Abstract

<p>The intensification of Northern Hemisphere glaciation (iNHG) at 2.73 Ma is associated in the subarctic Pacific Ocean with an abrupt drop in opal mass accumulation rates and the development of a halocline stratification. Uncertainty, however, remains around the extent to which these changes: 1) altered carbon dynamics in the water column; and 2) contributed to a reduction in atmospheric <em>p</em>CO<sub>2</sub> over this period. These issues can be resolved by applying the boron isotope (δ<sup>11</sup>B) proxy to quantify past changes in the pH and <em>p</em>CO<sub>2</sub> of ambient seawater. By analysing δ<sup>11</sup>B in diatom frustules, we document a surface water increase of 0.3 to 0.5 pH units in the subarctic Pacific Ocean over the iNHG. This confirms that the development of the halocline at 2.73 Ma both reorganised the vertical water column structure and limited CO<sub>2</sub> outgassing from the ocean interior. In conjunction with other external and internal processes, including changes in the Southern Ocean, these events would have contributed to a lowering of atmospheric <em>p</em>CO<sub>2</sub> and the long-term expansion of ice sheets across the Northern Hemisphere.</p> <p>This research demonstrates the potential for diatom δ<sup>11</sup>B measurements to be used to reconstruct changes in <em>p</em>CO<sub>2</sub>, particularly in high-latitude settings where diatom frustules are readily preserved and dominate the sediment record. Such analyses have the potential to complement δ<sup>11</sup>B measurements in foraminifera and so provide further insights into the carbon dynamics of the “warm Pliocene” and other periods of interest.</p>

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