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I understand why foram shells contain more $^{18}\text{O}$ when there are ice sheets present, since $^{16}\text{O}$ evaporates more readily and gets trapped in the ice, increasing the relative abundance of $^{18}\text{O}$ in seawater. However, in the absence of ice sheets: What is the reason for there being more $^{18}\text{O}$ in the foram shells in colder climates? Since I assume the evaporated $^{16}\text{O}$ would just get returned to the sea by rain and rivers if it's not being trapped in ice.

PS: This is an adaptation of a question asked in the private discussion board of a first year university course on Earth Sciences, that I'm copying here so a wider community can benefit from it and the corresponding answer. As suggested by the moderators, I'll donate any reputation received from this question in the form of a bounty awarded to exceptional answers (in particular by new or low-rep users).

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That is because the chemical reactivity of $^{18}\text{O}$ is slightly higher than that of $^{16}\text{O}$. For that reason, the biochemical reactions that produce calcium carbonate in foraminifera prefer $^{18}\text{O}$ over $^{16}\text{O}$.

However, the temperature dependence arise from the fact that the difference in reactivity is smaller when temperature increase. Therefore, in warmer temperatures the $\delta ^{18}\text{O}$ will be more similar to seawater (no preference for any isotope), but at colder temperatures the chemical preference for $^{18}\text{O}$ will be stronger and, therefore, the $\delta ^{18}\text{O}$ will increase.

This correlation with temperature is also known as the "paleotemperature equation", but as it is an empiric equation there are many slightly different versions, however all of them are pretty consistent. Several ones are summarized in figure 5 of the paper Oxygen isotopes in foraminifera: Overview and historical review (Pearson 2012) copied below, showing how the excess of $\delta ^{18}\text{O}$ in shells ($\delta ^{18}\text{O}_{\text{cc}}$) relative to the $\delta ^{18}\text{O}$ in seawater ($\delta ^{18}\text{O}_{\text{sw}}$) correlates with water temperature.

enter image description here

The deeper reason that explain the chemical preference for $^{18}\text{O}$ come from a process named "equilibrium isotope fractionation", associated to the vibrational characteristics of the light and heavy isotopes related to covalent atomic bonding. As explained by Gussone et. al (2003):

"Equilibrium fractionation occurs as a consequence of covalent atomic bonding. During molecule formation the incorporation of heavier isotopes is preferred because covalent atomic bonds formed with heavier isotopes show larger bonding energies and, hence, are more stable than covalent bonds formed with lighter isotopes."

There is a competing effect called "kinetic isotope fractionation", that that leads to a correlation with temperature in the opposite direction (because heavier isotopes have slower diffusion times and are slower crossing membranes), but in the case of Oxygen isotopes, its effects is overcome by equilibrium fractionation.

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  • $\begingroup$ Great Answer! - Are there open datasets for these fractionation experiments where I can create regression models from? To see how good the fits really are? In the right figure only smoothed lines can be seen, I'd be interested in how large the residuals actually were , etc. (Maybe I should ask this on opendata.SE, later) $\endgroup$
    – knb
    Commented Nov 4, 2019 at 8:39

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