Biogeochemical cycling of Cd, Mn, and Ce in the Eastern Tropical North Pacific oxygen-deficient zone

Oxygen-deficient zones (ODZs) play an important role in the distribution and cycling of trace metals in the ocean, as important sources of metals including Fe and Mn, and also as possible sinks of chalcophile elements such as Cd. The Eastern Tropical North Pacific (ETNP) ODZ is one of the three largest ODZs worldwide. Here, we present results from two sectional surveys through the ETNP ODZ conducted in 2018, providing high-resolution concentrations of several metals, along with complimentary measurements of nutrients and iodine speciation. We show that samples obtained from the ship's regular rosette are clean for Cd, Mn, Ni, and light rare earth elements, while uncontaminated Fe, Zn, Cu, and Pb samples cannot be obtained without a special trace-metal clean sampling system. Our results did not show evidence of Cd sulfide precipitation, even within the most oxygen-depleted water mass. High Mn and Ce concentrations and high Ce anomalies were observed in low-oxygen seawater. These maxima were most pronounced in the upper water column below the oxycline, coincident with the secondary nitrite maxima and the lowest oxygen concentrations, in what is generally considered the most microbially active part of the water column. High Mn and Ce features were also coincident with maxima in excess iodine, a tracer of shelf sediment sources. Mn and Ce maxima were most prominent within the 13 degrees C water mass, spanning a density horizon that enhances isopycnal transport from the shelf sediments, resulting in transport of Mn and Ce at least 2500 km offshore.