Rare Earth Elements in early-diagenetic foraminifer 'coatings': Pore-water controls and potential palaeoceanographic applications

Rare Earth Element (REE) distributions in the ocean bear the fingerprints of several key environmental processes, including vertical particle/organic carbon fluxes, water column/pore-water oxygenation and ocean transports. The use of ‘fossil’ REE analyses in the service of palaeoceanography as redox, water transport or nutrient cycling ‘proxies’ has long been a tantalizing possibility. Here we demonstrate the application of a novel laser-ablation microanalysis approach for the rapid and accurate measurement of the REE composition of early diagenetic ‘coatings’ on fossil foraminifera. By applying this new method to a range of core-top and multi-core samples, we show that ‘authigenic’ REE enrichments on planktonic foraminifer surfaces (REEfs) reflect a primary seawater signature that becomes overprinted during sediment burial due to early diagenetic processes that control the flux of REEs to pore-fluids. Thus ‘light’ REEs (LREEs), and eventually ‘middle’ REEs (MREEs) are generally enriched in foraminifer 'coatings' relative to seawater, while Ce-anomalies (Ce/Ce*) recorded in surface sediments are typically more positive than local seawater values and are further ‘eroded’ during burial with the onset of anoxic conditions in the sediment. Similar patterns have previously been observed in pore-fluid measurements. Indeed, we show that Mn and Fe concentrations measured in foraminifer ‘coatings’ track the availability of these elements in pore-water, indicating that they are not associated with a secondary oxide phase. We propose that these elements, along with REEs are instead adsorbed directly from pore-fluids. In contrast, U in authigenic coatings tracks the removal of this element from solution under sub-oxic conditions, supporting the use of U/Ca in foraminifer coatings as a redox proxy. Although our results confirm a significant early diagenetic influence on REEfs, we also demonstrate the potential utility of ‘Ce-enrichment’ relative to expected seawater values as a palaeo-oxygenation proxy. We support this proposal with down-core measurements of U/Ca and Ce-enrichment spanning the last deglaciation in the sub-Antarctic Atlantic, as well as a global array of LGM measurements, which are found to co-vary with parallel estimates of radiocarbon ventilation age, consistent with a widespread drop in oxygen suggesting an increase in the efficiency of the biological pump. Our results suggest that laser-ablation REEfs measurements may hold some promise for palaeoceanographic reconstruction, in particular through a shift in emphasis away from the reconstruction of primary seawater signals to the analysis of diagenetic impacts that are sensitive to changing hydrographic conditions