Rare earth element geochemistry of reef carbonates in the South China Sea since the Miocene: Insights into paleoclimatic significance

Seawater chemistry critically affects the functioning of ocean ecosystems. However, the evolution of the seawater chemistry in the South China Sea (SCS) since the Miocene is not fully resolved, and its links to tectonic and climate changes remain unclear. In-situ, shallow marine carbonates can provide insights into long-term changes in seawater chemistry and associated environmental processes. In this study, we conducted the rare earth element (REE) analysis of the NK-1 core in the southern SCS since the Miocene. The results reveal poor relationships between siliciclastic/diagenetic indicators (mineralogical, isotopic, and elemental data) and REE proxies, which demonstrate that the REE compositions are insensitive to non-carbonate contaminations and diagenesis. The results exhibit seawater-like REE patterns with LREE depletion, positive La anomaly, superchondritic Y/Ho ratio, and negative Ce anomaly, which demonstrate that this core has preserved a signal of the primary seawater REE composition. The Y/Ho ratios range from 45 to 80 and La anomalies range from 1.0 to 2.3 during ∼23–13 Ma, and they then decrease after ∼13 Ma, with the Y/Ho ratios ranging from 30 to 52 and La anomalies ranging from 0.6 to 1.5. Considering that seawater REE components are mainly sourced from terrigenous sources which exhibit lower La anomalies and Y/Ho ratios, our results indicate an enhanced terrigenous input since ∼13 Ma. We consider that the climate cooling and aridity since ∼13 Ma might be responsible for the phenomenon.