Understanding groundwater fracture-flow and near surface soil throughflow mixing within a mountain catchment using 36Cl/Cl, Yosemite National Park, California.

In high elevation montane basins, there are typically limited observations to characterize watersheds. In this study we successfully use 36Cl and Cl- to characterize groundwater and near-surface water contributions to the upper Merced River and it's tributaries from Happy Isles to El Portal. Water fluxes typically consist of a variety of surface, near-surface and groundwater flow paths, which are complicated by faulted, folded, and fractured terrain. Surface water, snow, groundwater, and springs were sampled seasonally from July 2004 to October 2007. Snow 36Cl/Cl ratios are 3-30 times lower than in the Merced River water, but 36Cl/Cl ratios in the river increase 3-7 times from baseflow to the snowmelt season. This observation can be explained by characterizing endmembers in the watershed, and by determining how these endmembers vary temporally. Three endmembers mix in the catchment, and they include near-surface water with Cl- concentrations of 0.09 mg/L and 36Cl/Cl of 9976x10-15, groundwater primarily in contact with granitic rock with Cl- of 0.39 mg/L and 36Cl/Cl of 10711x10-15, and groundwater primarily in contact with metasedimentary rock with Cl- of 32.7 mg/L and 36Cl/Cl of 71x10-15. Metamorphic- dominated groundwater and granitic-dominated groundwater are further characterized by Ca2+/Cl- ratios (granitic-dominated groundwater is greater than 5, and metamorphic-dominated groundwater is less than 1). As the season transitions from snowmelt to baseflow, Cl- and 36Cl/Cl in surface water becomes more characteristic of both granitic and metamorphic-dominated groundwater depending on location. Plotting 1/Cl- verses 36Cl/Cl elucidates mixing lines which indicate that both groundwater endmembers have undergone evapotranspiration, but only the metamorphic-dominated groundwater shows evidence of incorporating significant amounts of rock chloride. The near-surface water is the dominant endmember during the snowmelt season and has similar Cl- concentrations as snow (~0.1 mg/L), but 36Cl/Cl ratios in near-surface water are much higher than snow (220-306x10-15). The jump in 36Cl/Cl from snow to near-surface water and groundwater is most likely from retardation of the 36Cl bomb-pulse, indicating the strong role of chlorine biogeochemistry. Retardation of chloride appears to occur on a much larger scale in this montane system than has previously been observed in other sites.