Zinc isotope fractionation during the sorption of Zn to minerals and organic matter in sediment cores affected by anthropogenic pollution

Zinc stable isotopes (δ66Zn) serve as a widely fingerprinting tool for detecting anthropogenic Zn contamination. However, there is a limited understanding of δ66Zn behavior during the sorption of Zn to minerals and organic matter. In this study, we have determined the δ66Zn values in specific fractions to investigate their effectiveness in tracing anthropogenic Zn. The revised Community Bureau of Reference (BCR) extraction procedure was applied to a coastal marine core from Osaka Bay and from a lacustrine core from Lake Biwa, both with a history of anthropogenic metal pollution. The δ66Zn values varied from −0.14 ‰ to +1.00 ‰ across the four to five chemical fractions with up to 0.9 ‰ variation within a single horizon. The highest δ66Zn values in the acid-soluble fraction (up to +1.00 ‰) could be explained by the preferential sorption of 66Zn to carbonates and/or the preferential incorporation of 66Zn into calcite. The complex isotopic fractionation during the sorption of Zn to and co-precipitation with Fe–Mn oxyhydroxides likely resulted in an unclear pattern of the δ66Zn values of the reducible fraction. Low δ66Zn values in the oxidizable fraction (Osaka Bay) agree with the 64Zn enrichment in phytoplankton. Higher δ66Zn values of the reducible and oxidizable fractions of the Lake Biwa core indicate that environmental conditions (e.g. ionic strength) and for instance different phytoplankton species or dissolved and suspended particulate matter input drive the Zn isotope fractionation depending on the system (marine vs. lacustrine). The δ66Zn values of the acid-soluble fraction (Osaka Bay and Lake Biwa), of the reducible fraction (only Lake Biwa) and of oxidizable fraction (only Osaka Bay) better reflected the temporal changes in the Zn concentration than the bulk sediment, indicating that these fractions could be a sensitive fingerprinting tool for anthropogenic Zn contamination. •δ66Zn values were analyzed in fractions extracted sequentially from two polluted sediment cores.•Carbonates can explain the highest (up to +1.00 ‰) values in the acid-soluble fraction.•Unclear δ66Zn pattern of the reducible fraction due to different fractionation mechanisms.•Incorporation of 64Zn into phytoplankton can explain the lowest δ66Zn values (down to −0.14 ‰).•δ66Zn values of the acid-soluble fraction best reflected the temporal change in Zn concentration.