Processes controlling streamflow generation were determined using geochemical tracers for water years 2004-2007 at eight headwater catchments at the Kings River Experimental Watersheds in southern Sierra Nevada. Four catchments are snow-dominated, and four receive a mix of rain and snow. Results of diagnostic tools of mixing models indicate that Ca2+, Mg2+, K+ and Cl- behaved conservatively in the streamflow at all catchments, reflecting mixing of three endmembers. Using endmember mixing analysis, the endmembers were determined to be snowmelt runoff (including rain on snow), subsurface flow and fall storm runoff. In seven of the eight catchments, streamflow was dominated by subsurface flow, with an average relative contribution (% of streamflow discharge) greater than 60%. Snowmelt runoff contributed less than 40%, and fall storm runoff less than 7% on average. Streamflow peaked 2-4weeks earlier at mixed rain-snow than snow-dominated catchments, but relative endmember contributions were not significantly different between the two groups of catchments. Both soil water in the unsaturated zone and regional groundwater were not significant contributors to streamflow. The contributions of snowmelt runoff and subsurface flow, when expressed as discharge, were linearly correlated with streamflow discharge (R2 of 0.85-0.99). These results suggest that subsurface flow is generated from the soil-bedrock interface through preferential pathways and is not very sensitive to snow-rain proportions. Thus, a declining of the snow-rain ratio under a warming climate should not systematically affect the processes controlling the streamflow generation at these catchments. © 2012 John Wiley & Sons, Ltd.

Concentration-discharge (C-Q) relations can provide insight into the dynamic behavior of the Critical Zone (CZ), as C-Q relations integrate the spatial distribution and timing of watershed hydrogeochemical processes. This study blends geomorphologic analysis, C-Q relations and reactive-transport modeling using a rich dataset from an elevation gradient of eight watersheds in the Southern Sierra Nevada, California. We found that the CZ structure exerts a strong control on the C-Q relations, and on the hydrogeochemical behavior of headwater watersheds. Watersheds with thin regolith, a large stream network, and limited water storage have fast mean transit times along subsurface flow lines, and show limited seasonal variability in ionic concentrations in streamflow (i.e., chemostatic behavior). In contrast, watersheds with thicker regolith, a small stream network and more water storage have longer transit times along subsurface flow lines, and exhibit greater chemical variability (i.e., chemodynamic behavior). Independent estimates of mean transit times and water storage from other isotopic, hydrologic and geophysical studies were consistent with results from modeling C-Q relations. The stream chemistry and its variability were controlled by lateral flow within the regolith, and no mixing with deep groundwater was needed to explain the observed chemical variability. This study opens the possibility to estimate water-storage capacity and mean transit times, and thus drought resistance in watersheds, by using quantitative modeling of C-Q relations.

Streamflow generation in the semiarid, seasonally snow-covered, and forested mountain catchments of the Valles Caldera, New Mexico, was investigated using chemical tracers. Samples were collected from snow, subsurface flow from hillslopes, and streamflow at Redondo and La Jara Creeks from December 2004 to July 2005. A new modeling procedure was developed by combining diagnostic tools of mixing models and end-member mixing analysis to evaluate the assumptions of mixing models. This procedure was successfully used to determine conservative chemical tracers, identify the number of end-members that contribute to streamflow, and evaluate eligibility of end-members. The results show that streamflow at Redondo Creek was generated from two end-members: lateral subsurface flow (∼80%) and thermal meteoric water (∼20%). Streamflow at La Jara Creek was primarily from lateral subsurface flow alone. Overland flow of snowmelt was not a significant contributor to streamflow in either catchment. Lateral subsurface flow is an important process of streamflow generation in semiarid environments in the southwest United States and should play a critical role in regulating biogeochemical cycles. Copyright 2008 by the American Geophysical Union.