One of the greatest challenges in critical zone studies is to document the moisture dynamics, water flux,and solute chemistry of the unsaturated, fractured and weathered bedrock that lies between the soil and groundwater table. The central impediment to quantifying this component of the subsurface is the difficulty associated with direct observations. Here, we report solute chemistry as a function of depth collected over a full year across the shale-derived vadose zone of the Eel River Critical Zone Observatory using a set of novel sub-horizontal wellbores,referred to as the vadose zone monitoring system. The results of this first geochemical glimpse into the deep vadose zone indicate a dynamic temporal and depth-resolved structure. Major cation concentrations reflect seasonal changes in precipitation and water saturation, and normalized ratios span the full range of values reported for the world's largest rivers.
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