Climate influence on zinc isotope variations in a loess–paleosol sequence of the Chinese Loess Plateau

Abstract

Zinc (Zn) is an essential micronutrient, and its isotopes are increasingly applied to understand trace metal biogeochemical cycling. Atmospheric deposition from anthropogenic or natural origins can perturbate the nutrient supply globally. However, our understanding on Zn isotope variations in natural mineral dust and during dust–climate interaction is still rare. This study presents Zn isotope data and leaching experiments with ammonium acetate buffering solution (pH = 5) on a loess–paleosol profile (S0–L3) from the Yimaguan section in the central Chinese Loess Plateau. The loess–paleosol sequence records the contributions from Asian mineral dust accumulation and chemical weathering, and the response to glacial–interglacial climate changes. Bulk loess–paleosol samples display limited Zn/Al (3.5 × 10-4 – 4.5 × 10-4) and δ66Zn variations (0.17–0.30‰). The mean δ66Zn of paleosol (0.19 ± 0.01‰, 2SD/√n, n = 11) is slightly lower than that of loess (0.24 ± 0.01‰, 2SD/√n, n = 13). Correlations with magnetic susceptibility and grain size distribution suggest that bulk δ66Zn variations between loess and paleosol are not sensitive to glacial–interglacial source fluctuations or wind sorting, but could result from loess pedogenesis.The leachable Zn fractions have high δ66Zn values (0.80–1.29‰) and display good positive correlations with Ca, Sr, Mg, Fe and Mn (r > 0.7), suggesting that carbonates are enriched in heavy Zn isotopes. Although Zn contents in carbonates are low (<3%) and dissolution of carbonates alone cannot explain the bulk Zn/Al variations (∼7% of Zn loss), significant carbonate weathering and biotic activities during loess pedogenesis could modify soil conditions (pH) and provide dissolved bicarbonate ions and organic ligands, which may facilitate the transport of heavy Zn isotopes by soil liquids. Conversely, the bulk δ66Zn of loess developed during glacial times were not modified by the low degree of chemical weathering, and thus the mean value of 0.24‰ for loess can be regarded as the average composition of the upper continental crust.