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Abstract. Laboratory experiments showed that the isotopic fractionation of δ13C and of δ18O during calcite formation of planktic foraminifera are species-specific functions of ambient CO32- concentration. This effect became known as the carbonate ion effect (CIE), whose role for the interpretation of marine sediment data will be investigated here in an in-depth analysis of the 13C cycle. For this investigation, we constructed new 160 kyr long mono-specific stacks of changes in both δ13C and δ18O from either the planktic foraminifera Globigerinoides ruber (rub) or Trilobatus sacculifer (sac) from 112 and 40 marine records, respectively, from the wider tropics (latitudes below 38°). Both mono-specific time series Δ(δ13Crub) and Δ(δ13Csac) are very similar to each other, and a linear regression through a scatter plot of both data sets has a slope of ∼ 0.99 – although the laboratory-based CIE for both species differs by a factor of nearly 2, implying that they should record distinctly different changes in δ13C, if we accept that the carbonate ion concentration changes on glacial–interglacial timescales. For a deeper understanding of the 13C cycle, we use the Solid Earth version of the Box model of the Isotopic Carbon cYCLE (BICYLE-SE) to calculate how surface-ocean CO32- should have varied over time in order to be able to calculate the potential offsets which would by caused by the CIE quantified in culture experiments. Our simulations are forced with atmospheric reconstructions of CO2 and δ13CO2 derived from ice cores to obtain a carbon cycle which should at least at the surface ocean be as close as possible to expected conditions and which in the deep ocean largely agrees with the carbon isotope ratio of dissolved inorganic carbon (DIC), δ13CDIC, as reconstructed from benthic foraminifera. We find that both Δ(δ13Crub) and Δ(δ13Csac) agree better with changes in simulated δ13CDIC when ignoring the CIE than those time series which were corrected for the CIE. The combination of data- and model-based evidence for the lack of a role for the CIE in Δ(δ13Crub) and Δ(δ13Csac) suggests that the CIE as measured in laboratory experiments is not directly transferable to the interpretation of marine sediment records. The much smaller CIE-to-glacial–interglacial-signal ratio in foraminifera δ18O, when compared to δ13C, prevents us from drawing robust conclusions on the role of the CIE in δ18O as recorded in the hard shells of both species. However, theories propose that the CIE in both δ13C and δ18O depends on the pH in the surrounding water, suggesting that the CIE should be detectable in neither or both of the isotopes. Whether this lack of role of the CIE in the interpretation of planktic paleo-data is a general feature or is restricted to the two species investigated here needs to be checked with further data from other planktic foraminiferal species.
Köhler et al. (Thu,) studied this question.