Rare earth element and neodymium isotope tracing of sedimentary rock weathering

Chemical weathering plays an important role in sequestering atmospheric CO2, but its potential influence on global climate over geological timescales remains debated. To some extent, this uncertainty arises from the difficulty in separating the respective contribution of sedimentary and crystalline silicate rocks to past weathering rates in the geological record; two types of rocks having presumably different impact on the long-term carbon cycle. In this study, we investigate the use of rare earth element (REE) and neodymium isotopes (epsilon(Nd)) in leached iron oxide fractions of river sediments for tracing the origin of weathered rocks on continents. A new index, called `concavity index' (CI), is defined for measuring the degree of mid-REE enrichment in geological samples, which enables the determination of the source of iron oxides in sediments, such as seawater-derived Feoxyhydroxide phases, ancient marine Fe oxides derived from the erosion of sedimentary rocks, and recent secondary oxides formed in soils via alteration of crystalline silicate rocks or pyrite oxidation. Using this index, we demonstrate that the epsilon(Nd) difference between paired Fe-oxide and detrital fractions in river sediments (defined here as AeNd Feox-Det) directly reflects the relative contribution of sedimentary versus crystalline silicate rocks during weathering. While rivers draining old cratons and volcanic provinces display near-zero Delta epsilon(Nd) (Feox-Det)) values indicative of dominant silicate weathering (0.5 +/- 1.1; n = 30), multi-lithological catchments hosting sedimentary formations yield systematically higher values (2.7 +/- 1.2; n = 44), showing that sedimentary rock weathering can be traced by the occurrence of riverine Fe oxides having more radiogenic Nd isotope signatures compared to detrital fractions. This assumption is reinforced by the evidence that calculated Delta epsilon(Nd) (Feox-Det) values agree well with previous estimates for carbonate and silicate weathering rates in large river basins. Examining the influence of climate and tectonics on measured Nd isotopic compositions, we find that Delta epsilon(Nd) (Feox-Det) is strongly dependent on temperature in lowlands, following an Arrhenius-like relationship that reflects enhanced alteration of silicate rocks and formation of secondary Fe oxides in warmer climates. In contrast, in high-elevation catchments, Delta epsilon(Nd) (Feox-Det) defines striking correlation with maximum basin elevation, which we also interpret as reflecting the intensification of silicate weathering and associated Fe oxide formation as elevation decreases, due to the combined effects of thicker soils and warmer temperature. Overall, our new findings are consistent with previous assertions that the alteration of sedimentary rocks prevails in high-elevation environments, while silicate weathering dominates in floodplains. This novel approach combining REE and Nd isotopes opens new perspectives for disentangling the weathering signals of sedimentary and crystalline silicate rocks in the geologic record, which could be used in future studies to reassess the causal relationships between mountain uplift, erosion and climate throughout Earth's history.