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At least 73 records · Page 4

Lead isotopic compositions of airborne particulates collected from snow and from dry deposition in the East River Watershed, Colorado and at the Southern Sierra Critical Zone Observatory, California

The data set consists of lead (Pb) isotopic ratios (206Pb/207Pb and 208Pb/207Pb, as well as 206Pb/204Pb, 207Pb/204Pb, 208Pb/204Pb) for particulate samples collected from snow and dry deposition. This was part of a study (O’Day et al. 2020) that was looking at the speciation of phosphorous in splits of these samples to evaluate the flux and bio-availability of phosphorous to the mountain sites in the study. The Pb isotopic data allow sourcing of long-range transported Pb, specifically the fraction of Pb sourced in Asia, and so a comparison of the relative distances of PM sources between the high and low elevation sites. Samples were collected at the East River Watershed, CO (dry deposition collected over Sept.-Oct. 2016, show sampling winter 2017) and at the Southern Sierra Critical Zone Observatory (dry deposition collected over Sept-Nov 2016, July-Sept 2017, June-July 2017). The data includes Pb concentration data, as well as calculated fraction of the Pb sourced in Asia. This data set was published in part in O’Day et al. (2020) Phosphorus Speciation in Atmospherically Deposited Particulate Matter and Implications for Terrestrial Ecosystem Productivity. ES&T, https://dx.doi.org/10.1021/acs.est.9b06150

54 ENVIRONMENTAL SCIENCES↗

Linking Stream Chemistry to Subsurface Redox Architecture

As drinking-water scarcity grows worldwide, we need to improve predictions of the quantity and quality of our water resources. An overarching problem for model improvement is that we do not know the geological structure of aquifers in sufficient detail. In this work, we demonstrate that mineral-water reactions imprint structure in the subsurface that impacts the flow and transport of some chemical species. Specifically, pyrite, a ubiquitous mineral, commonly oxidizes and depletes in the upper layers of the weathering profile in most humid watersheds, only remaining at depths of meters. We hypothesize that variations in concentrations (C) of pyrite-derived sulfate released into rivers as a function of discharge (q) reflect the rate-limiting step and depth of pyrite-oxidizing layers. We found that log C - log q behaviors thus differ in small and large watersheds in the Susquehanna River Basin as well as in selected watersheds in the Western United States. Although coal mining changes pyrite oxidation from closed to open system with respect to O 2 , patterns in stream chemistry as a function of discharge are consistent with deep and shallow pyrite oxidation zones in small and large watersheds respectively. Therefore, understanding the subsurface patterns of mineral reactions and how they affect the architecture of aquifers will elucidate patterns of changing river chemistry and our ability to manage water resources in the future under accelerated land use and climate change.

54 ENVIRONMENTAL SCIENCES↗

Organic Matter Concentration and Composition in November 2021 and April 2022 from 12 Streams Impacted by the 2020 Holiday Farm Fire (v2)

This dataset represents results from a field study aiming to understand storm induced transport of pyrogenic materials to streams impacted by varying degrees of burn severity. Time series samples were collected at 5 sites within the McKenzie River Watershed (Oregon, USA) whose catchment were each completely engulfed by the 2020 Holiday Farm Fire. An additional 7 sites were sampled once during the storm. The samples were collected during storm events in November 2020, January 2021, November 2021, and April 2022. Samples were characterized for benezenepolycarboxylic acids (BPCA), ultra-high resolution mass spectrometry, dissolved organic carbon and optics (absorbance and fluorescence). Fourier-transform ion cyclotron resonance mass spectrometry (FTICR) and dissolved organic carbon data from the November 2020 (referred to as “EWEB_2020”) sampling can be found in a separate data package (doi: 10.15485/1869708). NOTE: The 2020 samples were run on FTICR-MS in two unique instances. The first run can be found in the previous data package (EWEB_2020). The second run is included in this data package. These samples were run for a second time so that the data were more directly interoperable with the other samples in this data package. We have not done any investigation into the differences/similarities between these datasets and the previously ran/published data in the other data package. This data package was originally published in November 2024. It was updated in April 2025 (v2; new and modified files). See the change history section below for more details. For details on how to navigate data packages generated by this project, see https://data.ess-dive.lbl.gov/portals/PNNLRiverCorridorSFA/About. This dataset contains (1) file-level metadata; (2) data dictionary; (3) data package readme; (4) metadata; (5) methods information; (6) dissolved organic carbon (DOC, measured as non-purgeable organic carbon, NPOC) data; (7) excitation emission matrix (EEM) methods; and (8) a sub-folder with processed EEM data (9) benzene polycarboxylic acid (BPCA) concentration data; (10) Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS) methods; and (11) folder of high-resolution characterization of organic matter via 12 Tesla FTICR-MS generated through the Environmental Molecular Sciences Laboratory (EMSL; https://www.pnnl.gov/environmental-molecular-sciences-laboratory). The EEMs sub-folder contains two additional folders; the Absorbance and Fluorescence folders which contain the processed EEMs absorbance and fluorescence data respectively. This package contains the following file types: csv, xml, pdf.

54 ENVIRONMENTAL SCIENCES↗

Modelling the Sensitivity of Yukon River Biogeochemical Dynamics to Environmental and Chemical Drivers: Implications for Dissolved Organic Carbon

Riverine dissolved organic carbon (DOC) is a critical biogeochemical component that transmits information from Arctic soils to the Arctic Ocean, significantly influencing carbon dynamics in this unique ecosystem. As DOC travels downstream, it undergoes transformations that alter its composition and fate. The Yukon River serves as an effective testbed for modelling these dynamics, offering sufficient scale to capture key biogeochemical processes while having a simpler hydrology than other major Arctic rivers, as well as long-term DOC observational data for model validation. To investigate DOC transformations during transit in the Yukon River, we adapted our Arctic Riverine Organic Macromolecular Model by applying regional-specific parameterisations. Our model simulates the transport and transformation of 15 organic macromolecules, including CDOM (coloured dissolved organic matter), proteins, polysaccharides, lipids, lignin phenols, and humic substances. Initial DOC concentrations were derived from observed soil organic carbon stocks in the surrounding watershed, while chemical transformations and hydrological dynamics were modelled along the river's course. Sensitivity and uncertainty analyses were conducted using a Monte Carlo approach under two experimental setups. Results revealed that variability in DOC and CDOM concentrations at the river mouth were predominantly driven by initial DOC concentration (~70% of variability explained) and dilution at confluence points (~10%). The refractory fraction of DOC explained 21%–88% of the variability in 14 macromolecular concentrations and ranked in the top five sensitive parameters for all outputs when a uniform parameter distribution was assumed. However, when a more likely variability was applied to this parameter, its influence on DOC and CDOM decreased. Given that refractory DOC accounts for ~80% of total DOC in Arctic Rivers, this suggests that most DOC resists degradation and retains its chemical composition during transport to the coastal environment. River velocity, which determines residence time, explained 8%–47% of the variability in protein, polysaccharide, lipid, pigments, and lignin phenols at the river mouth. In contrast, chemical turnover times contributed only 1%–5% to output variability. Our findings underscore the need for improved land-specific headwater observations, including seasonal soil moisture and lateral transport dynamics that control the initial tributary-specific DOC inputs. With accelerated permafrost thaw and increasing river discharge, extending our model to other Arctic River systems and seasons will enhance understanding of Arctic riverine carbon fluxes and their contributions to the Arctic Ocean.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Postfire Biogeochemical Processes: Implications to Source Water Quality in Fire-Influenced Watersheds

Forested watersheds are instrumental in providing purified and reliable water to millions of people worldwide. The changing climate has increased the frequency and severity of global fire events. Forested watersheds and their ecosystem functions are greatly disrupted during fire activity. Postfire concerns in forested watersheds include unpredictable and potentially simultaneous alterations in source water quality and hydro-biogeochemical processes. Here, the degree of fire severity can complexly modify water quality through the production of fire-transformed constituents on the burned forest floor (i.e., nutrients, metal(loid)s, dissolved organic matter, and the formation of disinfection byproducts). Correspondingly, fire severity and postfire rainfall patterns can refine hydro-biogeochemical processes that influence the transport of the fire-transformed constituents (i.e., vegetation function, soil structure, hydrological pathways, and microbial communities). Postfire alterations to water quality and hydro-biogeochemical processes introduce further complexity with varying temporal influence, which ranges from months to decades. As postfire water quality and watershed response research progresses, it is essential to homogenize interdisciplinary expertise to bridge knowledge gaps between fields ranging from forest ecology, hydrology, microbiology, and geochemistry. A multidisciplinary approach in wildfire research will facilitate a comprehensive perception of the diverse water quality risks associated with fire activity and mitigate fire concerns on a global level.

Disinfection Byproducts↗

Surface Water Quality Data from Beaver-Impacted Streams; Trail Creek and East River, Colorado 2025

This data package contains surface water chemistry measurements collected in 2025 to evaluate how beaver damming and low-tech process-based stream restoration influence water quality and metal mobility in mountainous headwater systems of the Upper Colorado River Basin. Sampling was conducted at Trail Creek (Taylor Park watershed, Colorado), a tributary undergoing restoration through installation of low-tech process-based structures (i.e., beaver dam analogs), and at off-channel beaver ponds within the East River floodplain (East River watershed, Colorado). Samples were collected along longitudinal transects spanning upstream control reaches, beaver-influenced ponded reaches, and downstream segments. Additional samples were collected from near-surface pore waters within a beaver dam seepage face. The dataset includes concentrations of major and trace elements measured by inductively coupled plasma–mass spectrometry (ICP-MS) and inductively coupled plasma–optical emission spectrometry (ICP-OES), major anions measured by ion chromatography (IC), and dissolved organic carbon (DOC; reported as non-purgeable organic carbon, NPOC). Samples were size-fractionated at 0.45 micrometers (µm), 0.22 µm, and 0.02 µm to distinguish particulate (>0.45 µm), colloidal (0.22–0.02 µm), and dissolved (<0.02 µm) fractions. The data package consists of comma-separated value (.csv) files containing tabulated chemical concentration data, sample metadata (site identifiers, geographic coordinates, sampling dates, fraction type), and quality control flags. All files are provided in open, non-proprietary formats that can be accessed using standard data analysis software such as Microsoft Excel, R, Python, MATLAB, or other programs capable of reading .csv files. Units, detection limits, and analytical methods are documented in accompanying metadata files. The dataset is designed to support analyses of (1) how beaver impoundment and restoration structures alter elemental partitioning and transport, (2) the role of iron and organic carbon in mediating trace metal mobility, and (3) reach-scale changes in water quality across restoration gradients. This work was supported by the Watershed Function Science Focus Area at Lawrence Berkeley National Laboratory funded by the US Department of Energy, Office of Science, Biological and Environmental Research under Contract No. DE-AC02-05CH11231. Part of this work was performed at SLAC Accelerator Laboratory funded by the US Department of Energy, Office of Science, Biological and Environmental Research under Contract No. DE-AC02-76SF00515.

Anions↗

Orthoimagery and Shapefiles Documenting Pre- and Post-August 2019 Slope Disturbances, Teller Road Site, Seward Peninsula, Alaska, 2018-2019

This dataset was derived from UAS aerial photos and dGPS data collected at the Teller mile marker 47 site in 2018 and 2019 and used to support research quantifying the timing and rate of surface movements and analyze soil transport process in Arctic landscapes. In July 2018, a Phantom uncrewed aerial system (UAS) collected >6800 high resolution aerial photos of the lower portion of the Teller 47 watershed (see for raw photos; pending archive NGA281). During the UAS survey, 25 x 25 cm tile ground control points (GCPs) were laid out and secured with one rebar rod in the center. The four corners and rebar tops were surveyed with differential GPS, and these coordinates were used to construct and validate an orthomosaic of the site. These points were resurveyed in August 2019 and used to track annual movement. Changes in position between the two surveys are reported in (Lathrop et al. 2022; NGA254). Agisoft Metashape photogrammetry software was used to construct a georeferenced orthomosaic image (*.tif file) of a portion (0.68 km2) of the watershed with a final resolution of ~1 cm. Manual delineation of the perimeters of failures visible in the UAS imagery (*.tif files) was conducted to create shapefile polygons (two *.zip files). The failures were identified by the exposure of bare mineral soils, which were made visible by disruption of the overlying tundra vegetation. The shapefiles were then used to analyse the topographic distribution and sizes of the failures. In August 2019 an additional ~300 georeferenced UAS images of slope instability features were collected (data pending submission) and compared with the 2018 orthomosaic. Overview maps of the failure locations included as a *.pdf.The Next-Generation Ecosystem Experiments: Arctic (NGEE Arctic), was a research effort to reduce uncertainty in Earth System Models by developing a predictive understanding of carbon-rich Arctic ecosystems and feedbacks to climate. NGEE Arctic was supported by the Department of Energy's Office of Biological and Environmental Research.The NGEE Arctic project had two field research sites: 1) located within the Arctic polygonal tundra coastal region on the Barrow Environmental Observatory (BEO) and the North Slope near Utqiagvik (Barrow), Alaska and 2) multiple areas on the discontinuous permafrost region of the Seward Peninsula north of Nome, Alaska.Through observations, experiments, and synthesis with existing datasets, NGEE Arctic provided an enhanced knowledge base for multi-scale modeling and contributed to improved process representation at global pan-Arctic scales within the Department of Energy's Earth system Model (the Energy Exascale Earth System Model, or E3SM), and specifically within the E3SM Land Model component (ELM).

54 ENVIRONMENTAL SCIENCES↗

Antecedent Hydrologic Conditions Reflected in Stream Lithium Isotope Ratios During Storms

Antecedent hydrological conditions are recorded through the evolution of dissolved lithium isotope signatures (δ 7 Li) by juxtaposing two storm events in an upland watershed subject to a Mediterranean climate. Discharge and δ 7 Li are negatively correlated in both events,but mean δ 7 Li ratios and associated ranges of variation are distinct between them. We apply a previously developed reactive transport model (RTM) for the site to these event-scale flow perturbations, but observed shifts in stream δ 7 Li are not reproduced. To reconcile the stability of the subsurface solute weathering profile with our observations of dynamic stream δ 7 Li signatures, we couple the RTM to a distribution of fluid transit times that evolve based on storm hydrographs. The approach guides appropriate flux-weighting of fluid from the RTM over a range of flow path lengths, or equivalently fluid residence times. This flux-weighted RTM approach accurately reproduces dynamic storm δ 7 Li-discharge patterns distinguished by the antecedent conditions of the watershed.

58 GEOSCIENCES↗

Development of a molecularly informed biogeochemical framework for reactive transport modeling of subsurface carbon inventories, transformations and fluxes (Final Report)

The overall objective of the project was to combine new molecular-level characterization strategies with soil carbon flux measurements to develop and evaluate model representations of subsurface carbon cycling. We expanded on existing studies in the East River watershed, Colorado, in collaboration with the Berkeley Lab Watershed Function Scientific Focus Area (SFA), SLAC Groundwater Quality SFA, and Rocky Mountain Biological Laboratory (RMBL) to develop an elevation and vegetation gradient that is now the subject of long-term monitoring by the USGS. To achieve the overall objective, we combined field studies of soil respiration with laboratory analyses, ranging from spectroscopy to incubation studies. This combination of techniques enabled us to develop a new understanding of the drivers of high-elevation soil respiration. In the process, we developed three new modeling approaches that improve our ability to conceptualize and ultimately to represent soil respiration in numerical models. The first approach is a plot-scale transient inverse model that can be used to determine in situ CO 2 production rates from measured concentration profiles and surface fluxes. Application of this method revealed the importance of plant phenology and deep CO 2 production in moderating CO 2 fluxes to the atmosphere. The second modeling approach is a molecular-scale tool that enables spectroscopic and elemental data for carbon speciation to be transformed into functional group abundances, or the ‘SOC-fga model’. This method uniquely enables carbon speciation to be tracked within a reactive transport framework to partition carbon among different pathways and storage zones within the soil. The third modeling tool builds strongly on the previous approaches and captures the microbial processes driving heterotrophic respiration. This ‘dormancy model’ allows the native soil microbial population to respond transiently to the presence or absence of water in order to catalyze carbon respiration. This approach was also compared to the simpler and more widely used first-order model using two experimental datasets with different temporal and spatial resolutions. Our results illustrate that the simpler first order model provides a robust and efficient representation of deep (>1 meter) soil respiration, but that shallow soils, where most respiration occurs, require explicit representation of moisture-dependent activation and dormancy rates. By assessing soil organic carbon turnover at multiple scales, we see a complex array of controls emerge. Atte scale of a hillslope, spatial heterogeneity in soil respiration rates dominates and is uncorrelated with instantaneous soil moisture and plant community. At the profile scale, the balance between plant inputs and water availability is the dominant control. At the microbial to molecular scale, physiological processes associated with carbon use and carbon speciation are important controls. These scale-dependent controls emphasize the need for new modeling approaches that examine their interactions and hierarchies.

54 ENVIRONMENTAL SCIENCES↗

FTICR-MS, Sensor, and Environmental Data from 5 Streams Impacted by the 2020 Holiday Farm Fire Associated with: "Spatiotemporal controls on the delivery of dissolved organic matter to streams following a wildfire"

This data package is associated with the publication "Spatiotemporal Controls on the Delivery of Dissolved Organic Matter to Streams Following a Wildfire" submitted to Geophysical Research Letters (Roebuck et al., 2022). The study aims to understand storm induced transport of pyrogenic materials to streams impacted by varying degrees of burn severity. Time series samples (24 samples in 1-hour intervals) were collected at 5 sites within the McKenzie River Watershed (Oregon, USA) whose catchment were each completely engulfed by the 2020 Holiday Farm Fire. The samples were collected in November 2020 during the first major storm pulse following the conclusion of the wildfire. Samples were characterized for dissolved organic carbon, total dissolved nitrogen, and by ultra-high resolution mass spectrometry. In situ turbidity data also collected.This data package contains 4 primary folders that include the following: 1) Metadata, 2) EnvData (Environmental Data), 3) SensorData, and 4) FTICR_SupportingData. The package contains a single file-level metadata (flmd) file. Each primary folder also contains individual data dictionaries (dd) to define and provide descriptors of column/row headers and data flags. The FTICR_SupportingData, folder 4, contains raw, unprocessed FTICR-MS Data files in addition to a csv containing processed FTICR-MS data. This package contains the following file types: csv, xml, pdf.

54 ENVIRONMENTAL SCIENCES↗

Community-Informed Urban Flood Modeling for Impact Mitigation

The intensification of the hydrologic cycle due to climate change poses a threat to aging and under-designed water infrastructure systems which cannot adequately manage intense storm events. Developing a comprehensive plan for managing rain-driven flooding events is challenging due to uncertainties in the magnitude and frequency of future storm events and conflicting stakeholder objectives. In the City of Baltimore, Maryland, stormwater infrastructure is struggling to keep up with rainfall-driven (pluvial) flooding events, which regularly damage housing and disrupt transportation for residents. In this study, a hybrid of community engagement, numerical modeling, and artificial intelligence techniques are employed to explore prospective urban flooding adaptations. Community engagement drives the development of an urban flooding model (EPA Storm Water Management Model) for the Baltimore Harbor watershed. The model integrates complex surface and subsurface stormwater infrastructure data from the City, high-resolution spatial data, insights from local public works experts, and the lived experiences of City residents. This co-developed model simulates adaptations of interest to stakeholders in the city, including green and grey infrastructure and operational management strategies. Stormwater management scenarios focused on inlet cleaning and spatially concentrated green infrastructure are found to be the most effective in reducing flood depths in community priority locations. Together, these adaptations can reduce the duration of intersection inundation by more than twenty minutes, allowing for quicker emergency response and restoration of typical transportation systems. Future work will combine this community engaged flooding model with the Deep Uncertainties Pathways framework to explore tradeoffs between adaptations and develop dynamic adaptations which align with community objectives, enhance climate resilience in Baltimore, and can be adjusted in response to changing future conditions.

Ava, Spangler [Pennsylvania State University]↗

Modeling the Effects of Artificial Drainage on Agriculture-dominated Watersheds using a Fully Distributed Integrated Hydrology Model: Datasets, scripts, model files

This model-data archive supports the research paper that demonstrates the integration of agricultural drainage features—specifically, narrow engineered ditches and tile drains—into a fully distributed, basin-scale integrated surface-subsurface hydrology model (ISSHM), Amanzi-ATS. The model employs innovative computational meshes aligned with agricultural ditches and incorporates the physically based Hooghoudt's drainage equation to simulate tile drainage, offering a novel strategy that enhances the accuracy of hydrological simulations.The archived dataset includes input parameters, model configurations, and select simulation outputs for the Amanzi-ATS model that successfully captured the streamflow patterns in the Portage River Watershed as validated by USGS gauge readings. Jupyter notebook for the preparation of model inputs and post-processing of outputs are also included. The model's predictive performance achieved a normalized Kling-Gupta Efficiency (KGE) of 0.81, surpassing SWAT without the necessity for site-specific calibration.The Amanzi-ATS model presented in this modeL-data archive allows for numerical experiments to explore the shifts in the flow structure under different drainage scenarios. As a tool for advancing the understanding of distributed hydrological responses and nutrient cycling, this archived model provides valuable insights for researchers, modelers, and decision-makers involved in watershed management and environmental modeling.The Watershed Workflow package is implemented in Python3. The Jupyter notebooks can be executed through multiple open-source tools, for example, Anaconda Jupyter Lab, VS Studio Code, etc. Other data files include CSV and HDF5 files, which can be read through Python scripts. The input files for the ATS model, open-source integrated hydrology, and transport model, are in XML format and can be edited in any commonly used text editors.

54 ENVIRONMENTAL SCIENCES↗

Matrix Diffusion Controls Mountain Hillslope Groundwater Ages and Inferred Storage Dynamics

Groundwater age distributions provide fundamental insights on coupled water and biogeochemical processes in mountain watersheds. Field-based studies have found mixtures of young and old-aged groundwater in mountain catchments underlain by bedrock; yet, the processes that dictate these groundwater age distributions are poorly understood. In this work, we use the coupled ParFlow-CLM integrated hydrologic and EcoSLIM particle tracking models to simulate groundwater age distributions on a lower montane hillslope in the East River Watershed, Colorado (USA). We develop a convolution-based approach to propagate fracture-matrix diffusion processes to the EcoSLIM advection-dominated age distributions. We compare observed 3 H and 4 He concentrations from two groundwater wells against model predictions that have varying advective transport times and matrix diffusion magnitudes. Based on a Monte Carlo analysis that considers uncertain matrix and fracture parameters, we find that matrix diffusion is needed to jointly predict 3 H and 4 He observations at both wells. The advection-dominated age distributions lack adequate mixing of young and old-aged water to capture the observed co-occurrence of 3 H and 4 He. The model scenario that best matches the 3 H, 4 He, and water level observations when considering both advective flowpath and matrix diffusion mixing processes has a dynamic bedrock groundwater reservoir that is susceptible to considerable storage losses during low-snow periods. This dynamic groundwater system amplifies the need to assimilate deeper bedrock groundwater into watershed hydro-biogeochemical predictions. This work further highlights the importance of considering matrix diffusion when interpreting environmental tracers in bedrock groundwater systems.

54 ENVIRONMENTAL SCIENCES↗

Sinuosity‐Driven Hyporheic Exchange: Hydrodynamics and Biogeochemical Potentials

Abstract Hydrologic exchange processes are critical for ecosystem services along river corridors. Meandering contributes to this exchange by driving channel water, solutes, and energy through the surrounding alluvium, a process called sinuosity‐driven hyporheic exchange. This exchange is embedded within and modulated by the regional groundwater flow (RGF), which compresses the hyporheic zone and potentially diminishes its overall impact. Quantifying the role of sinuosity‐driven hyporheic exchange at the reach‐to‐watershed scale requires a mechanistic understanding of the interplay between drivers (meander planform) and modulators (RGF) and its implications for biogeochemical transformations. Here, we use a 2D, vertically integrated numerical model for flow, transport, and reaction to analyze sinuosity‐driven hyporheic exchange systematically. Using this model, we propose a dimensionless framework to explore the role of meander planform and RGF in hydrodynamics and how they constrain nitrogen cycling. Our results highlight the importance of meander topology for water flow and age. We demonstrate how the meander neck induces a shielding effect that protects the hyporheic zone against RGF, imposing a physical constraint on biogeochemical transformations. Furthermore, we explore the conditions when a meander acts as a net nitrogen source or sink. This transition in the net biogeochemical potential is described by a handful of dimensionless physical and biogeochemical parameters that can be measured or constrained from literature and remote sensing. This work provides a new physically based model that quantifies sinuosity‐driven hyporheic exchange and biogeochemical reactions, a critical step toward their representation in water quality models and the design and assessment of river restoration strategies.

54 ENVIRONMENTAL SCIENCES↗

Hidden Features: How Subsurface and Landscape Heterogeneity Govern Hydrologic Connectivity and Stream Chemistry in a Montane Watershed

ABSTRACT Hydrologic connectivity is defined as the connection among stores of water within a watershed and controls the flux of water and solutes from the subsurface to the stream. Hydrologic connectivity is difficult to quantify because it is goverened by heterogeniety in subsurface storage and permeability and responds to seasonal changes in precipitation inputs and subsurface moisture conditions. How interannual climate variability impacts hydrologic connectivity, and thus stream flow generation and chemistry, remains unclear. Using a rare, four‐year synoptic stream chemistry dataset, we evaluated shifts in stream chemistry and stream flow source of Coal Creek, a montane, headwater tributary of the Upper Colorado River. We leveraged compositional principal component analysis and end‐member mixing to evaluate how seasonal and interannual variation in subsurface moisture conditions impacts stream chemistry. Overall, three main findings emerged from this work. First, three geochemically distinct end members were identified that constrained stream flow chemistry: reach inflows, and quick and slow flow groundwater contributions. Reach inflows were impacted by historic base and precious metal mine inputs. Bedrock fractures facilitated much of the transport of quick flow groundwater and higher‐storage subsurface features (e.g., alluvial fans) facilitated the transport of slow flow groundwater. Second, the contributions of different end members to the stream changed over the summer. In early summer, stream flow was composed of all three end members, while in late summer, it was composed predominantly of reach inflows and slow flow groundwater. Finally, we observed minimal differences in proportional composition in stream chemistry across all four years, indicating seasonal variability in subsurface moisture and spatial heterogeneity in landscape and geologic features had a greater influence than interannual climate fluctuation on hydrologic connectivity and stream water chemistry. These findings indicate that mechanisms controlling solute transport (e.g., hydrologic connectivity and flow path activation) may be resilient (i.e., able to rebound after perturbations) to predicted increases in climate variability. By establishing a framework for assessing compositional stream chemistry across variable hydrologic and subsurface moisture conditions, our study offers a method to evaluate watershed biogeochemical resilience to variations in hydrometeorological conditions.

Johnson, Keira [College of Earth, Ocean, and Atmos↗

A radioisotope - enabled reactive transport model for deep vadose zone carbon

In mountainous regions, which constitute the principle source of recharge to major rivers and regional aquifers, infiltration occurs through fractured, partially saturated, weathered bedrock that acts as a boundary layer between saturated aquifers and surface soil. Commonly this deep vadose zone (DVZ) is many meters thick, and yet its role in regulating the generation, retention and mobility of reactive solutes, including nutrients, contaminants and weathering products, is largely unknown. In particular, many of the key reactions that drive the formation of the weathered DVZ and the quality of water moving through it are redox processes, regulated by the availability of organic carbon and oxygen below the soil layer. The role of the DVZ is thus also poorly constrained in the context of carbon stocks and mobility, particularly in lithologies that are naturally high in organic carbon, such as shales. The overarching hypothesis of this study is that upland regions developed in geologic settings with abundant petrogenic carbon store and actively cycle carbon in the weathered DVZ below the soil and above the water table at rates that are significant and currently unconstrained. In order to quantify this cycling, the current study combines novel instrumentation techniques allowing new direct sampling of DVZ systems with advanced numerical reactive transport simulations of carbon transport and transformation. Critically, these simulations will explicitly treat the three isotopes of carbon (the abundant 12C, the stable rare 13C and the radioactive 14C) in a unified framework, thus clearly parsing between the contributions of modern surface derived carbon and lithologic carbon sources in integrated measurements of fluid and gas phase fluxes. This novel model capability will be applied to test the role of DVZ carbon cycling as a regulator of water quality and geological weathering in two complementary field sites both located in organic carbon rich shale lithologies. The first is the Eel River Critical Zone Observatory (ERCZO) in Mendocino County, California, and the second is the Lawrence Berkeley National Laboratory Watershed Function Scientific Focus Area (SFA) in the East River watershed, near Crested Butte, Colorado. At the ERCZO, a novel vadose zone monitoring system has been installed in a 20 m thick, partially saturated, weathered shale hillslope, and preliminary data already indicate substantial CO2 flux generated many meters below the soil surface. At the SFA field site, an instrumented hillslope transect indicates a more complex multi-dimensional fluid and solute transport regime, which will serve as a key test of the calibrated models. Collectively, this project will advance understanding of the cycling of carbon belowground and in relation to transport pathways across the poorly constrained DVZ characteristic of primary water recharge areas. The key product of this work will be enhanced isotope simulation capabilities that are robust and publicly available for application across a broad diversity of systems.

58 GEOSCIENCES↗

Trace elements and their isotopes in streams and rivers

The occurrence and speciation of trace elements in streams and rivers are controlled by interconnected hydrogeological, biogeochemical, and anthropogenic factors that include rock weathering, climate, vegetation, and land use within the watershed. This chapter provides a broad overview of trace element abundance, speciation, and mobility in streams and rivers, including an assessment of how trace elements are partitioned into dissolved, colloidal, and particulate phases. We also discuss how trace elements are mobilized into stream networks and transformed during transport. Select isotopic systems are reviewed to provide examples of how isotopic analyses can be used to understand geochemical and anthropogenic processes.

Herndon, Elizabeth [ORNL] (ORCID:0000000291945493)↗