Anomalous biogeochemical behavior of cadmium in subantarctic surface waters: Mechanistic constraints from cadmium isotopes

Cadmium, a highly toxic metal, exhibits a nutrient-type profile in the oceans that is closely correlated to that of the major nutrients phosphate and nitrate. Despite its complexity, the relationship between cadmium and phosphate has been used to infer historic phosphate utilization and biological controls on oceanic CO2 concentrations. Cadmium isotopes offer the potential to constrain the mechanisms controlling cadmium cycling in the oceans, reducing uncertainty associated with the cadmium paleonutrient proxy. Using techniques in double spiking and MC-ICPMS, we report seasonal Cd isotopic and concentration data along with major nutrients and other essential trace metal (Fe, Zn, and Co) concentrations from subantarctic surface waters. We show, for the first time, a 50-fold seasonal decrease in dissolved cadmium concentrations in subantarctic waters that is due to biological uptake. However, this drawdown in Cd is decoupled from phosphate and shows no coincident shift in cadmium isotopic composition. These data, along with the preferential removal of Cd from surface waters relative to Zn, imply that cadmium is supply-limited to phytoplankton and may have a more significant biological role in these low Zn subantarctic surface waters than in regions with higher Zn concentrations.