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Meteoric waters move along pathways in the subsurface that differ as a function of lithology because of the effects of chemical and physical weathering. To explore how this affects stream chemistry, we investigated watersheds around an igneous intrusion in the Luquillo Mountains (Puerto Rico). We analyzed streams on 1) unmetamorphosed country rock (volcaniclastic sedimentary strata, VC) surrounding an igneous intrusion, 2) the quartz-diorite intrusion (QD), and 3) the metamorphosed aureole rock (hornfels-facies volcaniclastics, HF). These lithologies differ physically and chemically but weather under the same tropical rain forest conditions. The sedimentary VC lithology is pervasively fractured while the massive QD and HF lithologies are relatively unfractured. However, the QD fractures during weathering to produce spheroidally-weathered corestones surrounded by cm-thick rindlets of increasingly weathered rock. Meteoric waters flow pervasively through the network of already-fractured VC rock and the spheroidally weathered rindlets on the QD, but only access a limited fraction of the HF, explaining why streams draining HF are the most dilute in the mountains. This results in various thicknesses of regolith from thick (VC) to moderate (QD) to thin or nonexistent (HF). The pervasive fractures allow groundwater to flow deeply through the VC and then return to the mainstem river (Río Mameyes) at lower elevations. These “rock waters” drive concentrations of rock-derived solutes (silica, base cations, sulfate, phosphate) higher in the lower reaches of the stream. Water also flows through weathering-induced fractures on the QD at high elevations where rindletted corestones are present in stacks, and this water flux dissolves plagioclase and hornblende and oxidizes biotite. This “QD rock water” is not generated at lower elevations in the Río Icacos watershed, where stacks of corestones are absent, and contributions to stream solutes derive from weathering of feldspar- and hornblende-depleted saprolite. The stream chemistry in the QD-dominated watershed (Río Icacos) thus varies from concentrated QD-rock water at channel heads below steep ridgelines toward more diluted “saprolite water” downstream. These observations emphasize the importance of lithology and fracture patterns in dictating water flowpaths, stream chemistry, and regolith development in headwater catchments. 

The rate of chemical weathering has been observed to increase with the rate of physical erosion in published comparisons of many catchments, but the mechanisms that couple these processes are not well understood. We investigated this question by exam- ining the chemical weathering and porosity profiles from catchments developed on marine shale located in Pennsylvania, USA (Susquehanna Shale Hills Critical Zone Observatory, SSHCZO); California, USA (Eel River Critical Zone Observatory, ERC- ZO); and Taiwan (Fushan Experimental Forest). The protolith compositions, protolith porosities, and the depths of regolith at these sites are roughly similar while the catchments are characterized by large differences in erosion rate (1–3 mm yr􏱝1 in Fushan 􏱞 0.2–0.4 mm yr􏱝1 in ERCZO 􏱞 0.01–0.025 mm yr􏱝1 in SSHCZO). The natural experiment did not totally isolate erosion as a variable: mean annual precipitation varied along the erosion gradient (4.2 m yr􏱝1 in Fushan > 1.9 m yr􏱝1 in ERCZO > 1.1 m yr􏱝1 in SSHCZO), so the fastest eroding site experiences nearly twice the mean annual temperature of the other two. Even though erosion rates varied by about 100􏱟, the depth of pyrite and carbonate depletion (defined here as regolith thickness) is roughly the same, consistent with chemical weathering of those minerals keeping up with erosion at the three sites. These minerals were always observed to be the deepest to react, and they reacted until 100% depletion. In two of three of the catchments where borehole observations were available for ridges, these minerals weathered across narrow reaction fronts. On the other hand, for the rock-forming clay mineral chlorite, the depth interval of weathering was wide and the extent of depletion observed at the land surface decreased with increasing erosion/precipitation. Thus, chemical weathering of the clay did not keep pace with erosion rate. But perhaps the biggest difference among the shales is that in the fast-eroding sites, microfractures account for 30–60% of the total porosity while in the slow-eroding shale, dissolution could be directly related to secondary porosity. We argue that the microfractures increase the influx of oxygen at depth and decrease the size of diffusion-limited internal domains of matrix, accelerating weathering of pyrite and carbonate under high erosion-rate condi- tions. Thus, microfracturing is a process that can couple physical erosion and chemical weathering in shales. 

Abstract. Solute concentrations in stream water vary with discharge in patterns that record complex feedbacks between hydrologic and biogeochemical processes. In a comparison of three shale-underlain headwater catchments located in Pennsylvania, USA (the forested Shale Hills Critical Zone Observatory), and Wales, UK (the peatland-dominated Upper Hafren and forest-dominated Upper Hore catchments in the Plynlimon forest), dissimilar concentration–discharge (C–Q) behaviors are best explained by contrasting landscape distributions of soil solution chemistry – especially dissolved organic carbon (DOC) – that have been established by patterns of vegetation and soil organic matter (SOM). Specifically, elements that are concentrated in organic-rich soils due to biotic cycling (Mn, Ca, K) or that form strong complexes with DOC (Fe, Al) are spatially heterogeneous in pore waters because organic matter is heterogeneously distributed across the catchments. These solutes exhibit non-chemostatic behavior in the streams, and solute concentrations either decrease (Shale Hills) or increase (Plynlimon) with increasing discharge. In contrast, solutes that are concentrated in soil minerals and form only weak complexes with DOC (Na, Mg, Si) are spatially homogeneous in pore waters across each catchment. These solutes are chemostatic in that their stream concentrations vary little with stream discharge, likely because these solutes are released quickly from exchange sites in the soils during rainfall events. Furthermore, concentration–discharge relationships of non-chemostatic solutes changed following tree harvest in the Upper Hore catchment in Plynlimon, while no changes were observed for chemostatic solutes, underscoring the role of vegetation in regulating the concentrations of certain elements in the stream. These results indicate that differences in the hydrologic connectivity of organic-rich soils to the stream drive differences in concentration behavior between catchments. As such, in catchments where SOM is dominantly in lowlands (e.g., Shale Hills), we infer that non-chemostatic elements associated with organic matter are released to the stream early during rainfall events, whereas in catchments where SOM is dominantly in uplands (e.g., Plynlimon), these non-chemostatic elements are released later during rainfall events. The distribution of SOM across the landscape is thus a key component for predictive models of solute transport in headwater catchments.

 

Solute concentrations in stream water vary with discharge in patterns that record complex feedbacks between hydrologic and biogeochemical processes. In a comparison of headwater catchments underlain by shale in Pennsylvania, USA (Shale Hills) and Wales, UK (Plynlimon), dissimilar concentration-discharge behaviors are best explained by contrasting landscape distributions of soil solution chemistry – especially dissolved organic carbon (DOC) – that have been established by patterns of vegetation. Specifically, elements that are concentrated in organic-rich soils due to biotic cycling (Mn, Ca, K) or that form strong complexes with DOC (Fe, Al) are spatially heterogeneous in pore waters because organic matter is heterogeneously distributed across the catchments. These solutes exhibit non-chemostatic "bioactive" behavior in the streams, and solute concentrations either decrease (Shale Hills) or increase (Plynlimon) with increasing discharge. In contrast, solutes that are concentrated in soil minerals and form only weak complexes with DOC (Na, Mg, Si) are spatially homogeneous in pore waters across each catchment. These solutes are chemostatic in that their stream concentrations vary little with stream discharge, likely because these solutes are released quickly from exchange sites in the soils during rainfall events. Differences in the hydrologic connectivity of organic-rich soils to the stream drive differences in concentration behavior between catchments. As such, in catchments where soil organic matter (SOM) is dominantly in lowlands (e.g., Shale Hills), bioactive elements are released to the stream early during rainfall events, whereas in catchments where SOM is dominantly in uplands (e.g., Plynlimon), bioactive elements are released later during rainfall events. The distribution of vegetation and SOM across the landscape is thus a key component for predictive models of solute transport in headwater catchments. 

Projections of future conditions within the critical zone—earthcasts—can be used to understand the potential effects of changes in climate on processes affecting landscapes. We are developing an approach to earthcast how weathering will change in the future using scenarios of climate change. As a first step here, we use the earthcasting approach to model aspect‐related effects on soil water chemistry and weathering on hillsides in a well‐studied east‐west trending watershed (Shale Hills, Pennsylvania, USA). We completed model simulations of solute chemistry in soil water with and without the effect of aspect for comparison to catchment observations. With aspect included, aqueous weathering fluxes were higher on the sunny side of the catchment. But the effect of aspect on temperature (0.8 °C warmer soil on sunny side) and recharge (100 mm/year larger on shaded side) alone did not explain the magnitude of the observed higher weathering fluxes on the sunny side. Modeled aspect‐related differences in weathering fluxes only approach field observations when we incorporated the measured differences in clay content observed in augered soils on the two hillslopes. We also had to include a biolifting module to accurately describe cation concentrations in soil water versus depth. Biolifting lowered some mineral dissolution rates while accelerating kaolinite precipitation. These short‐duration simulations also highlighted that the inherited differences in particle size on the two sides of the catchment might in themselves be explained by weathering under different microclimates caused by aspect—over longer durations than simulated with our models.

 

Earth System Models (ESMs) are essential tools for understanding and predicting global change, but they cannot explicitly resolve hillslope‐scale terrain structures that fundamentally organize water, energy, and biogeochemical stores and fluxes at subgrid scales. Here we bring together hydrologists, Critical Zone scientists, and ESM developers, to explore how hillslope structures may modulate ESM grid‐level water, energy, and biogeochemical fluxes. In contrast to the one‐dimensional (1‐D), 2‐ to 3‐m deep, and free‐draining soil hydrology in most ESM land models, we hypothesize that 3‐D, lateral ridge‐to‐valley flow through shallow and deep paths and insolation contrasts between sunny and shady slopes are the top two globally quantifiable organizers of water and energy (and vegetation) within an ESM grid cell. We hypothesize that these two processes are likely to impact ESM predictions where (and when) water and/or energy are limiting. We further hypothesize that, if implemented in ESM land models, these processes will increase simulated continental water storage and residence time, buffering terrestrial ecosystems against seasonal and interannual droughts. We explore efficient ways to capture these mechanisms in ESMs and identify critical knowledge gaps preventing us from scaling up hillslope to global processes. One such gap is our extremely limited knowledge of the subsurface, where water is stored (supporting vegetation) and released to stream baseflow (supporting aquatic ecosystems). We conclude with a set of organizing hypotheses and a call for global syntheses activities and model experiments to assess the impact of hillslope hydrology on global change predictions.