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Antecedent hydrological conditions are recorded through the evolution of dissolved lithium isotope signatures (δ7 ${\delta }^{7}$Li) by juxtaposing two storm events in an upland watershed subject to a Mediterranean climate. Discharge and δ7 ${\delta }^{7}$Li are negatively correlated in both events, but mean δ7 ${\delta }^{7}$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 δ7 ${\delta }^{7}$Li are not reproduced. To reconcile the stability of the subsurface solute weathering profile with our observations of dynamic stream δ7 ${\delta }^{7}$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 δ7 ${\delta }^{7}$Li‐discharge patterns distinguished by the antecedent conditions of the watershed. Plain Language Summary: Storm events often cause characteristic shifts in stream solute chemistry. Interpreting these signals offers insight into the water‐rock interactions occurring within watersheds. Here, we use lithium stable isotopes and reactive transport modeling to relate how long water spends in a catchment, or how deep water infiltrates through a catchment, to the extent of chemical weathering. We show that the first significant storm after a dry season exports more chemically evolved water, while a wet season storm releases less evolved, shallower, and younger water. Our results indicate that stream flow δ7 ${\delta }^{7}$Li in small watersheds offers a sensitive record of hydrological conditions prior to the storm, reflecting subtle shifts in the efficiency of the Critical Zone to generate, transport, and ultimately export solutes. Key Points: Stream lithium stable isotope ratios (δ7Li) recorded at high frequency over storm events are sensitive to antecedent conditionsA reactive transport model cannot produce observed shifts in stream chemistry through variations in flow rate aloneFlux‐weighting of model fluid outputs based on time‐varying fluid transit time distributions describes stream δ7Li over storm hydrographs [ABSTRACT FROM AUTHOR]

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. Plain Language Summary: Chemical weathering of silicate minerals by meteoric water serves as a long‐term regulator of atmospheric CO2. The extent to which these reactions produce secondary minerals dictates the chemical composition of soils and rivers. The isotope composition of metals is a potent tracer of this chemical weathering and significant progress has been gained in application of lithium stable isotopes for this purpose. Here, we demonstrate that water draining a mountainous landscape subject to a wet, temperate climate in Southern France produces isotopically heavy lithium in stream water. These signatures suggest an environment in which chemical weathering rates keep pace with the rates of soil erosion. To reveal the underlying causes of this behavior, we develop a numerical model that simulates the flow of water and its interaction with rock in the subsurface using measured data from the field site, including soil, bedrock, and water chemistry. We show that new minerals formed in the subsurface resist dissolution and effectively retain lithium. This work leverages the sensitivity of lithium isotopes to analyze weathering conditions that typify upland watersheds subject to cool, wet climates. Key Points: Small, upland watersheds under Mediterranean climate display characteristically high lithium stable isotope ratios (δ7Li)In a watershed in southern France subject to strong atmospheric inputs, weathering incongruence leads to high stream δ7Li valuesIsotope‐enabled reactive transport modeling indicates that at this site soil clays retain lithium and are resilient to (re‐)solubilization [ABSTRACT FROM AUTHOR]

The Huanghe (Yellow River), one of the largest turbid river systems in the world, has long been recognized as a major contributor of suspended particulate matter (SPM) to the ocean. However, over the last few decades, the SPM export flux of the Huanghe has decreased over 90 % due to the high management, impacting the global export of particulate organic carbon (POC). To better constrain sources and modes of transport of POC beyond the previously investigated transportation of POC near the channel surface, SPM samples were for the first time collected over a whole channel cross-section in the lower Huanghe. Riverine SPM samples were analyzed for particle size and major element contents, as well as for POC content and dual carbon isotopes (13C and 14C). Clear vertical and lateral heterogeneities of the physical and chemical properties of SPM are observed within the river cross-section. For instance, finer SPM carry more POC in general with higher 14C activity near the surface of the right bank. Notably, we discuss how bank erosion in the alluvial plain is likely to generate lateral heterogeneity in POC composition. The Huanghe POC is millennial-aged (4020 ± 500 radiocarbon years) and dominated by organic carbon (OC) from the biosphere, while the lithospheric fraction is ca. 12 %. The mobilization of aged and refractory OC, including radiocarbon-dead biospheric OC, from deeper soil horizons of the loess–paleosol sequence through erosion in the Chinese Loess Plateau is an important mechanism contributing to fluvial POC in the Huanghe drainage basin. Altogether, anthropogenic activities can drastically change the compositions and transport dynamics of fluvial POC, consequentially altering the feedback of the source-to-sink trajectory of a river system to regional and global carbon cycles. [ABSTRACT FROM AUTHOR]