Riverine Li isotope fractionation in the Amazon River basin controlled by the weathering regimes

We report Li isotope composition (δ7Li) of river-borne dissolved and solid material in the largest River system on Earth, the Amazon River basin, to characterize Li isotope fractionation at a continental scale. The δ7Li in the dissolved load (+1.2‰ to +32‰) is fractionated toward heavy values compared to the inferred bedrock (−1‰ to 5‰) and the suspended sediments (−6.8‰ to −0.5‰) as a result of the preferential incorporation of 6Li into secondary minerals during weathering. Despite having very contrasted weathering and erosion regimes, both Andean headwaters and lowland rivers share similar ranges of dissolved δ7Li (+1.2‰ to +18‰). Correlations between dissolved δ7Li and Li/Na and Li/Mg ratios suggest that the proportion of Li incorporated in secondary minerals during weathering act as the main control on the δ7Lidiss across the entire Amazon basin. A “batch” steady-state fractionation model for Andean and lowland rivers satisfactorily reproduces these variations, with a fractionation factor between weathering products and dissolved load (αsec-dis) of 0.983±0.002. Two types of supply-limited weathering regimes can be identified for the lowlands: “clearwaters” with dominant incorporation of Li in secondary minerals, and “black waters” (e.g., Rio Negro) where dissolution of secondary minerals enhanced by organic matter produces low δ7Li. Apart from the black waters, the δ7Li of Andean and lowland rivers is negatively correlated to the denudation rates with the lowest δ7Li corresponding to the rivers having the highest denudation rates. In contrast, the main tributaries draining both the Andes and the lowlands have higher δ7Li compared to other rivers. We propose that part of the dissolved Li derived from weathering in the Andes is re-incorporated in sediments during transfer of water and sediments in floodplains and that this results in an increase of the dissolved δ7Li along the course of these rivers. Unlike other rivers, the dissolved δ7Li in the main tributaries is best described by a Rayleigh fractionation model with a fractionation factor αsec-dis of 0.991. Altogether, the control imposed by residence time in the weathering zone and floodplain processes results in (i) a non-linear correlation between dissolved δ7Li and the weathering intensity (defined as W/D) and (ii) a positive relationship between the dissolved Li flux and the denudation rate. These results have important implications for the understanding of past ocean δ7Li and its use as a paleo