Zinc and cadmium stable isotopes in the geological record: A case study from the post-snowball Earth Nuccaleena cap dolostone
Abstract Zinc and cadmium are important biologically cycled nutrients in the modern ocean. Recent analytical advances and sampling efforts such as GEOTRACES have led to measurements of the global distribution of Zn and Cd and their stable isotope ratios (δ66Zn and δ114Cd), providing an understanding of how biological processes cycle these elements and their isotopes in the modern ocean. This opens the door to better application of δ66Zn and δ114Cd as tracers of biogeochemical processes archived in the geological record. Here we present new measurements of [Cd] and δ114Cd on samples from the Nuccaleena cap dolostone in South Australia, which was deposited during deglaciation of the ca. 635 Ma old Marinoan snowball Earth. Our new data are combined with previously measured δ66Zn data from the same samples. The combined record of δ114Cd and δ66Zn is used to explore various hypotheses about the sources and sinks of Cd and Zn in the post-Marinoan ocean. Key features of this record are that [Zn] and [Cd] remain relatively similar throughout, that δ66Zn and δ114Cd change at the same stratigraphic level and in the same direction, and that δ66Zn changes are about four times larger than δ114Cd changes even though both quantities reflect a similar fractional mass difference. We suggest that both Zn and Cd concentration and isotopic data are consistent with a change in the sink by which Zn and Cd are removed from the oceans. We propose that no isotope fractionation is expressed during removal of Zn and Cd as sulfides, while Zn and Cd removed with biological material are about 0.6‰ and 0.2‰ lighter than deep ocean δ66Zn and δ114Cd, respectively. Many previous studies attribute the burial of isotopically light biological Zn to preferential assimilation of isotopically lighter Zn by phytoplankton. In contrast, we propose that lighter biological δ66Zn occurs mostly because isotopically heavy Zn was scavenged by organic matter, which causes dissolved δ66Zn in the surface ocean to be lighter than deep ocean δ66Zn. The organic matter originated from primary producers that thrived in the surface ocean during deglaciation. For Cd, whose isotope cycling in the modern ocean is dominated by preferential assimilation of isotopically lighter Cd by phytoplankton, much less biological fractionation is expressed. The combined analyses of δ66Zn and δ114Cd provide insight into the biogeochemical processes which occurred after the Marinoan snowball Earth glaciation, and may be a useful new tool to explore the history of life on Earth in other geological records as well.