://doi.org/10.1002/2017GC007089, 2018.
Lewis, E. and Wallace, D.: Program Developed for CO2 System Calculations, CDIAC, ESS-DIVE repository [data set], https://doi.org/10.15485/1464255, 1998.
Matyash, V., Liebisch, G., Kurzchalia, T., Shevchenko, A., and Schwudke, D.: Lipid extraction by methyl-terf-butyl ether for high-throughput lipidomics, J. Lipid Res., 49, 1137–1146, https://doi.org/10.1194/jlr.D700041-JLR200, 2008.
McClelland, H., Bruggeman, J., Hermoso, M., and Rickaby, R.: The origin of carbon isotope vital effects in coccolith calcite, Nat. Commun., 8, 14511, https://doi.org/10.1038/ncomms14511, 2017.
McConnaughey, T.: 13C and 18O isotopic disequilibrium in biological carbonates: II. in vitro simulation of kinetic isotope effects, Geochim. Cosmochim. Ac., 53, 163–171, https://doi.org/10.1016/0016-7037(89)90283-4, 1989.
Meckler, A., Ziegler, M., Millán, M., Breitenbach, S., and Bernasconi, S.: Long-term performance of the Kiel carbonate device with a new correction scheme for clumped isotope measurements, Rapid Commun. Mass Sp., 28, 1705–1715, https://doi.org/10.1002/rcm.6949, 2014.
Meinicke, N., Ho, S., Hannisdal, B., Nürnberg, D., Tripati, A., Schiebel, R., and Meckler, A.: A robust calibration of the clumped isotopes to temperature relationship for foraminifers, Geochim. Cosmochim. Ac., 270, 160–183, https://doi.org/10.1016/j.gca.2019.11.022, 2020.
Meinicke, N., Reimi, M., Ravelo, A., and Meckler, A.: Coupled and Clumped Isotope Measurements Indicate Lack of Substantial Mixed Layer Cooling in the Western Pacific Warm Pool During the Last ∼ 5 Million Years, Paleoceanography, 36, e2020PA004115, https://doi.org/10.1029/2020PA004115, 2021.
Moolna, A. and Rickaby, R.: Interaction of the coccolithophore Gephyrocapsa oceanica with its carbon environment: Response to a recreated high-CO2 geological past, Geobiology, 10, 72–81, https://doi.org/10.1111/j.1472-4669.2011.00308.x, 2012.
Müller, I., Fernandez, A., Radke, J., van Dijk, J., Bowen, D., Schwieters, J., and Bernasconi, S.: Carbonate clumped isotope analyses with the long-integration dual-inlet (LIDI) workflow: scratching at the lower sample weight boundaries, Rapid Commun. Mass Sp., 31, 1057–1066, https://doi.org/10.1002/rcm.7878, 2017.
Müller, I., Rodriguez-Blanco, J., Storck, J., do Nascimento, G., Bontognali, T., Vasconcelos, C., Benning, L., and Bernasconi, S.: Calibration of the oxygen and clumped isotope thermometers for (proto-)dolomite based on synthetic and natural carbonates, Chem. Geol., 525, 1–17, https://doi.org/10.1016/j.chemgeo.2019.07.014, 2019.
Nimer, N., Guan, Q., and Merrett, M.: Extra- and intra-cellular carbonic anhydrase in relation to culture age in a high-calcifying strain of Emiliania huxleyi Lohmann, New Phytol., 126, 601–607, https://doi.org/10.1111/j.1469-8137.1994.tb02954.x, 1994.
Peral, M., Daëron, M., Blamart, D., Bassinot, F., Dewilde, F., Smialkowski, N., Isguder, G., Bonnin, J., Jorissen, F., Kissel, C., Michel, E., Vazquez Riveiros, N., and Waelbroeck, C.: Updated calibration of the clumped isotope thermometer in planktonic and benthic foraminifera, Geochim. Cosmochim. Ac., 239, 1–16, https://doi.org/10.1016/j.gca.2018.07.016, 2018.
Peral, M., Bassinot, F., Daëron, M., Blamart, D., Bonnin, J., Jorissen, F., Kissel, C., Michel, E., Waelbroeck, C., Rebaubier, H., and Gray, W.: On the combination of the planktonic foraminiferal , clumped (Δ47) and conventional (δ18O) stable isotope paleothermometers in palaeoceanographic studies, Geochim. Cosmochim. Ac., 339, 22–34, https://doi.org/10.1016/j.gca.2022.10.030, 2022.
Perez, F. and Fraga, F.: Association Constant of Fluoride and Hydrogen ions in seawater, Mar. Chem., 21, 168, https://doi.org/10.1016/0304-4203(87)90036-3, 1987.
Phelps, S., Stoll, H., Bolton, C., Beaufort, L., and Polissar, P.: Controls on Alkenone Carbon Isotope Fractionation in the Modern Ocean, Geochem. Geophy. Geosy., 22, e2021GC009658, https://doi.org/10.1029/2021GC009658, 2021.
Piasecki, A., Bernasconi, S., Grauel, A., Hannisdal, B., Ho, S., Leutert, T., Marchitto, T., Meinicke, N., Tisserand, A., and Meckler, N.: Application of Clumped Isotope Thermometry to Benthic Foraminifera, Geochem. Geophy. Geosy., 20, 2082–2090, https://doi.org/10.1029/2018GC007961, 2019.
Quinn, P., Bowers, R., Zhang, X., Wahlund, T., Fanelli, M., Olszova, D., and Read, B.: cDNA microarrays as a tool for identification of biomineralization proteins in the coccolithophorid Emiliania huxleyi (Haptophyta), Appl. Environ. Microb., 72, 5512–5526, https://doi.org/10.1128/AEM.00343-06, 2006.
Richier, S., Fiorini, S., Kerros, M., von Dassow, P., and Gattuso, J.: Response of the calcifying coccolithophore Emiliania huxleyi to low pH/high pCO2: From physiology to molecular level, Mar. Biol., 158, 551–560, https://doi.org/10.1007/s00227-010-1580-8, 2011.
Rickaby, R. E. M., Henderiks, J., and Young, J. N.: Perturbing phytoplankton: response and isotopic fractionation with changing carbonate chemistry in two coccolithophore species, Clim. Past, 6, 771–785, https://doi.org/10.5194/cp-6-771-2010, 2010.
Rost, B., Riebesell, U., Burkhardt, S., and Sültemeyer, D.: Carbon acquisition of bloom-forming marine phytoplankton, Limnol. Oceanogr., 48, 55–67, https://doi.org/10.4319/lo.2003.48.1.0055, 2003.
Sand, K., Pedersen, C., Sjöberg, S., Nielsen, J., Makovicky, E., and Stipp, S.: Biomineralization: Long-term effectiveness of polysaccharides on the growth and dissolution of calcite, Cryst. Growth Des., 14, 5486–5494, https://doi.org/10.1021/cg5006743, 2014.
Shackleton, N.: Attainment of isotopic equilibrium between ocean water and the benthonic foraminifera genus Uvigerina: isotopic changes in the ocean during the last glacial, in: Les Méthodes quantitatives d’étude des variations du climat au cours du Pléistocène, Colloques Internationaux du C.N.R.S., vol. 219, 203–209, 1974.
Schauble, E., Ghosh, P., and Eiler, J.: Preferential formation of 13C–18O bonds in carbonate minerals, estimated using first-principles lattice dynamics, Geochim. Cosmochim. Ac., 70, 2510–2529, https://doi.org/10.1016/j.gca.2006.02.011, 2006.
Schiebel, R., and Hemleben, C.: Planktic foraminifers in the modern ocean, Springer-Verlag Berlin Heidelberg, 366 pp., ISBN 978-3-662-50295-2, 2017.
Sett, S., Bach, L., Schulz, K., Koch-Klavsen, S., Lebrato, M., and Riebesell, U.: Temperature modulates coccolithophorid sensitivity of growth, photosynthesis and calcification to increasing seawater pCO2, PLoS ONE, 9, e88308, https://doi.org/10.1371/journal.pone.0088308, 2014.
Soto, A., Zheng, H., Shoemaker, D., Rodriguez, J., Read, B., and Wahlund, T.: Identification and preliminary characterization of two cDNAs encoding unique carbonic anhydrases from the marine alga Emiliania huxleyi, Appl. Environ. Microb., 72, 5500–5511, https://doi.org/10.1128/AEM.00237-06, 2006.
Spero, H., Bijma, J., Lea, D., andBemis, B.: Effect of seawater carbonate concentration on foraminiferal carbon and oxygen isotopes, Nature, 390, 497–500, https://doi.org/10.1038/37333, 1997.
Spooner, P., Guo, W., Robinson, L., Thiagarajan, N., Hendry, K., Rosenheim, B., and Leng, M.: Clumped isotope composition of cold-water corals: A role for vital effects?, Geochim. Cosmochim. Ac., 179, 123–141, https://doi.org/10.1016/j.gca.2016.01.023, 2016.
Stevenson, E., Hermoso, M., Rickaby, R., Tyler, J., Minoletti, F., Parkinson, I., Mokadem, F., and Burton, K.: Controls on stable strontium isotope fractionation in coccolithophores with implications for the marine Sr cycle, Geochim. Cosmochim. Ac., 128, 225–235, https://doi.org/10.1016/j.gca.2013.11.043, 2014.
Stoll, H., Ruiz Encinar, J., Ignacio Garcia Alonso, J., Rosenthal, Y., Probert, I., and Klaas, C.: A first look at paleotemperature prospects from Mg in coccolith carbonate: Cleaning techniques and culture measurements, Geochem. Geophy. Geosy., 2, 2000GC000144, https://doi.org/10.1029/2000GC000144, 2001.
Subhas, A., McCorkle, D., Quizon, A., McNichol, A., and Long, M.: Selective Preservation of Coccolith Calcite in Ontong-Java Plateau Sediments, Paleoceanography and Paleoclimatology, 34, 2141–2157, https://doi.org/10.1029/2019PA003731, 2019.
Thierstein, H. and Young, J. (Eds.): Coccolithophores, Springer Berlin Heidelberg, https://doi.org/10.1007/978-3-662-06278-4, 2004.
Swart, P., Murray, S., Staudigel, P., and Hodell, D.: Oxygen isotopic exchange between CO2 and phosphoric acid: Implications for the measurement of clumped isotopes in carbonates, Geochem. Geophy. Geosy., 20, 3730–3750, https://doi.org/10.1029/2019GC008209, 2019.
Taylor, A., Brownlee, C., and Wheeler, G.: Coccolithophore Cell Biology: Chalking Up Progress, Annu. Rev. Mar. Sci., 9, 283–310, https://doi.org/10.1146/annurev-marine-122414-034032, 2017.
Torres-Romero, I., Clark, A., Wijker, R., Jaggi, M., Zhang, H., and Stoll, H.: Temperature-dependent carbon isotope fractionation in coccolithophores, Front. Earth Sci., 12, 1331179, https://doi.org/10.3389/feart.2024.1331179, 2024.
Uchikawa, J. and Zeebe, R.: The effect of carbonic anhydrase on the kinetics and equilibrium of the oxygen isotope exchange in the CO2-H2O system: Implications for δ18O vital effects in biogenic carbonates, Geochim. Cosmochim. Ac., 95, 15–34, https://doi.org/10.1016/j.gca.2012.07.022, 2012.
Uchikawa, J., Chen, S., Eiler, J., Adkins, J., and Zeebe, R.: Trajectory and timescale of oxygen and clumped isotope equilibration in the dissolved carbonate system under normal and enzymatically-catalyzed conditions at 25 °C, Geochim. Cosmochim. Ac., 314, 313–333, https://doi.org/10.1016/j.gca.2021.08.014, 2021.
von Dassow, P., Muñoz Farías, P., Pinon, S., Velasco-Senovilla, E., and Anguita-Salinas, S.: Do Differences in Latitudinal Distributions of Species and Organelle Haplotypes Reflect Thermal Reaction Norms Within the Emiliania/Gephyrocapsa Complex?, Front. Mar. Sci., 8, 785763, https://doi.org/10.3389/fmars.2021.785763, 2021.
Walker, C., Heath, S., Salmon, D., Smirnoff, N., Langer, G., Taylor, A., Brownlee, C., andWheeler, G.: An Extracellular Polysaccharide-Rich Organic Layer Contributes to Organization of the Coccosphere in Coccolithophores, Front. Mar. Sci., 5, 00306, https://doi.org/10.3389/fmars.2018.00306, 2018.
Walker, J., Marzec, B., Lee, R., Vodrazkova, K., Day, S., Tang, C., Rickaby, R., and Nudelman, F.: Polymorph Selectivity of Coccolith-Associated Polysaccharides from Gephyrocapsa Oceanica on Calcium Carbonate Formation In Vitro, Adv. Funct. Mater., 29, 1807168, https://doi.org/10.1002/adfm.201807168, 2019.
Watkins, J. and Devriendt, L.: A Combined Model for Kinetic Clumped Isotope Effects in the CaCO3-DIC-H2O System, Geochem. Geophy. Geosy., 23, e2021GC010200, https://doi.org/10.1029/2021GC010200, 2022.
Watkins, J. and Hunt, J.: A process-based model for non-equilibrium clumped isotope effects in carbonates, Earth Planet. Sc. Lett., 432, 152–165, https://doi.org/10.1016/j.epsl.2015.09.042, 2015.
Watkins, J., Nielsen, L., Ryerson, F., and DePaolo, D.: The influence of kinetics on the oxygen isotope composition of calcium carbonate, Earth Planet. Sc. Lett., 375, 349–360, https://doi.org/10.1016/j.epsl.2013.05.054, 2013.
Watkins, J., Hunt, J., Ryerson, F., and DePaolo, D.: The influence of temperature, pH, and growth rate on the δ18O composition of inorganically precipitated calcite, Earth Planet. Sc. Lett., 404, 332–343, https://doi.org/10.1016/j.epsl.2014.07.036, 2014.
Williamson, J.: Least-squares fitting of a straight line, Can. J. Phys., 18, 1845–1847, https://doi.org/10.1139/p68-523, 1968.
York, D., Evensen, N., Martìnez, M., and De Basabe Delgado, J.: Unified equations for the slope, intercept, and standard errors of the best straight line, Am. J. Phys., 72, 367–375, https://doi.org/10.1119/1.1632486, 2004.
Zeebe, R. and Wolf-Gladrow, D.: CO2 in seawater: equilibrium, kinetics, isotopes, Elsevier Oceanography Series, Vol. 65, Gulf Professional Publishing, ISBN 0-444-50579-2, 2001.
Zhang, H., Blanco-Ameijeiras, S., Hopkinson, B., Bernasconi, S., Mejia, L., Liu, C., and Stoll, H.: An isotope label method for empirical detection of carbonic anhydrase in the calcification pathway of the coccolithophore Emiliania huxleyi, Geochim. Cosmochim. Ac., 292, 78–93, https://doi.org/10.1016/j.gca.2020.09.008, 2021.
Zhang, H., Torres-Romero, I., Anjewierden, P., Jaggi, M., and Stoll, H.: The DIC carbon isotope evolutions during CO2 bubbling: Implications for ocean acidification laboratory culture, Front. Mar. Sci., 9, 1045634, https://doi.org/10.3389/fmars.2022.1045634, 2022.
Ziveri, P., Stoll, H., Probert, I., Klaas, C., Geisen, M., Ganssen, G., and Young, J.: Stable isotope “vital effects” in coccolith calcite, Earth Planet Sc. Lett., 210, 137–149, https://doi.org/10.1016/S0012-821X(03)00101-8, 2003.
Ziveri, P., de Bernardi, B., Baumann, K., Stoll, H., and Mortyn, P.: Sinking of coccolith carbonate and potential contribution to organic carbon ballasting in the deep ocean, Deep-Sea Res. Pt. II, 54, 659–675, https://doi.org/10.1016/j.dsr2.2007.01.006, 2007.
Ziveri, P., Thoms, S., Probert, I., Geisen, M., and Langer, G.: A universal carbonate ion effect on stable oxygen isotope ratios in unicellular planktonic calcifying organisms, Biogeosciences, 9, 1025–1032, https://doi.org/10.5194/bg-9-1025-2012, 2012.
Short summary
Coccoliths are abundant in sediments across the world’s oceans, yet it is difficult to apply traditional carbon or oxygen isotope methodologies for temperature reconstructions. We show that our coccolith clumped isotope temperature calibration with well-constrained temperatures systematically differs from inorganic carbonate calibrations. We suggest the use of our well-constrained calibration for future coccolith carbonate temperature reconstructions.
Coccoliths are abundant in sediments across the world’s oceans, yet it is difficult to apply...