A tandem Mg/Ca-clumped isotope approach for palaeotemperature estimation of past climate
Lead Research Organisation:
UNIVERSITY OF CAMBRIDGE
Department Name: Earth Sciences
Abstract
The estimation of the magnitude of global temperature change is central for predicting future climate. However, most numerical climate modeling studies have focused on the instrumental period, which covers only a relatively small amount of time (<100 years). To better understand future climate change and to test the robustness of these models, it is important to reconstruct past temperature changes throughout Earth history. This is not a trivial problem, however, because we must rely on proxies of temperature change that often yield ambiguous results.
Over the past decades several proxies of past ocean temperature have been developed including palaeoecological transfer functions, Mg/Ca, and biomarkers (Uk'37, TEX86). Among the newest advances in palaeothermometry is the application of "clumped isotopes" which is based on the abundance of 13C-18O bounds in carbonates. The advantage of this method is that the formation of 13C18O16O2 is temperature dependent but independent of the dissolved inorganic carbon and the d18O of seawater. Therefore, the simultaneous measurement of "clumped isotopes" and traditional oxygen isotopes provides a unique solution to the carbonate palaeotemperature equation by constraining both temperature and d18O of water. The Mg/Ca ratio of foraminiferal calcite has been similarly shown to be temperature dependent. Hence, paired measurements of Mg/Ca and oxygen isotopes from the same foraminiferal specimens permit reconstruction of the oxygen isotopes of the sea water.
The main aim of the proposal is to combine Mg/Ca and clumped isotope measurements of the same foraminiferal tests to produce independent estimates of temperature. By combining the Mg/Ca and clumped isotopes palaeotemperature equations, the expected relationship between Mg/Ca and clumped isotopes can be predicted. Adherence to the expected relationship in fossil foraminifera will provide confidence in the palaeotemperature estimates or, if they diverge from the expected relationship, will identify problems with either one or both proxies.
Initially, we will test the predicted relationship using modern foraminifera which cover a temperature range from approx. 6 to 28 degree to verify and calibrate the method. Next, we will test the application of the method during the last glacial period using a transect of well-dated sediment cores in the north Atlantic.
The magnitude of abrupt climate change events during the last deglacial is still under debate in the scientific community. For example, large discrepancies exist in estimates of tropical cooling inferred from marine (~2-4 degree) and terrestrial (~6-10 degree) archives during these extreme events. This discrepancy may be the result of seasonal bias of the temperature proxies. However, the temperature range is much larger than expected for average seasonal temperature differences in the tropics. This raises the question whether these discrepancies are real or caused by differences in the sensitivity or reliability of specific proxies. With tandem measurements of Mg/Ca and clumped isotopes it will be possible to determine the magnitude of temperature change and estimate its spatial extent during abrupt climate change events of the last glacial. Furthermore, the well-dated cores of the late quaternary provide an ideal test case for our tandem Mg/Ca-clumped isotope palaeothermometer whose successful development and application will permit to investigate many relevant open questions about earth's climate history.
Over the past decades several proxies of past ocean temperature have been developed including palaeoecological transfer functions, Mg/Ca, and biomarkers (Uk'37, TEX86). Among the newest advances in palaeothermometry is the application of "clumped isotopes" which is based on the abundance of 13C-18O bounds in carbonates. The advantage of this method is that the formation of 13C18O16O2 is temperature dependent but independent of the dissolved inorganic carbon and the d18O of seawater. Therefore, the simultaneous measurement of "clumped isotopes" and traditional oxygen isotopes provides a unique solution to the carbonate palaeotemperature equation by constraining both temperature and d18O of water. The Mg/Ca ratio of foraminiferal calcite has been similarly shown to be temperature dependent. Hence, paired measurements of Mg/Ca and oxygen isotopes from the same foraminiferal specimens permit reconstruction of the oxygen isotopes of the sea water.
The main aim of the proposal is to combine Mg/Ca and clumped isotope measurements of the same foraminiferal tests to produce independent estimates of temperature. By combining the Mg/Ca and clumped isotopes palaeotemperature equations, the expected relationship between Mg/Ca and clumped isotopes can be predicted. Adherence to the expected relationship in fossil foraminifera will provide confidence in the palaeotemperature estimates or, if they diverge from the expected relationship, will identify problems with either one or both proxies.
Initially, we will test the predicted relationship using modern foraminifera which cover a temperature range from approx. 6 to 28 degree to verify and calibrate the method. Next, we will test the application of the method during the last glacial period using a transect of well-dated sediment cores in the north Atlantic.
The magnitude of abrupt climate change events during the last deglacial is still under debate in the scientific community. For example, large discrepancies exist in estimates of tropical cooling inferred from marine (~2-4 degree) and terrestrial (~6-10 degree) archives during these extreme events. This discrepancy may be the result of seasonal bias of the temperature proxies. However, the temperature range is much larger than expected for average seasonal temperature differences in the tropics. This raises the question whether these discrepancies are real or caused by differences in the sensitivity or reliability of specific proxies. With tandem measurements of Mg/Ca and clumped isotopes it will be possible to determine the magnitude of temperature change and estimate its spatial extent during abrupt climate change events of the last glacial. Furthermore, the well-dated cores of the late quaternary provide an ideal test case for our tandem Mg/Ca-clumped isotope palaeothermometer whose successful development and application will permit to investigate many relevant open questions about earth's climate history.
Planned Impact
The primarily beneficiaries are members of the academic community who are interested in proxy development and Pleistocene climate change. Other beneficiaries are policy-makers and the wider public who are interested in climate history and rapid climate change events. Key scientific results will therefore be disseminated through public and academic talks, workshops, and conference papers. Two internships and two information days will provide students with an exposure to earth system science which might encourage them to consider a career in Earth Sciences.
Publications

Bernasconi SM
(2018)
Reducing Uncertainties in Carbonate Clumped Isotope Analysis Through Consistent Carbonate-Based Standardization.
in Geochemistry, geophysics, geosystems : G(3)

Bernasconi, Stefano M.
(2018)
Reducing Uncertainties in Carbonate Clumped Isotope Analysis Through Consistent Carbonate-Based Standardization

Breitenbach S
(2018)
Coupled Mg/Ca and clumped isotope analyses of foraminifera provide consistent water temperatures
in Geochimica et Cosmochimica Acta

Breitenbach, Sebastian F.M.
(2018)
Coupled Mg/Ca and clumped isotope analyses of foraminifera provide consistent water temperatures

Grauel A
(2016)
Quantitative estimates of tropical temperature change in lowland Central America during the last 42 ka
in Earth and Planetary Science Letters

Gázquez F
(2018)
Quantification of paleo-aquifer changes using clumped isotopes in subaqueous carbonate speleothems
in Chemical Geology

Petersen S
(2019)
Effects of Improved 17 O Correction on Interlaboratory Agreement in Clumped Isotope Calibrations, Estimates of Mineral-Specific Offsets, and Temperature Dependence of Acid Digestion Fractionation
in Geochemistry, Geophysics, Geosystems

Swart P
(2019)
Oxygen Isotopic Exchange Between CO 2 and Phosphoric Acid: Implications for the Measurement of Clumped Isotopes in Carbonates
in Geochemistry, Geophysics, Geosystems
Description | The reliable determination of past seawater temperature is fundamental to paleoclimate studies. We tested the robustness of two paleotemperature proxies by combining Mg/Ca and clumped isotopes (?47) on the same specimens of core top planktonic foraminifera. The strength of this approach is that Mg/Ca and ?47 are measured on the same specimens of foraminifera, thereby providing two independent estimates of temperature. This replication constitutes a rigorous test of individual methods with the advantage that the same approach can be applied to fossil specimens. Aliquots for Mg/Ca and clumped analyses are treated in the same manner following a modified cleaning procedure of foraminifera for trace element and isotopic analyses. We analysed eight species of planktonic foraminifera from core top samples over a wide range of temperatures from 2 to 29oC. We provide a new clumped isotope temperature calibration using subaqueous cave carbonates, which is consistent with recent studies. Tandem Mg/Ca-?47 results follow an exponential curve as predicted by temperature calibration equations. Observed deviations from the predicted Mg/Ca-?47 relationship are attributed to the effects of Fe-Mn oxide coatings, contamination, or dissolution of foraminifer tests. This coupled approach provides a high degree of confidence in temperature estimates when Mg/Ca and ?47 yield concordant results, and can be used to infer the past d18O of seawater (d18Osw) for paleoclimate studies. In addition, we have collaborated with the international clumped isotope community in the standardization and calibration of clumped isotope measurements. |
Exploitation Route | We developed a new tandem method for palaeotemperature reconstruction that will be adopted by other researchers in palaeoclimatology. In collaboration with other laboratories, we have significantly advanced the intra-laboratory calibration and standardisation of clumped isotope measurements and palaeothermometry. |
Sectors | Environment |
Description | EPSRC Core Equipment Bid for Isotope Ratio Mass Spectrometer (IRMS) |
Amount | £250,000 (GBP) |
Organisation | Engineering and Physical Sciences Research Council (EPSRC) |
Sector | Public |
Country | United Kingdom |
Start | 12/2019 |
End | 06/2021 |
Title | Discrete bin temperatures from carbonate clumped isotope measurements performed on middle Miocene planktic foraminifera from ODP Hole 189-1171C |
Description | This table includes temperatures calculated from carbonate clumped isotope measurements performed on middle Miocene planktic foraminifera from Ocean Drilling Program (ODP) Hole 189-1171C, South Tasman Rise.A complete set of individual measurement data, including sample labels, depth and raw mass spectrometer data, can be found on the EarthChem database (doi:10.26022/IEDA/111547). |
Type Of Material | Database/Collection of data |
Year Produced | 2020 |
Provided To Others? | Yes |
URL | https://doi.pangaea.de/10.1594/PANGAEA.919353 |
Title | Stable isotopes of Siphonodosaria lepidula of ODP Site 202-1242 |
Description | This data contains oxygen and carbon isotope measurments on the benthic foraminiferal species Siphonodosaria lepidula of ODP Site 202-1242. Isotopic measurements were carried out on 2 and 3 individuals of Siphonodosaria lepidula from the >400 µm fraction. Samples were measured using a GasBench II coupled to a Delta V mass spectrometer as described in Breitenbach and Bernasconi (2011). Foraminifera were placed in vials and reacted with 104% phosphoric acid at 70ºC. The instrument was calibrated with the internal standards MS2 (d13C = +2.13 ‰, d18O = -1.81 ‰) and ETH-4 (d13C = -10.19 ‰, d18O = -18.71 ‰) which are calibrated to the international reference materials NBS 19 (d13C = +1.95‰, d18O = -2.2‰) and NBS 18 (d13C = -5.01‰, d18O = -23.00‰; Bernasconi et al., 2018). Values are reported in the conventional delta notation with respect to VPDB. Long term reproducibility is better than 0.1‰ for both carbon and oxygen isotopes. Measures were carried out in the Geological Institute, ETH Zürich, Switzerland. |
Type Of Material | Database/Collection of data |
Year Produced | 2020 |
Provided To Others? | Yes |
URL | https://doi.pangaea.de/10.1594/PANGAEA.911963 |
Description | Clumped isotope community collaboration |
Organisation | ETH Zurich |
Country | Switzerland |
Sector | Academic/University |
PI Contribution | The clumped isotope community has undertaken a number of inter-laboratory calibrations to improve standardization and reporting of clumped isotope results. Cambridge has participated in these collaborations resulting in two important papers for the community (Bernasconi et al, 2018; Petersen et al., 2019). In addition, the Godwin Laboratory hosted a sabattical for Prof. Peter Swart who collaborated with the PI on the determination of clumped fractionation factors between carbonate and phosphric acid (Swart et al., 2019). |
Collaborator Contribution | Anaylzed samples and standards for international effort to standardization of clumped isotope measurements and temperature calibration. |
Impact | three publications: Bernasconi et al, 2018; Petersen et al., 2019; Swart et al., 2019 |
Start Year | 2018 |
Description | Clumped isotope community collaboration |
Organisation | University of Miami |
Country | United States |
Sector | Academic/University |
PI Contribution | The clumped isotope community has undertaken a number of inter-laboratory calibrations to improve standardization and reporting of clumped isotope results. Cambridge has participated in these collaborations resulting in two important papers for the community (Bernasconi et al, 2018; Petersen et al., 2019). In addition, the Godwin Laboratory hosted a sabattical for Prof. Peter Swart who collaborated with the PI on the determination of clumped fractionation factors between carbonate and phosphric acid (Swart et al., 2019). |
Collaborator Contribution | Anaylzed samples and standards for international effort to standardization of clumped isotope measurements and temperature calibration. |
Impact | three publications: Bernasconi et al, 2018; Petersen et al., 2019; Swart et al., 2019 |
Start Year | 2018 |
Description | Clumped isotope community collaboration |
Organisation | University of Michigan |
Country | United States |
Sector | Academic/University |
PI Contribution | The clumped isotope community has undertaken a number of inter-laboratory calibrations to improve standardization and reporting of clumped isotope results. Cambridge has participated in these collaborations resulting in two important papers for the community (Bernasconi et al, 2018; Petersen et al., 2019). In addition, the Godwin Laboratory hosted a sabattical for Prof. Peter Swart who collaborated with the PI on the determination of clumped fractionation factors between carbonate and phosphric acid (Swart et al., 2019). |
Collaborator Contribution | Anaylzed samples and standards for international effort to standardization of clumped isotope measurements and temperature calibration. |
Impact | three publications: Bernasconi et al, 2018; Petersen et al., 2019; Swart et al., 2019 |
Start Year | 2018 |