The isotopic composition of sedimentary organic zinc and implications for the global Zn isotope mass balance

Zinc (Zn) is a bioessential element whose cycling in the marine environment is closely linked to the biological pump. As a vital micronutrient, Zn is depleted in marine surface waters and enriched in deep waters. This has given rise to the longstanding hope that Zn could serve as a robust paleoproductivity proxy. There has been a recent focus on how Zn isotope signatures can be used to track the evolution of the biological pump. However, the factors controlling variations in the sedimentary Zn isotope composition of core-top sediments are debated and these values are influenced by changes in the relative contributions of biological uptake and scavenging processes and by mineral fractionations. In order to provide a new perspective on the Zn isotopic signature of marine core-top sediments and their potential for tracing ocean biogeochemical processes, we developed a sample preparation procedure to extract organically bound Zn (excluding inorganic Zn) without a significant isotope fractionation. We tested five potential organic solvents and found that the isopropanol extraction procedure provided a reproducible and robust result that yielded the highest recovery rate of organically bound Zn without a significant associated isotopic fractionation and appeared to exclude common mineral bound forms of Zn. This extraction procedure was used to analyze the Zn concentrations and isotopic compositions (δ66Zn) of core-top sediment samples from Long Island Sound and the Peruvian continental margin. Our results suggest that the δ66Zn value of organic Zn increases with water depth, thus providing additional support for the finding that burial of isotopically light Zn occurs predominantly in shallow high-productivity sediments. However, we also found that the δ66Zn values of the estimated authigenic Zn component are consistently lighter than those of the organic Zn fraction, consistent with diagenetic (sediment pile) scavenging of organic derived Zn in sulfides imparting an isotope fractionation.