A bulk extraction method to determine the stable isotope ratios of iron,nickel,copper,zinc,and cadmium in seawater using multi-collector inductively coupled plasma mass spectrometry

The oceanic trace metals iron(Fe),nickel(Ni),copper(Cu),zinc(Zn),and cadmium(Cd)are crucial to marine phytoplankton growth and global carbon cycle,and the analysis of their stable isotopes can provide valuable insights into their biogeochemical cycles within the ocean.However,the simultaneous isotopic analysis of multiple elements present in seawater is challenging because of their low concentrations,limited volumes of the test samples,and high salt matrix.In this study,we present the novel method developed for the simultaneous analysis of five isotope systems by 1 L seawater sample.In the developed method,the NOBIAS Chelate-PA1 resin was used to extract metals from seawater,the AG MP-1M anion-exchange resin to purify Cu,Fe,Zn,Cd,and the NOBIAS Chelate-PA1 resin to further extract Ni from the matrix elements.Finally,a multi-collector inductively coupled plasma mass spectroscope(MC-ICPMS)was employed for the isotopic measurements using a doublespike technique or sample-standard bracketing combined with internal normalization.This method exhibited low total procedural blanks(0.04 pg,0.04 pg,0.21 pg,0.15 pg,and 3 pg for Ni,Cu,Fe,Zn,and Cd,respectively)and high extraction efficiencies(100.5%±0.3%,100.2%±0.5%,97.8%±1.4%,99.9%±0.8%,and 100.1%±0.2%for Ni,Cu,Fe,Zn,and Cd,respectively).The external errors and external precisions of this method could be considered negligible.The proposed method was further tested on the seawater samples obtained from the whole vertical profile of a water column during the Chinese GEOTRACES GP09 cruise in the Northwest Pacific,and the results showed good agreement with previous related data.This innovative method will contribute to the advancement of isotope research and enhance our understanding of the marine biogeochemical cycling of Fe,Ni,Cu,Zn,and Cd.