Shale Hills Critical Zone Observatory Research Articles

RSHUD v2.0: advancing the Simulator for Hydrologic Unstructured Domains and unstructured hydrological modeling in the R environment

Abstract. Hydrological modeling is a crucial component in hydrology research, particularly for projecting future scenarios. However, achieving reproducibility and automation in distributed hydrological modeling research for modeling, simulation, and analysis is challenging. This paper introduces rSHUD v2.0, an innovative, open-source toolkit developed in the R environment to enhance the deployment and analysis of the Simulator for Hydrologic Unstructured Domains (SHUD). The SHUD is an integrated surface–subsurface hydrological model that employs a finite-volume method to simulate hydrological processes at various scales. The rSHUD toolkit includes pre- and post-processing tools, facilitating reproducibility and automation in hydrological modeling. The utility of rSHUD is demonstrated through case studies of the Shale Hills Critical Zone Observatory in the USA and the Waerma watershed in China. The rSHUD toolkit's ability to quickly and automatically deploy models while ensuring reproducibility has facilitated the implementation of the Global Hydrological Data Cloud (https://ghdc.ac.cn, last access: 1 September 2023), a platform for automatic data processing and model deployment. This work represents a significant advancement in hydrological modeling, with implications for future scenario projections and spatial analysis.

Geo-electrical anisotropy corrections derived from square array data to improve Earth resistivity models of the Shale Hills' critical zone

Geo-electric anisotropy in the shallow subsurface, often expressed as the “paradox of anisotropy”, is seldom accounted for in colinear array resistivity models of the critical zone. The paradox of anisotropy can be observed in areas of inclined bedding planes or fractures where longitudinal apparent resistivities are greater than transverse apparent resistivities, which is opposite of the true resistivities. In this study, we illustrate the paradox of anisotropy for fractured shale bedrock in Pennsylvania's Susquehanna Shale Hills Critical Zone Observatory (Shale Hills) using square and Wenner array data, and derive an anisotropy correction from the square array data, which is not influenced by the anisotropy. Square array measurements were made around a center point near the middle of a planar slope on the north-facing side of the Shale Hills watershed at four a-spacings (5, 10, 25, and 50 m), each rotated at 15° increments until a full rotation (0° to 165°) of measurements were collected. Coefficients of anisotropy, estimated from the square array data, were then applied to Wenner array data collected at the same location in the watershed to correct the anisotropic flow of current affecting the colinear (i.e., Wenner) array data. Correction of Wenner array data for profiles parallel and orthogonal to bedding strike yield favorable model results when compared to expected resistivity ranges with respect to bedding strike. We further demonstrate that application of the anisotropy corrections to several Wenner array profiles, followed by a pseudo 3D inversion of the profiles, yields a resistivity model of the subsurface providing new insights into groundwater flow through the Shale Hills' critical zone.

Low rates of rock organic carbon oxidation and anthropogenic cycling of rhenium in a slowly denuding landscape

AbstractThe oxidation of petrogenic organic carbon (OCpetro) is a source of carbon dioxide to the atmosphere over geological timescales. The rates of OCpetro oxidation in locations that experience low rates of denudation remain poorly constrained, despite these landscapes dominating Earth's continental surface area. Here, we track OCpetro oxidation using radiocarbon and the trace element rhenium (Re) in the deep weathering profiles, soils and stream waters of the Susquehanna Shale Hills Critical Zone Observatory (PA, USA). In a ridge‐top borehole, radiocarbon measurements reveal the presence of a broad OCpetro weathering front, with a first‐order assessment of ~40% loss occurring over ~6 m. However, the low OCpetro concentration (< 0.05 wt%) and inputs of radiocarbon throughout the deepest parts of the profile complicate the assessment of OCpetro loss. The OCpetro weathering front coincides with a zone of Re depletion (~90% loss), and we estimate that > 80% of Re in the rock is associated with OCpetro, based on Re/Na and Re/S ratios. Using estimates of long‐term denudation rates, the observed OCpetro loss and the Re proxy are equivalent to a low OCpetro oxidation yield of < 1.7 × 10−2 tC km−2 yr−1. This is consistent with the low OCpetro concentrations and low denudation rates at this location. In addition, we find the surface cycle of Re is decoupled from that of deep weathering, with an enrichment of Re in surface soils and elevated Re concentrations in stream water, precipitation, and shallow groundwater. A mass balance model shows that this can be explained by a historical anthropogenic contribution of Re through atmospheric deposition. We estimate that the topsoil Re pool could take decades to centuries to deplete and call for a renewed focus on anthropogenic perturbation of the surface Re cycle in low denudation rate settings.

Critical Zone Structure by Elastic Full Waveform Inversion of Seismic Refractions in a Sandstone Catchment, Central Pennsylvania, USA

AbstractSeismic imaging provides key information for revealing structures within Earth's critical zone (CZ) and quantifying subsurface fluid properties. The P‐wave velocity (Vp) models estimated by seismic refraction tomography or acoustic full waveform inversion (FWI) are useful to delineate the thicknesses of weathered bedrock but ambiguously map fluid properties in CZ. Considering the complementary sensitivity of S‐wave to subsurface fluid saturation, we explore advanced elastic full waveform inversion (EFWI) to estimate both Vp and S‐wave velocity (Vs) models simultaneously. Several strategies are proposed for robust EFWI implementation of noisy single (vertical) component refraction data: (a) we window seismic data to preserve early arrivals mainly including P‐wave, converted waves, and S‐wave refractions; (b) we use a correlative misfit rather than the classic L2 misfit to alleviate the interference of unreliable data amplitudes; and (c) we perform inversion using a multiscale frequency strategy with the iterative constraint with the rule of Vp/Vs > 1. We validate that the EFWI approach reliably reconstructs Vp and Vs models using synthetic data. Then, we apply our EFWI approach to seismic refraction data acquired at the Garner Run site of the Susquehanna Shale Hills Critical Zone Observatory. The inverted Vp and Vs models indicate three distinguished layers and with significant lateral and depth heterogeneities (e.g., low Vp and Vs zones). Joint analyses of Vp, Vs, and Vp/Vs with rock‐physics knowledge reveal potential gas or water gathering zones.

Microbial chemolithotrophic oxidation of pyrite in a subsurface shale weathering environment: Geologic considerations and potential mechanisms.

Oxidative weathering of pyrite plays an important role in the biogeochemical cycling of Fe and S in terrestrial environments. While the mechanism and occurrence of biologically accelerated pyrite oxidation under acidic conditions are well established, much less is known about microbially mediated pyrite oxidation at circumneutral pH. Recent work (Percak-Dennett et al., 2017, Geobiology, 15, 690) has demonstrated the ability of aerobic chemolithotrophic microorganisms to accelerate pyrite oxidation at circumneutral pH and proposed two mechanistic models by which this phenomenon might occur. Here, we assess the potential relevance of aerobic microbially catalyzed circumneutral pH pyrite oxidation in relation to subsurface shale weathering at Susquehanna Shale Hills Critical Zone Observatory (SSHCZO) in Pennsylvania, USA. Specimen pyrite mixed with native shale was incubated in groundwater for 3months at the inferred depth of in situ pyrite oxidation. The colonized materials were used as an inoculum for pyrite-oxidizing enrichment cultures. Microbial activity accelerated the release of sulfate across all conditions. 16S rRNA gene sequencing and metagenomic analysis revealed the dominance of a putative chemolithoautotrophic sulfur-oxidizing bacterium from the genus Thiobacillus in the enrichment cultures. Previously proposed models for aerobic microbial pyrite oxidation were assessed in terms of physical constraints, enrichment culture geochemistry, and metagenomic analysis. Although we conclude that subsurface pyrite oxidation at SSCHZO is largely abiotic, this work nonetheless yields new insight into the potential pathways by which aerobic microorganisms may accelerate pyrite oxidation at circumneutral pH. We propose a new "direct sulfur oxidation" pathway, whereby sulfhydryl-bearing outer membrane proteins mediate oxidation of pyrite surfaces through a persulfide intermediate, analogous to previously proposed mechanisms for direct microbial oxidation of elemental sulfur. The action of this and other direct microbial pyrite oxidation pathways have major implications for controls on pyrite weathering rates in circumneutral pH sedimentary environments where pore throat sizes permit widespread access of microorganisms to pyrite surfaces.

Drivers of Dissolved Organic Carbon Mobilization From Forested Headwater Catchments: A Multi Scaled Approach

Understanding and predicting catchment responses to a regional disturbance is difficult because catchments are spatially heterogeneous systems that exhibit unique moderating characteristics. Changes in precipitation composition in the Northeastern U.S. is one prominent example, where reduction in wet and dry deposition is hypothesized to have caused increased dissolved organic carbon (DOC) export from many northern hemisphere forested catchments; however, findings from different locations contradict each other. Using shifts in acid deposition as a test case, we illustrate an iterative “process and pattern” approach to investigate the role of catchment characteristics in modulating the steam DOC response. We use a novel dataset that integrates regional and catchment-scale atmospheric deposition data, catchment characteristics and co-located stream Q and stream chemistry data. We use these data to investigate opportunities and limitations of a pattern-to-process approach where we explore regional patterns of reduced acid deposition, catchment characteristics and stream DOC response and specific soil processes at select locations. For pattern investigation, we quantify long-term trends of flow-adjusted DOC concentrations in stream water, along with wet deposition trends in sulfate, for USGS headwater catchments using Seasonal Kendall tests and then compare trend results to catchment attributes. Our investigation of climatic, topographic, and hydrologic catchment attributes vs. directionality of DOC trends suggests soil depth and catchment connectivity as possible modulating factors for DOC concentrations. This informed our process-to-pattern investigation, in which we experimentally simulated increased and decreased acid deposition on soil cores from catchments of contrasting long-term DOC response [Sleepers River Research Watershed (SRRW) for long-term increases in DOC and the Susquehanna Shale Hills Critical Zone Observatory (SSHCZO) for long-term decreases in DOC]. SRRW soils generally released more DOC than SSHCZO soils and losses into recovery solutions were higher. Scanning electron microscope imaging indicates a significant DOC contribution from destabilizing soil aggregates mostly from hydrologically disconnected landscape positions. Results from this work illustrate the value of an iterative process and pattern approach to understand catchment-scale response to regional disturbance and suggest opportunities for further investigations.

Seismic Ambient Noise Analyses Reveal Changing Temperature and Water Signals to 10s of Meters Depth in the Critical Zone

AbstractThe critical zone sustains terrestrial life, but we have few tools to explore it efficiently beyond the first few meters of the subsurface. Using analyses of high‐frequency ambient seismic noise from densely spaced seismometers deployed in the forested Shale Hills subcatchment of the Susquehanna Shale Hills Critical Zone Observatory (SSHCZO), we show that temporal changes in seismic velocities at depths from ∼1 m to tens of m can be detected. These changes are driven by variations at the land surface. The Moving‐Window Cross‐Spectral (MWCS) method was employed to measure seismic‐velocity changes in coda waves at hourly resolution in 10 different frequency bands. We observed a diurnal signal, a seasonal signal, and a meteorological‐event‐based signal. These signals were compared to time‐series measurements of precipitation, well water levels, soil moisture, soil temperature, air temperature, latent heat flux, and air pressure in the heavily instrumented catchment. Most of the velocity changes can be explained by variations in temperature that result in thermoelastic strains that propagate to depth. But some double minima in seismic velocity time‐series observed after large rain events were attributed in part to the effects of water infiltration. These results show that high‐frequency ambient noise data may in some locations be used to detect changes in the critical zone from ∼1 to ∼100 m or greater depth with hourly resolution. But interpretation of such data requires multiple environmental data sets to deconvolve the complex interrelationships among thermoelastic and hydrological effects in the subsurface critical zone.

An Empirical Orthogonal Function-Based Approach for Spatially- and Temporally-Extensive Soil Moisture Data Combination

Modeling and prediction of soil hydrologic processes require identifying soil moisture spatial-temporal patterns and effective methods allowing the data observations to be used across different spatial and temporal scales. This work presents a methodology for combining spatially- and temporally-extensive soil moisture datasets obtained in the Shale Hills Critical Zone Observatory (CZO) from 2004 to 2010. The soil moisture was investigated based on Empirical Orthogonal Function (EOF) analysis. The dominant soil moisture patterns were derived and further correlated with the soil-terrain attributes in the study area. The EOF analyses indicated that one or two EOFs of soil moisture could explain 76–89% of data variation. The primary EOF pattern had high values clustered in the valley region and, conversely, low values located in the sloping hills, with a depth-dependent correlation to which curvature, depth to bedrock, and topographic wetness index at the intermediate depths (0.4 m) exhibited the highest contributions. We suggest a novel approach to integrating the spatially-extensive manually measured datasets with the temporally-extensive automatically monitored datasets. Given the data accessibility, the current data merging framework has provided the methodology for the coupling of the mapped and monitored soil moisture datasets, as well as the conceptual coupling of slow and fast pedologic and hydrologic functions. This successful coupling implies that a combination of diverse and extensive moisture data has provided a solution of data use efficiency and, thus, exciting insights into the understanding of hydrological processes at multiple scales.

Developing boron isotopes to elucidate shale weathering in the critical zone

To further develop boron isotopes as a tool for understanding shale weathering, we explored patterns of boron concentrations and isotopes across the forested Susquehanna Shale Hills Critical Zone Observatory (CZO). We present boron measurements for all watershed components that provided a foundation for examining water-rock interactions in a shale dominated watershed, including water compartments (e.g., precipitation, stream water, groundwater) and solid compartments (e.g., soil, bedrock, stream sediments, suspended load, and leaf litter). Results show boron isotopes (δ11B) in the bedrock (− 4.6‰) and soil (− 5.9 to - 4.2‰) were very similar. All waters were enriched in 11B by comparison: precipitation (7.2 to 22.6‰), stream (10.3 to 15.5‰), and groundwater (2.2 to 17.4‰). Modeling revealed that isotopic fractionation observed in the surface water and groundwater could mainly be explained by water-rock interactions including clay mineral dissolution (e.g., chlorite) and coprecipitation/adsorption processes (e.g., coatings on illite particles), likely in the near surface soils (~2 m deep). We found that leaching, the loss of boron from vegetation to stream water, plays a secondary role. Specifically, such leaching likely contributes the equivalent of 10 to 26% of the B fluxes from the watershed outlet. Boron mass balance between bedrock and precipitation inputs and the exported flux of dissolved and solid pools identified a “missing” isotopically light solid flux (δ11B of −12.2 ± 5.3‰ at ~4.4 ± 3.8 mol/ha/y of B; uncertainty reported as 2 SD). We did not sample any pool with this isotopic signature. Here our data suggest the composition of this pool is more likely related to precipitation of secondary clays rather than adsorption or (co)precipitation on Fe oxides. We propose two hypotheses to explain the missing light B pool: 1) a significant portion of the particles carrying the missing 10B are not sampled because they enter groundwater at depth and are transported out of the catchment under the stream; and/or 2) the inputs and outputs of boron are not operating at steady state in the catchment today, suggesting that the missing boron particles were lost in the past in proportions higher than today. When this B budget is paired with studies of δ26Mg and δ56Fe from Shale Hills, both of which also show missing isotopic pools, the pattern indicates a fundamental gap in understanding of shale weathering. We concluded that light B particles, presumably generated in the upper soils, are likely transported deep beneath the surface in the groundwater system or episodically in the past through riverine fluxes.

Non‐linear quickflow response as indicators of runoff generation mechanisms

AbstractLinking quickflow response to subsurface state can improve our understanding of runoff processes that drive emergent catchment behaviour. We investigated the formation of non‐linear quickflows in three forested headwater catchments and also explored unsaturated and saturated storage dynamics, and likely runoff generation mechanisms that contributed to threshold formation. Our analyses focused on two reference watersheds at the Coweeta Hydrologic Laboratory (CHL) in western North Carolina, USA, and one reference watershed at the Susquehanna Shale Hills Critical Zone Observatory (SHW) in Central Pennsylvania, USA, with available hourly soil moisture, groundwater, streamflow, and precipitation time series over several years. Our study objectives were to characterise (a) non‐linear runoff response as a function of storm characteristics and antecedent conditions, (b) the critical levels of shallow unsaturated and saturated storage that lead to hourly flow response, and (c) runoff mechanisms contributing to rapidly increasing quickflow using measurements of soil moisture and groundwater. We found that maximum hourly rainfall did not significantly contribute to quickflow production in our sites, in contrast to prior studies, due to highly conductive forest soils. Soil moisture and groundwater dynamics measured in hydrologically representative areas of the hillslope showed that variable subsurface states could contribute to non‐linear runoff behaviour. Quickflow generation in watersheds at CHL were dominated by both saturated and unsaturated pathways, but the relative contributions of each pathway varied between catchments. In contrast, quickflow was almost entirely related to groundwater fluctuations at SHW. We showed that co‐located measurements of soil moisture and groundwater supplement threshold analyses providing stronger prediction and understanding of quickflow generation and indicate dominant runoff processes.

Observing and Simulating Spatial Variations of Forest Carbon Stocks in Complex Terrain

AbstractThe terrestrial carbon (C) cycle remains the least constrained component in the global C cycle, partly due to the difficulty of quantifying C sources and sinks in complex terrain. In this paper, we used observations at the Shale Hills Critical Zone Observatory and a biogeochemistry model, Biome‐BGC, to study the spatial distribution of C stocks and fluxes in a first‐order watershed. The model simulated the average C pools and fluxes in the watershed after constraining three model parameters with observations. The model was able to generate the observed spatial patterns of C pools in the watershed, with higher biomass and soil C in the valley and lower values on the ridgetop, though the model underestimated the ridgetop to valley differences. We examined the simulated effect of four environmental factors, soil moisture, soil temperature, nitrogen (N) availability and solar radiation, on the spatial distribution of C pools. Among these factors, soil water and N availability coupled together dominate the spatial distribution of aboveground biomass. Soil water was the most important factor controlling soil C. These results are highly sensitive to van Genuchten parameters, which describe the soil water retention curve. This study highlights the importance of the hydrologic system in describing within‐watershed structure in terrestrial C stocks.

Ideas and perspectives: Proposed best practices for collaboration at cross-disciplinary observatories

Abstract. Interdisciplinary science affords new opportunities but also presents new challenges for biogeosciences collaboration. Since 2007, we have conducted site-based interdisciplinary research in central PA, USA, at the Susquehanna Shale Hills critical zone observatory. Early in our collaboration, we realized the need for some best practices that could guide our project team. While we found some guidelines for determining authorship on papers, we found fewer guidelines describing how to collaboratively establish field sites, share instrumentation, share model code, and share data. Thus, we worked as a team to develop a best practices document that is presented here. While this work is based on one large team project, we think many of the themes are universal, and we present our example to provide a building block for improving the function of interdisciplinary biogeoscience science teams.

Chemical reactions, porosity, and microfracturing in shale during weathering: The effect of erosion rate

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 examining 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, ERCZO); 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 conditions. Thus, microfracturing is a process that can couple physical erosion and chemical weathering in shales.

Soil CO2 and O2 Concentrations Illuminate the Relative Importance of Weathering and Respiration to Seasonal Soil Gas Fluctuations

Soil CO2 and O2 cycles are coupled in some processes (e.g., respiration) but uncoupled in others (e.g., silicate weathering). One benchmark for interpreting soil biogeochemical processes affected by soil pCO2 and pO2 is to calculate the apparent respiratory quotient (ARQ). When aerobic respiration and diffusion are the dominant controls on gas concentrations, ARQ equals 1; ARQ deviates from 1 when other processes dominate soil CO2 and O2 chemistry. Here, we used ARQ to understand lithologic, hillslope, and seasonal controls on soil gases at the Susquehanna Shale Hills Critical Zone Observatory in central Pennsylvania. We measured soil pCO2 and pO2 at three depths from the soil surface to bedrock across catenas in one shale and one sandstone watershed over three growing seasons. We found that both parent lithology and hillslope position significantly affect soil gas concentrations and ARQ. Soil pCO2 was highest (>5%) and pO2 was lowest (<16%) in the valley floors. Controlling for depth, pCO2 was higher and pO2 was lower across all sites in the sandstone watershed. We attribute this pattern to higher macroporosity in sandstone lithologies, which results in greater root respiration at depth. We recorded seasonal variation in ARQ at all sites, with ARQ rising above 1 during July through September, and dipping below 1 in the early spring. We hypothesize that this seasonal fluctuation arises from anaerobic respiration in reducing microsites July through September when the soils are wet and demand for O2 is high, followed by oxidation of reduced species when the soils drain and re‐oxygenate. We estimate that this anaerobic respiration in microsites contributes 36 g C m−2 yr−1 to the soil C flux. Our results provide evidence for a conceptual model of metal cycling in temperate watersheds and point to the importance of anaerobic respiration to the carbon flux from forest soils.Core Ideas Hillslope position and lithology affect soil CO2 and O2 in humid temperate forests. The ratio of CO2 and O2 (ARQ) fluctuates over the growing season. The ARQ fluctuations indicate seasonal metal redox cycling at all hillslope positions. Anaerobic respiration is important to soil CO2 flux during the late growing season.

Preferential flow through shallow fractured bedrock and a 3D fill-and-spill model of hillslope subsurface hydrology

The role of preferential flow through unsaturated saprock (fractured bedrock with weathering restricted to fracture margins) in hillslope hydrology remains inadequately described. To address this issue, ground-penetrating radar (GPR), controlled infiltration, and high-frequency subsurface moisture monitoring were integrated to characterize saprock preferential flow (SPF) in the Susquehanna Shale Hills Critical Zone Observatory in Pennsylvania, U.S.A. In a planar hillslope with shallow fractured shale bedrock (starting at 0.1–0.3 m below ground), two pulses of water (79.5 L in total) were released followed by time-lapse GPR surveys. Differentiating GPR images collected before and after infiltration revealed lateral SPF in the direction of bedding plane fractures near the infiltration trench but with limited development of SPF down gradient along the hillslope. This was confirmed by soil and saprock moisture monitoring at a soil pit (0.2 m downslope of the GPR grid) where only one out of fifteen probes responded to the controlled infiltration. Lateral SPF frequently occurred at the GPR grid during a 24-day period with ten rainfall events, especially under the wet initial conditions. Additional infiltration experiments in a convex hillslope and a nearby bare slope with exposed saprock demonstrated the impact of fracture patterns on the routing of SPF. Three types of SPF in hillslope hydrology were identified, including (1) vertical percolation, (2) exfiltration from saprock to soil, and (3) stormwater transported downslope from planar and convex hillslopes to concave hillslopes. A 3D fill-and-spill model is proposed for the study site and similar areas that recognizes the importance of subsurface flow networks, with shallow saprock and concave hillslopes as essential controls of hillslope subsurface flow.

Biological Cycling of Mineral Nutrients in a Temperate Forested Shale Catchment

AbstractBiological pumping of mineral elements (root uptake from the soil and concentration at the surface via litterfall) may be an important mechanism influencing their loss from terrestrial ecosystems by accelerating transport in runoff, though few estimates exist to assess this. In the Susquehanna Shale Hills Critical Zone Observatory (a temperate forested watershed in central Pennsylvania), we compared two independent methods (litterfall‐based and transpiration flow‐based) for estimating the total uptake of elements (Ca, K, Mg, Mn, Si, Sr, and Al) by canopy trees. Elemental concentrations were measured monthly in leaf tissue and xylem sap of dominant species Quercus rubra (chestnut oak), Q. prinus (red oak), and Acer saccharum (sugar maple) for two growing seasons. Species‐specific litterfall and transpiration (estimated by eddy covariance) were used to scale concentrations to annual fluxes. For most elements, both methods generated comparable gross fluxes in the range of 53–85 (Ca), 9–19 (Mg), 14–28 (Mn), 0.2–0.6 (Al), and 0.1–0.3 (Sr) kg·ha−1·year−1. For K, litterfall‐based methods generated substantially lower estimates than transpiration, though neither accounted comprehensively for leaching from live foliage, resorption, or potential recycling within the growing season. For most elements, uptake rates were similar in magnitude to stream losses, implying a low degree of recycling. For K and Mn however, biological uptake exceeded losses by 1–2 orders of magnitude, suggesting a biological role in ecosystem retention. We conclude that litter‐ and transpiration‐based methods can be combined to broadly estimate the magnitude of biological pumping, with additional measures of wood‐/root‐based turnover necessary for more accurate budgets.

Particle fluxes in groundwater change subsurface shale rock chemistry over geologic time

Most models of landscape evolution posit that particles leave the land surface by physical weathering (i.e., erosion) and solutes leave the subsurface by chemical weathering. They assume that erosion does not affect the rock and soil chemistry. However, in this study of a shale catchment we discovered that particles are mobilized out of soil and weathering rock and are transported through the subsurface, resulting in changes in the rock and soil chemistry. We studied the solute and particle fluxes during six storms in the Susquehanna Shale Hills Critical Zone Observatory in Pennsylvania, USA and compared those to the record in regolith chemistry. The stream's suspended particles primarily consisted of platy-shaped, μm-sized illite, commonly coated with patchy, amorphous, submicron-sized Al-, Fe- and Si-rich oxides. The chemistry of the stream particles always differed from that of surface soils except during intense dry-season rainstorms. Stream particles were chemically similar to the laboratory-extracted soil colloids at high discharge but to groundwater particles at low discharge, implying a central role of flow path variations in controlling subsurface particle transport. Zr was effectively immobile in Shale Hills. Regolith chemistry revealed that the cumulative effects of particle loss to depths of 5–8 m in the fractured bedrock zone were estimated to account for 58% of K and 24% of Mg losses. In shale landscapes, we propose that subsurface particle transport must be considered in landscape evolution models as an important contributor to changes in rock and soil chemistry over geologic time periods.

Perennial flow through convergent hillslopes explains chemodynamic solute behavior in a shale headwater catchment

Stream chemistry reflects the mixture of complex biogeochemical reactions that vary across space and time within watersheds. For example, streams experience changing hydrologic connectivity to heterogeneous water sources under different flow regimes; however, it remains unclear how seasonal flow paths link these different sources and regulate concentration-discharge behavior, i.e., changes in stream solute concentration as a function of discharge. At the Susquehanna Shale Hills Critical Zone Observatory (SSHCZO) in central Pennsylvania, USA, concentrations of chemostatic solutes (K, Mg, Na, Si, Cl) vary little across a wide range of discharge values while concentrations of chemodynamic solutes (Fe, Mn, Ca) decrease sharply with increasing stream discharge. To elucidate controls on chemodynamic solute behavior, we investigated the chemistry of surface water and shallow subsurface water at the SSHCZO in early autumn when discharge was negligible and concentrations of chemodynamic solutes were high. Dissolved ions, colloids, and micron-sized particles were extracted from hillslope soils and stream sediments to evaluate how elements were mobilized into pore waters and transported from hillslopes to the stream.During the study period when flow was intermittent, the stream consisted of isolated puddles that were chemically variable along the length of the channel. Inputs of subsurface water to the stream were limited to an area of upwelling near the stream headwaters, and the water table remained over a meter below the stream bed along the rest of the channel. Chemodynamic elements Fe and Mn were preferentially mobilized from organic-rich soils as a mixture of dissolved ions, colloids, and micron-sized particles; consequently, subsurface water draining organic-rich soils in the upper catchment was enriched in Fe and Mn. Conversely, Ca increased towards the catchment outlet and was primarily mobilized from stream sediments as Ca2+. Concentrations of chemostatic solutes were relatively invariable throughout the catchment.We conclude that chemodynamic behavior at SSHCZO is driven by seasonally variable connectivity between the stream and hillslope soils. During the dry season, stream water derives from a shallow perched water table (interflow) that upwells to generate metal-rich stream headwaters. High concentrations of soluble Fe and Mn at low discharge occur when metal-rich headwaters are flushed to the catchment outlet during periodic rain events. Interflow during the dry season originates from water that infiltrates through organic-rich swales; thus, metals in the stream at low flow are ultimately derived from convergent hillslopes where biological processes have concentrated and/or mobilized these chemodynamic elements. In contrast, high concentrations of Ca2+ at low discharge are likely mobilized from stream sediments that contain secondary calcite precipitates. We infer that chemodynamic solutes are diluted at high discharge primarily due to increased flow through planar hillslopes. This study highlights how spatially heterogeneous biogeochemistry and seasonally variable flow paths regulate concentration-discharge behavior within catchments.

Nitrogen Budget and Topographic Controls on Nitrous Oxide in a Shale‐Based Watershed

AbstractThe high spatial and temporal variabilities of nitrous oxide (N2O) emissions from the soil surface have made it difficult to predict flux patterns at the ecosystem scale, leading to imbalances in nitrogen (N) budgets at all scales. Our research sought to quantify topographic controls on the sources or sinks of N2O in the soil profile to improve our ability to predict soil‐atmosphere N2O fluxes and their contribution to watershed N budgets. We monitored surface‐to‐atmosphere N2O fluxes for 2 years in the Susquehanna Shale Hills Critical Zone Observatory in central Pennsylvania. Topographically convergent flow path locations had significantly higher surface N2O flux rates than nonconvergent flow path locations in the summer, but not other seasons. Overall, N2O fluxes were a large percentage (~19%) of total ecosystem N losses, and nearly twice as large as stream N export. Surface N2O fluxes were better correlated with concentrations of O2, N2O, and NO3− in shallow soil layers (<30 cm) than deeper soils. Following decades of anthropogenic atmospheric deposition and additional N from shale weathering, watershed N inputs (~8 kgN ha−1 yr−1) are greater than outputs (~3.7 kgN ha−1 yr−1). Our research revealed patterns of N cycling that are distinct from many other watersheds that have been extensively studied to understand N saturation; despite showing no other symptoms of N saturation, the watershed had high upland N2O losses, especially in convergent flow paths during summer. High upland N gas losses may be a mechanism that maintains N limitation to biota in the Shale Hills catchment.

The Effect of Lithology and Agriculture at the Susquehanna Shale Hills Critical Zone Observatory

Core Ideas Two new subcatchments are used to test the importance of lithology and land use. Differences in lithology and land use result in differences in soils and waters. Despite differences, all catchments have a shallow and a deep water table. The relative importance of flow paths controls distinct chemistry response to discharge. Cross‐site comparison will ultimately enable upscaling from the catchment to large scale. The footprint of the Susquehanna Shale Hills Critical Zone Observatory was expanded in 2013 from the forested Shale Hills subcatchment (0.08 km2) to most of Shavers Creek watershed (163 km2) in an effort to understand the interactions among water, energy, gas, solute, and sediment. The main stem of Shavers Creek is now monitored, and instrumentation has been installed in two new subcatchments: Garner Run and Cole Farm. Garner Run is a pristine forested site underlain by sandstone, whereas Cole Farm is a cultivated site on calcareous shale. We describe preliminary data and insights about how the critical zone has evolved on sites of different lithology, vegetation, and land use. A notable conceptual model that has emerged is the “two water table” concept. Despite differences in critical zone architecture, we found evidence in each catchment of a shallow and a deep water table, with the former defined by shallow interflow and the latter defined by deeper groundwater flow through weathered and fractured bedrock. We show that the shallow and deep waters have distinct chemical signatures. The proportion of contribution from each water type to stream discharge plays a key role in determining how concentrations, including nutrients, vary as a function of stream discharge. This illustrates the benefits of the critical zone observatory approach: having common sites to grapple with cross‐disciplinary research questions, to integrate diverse datasets, and to support model development that ultimately enables the development of powerful conceptual and numerical frameworks for large‐scale hindcasting and forecasting capabilities.