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Abstract Antecedent hydrological conditions are recorded through the evolution of dissolved lithium isotope signatures (Li) by juxtaposing two storm events in an upland watershed subject to a Mediterranean climate. Discharge and Li are negatively correlated in both events, but mean Li ratios and associated ranges of variation are distinct between them. We apply a previously developed reactive transport model (RTM) for the site to these event‐scale flow perturbations, but observed shifts in stream Li are not reproduced. To reconcile the stability of the subsurface solute weathering profile with our observations of dynamic stream Li signatures, we couple the RTM to a distribution of fluid transit times that evolve based on storm hydrographs. The approach guides appropriate flux‐weighting of fluid from the RTM over a range of flow path lengths, or equivalently fluid residence times. This flux‐weighted RTM approach accurately reproduces dynamic storm Li‐discharge patterns distinguished by the antecedent conditions of the watershed. 

Abstract Lithium isotope ratios (δ⁷Li) of rivers are increasingly serving as a diagnostic of the balance between chemical and physical weathering contributions to overall landscape denudation rates. Here, we show that intermediate weathering intensities and highly enriched stream δ⁷Li values typically associated with lowland floodplains can also describe small upland watersheds subject to cool, wet climates. This behavior is revealed by stream δ⁷Li between +22.4 and +23.5‰ within a Critical Zone observatory located in the Cévennes region of southern France, where dilute stream solute concentrations and significant atmospheric deposition otherwise mask evidence of incongruence. The water‐rock reaction pathways underlying this behavior are quantified through a multicomponent, isotope‐enabled reactive transport model. Using geochemical characterization of soil profiles, bedrock, and long‐term stream samples as constraints, we evolve the simulation from an initially unweathered granite to a steady state weathering profile which reflects the balance between (a) fluid infiltration and drainage and (b) bedrock uplift and soil erosion. Enriched stream δ⁷Li occurs because Li is strongly incorporated into actively precipitating secondary clay phases beyond what prior laboratory experiments have suggested. Chemical weathering incongruence is maintained despite relatively slow reaction rates and moderate clay accumulation due to a combination of two factors. First, reactive primary mineral phases persist across the weathering profile and effectively “shield” the secondary clays from resolubilization due to their greater solubility. Second, the clays accumulating in the near‐surface profile are relatively mature weathering byproducts. These factors promote characteristically low total dissolved solute export from the catchment despite significant input of exogenous dust. 

Abstract Silicon stable isotope ratios (³⁰Si) of over 150 stream water samples were measured during seven storm events in six small critical zone observatory (CZO) catchments spanning a wide range in climate (sub‐humid to wet, tropical) and lithology (granite, volcanic, and mixed sedimentary). Here we report a cross‐site analysis of this dataset to gain insight into stream³⁰Si variability across low‐order catchments and to identify potential climate (i.e., runoff), hydrologic, lithologic, and biogeochemical controls on observed stream Si chemical and isotopic signatures. Event‐based³⁰Si exhibit variability both within and across sites (−0.22‰ to +2.27‰) on the scale of what is observed globally in both small catchments and large rivers. Notably, each site shows distinct³⁰Si signatures that are preserved even after normalization for bedrock composition. Successful characterization of observed cross‐site behavior requires the merging of two distinct frameworks in a novel combined model describing both non‐uniform fluid transit time distributions and multiple fractionating pathways in application to low‐order catchments. The combined model reveals that site‐specific architecture (i.e., biogeochemical reaction pathways and hydrologic routing) regulates stream silicon export signatures even when subject to extreme precipitation events.