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Groundwater is one of the largest reservoirs of water on Earth but has relatively small fluxes compared to its volume. This behavior is exaggerated at depths below 500 m, where the majority of groundwater exists and where residence times of millions to even a billion years have been documented. However, the extent of interactions between deep groundwater (>500 m) and the rest of the terrestrial water cycle at a global scale are unclear because of challenges in detecting their contributions to streamflow. Here, we use a chloride mass balance approach to quantify the contribution of deep groundwater to global streamflow. Deep groundwater likely contributes <0.1% to global streamflow and is only weakly and sporadically connected to the rest of the water cycle on geological timescales. Despite this weak connection to streamflow, we found that deep groundwaters are important to the global chloride cycle, providing ~7% of the flux of chloride to the ocean.

Mountain‐front recharge (MFR), or all inflow to a basin‐fill aquifer with its source in the mountain block, is an important component of recharge to basin‐fill aquifer systems. Distinguishing and quantifying the surface from subsurface components of MFR is necessary for water resource planning and management, particularly as climate change may impact these components in distinct ways. This study tests the hypothesis that MFR components can be distinguished in long‐screened, basin‐fill production wells by (1) groundwater age and (2) the median elevation of recharge. We developed an MFR characterization approach by combining age distributions in six wells using tritium, krypton‐85, argon‐39, and radiocarbon, and median recharge elevations from noble gas thermometry combined with numerical experiments to determine recharge temperature lapse rates using flow and energy transport modeling. We found that groundwater age distributions provided valuable information for characterizing the dominant flow system behavior captured by the basin‐fill production wells. Tracers indicated the presence of old (i.e., no detectable tritium) water in a well completed in weathered bedrock located close to the mountain front. Two production wells exhibited age distributions of binary mixing between modern and a small fraction of old water, whereas the remaining wells captured predominantly modern flow paths. Noble gas thermometry provided important complementary information to the age distributions; however, assuming constant recharge temperature lapse rates produced improbable recharge elevations. Numerical experiments suggest that surface MFR, if derived from snowmelt, can locally suppress water table temperatures in the basin‐fill aquifer, with implications for recharge elevations estimated from noble gas thermometry.

Mountain‐block recharge (MBR) is the subsurface inflow of groundwater to lowland aquifers from adjacent mountains. MBR can be a major component of recharge but remains difficult to characterize and quantify due to limited hydrogeologic, climatic, and other data in the mountain block and at the mountain front. The number of MBR‐related studies has increased dramatically in the 15 years since the last review of the topic was conducted by Wilson and Guan (2004), generating important advancements. We review this recent body of literature, summarize current understanding of factors controlling MBR, and provide recommendations for future research priorities. Prior to 2004, most MBR studies were performed in the southwestern United States. Since then, numerous studies have detected and quantified MBR in basins around the world, typically estimating MBR to be 5–50% of basin‐fill aquifer recharge. Theoretical studies using generic numerical modeling domains have revealed fundamental hydrogeologic and topographic controls on the amount of MBR and where it originates within the mountain block. Several mountain‐focused hydrogeologic studies have confirmed the widespread existence of mountain bedrock aquifers hosting considerable groundwater flow and, in some cases, identified the occurrence of interbasin flow leaving headwater catchments in the subsurface—both of which are required for MBR to occur. Future MBR research should focus on the collection of high‐priority data (e.g., subsurface data near the mountain front and within the mountain block) and the development of sophisticated coupled models calibrated to multiple data types to best constrain MBR and predict how it may change in response to climate warming.

High‐elevation mountain catchments are often subject to large climatic and topographic gradients. Therefore, high‐density hydrogeochemical observations are needed to understand water sources to streamflow and the temporal and spatial behaviour of flow paths. These sources and flow paths vary seasonally, which dictates short‐term storage and the flux of water in the critical zone (CZ) and affect long‐term CZ evolution. This study utilizes multiyear observations of chemical compositions and water residence times from the Santa Catalina Mountains Critical Zone Observatory, Tucson, Arizona to develop and evaluate competing conceptual models of seasonal streamflow generation. These models were tested using endmember mixing analysis, baseflow recession analysis, and tritium model “ages” of various catchment water sources. A conceptual model involving four endmembers (precipitation, soil water, shallow, and deep groundwater) provided the best match to observations. On average, precipitation contributes 39–69% (55 ± 16%), soil water contributes 25–56% (41 ± 16%), shallow groundwater contributes 1–5% (3 ± 2%), and deep groundwater contributes ~0–3% (1 ± 1%) towards annual streamflow. The mixing space comprised two principal planes formed by (a) precipitation‐soil water‐deep groundwater (dry and summer monsoon season samples) and (b) precipitation‐soil water‐shallow groundwater (winter season samples). Groundwater contribution was most important during the wet winter season. During periods of high dynamic groundwater storage and increased hydrologic connectivity (i.e., spring snowmelt), stream water was more geochemically heterogeneous, that is, geochemical heterogeneity of stream water is storage‐dependent. Endmember mixing analysis and³H model age results indicate that only 1.4 ± 0.3% of the long‐term annual precipitation becomes deep CZ groundwater flux that influences long‐term deep CZ development through both intercatchment and intracatchment deep groundwater flows.

Despite a multitude of small catchment studies, we lack a deep understanding of how variations in critical zone architecture lead to variations in hydrologic states and fluxes. This study characterizes hydrologic dynamics of 15 catchments of the U.S. Critical Zone Observatory (CZO) network where we hypothesized that our understanding of subsurface structure would illuminate patterns of hydrologic partitioning. The CZOs collect data sets that characterize the physical, chemical, and biological architecture of the subsurface, while also monitoring hydrologic fluxes such as streamflow, precipitation, and evapotranspiration. For the first time, we collate time series of hydrologic variables across the CZO network and begin the process of examining hydrologic signatures across sites. We find that catchments with low baseflow indices and high runoff sensitivity to storage receive most of their precipitation as rain and contain clay‐rich regolith profiles, prominent argillic horizons, and/or anthropogenic modifications. In contrast, sites with high baseflow indices and low runoff sensitivity to storage receive the majority of precipitation as snow and have more permeable regolith profiles. The seasonal variability of water balance components is a key control on the dynamic range of hydraulically connected water in the critical zone. These findings lead us to posit that water balance partitioning and streamflow hydraulics are linked through the coevolution of critical zone architecture but that much work remains to parse these controls out quantitatively.