Calcium isotopes tracing secondary mineral formation in the high-relief Yalong River Basin, Southeast Tibetan Plateau.

Calcium is a critical element in the global carbon cycle due to its role in carbon sequestration via silicate weathering and carbonate formation. Here we apply calcium (δ44/40Ca) and strontium (87Sr/86Sr) isotopes to explore such chemical weathering processes in a river system draining a diverse range of geologic and climatic environments: the Yalong River, China, and its tributaries. This river originates on the Tibetan Plateau and represents one of the upper reaches of the Changjiang River, China. The Ca isotopic composition of the dissolved load of the Yalong River ranges from 0.60‰ to 1.02‰ (relative to the NIST standard SRM 915a). Higher δ44/40Ca values were found in the plateau and lowland rivers, with lower values in the mountainous rivers. Correlations between riverine dissolved δ44/40Ca values, Sr/Ca ratios, and calcite saturation index indicate that the precipitation of secondary carbonates governs the Ca isotopic composition and carbon transformation in most of this river system. However, such correlations are not seen in the lowland tributaries, where the relationship between δ44/40Ca and lithium (Li) isotopes instead suggests a control by topography and climate, via secondary clay mineral formation. Specifically, heavy rainfall in the lowland regions lowers the pH of the soil solution, which inhibits the precipitation of secondary carbonates. In addition, the flat terrain and thick soils increase the time for water-rock interaction, which favours the formation of secondary clay minerals that preferentially incorporate the lighter Ca isotopes. Overall, this study highlights the potential of stable Ca isotopes, when used in combination with other isotope systems (e.g. Sr and Li isotopes), to quantify secondary mineral formation processes in large river basins.