Dynamic chemistry in the perched groundwater flowing through weathered bedrock underling a steep forested hillslope, north California

The spatial and temporal pattern of groundwater chemistry in the seasonally perched groundwater systems that develop in the weathered bedrock zone under hillslopes have rarely been documented, yet chemical evolution of water here dictates the runoff chemistry to streams in many places. Here we exploit an intensively instrumented hillslope to document water well chemistry at three wells and adjacent stream. We have been sampling groundwater at daily frequency since October 2008 on a forested hillslope, "Rivendell", at the Angelo Coast Range Reserve located at the headwaters of the Eel River, California. The site is typical of California's coastal Mediterranean climate. The groundwater samples have been collected from a depth near the boundary between the weathered and fresh bedrock at three locations along the hillslope: Well 1 (bottom of hillslope), Well 3 (mid-slope), and Well 10 (near the ridge). Bulk rainwater and throughfall samples were collected at a meadow across the hillslope and at the middle of the slope, respectively, as well. Near the ridge (Well 10), during the first significant rainstorms of 2009 (133mm/42.5hours) and 2010 (220mm/42hours), when the water table changed only 0.32m and 0.66m, respectively, the concentration of Ca, Mg, and Na started to increase rapidly compared to the dry season (e.g. 2-6 μM vs 0.02-0.2μM [Mg]/day). However, during these same storms, K concentration sharply increased to 50-60 μM and decreased to 20-30μM, synchronizing with the water table responses. Throughfalls of these storms had at least 10 fold lower Ca, Mg, and Na concentrations than the well water while they had 10 fold higher K compared to the pre-event groundwater values. When the total seasonal cumulative rainfall exceeds 600 mm, the Well 10 solute concentration was diluted nearly 3 fold (e.g. [Mg] 0.3 mM vs. 0.1 mM) and the water table was raised significantly (2-6 meters). Throughout the rainy season, Well10 retained its diluted chemistry signature and on average the water table remained elevated as subsequent rainstorms repeatedly recharged the system. Well10 solute concentration slowly increased at the end of the rainy season when the water table fell. In contrast, at the foot of the hill slope, even though the water table was responsive to each rainfall event, its water chemistry developed a strong dilution signatures only during the intense rainstorms (total rainfall > 70mm); the solute concentration decreased (e.g. [Mg] = 0.1mM) during the rising limb of the well hydrograph and recovered back to its pre-event value (e.g. [Mg] = 0.3mM) during the falling limb of the well hydrograph. During small storms, the solute concentration of Well 1 either did not change or slightly increased. Mid-slope showed similar behavior to Well 1. The Well 3 solute concentration was diluted about 3 fold (e.g. [Mg] 0.3mM to 0.1mM) as the water table rose and increased as the water table receded. However unlike Well 1, the water chemistry of Well 3 did not recover to its pre-event composition at any point during the rainy season and the recovery rate was slower than that of Well 1. These water chemistry observations provide insight into the dynamics of water movement within the fractured, weathered bedrock zone, and point to both vertical and lateral mixing processes that influence the chemical evolution of waters.