The hydrologic connectivity between hillslopes and streams impacts the geomorphological evolution of catchments. Here, we propose a conceptual model for hydrogeomorphological evolution of the Susquehanna Shale Hills Critical Zone Observatory (SSHCZO), a first-order catchment developed on shale in central Pennsylvania, U.S.A. At SSHCZO, the majority of available water (the difference between incoming meteoric water and outgoing evapotranspiration) flows laterally to the catchment outlet as interflow, while the rest is transported by regional groundwater flow. Interflow, shallow hillslope flow, is limited to the upper 5 to 8 m of highly fractured bedrock, thought to have formed during periglacial conditions in the late Pleistocene. In contrast, groundwater flowpaths are influenced by the primary permeability of the varying stratigraphic units. Both flowpaths respond to weathering-related secondary permeability. O₂-rich interflow mixes with deep O₂-poor groundwater under the catchment outlet at depths of 5–8 m. Penetration of this oxygenated interflow under the valley results in pyrite oxidation, release of sulfuric acid, dissolution of minerals, and weakening of bedrock. This is hypothesized to enhance channel incision and, in turn, to promote drainage of deep groundwater from the ridges. Drainage subsequently lowers the catchment water table, advancing the cascade of reactions that produce regolith. Weathering in the catchment is characterized by both sharp and diffuse reaction fronts. Relatively sharp fronts (pyrite, carbonate) mark where vertical, unsaturated flow changes to horizontal, saturated flow, while diffuse fronts (illite, chlorite, feldspar) mark where flow is largely vertical and unsaturated. According to this model, catchment morphology reflects subsurface pyrite reactions due to mixing of interflow and groundwater flow under the valley floor that ultimately results in clay weathering and regolith production nearer the land surface.

Significant solute flux from the weathered bedrock zone – which underlies soils and saprolite – has been suggested by many studies. However, controlling processes for the hydrochemistry dynamics in this zone are poorly understood. This work reports the first results from a four-year (2009–2012) high-frequency (1–3day) monitoring of major solutes (Ca, Mg, Na, K and Si) in the perched, dynamic groundwater in a 4000m2 zero-order basin located at the Angelo Coast Range Reserve, Northern California. Groundwater samples were autonomously collected at three wells (downslope, mid-slope, and upslope) aligned with the axis of the drainage. Rain and throughfall samples, profiles of well headspace pCO2, vertical profiles and time series of groundwater temperature, and contemporaneous data from an extensive hydrologic and climate sensor network provided the framework for data analysis.All runoff at this soil-mantled site occurs by vertical unsaturated flow through a 5–25m thick weathered argillite and then by lateral flows to the adjacent channel as groundwater perched over fresher bedrock. Driven by strongly seasonal rainfall, over each of the four years of observations, the hydrochemistry of the groundwater at each well repeats an annual cycle, which can be explained by two end-member processes. The first end-member process, which dominates during the winter high-flow season in mid- and upslope areas, is CO2 enhanced cation exchange reaction in the vadose zone in the more shallow conductive weathered bedrock. This process rapidly increases the cation concentrations of the infiltrated rainwater, which is responsible for the lowest cation concentration of groundwater. The second-end member process occurs in the deeper perched groundwater and either dominates year-round (at the downslope well) or becomes progressively dominant during low flow season at the two upper slope wells. This process is the equilibrium reaction with minerals such as calcite and clay minerals, but not with primary minerals, suggesting the critical role of the residence time of the water. Collectively, our measurements reveal that the hydrochemistry dynamics of the groundwater in the weathered bedrock zone is governed by two end-member processes whose dominance varies with critical zone structure, the relative importance of vadose versus groundwater zone processes, and thus with the seasonal variation of the chemistry of recharge and runoff

Quantitative assessments of long-term, national-scale responses of groundwater quality to pesticide applications are essential to evaluate the effectiveness of pesticide regulations. Retardation time in the unsaturated zone (R_u) was estimated for selected herbicides (atrazine, simazine, and bentazon) and degradation products (desethylatrazine (DEA), desisopropylatrazine (DIA), desethyldesisopropylatrazine (DEIA), and BAM) using a multidecadal time series of groundwater solute chemistry (∼30 years) and herbicide sales (∼60 years). The sampling year was converted to recharge year using groundwater age. Then, R_u was estimated using a cross-correlation analysis of the sales and the frequencies of detection and exceedance of the drinking water standard (0.1 μg/L) of each selected compound. The results showed no retardation of the highly polar, thus mobile, parent compounds (i.e., bentazon), while R_u of the moderately polar compounds (i.e., simazine) was about a decade, and their degradation products showed even longer R_u. The temporal trends of the degradation products did not mirror those of the sale data, which were attributed to the various sale periods of the parent compounds, sorption of the parent compounds, and complex degradation pathways. The longer R_u in clayey/organic sediments than in sandy sediments further confirmed the role of soil-specific retardation as an important factor to consider in groundwater protection.