Subsurface weathering signatures in stream chemistry during an intense storm

Long-term relationships between stream chemistry and discharge are regulated by watershed subsurface structure and biogeochemical functioning. The extent to which these mechanisms are expressed and may be explored in the geochemical response of streams during storm events remains an open question. Here, we monitor an intense storm as it infiltrated an upland hillslope draining into a small steep canyon stream that is typified by chemostatic concentration-discharge relationships in rock-derived solutes. Our approach couples a high-frequency record of stable lithium isotope ratios (δ⁷Li) in the stream with novel sampling of rock moisture within the hillslope. At peak discharge, lithium-sodium ratios (Li/Na) increased from 0.58 μM/mM to 0.82 μM/mM and δ⁷Li decreased from +28.9±0.1‰ to +26.4±0.4‰ in the stream. Hillslope hydrologic monitoring reveals that the rainwater infiltrated the subsurface, yet attenuated breakthrough of the heavily depleted δD signal of this storm (as low as −86‰) only reached the upper 3-4 meters of the vadose zone. These δD data show that the storm water mixed with previously stored rock moisture and displaced stored fluid to deeper depths, causing an observable rise in the water table. Groundwater ⁸⁷Sr/⁸⁶Sr and δ⁷Li demonstrate consistency in the fluid-rock interactions that occur below the water table prior to and during the storm. In total, these observations indicate that the transfer of fluid and generation of solutes through the interior of the hillslope produce the variability of Li/Na and δ⁷Li within the stream during the storm, and support application of a previously established 1-D reactive transport model framework developed for the evolution of lithium within the hillslope to this extreme hydrologic event. Based on the model, both Li/Na and δ⁷Li versus discharge relationships reflect an overall shorter transit time of fluid through the interior of the hillslope. These model results are consistent with our hydrologic observations and indicate that Li from further upslope (where the vadose zone becomes thicker) contributes to stream solute chemistry at the height of the storm. We conclude that in this system, stream lithium isotope signatures record the routing of water and generation of solutes within the hillslope even during intense storm events.