A new method for precise determination of iron, zinc and cadmium stable isotope ratios in seawater by double-spike mass spectrometry.

The study of Fe, Zn and Cd stable isotopes (δ(56)Fe, δ(66)Zn and δ(114)Cd) in seawater is a new field, which promises to elucidate the marine cycling of these bioactive trace metals. However, the analytical challenges posed by the low concentration of these metals in seawater has meant that previous studies have typically required large sample volumes, highly limiting data collection in the oceans. Here, we present the first simultaneous method for the determination of these three isotope systems in seawater, using Nobias PA-1 chelating resin to extract metals from seawater, purification by anion exchange chromatography, and analysis by double spike MC-ICPMS. This method is designed for use on only a single litre of seawater and has blanks of 0.3, 0.06 and <0.03 ng for Fe, Zn and Cd respectively, representing a 1-20 fold reduction in sample size and a 4-130 decrease in blank compared to previously reported methods. The procedure yields data with high precision for all three elements (typically 0.02-0.2‰; 1σ internal precision), allowing us to distinguish natural variability in the oceans, which spans 1-3‰ for all three isotope systems. Simultaneous extraction and purification of three metals makes this method ideal for high-resolution, large-scale endeavours such as the GEOTRACES program.