The evolution of lithium isotope signatures in fluids draining actively weathering hillslopes

The stable isotopes of lithium (Li) serve as a robust proxy of silicate weathering. The fate and transport of these isotopes in the dissolved load of major rivers have been characterized to infer changes in both contemporary weathering regimes and paleo-conditions. In this contribution, we deconvolve this integrated signal into the individual processes that fractionate Li at the inception of silicate weathering by directly measuring Li isotope ratios of waters (δ⁷Li) transiting through a rapidly eroding first-order hillslope. We use these data to develop a multicomponent reactive transport framework, which shows that net dissolution of weathered material generates light δ⁷Li signatures (as low as −9.2‰) in the shallow portion of the vadose zone. An increase in δ⁷Li deeper into the vadose zone (as much as +18‰) reflects an increasing contribution of secondary mineral formation. Below the water table, congruent weathering occurs and imparts elevated cation concentrations and bedrock δ⁷Li. Silicate weathering continues within the saturated zone as groundwater travels downslope (δ⁷Li = +13 to + 24‰) to the stream. The stream signatures (δ⁷Li = +28 to +29‰) reflect the terminus of this network of silicate weathering reactions and the relative magnitude of each contributing process (e.g., transitions in secondary mineral formation, dissolution of weathered material). We show that fluid progressing through the weathering profile of this first-order hillslope is distinguished by a sequence of characteristic Li isotope signatures, which can be reproduced in a forward, process-based model framework. This model development offers an improved quantitative basis for the use of metal(loid) stable isotopes in disentangling catchment-scale chemical weathering fluxes.