We investigated controls on concentration‐discharge relationships of a catchment underlain by argillite by monitoring both groundwater along a hillslope transect and stream chemistry. Samples were collected at 1–3 day intervals over 4 years (2009–2013) in Elder Creek in the Eel River Critical Zone Observatory in California. Runoff at our study hillslope is driven by vadose zone flux through deeply weathered argillite (5–25 m thick) to a perched, seasonally dynamic groundwater that then drains to Elder Creek. Low flow derives from the slowly draining deepest perched groundwater that reaches equilibrium between primary and secondary minerals and saturation with calcite under high subsurface pCO2. Arriving winter rains pass through the thick vadose zone, where they rapidly acquire solutes via cation exchange reactions (driven by high pCO2), and then recharge the groundwater that delivers runoff to the stream. These new waters displayed lower solute concentrations than the deep groundwater by less than a factor of 5 (except for Ca). Up to 74% of the total annual solute flux is derived from the vadose zone. The deep groundwater's Ca concentration decreased as it exfiltrates to the stream due to CO2 degassing and this Ca loss is equivalent of 30% of the total chemical weathering flux of Elder Creek. The thick vadose zone in weathered bedrock and the perched groundwater on underlying fresh bedrock result in two distinct processes that lead to the relatively invariant (chemostatic) concentration‐discharge behavior. The processes controlling solute chemistry are not evident from stream chemistry and runoff analysis alone.
O 2 and CO 2 , the two essential reactants in weathering along with water and minerals, are important in deep regolith development because they diffuse to weathering fronts at depth. We monitored the dynamics of these gas concentrations in the hand-augerable zone on three ridgetops-one on granite and two on diabase-in Virginia (VA) and Pennsylvania (PA), U.S.A. and related the gas chemistry to regolith development. The VA granite and the PA diabase protoliths were more deeply weathered than the VA diabase. We attribute this to high protolith fracture density. The pO 2 and pCO 2 measurements of these more fractured sites displayed the characteristics of aerobic respiration year round. In contrast, the relation of pO 2 versus pCO 2 on the more massive VA diabase is consistent with seasonal changes in the dominant electron acceptor from O 2 to Fe(III), likely regulated by the expansion/contraction of nontronite in the soil BC horizon. These observations suggest that the fracture density is a first order control on deep regolith gas chemistry. However, fractures can be present in protolith but also can be caused by oxidation of ferrous minerals. We propose that subsurface pO 2 and weatheringinduced fracturing can create positive feedbacks in some lithologies that cause regolith to thicken while nonetheless maintaining aerobic respiration at depth. In contrast, in the absence of weathering-induced fracturing and depletion of pO 2 , a negative feedback that may be modulated by soil micro-biota ultimately results in thin regolith. These feedbacks may have been important in weathering systems over much of earth's history.
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