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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Revealing the Predominant Surface Facets of Rough Cu Electrodes under Electrochemical Conditions

Metal electrodes with rough surfaces are frequently found to convert CO or CO 2 to hydrocarbons and oxygenates with high selectivity and at high reaction rates in comparison with their smooth counterparts. The atomic-level morphology of a rough electrode is likely one key factor responsible for its comparatively high catalytic selectivity and activity. However, few methods are capable of probing the atomic-level structure of rough metal electrodes under electrocatalytic conditions. As a result, the nuances in the atomic-level surface morphology that control the catalytic characteristics of these electrodes have remained largely unexplored. Because the C≡O stretching frequency of atop-bound CO (CO atop ) depends on the coordination of the underlying metal atom, the IR spectrum of this reaction intermediate on the copper electrode could, in principle, provide structural information about the catalytic surface during electrolysis. However, other effects, such as dynamic dipole coupling, easily obscure the dependence of the frequency on the surface morphology. Further, in the limit of low CO atop coverage, where coupling effects are small, the C≡O stretching frequencies of CO atop on Cu(111) and Cu(100) facets are virtually identical. Therefore, on the basis of the C≡O stretching frequency, it is not straightforward to distinguish between these two ubiquitous surface facets, which exhibit vastly different CO reduction activities. Herein, we show that key features of the atomic-level surface morphology of rough copper electrodes can be inferred from the potential dependence of the line shape of the C≡O stretching band of CO atop . Specifically, we compared two types of rough copper thin-film electrodes that are routinely employed in the context of surface-enhanced infrared absorption spectroscopy (SEIRAS). We found that copper films that are electrochemically deposited on Si-supported Au films (CuAu–Si) are poor catalysts for the reduction of CO to ethylene in comparison to copper films (Cu–Si) that are electrolessly deposited onto Si crystals. As quantified by differential electrochemical mass spectrometry (DEMS), the onset potential for ethylene is ~200 ± 65 mV more cathodic for CuAu–Si than that for Cu–Si. To reveal the origin of the disparate catalytic properties of Cu–Si and CuAu–Si, we probed the surfaces of the electrodes with cyclic voltammetry (CV) and SEIRAS. The CV characterization suggests that the (111) surface facet predominates on CuAu–Si, whereas the (100) facet is more common on Cu–Si. SEIRAS reveals that the line shape of the C≡O stretching of CO atop is composed of two bands that are attributable to CO atop on terrace and defect sites. The different surface structures manifest themselves in the form of starkly different potential dependences of the line shape of the C≡O stretching mode of CO atop on the two types of electrodes. With a simple Boltzmann model that considers the different adsorption energies of CO atop on terrace and defect sites, and the resulting CO atop populations on terrace and defect sites, we deduced that the observed electrode-specific potential dependence of the line shape is consistent with the presence of different predominant terrace sites on the two types of films. This strategy for assessing the atomic-level morphology is not restricted to SEIRAS but could also be applied to the C≡O stretching bands recorded with surface-enhanced Raman spectroscopy (SERS), which is suitable for probing a wide range of rough copper electrodes. Therefore, with this work, we establish the potential dependence of the C≡O stretching band of CO atop as a probe of the atomic-level surface structure of rough metal electrodes under electrochemical conditions. When it is coupled with complementary techniques, this methodology provides essential structural information for further improvement in the reaction selectivity of rough metal electrodes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Integrated Reference Electrodes in Anion-Exchange-Membrane Electrolyzers: Impact of Stainless-Steel Gas-Diffusion Layers and Internal Mechanical Pressure

Alkaline-membrane electrolyzers operating in pure water might provide scalable low-cost H 2 production but currently lag in performance and durability compared to commercial technologies. Typically, membrane–electrode assemblies (MEAs) are optimized in electrolyzers by changing one parameter at a time and assessing the resulting system performance via two-electrode polarization and impedance measurements. These approaches are limited in their ability to assign performance changes and durability to specific electrodes or processes. We integrate a reference electrode with the MEA to separate anode and cathode responses in both polarization and impedance measurements. Here we illustrate the power of the approach by showing how the fiber diameter of stainless-steel gas-diffusion layers (GDLs) affects performance solely at the anode, while changing the thickness of the cathode GDL simultaneously affects the performance of the anode and cathode due to changes in internal pressure from mechanical compression. This finding was obscured in conventional two-electrode measurements. The work thus guides both high-performance alkaline-membrane water-electrolyzer development and illustrates a useful strategy to study structure–activity relationships in the MEA.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Simply Fabricatable Reference Electrode for Studying Li Metal Interfaces Operando

Reference electrodes are essential for studying Li metal interfaces, yet their integration into coin cells remains challenging due to geometric constraints and assembly complexity. Here, we present a simple three-electrode coin cell design in which a thin Cu film is evaporated directly onto a trilayer PP/PE/PP separator, forming a conductive and flexible in situ current collector. The microporous Cu preserves separator porosity and pressure uniformity, avoiding artifacts introduced by wire- or mesh-type references. It is easily activated by Li plating and provides stable potentials for over 10 days in ether-based electrolytes without affecting Coulombic efficiency (>99%) or Li deposition morphology. Operando measurements using this design reveal electrode-specific impedance evolution and voltage responses otherwise obscured in two-electrode setups, uncovering a correlation between the SEI resistance and electrolyte ionic conductivity. This microporous Cu reference electrode offers a robust and accessible platform for characterizing reactive interfaces under realistic cycling conditions.

Sacci, Robert [ORNL] (ORCID:0000000200735221)↗
DOE OSTI2025

Real-Time Measurements of Gas-Phase Medium-Chain Chlorinated Paraffins Reveal Daily Changes in Gas-Particle Partitioning Controlled by Ambient Temperature

Chlorinated paraffins (CPs) are synthetic polychlorinated n-alkanes produced as mixtures of a range of C x Cl y H 2x–y+2 formulas. CPs have numerous industrial applications but are toxic, long-lived, and environmentally ubiquitous with environmental releases occurring throughout their production, use, and disposal. Short-chain chlorinated paraffins (SCCPs, C 10–13 ) have been regulated by the United States Environmental Protection Agency since 2009 and by the Stockholm Convention since 2017. SCCP regulation is expected to cause increased production of medium-chain chlorinated paraffins (MCCPs; C 14–17 ), which are currently under consideration for Stockholm Convention regulations. Thus, there is a need to improve the understanding of MCCP environmental transport, distribution, and fate. Existing measurements are limited in their spatial and temporal coverage. Measurements of CP atmospheric loading are particularly scarce. Historically, these measurements have required long sampling times, obscuring the temporal behavior of atmospheric CPs. We report real-time in situ measurements of 18 gas-phase MCCPs. These measurements were made in the United States Southern Great Plains with nitrate ion chemical ionization mass spectrometry (NO 3 –CIMS). Here, the estimated average lower-limit concentration of MCCPs is on the order of single-digit ng/m 3 . MCCP diel behavior is partially explained by gas-particle partitioning with implications for MCCP transport and lifetimes.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2024

Direct Observation and Analysis of Low-Energy Magnons with Raman Spectroscopy in Atomically Thin NiPS 3

van der Waals (vdW) magnets have rapidly emerged as a fertile playground for fundamental physics and exciting applications. Despite the impressive developments over the past few years, technical limitations pose a severe challenge to many other potential breakthroughs. High on the list is the lack of suitable experimental tools for studying spin dynamics on atomically thin samples. Here, Raman scattering techniques are employed to directly observe the low-lying magnon (~1 meV) even in bilayer NiPS 3 . Further, the advantage is that it offers excellent energy resolutions far better on low-energy sides than most inelastic neutron spectrometers can offer. More importantly, with appropriate theoretical analysis, the polarization dependence of the Raman scattering by those low-lying magnons also provides otherwise hidden information on the dominant spin-exchange scattering paths for different magnons. By comparing with high-resolution inelastic neutron scattering data, these low-energy Raman modes are confirmed to be indeed of magnon origin. Because of the different scattering mechanisms involved in inelastic neutron and Raman scattering, this information is fundamental in pinning down the final spin Hamiltonian. This work demonstrates the capability of Raman spectroscopy to probe the genuine two-dimensional spin dynamics in atomically thin vdW magnets, which can provide insights that are obscured in bulk spin dynamics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Topology-Dependent Polymer Stretching and Scission in Solution at Extreme Shear Rates

There has been significant interest in the engineering of polymer topology to control rheology and mechanical stability in dilute solutions for applications involving extreme shear rate flows. However, methods to experimentally probe properties at relevant shear rates (≈ 10 4 –10 6 s –1 ) have remained ex situ, obscuring access to measures of polymer deformation and rheology that would otherwise provide mechanistic insight into the topology-dependent properties that control their behavior in extreme shear flows. In this study, we used novel in situ small angle neutron scattering measurements in a capillary rheometer (capillary rheo-SANS) to simultaneously measure solution viscosities and polymer deformations in high shear on a series of chemically homologous topology-defined polymers including linear, randomly branched, and star-shaped molecules. We demonstrate that differences in the onset of chain stretching and shear thinning of these polymers in dilute solution are controlled primarily by differences in their molecular relaxation time. These differences correlate with differences in chain scission inferred from ex situ measurements at more extreme shear rates. Together, the results demonstrate a direct coupling between chain deformation and scission, and suggest that the dominant effect of branching as a means to impart resilience against mechanical degradation is through differences in relaxation dynamics due to branching. We anticipate that these results will provide key insights to engineer topology-controlled polymers for rheological modification, mechanical stability, and controlled mechano-chemistry.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗
DOE OSTI2021

Demonstration of Selective Single-Barium Ion Detection with Dry Diazacrown Ether Naphthalimide Turn-on Chemosensors

Single-molecule fluorescence imaging (SMFI) of gas-phase ions has been proposed for “barium tagging,” a burgeoning area of research in particle physics to detect individual barium daughter ions. This has potential to significantly enhance the sensitivity of searches for neutrinoless double-beta decay (0νββ) that is obscured by background radiation events. The chemistry required to make such sensitive detection of Ba 2+ by SMFI in dry Xe gas at solid interfaces has implications for solid-phase detection methods but has not been demonstrated. Here, we synthesized simple, robust, and effective Ba 2+ -selective chemosensors capable of function within ultrapure high-pressure 136 Xe gas. Turn-on fluorescent naphthalimide-(di)azacrown ether chemosensors were Ba 2+ -selective and achieved SMFI in a polyacrylamide matrix. Here, fluorescence and NMR experiments supported a photoinduced electron transfer mechanism for turn-on sensing. Ba 2+ selectivity was achieved with computational calculations correctly predicting the fluorescence responses of sensors to barium, mercury, and potassium ions. With these molecules, dry-phase single-Ba 2+ ion imaging with turn-on fluorescence was realized using an oil-free microscopy technique for the first time—a significant advance toward single-Ba 2+ ion detection within large volumes of 136 Xe, plausibly enabling a background-independent technique to search for the hypothetical process of 0νββ.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2024

Cooperative Effects Drive Water Oxidation Catalysis in Cobalt Electrocatalysts through the Destabilization of Intermediates

A barrier to understanding the factors driving catalysis in the oxygen evolution reaction (OER) is understanding multiple over- lapping redox transitions in the OER catalysts. The complexity of these transitions obscure the relationship between the coverage of adsorbates and OER kinetics, leading to an experimental challenge in measuring activity descriptors, such as binding energies, as well as adsorbate interactions, which may destabilize intermediates and modulate their binding energies. Herein, we utilize a newly designed optical spectroelectrochemistry system to measure these phenomena in order to contrast the behavior of two electrocatalysts, cobalt oxyhydroxide (CoOOH) and cobalt-iron hexacyanoferrate (cobalt-iron Prussian blue, CoFe-PB). Three distinct optical spectra are observed in each catalyst, corresponding to three separate redox transitions, the last of which we show to be active for the OER using time-resolved spectroscopy and electrochemical mass spectroscopy. By combining predictions from density functional theory with parameters obtained from electroadsorption isotherms, we demonstrate that a destabilization of catalytic intermediates occurs with increasing coverage. In CoOOH, a strong (~0.34 eV/ monolayer) destabilization of a strongly bound catalytic intermediate is observed, leading to a potential offset between the accumulation of the intermediate and measurable O 2 evolution. We contrast these data to CoFe-PB, where catalytic intermediate generation and O 2 evolution onset coincide due to weaker binding and destabilization (~0.19 eV/monolayer). By considering a correlation between activation energy and binding strength, we suggest that such adsorbate driven destabilization may account for a significant fraction of the observed OER catalytic activity in both materials. Finally, we disentangle the effects of adsorbate interactions on state coverages and kinetics to show how adsorbate interactions determine the observed Tafel slopes. Crucially, the case of CoFe-PB shows that, even where interactions are weaker, adsorption remains non-Nernstian, which strongly influences the observed Tafel slope.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Multimodal Nanoscale Mapping of Local Structure and CO 2 Adsorption in Metal–Organic Frameworks

Diamine functionalization of the metal−organic framework Mg 2 (dobpdc) (dobpdc 4− = 4,4′-dioxidobiphenyl-3,3′-dicarboxylate) significantly enhances its selectivity for CO 2 capture from flue gases and air. The structure and CO 2 capacity of such materials are typically assessed using bulk techniques that rely on averaging signal over large ensembles of unit cells, obscuring local heterogeneities, such as variations in CO 2 occupancy across individual nanocrystals. To resolve this limitation, we demonstrate a multimodal, nanoscale characterization of Mg 2 (dobpdc) appended with 1,3-diaminopropane. By employing recently developed characterization techniques at progressively smaller length scales, we uncover insights from correspondingly smaller populations of unit cells. First, we use parallel-beam 3D electron diffraction (3D ED) to identify a prominent expansion in lattice parameters upon desorption of CO 2 , as observed at the level of single nanocrystals. Second, we use convergent-probe 4D scanning transmission electron microscopy (4D-STEM) to quantify associated differences in lattice strain as a function of gas loading and diamine appending. These measurements sample small subvolumes within individual nanocrystals. Finally, we apply infrared scattering scanning near-field optical microscopy (IR s- SNOM) to confirm variable CO 2 chemisorption across adsorption sites at the surface of single nanocrystals. This multimodal, multiscale approach allows us to map heterogeneity within individual nanocrystals. Collectively, these findings emphasize the importance of local, nanoscale characterization of metal−organic frameworks in revealing previously unresolvable features that impact their performance.

Karstens, Sarah L. [University of California, Berk↗
DOE OSTI2019

Evolution Pathway from Iron Compunds to Fe 1 (II)-N 4 Sites through Gas-Phase Iron during Pyrolysis

Pyrolysis is indispensable for synthesizing highly active Fe–N–C catalysts for the oxygen reduction reaction (ORR) in acid, but how Fe, N, and C precursors transform to ORR-active sites during pyrolysis remains unclear. This knowledge gap obscures the connections between the input precursors and the output products, clouding the pathway toward Fe–N–C catalyst improvement. Here, we unravel the evolution pathway of precursors to ORR-active catalyst comprised exclusively of single-atom Fe 1 (II)–N 4 sites via in-temperature X-ray absorption spectroscopy. The Fe precursor transforms to Fe oxides below 300 °C and then to tetrahedral Fe 1 (II)–O 4 via a crystal-to-melt-like transformation below 600 °C. The Fe 1 (II)–O 4 releases a single Fe atom that diffuses into the N-doped carbon defect forming Fe 1 (II)–N 4 above 600 °C. This vapor-phase single Fe atom transport mechanism is verified by synthesizing Fe 1 (II)–N 4 sites via “noncontact pyrolysis” wherein the Fe precursor is not in physical contact with the N and C precursors during pyrolysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Gas-Phase Formation of Fulvenallene (C 7 H 6 ) via the Jahn–Teller Distorted Tropyl (C 7 H 7 ) Radical Intermediate under Single-Collision Conditions

The fulvenallene molecule (C 7 H 6 ) has been synthesized via the elementary gas-phase reaction of the methylidyne radical (CH) with the benzene molecule (C 6 H 6 ) on the doublet C 7 H 7 surface under single collision conditions. The barrier-less route to the cyclic fulvenallene molecule involves the addition of the methylidyne radical to the π-electron density of benzene leading eventually to a Jahn–Teller distorted tropyl (C 7 H 7 ) radical intermediate and exotic ring opening–ring contraction sequences terminated by atomic hydrogen elimination. The methylidyne-benzene system represents a benchmark to probe the outcome of the elementary reaction of the simplest hydrocarbon radical—methylidyne—with the prototype of a closed-shell aromatic molecule—benzene—yielding nonbenzenoid fulvenallene. Combined with electronic structure and statistical calculations, this bimolecular reaction sheds light on the unusual reaction dynamics of Hückel aromatic systems and remarkable (polycyclic) reaction intermediates, which cannot be studied via classical organic, synthetic methods, thus opening up a versatile path to access this previously largely obscure class of fulvenallenes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Investigating Thaw and Plant Productivity Constraints on Old Soil Carbon Respiration From Permafrost

Isotopic radiocarbon (Δ 14 C) signatures of ecosystem respiration (Reco) can identify old soil carbon (C) loss and serve as an early indicator of permafrost destabilization in a warming climate. Warming also stimulates plant productivity causing plant respiration to dominate Reco Δ 14 C signatures and potentially obscuring old soil C loss. Here, we investigate how a wide spatio-temporal gradient of permafrost thaw and plant productivity affects Reco Δ 14 C patterns and isotopic partitioning. Spatial gradients came from a warming experiment with doubling thaw depth and variable biomass, and a vegetation removal manipulation to eliminate plant contributions. We sampled in August and September to capture transitions from high to low plant productivity, decreased surface soil temperature, and relatively small seasonal thaw extensions. We found that surface processes dominate spatial variation in old soil C loss and a process-based partitioning approach was crucial for constraining old soil C loss. Resampling the same plots in different times of the year revealed that old soil C losses tripled with cooling surface temperature, and the largest old soil C losses were detected when the organic-to-mineral soil horizons thawed (~50–60 cm). We suggest that the measured increase in old soil respiration over the season and when the organic-to-mineral horizon thawed, may be explained by mobilization of nitrogen that stimulates microbial decomposition at depth. Our results suggest that soil C in the organic to mineral horizon may be an important source of soil C loss as the entire Arctic region warms and could lead to nonlinearities in projected permafrost climate feedbacks.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2020

Indicator Patterns of Forced Change Learned by an Artificial Neural Network

Abstract Many problems in climate science require the identification of signals obscured by both the “noise” of internal climate variability and differences across models. Following previous work, we train an artificial neural network (ANN) to predict the year of a given map of annual‐mean temperature (or precipitation) from forced climate model simulations. This prediction task requires the ANN to learn forced patterns of change amidst a background of climate noise and model differences. We then apply a neural network visualization technique (layerwise relevance propagation) to visualize the spatial patterns that lead the ANN to successfully predict the year. These spatial patterns thus serve as “reliable indicators” of the forced change. The architecture of the ANN is chosen such that these indicators vary in time, thus capturing the evolving nature of regional signals of change. Results are compared to those of more standard approaches like signal‐to‐noise ratios and multilinear regression in order to gain intuition about the reliable indicators identified by the ANN. We then apply an additional visualization tool (backward optimization) to highlight where disagreements in simulated and observed patterns of change are most important for the prediction of the year. This work demonstrates that ANNs and their visualization tools make a powerful pair for extracting climate patterns of forced change.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2022

Remote Sensing of Tundra Ecosystems Using High Spectral Resolution Reflectance: Opportunities and Challenges

Abstract Observing the environment in the vast regions of Earth through remote sensing platforms provides the tools to measure ecological dynamics. The Arctic tundra biome, one of the largest inaccessible terrestrial biomes on Earth, requires remote sensing across multiple spatial and temporal scales, from towers to satellites, particularly those equipped for imaging spectroscopy (IS). We describe a rationale for using IS derived from advances in our understanding of Arctic tundra vegetation communities and their interaction with the environment. To best leverage ongoing and forthcoming IS resources, including National Aeronautics and Space Administration’s Surface Biology and Geology mission, we identify a series of opportunities and challenges based on intrinsic spectral dimensionality analysis and a review of current data and literature that illustrates the unique attributes of the Arctic tundra biome. These opportunities and challenges include thematic vegetation mapping, complicated by low‐stature plants and very fine‐scale surface composition heterogeneity; development of scalable algorithms for retrieval of canopy and leaf traits; nuanced variation in vegetation growth and composition that complicates detection of long‐term trends; and rapid phenological changes across brief growing seasons that may go undetected due to low revisit frequency or be obscured by snow cover and clouds. We recommend improvements to future field campaigns and satellite missions, advocating for research that combines multi‐scale spectroscopy, from lab studies to satellites that enable frequent and continuous long‐term monitoring, to inform statistical and biophysical approaches to model vegetation dynamics.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2022

Identification of Acoustic Wave Signatures in the Ionosphere From Conventional Surface Explosions Using MF/HF Doppler Sounding

Here, we present an experiment to detect one ton TNT-equivalent chemical explosions using pulsed Doppler radar observations of isodensity layers in the ionospheric E region during two campaigns. The first campaign, conducted on 15 October 2019, produced potential detections of all three shots. The detections closely resemble the temporal and spectral properties predicted using the InfraGA ray tracing and weakly nonlinear waveform propagation model. Here the model predicts that within 6.5–7.25 min of each shot a waveform peaking between 0.9 and 0.4 Hz will impact the ionosphere at 100 km. As the waves pass through this region, they will imprint their signal on an isodensity layer, which is detectable using a Doppler radar operating at the plasma frequency of the isodensity. Within the time windows of each of the three shots in the first campaign, we detect enhanced wave activity peaking near 0.5 Hz. These waves were imprinted on the Doppler signal probing an isodensity layer at 2.785 MHz near 100 km altitude. Despite these detections, the method appears to be unreliable as none of the six shots from the second campaign, conducted on 10 July 2020 were detected. The observations from this campaign were characterized by an increased acoustic noise environment in the microbarom band and persistent scintillation on the radar returns. These effects obscured any detectable signal from these shots and the baseline noise was well above the detection levels of the first campaign.

47 OTHER INSTRUMENTATION↗
DOE OSTI2023

Constraining the Varied Response of Northern Hemisphere Winter Circulation Waviness to Climate Change

Abstract While a large latitudinal displacement of the westerly jet brings about disproportionate socioeconomic impacts over Northern Hemisphere midlatitude continents, it is not well understood as to whether the winter circulation will become wavier or less in response to climate change. Here, using observations and large ensembles of climate models, we show that changes in atmospheric waviness can be estimated from the optimal structures of the westerly jet for wavier circulation, which are obtained from an advection‐diffusion model. Thus, the changes in westerly jet structure in climate models under climate change provide a physical constraint on changes in atmospheric waviness, indicating that the North Atlantic wave activity will experience a robust decline in a warmer climate, while future North Pacific wave activity is obscured by model uncertainty rather than internal variability. These findings highlight the changes to jet stream structure as a constraint for regional circulation waviness in a changing climate.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2023

Accounting for Changes in Radiation Improves the Ability of SIF to Track Water Stress-Induced Losses in Summer GPP in a Temperate Deciduous Forest

Global observations of solar-induced chlorophyll fluorescence (SIF) are available from multiple satellite platforms, and SIF is increasingly used as a proxy for photosynthetic activity and ecosystem productivity. Because the relationship between SIF and gross primary productivity (GPP) depends on a variety of factors including ecosystem type and environmental conditions, it is necessary to study SIF observations across various spatiotemporal scales and ecosystems. To explore how SIF signals relate to productivity over a temperate deciduous forest, we deployed a PhotoSpec spectrometer system at the University of Michigan Biological Station AmeriFlux site (US-UMB) in the northern Lower Peninsula of Michigan during the 2018 and 2019 growing seasons. We found that SIF correlated with GPP across diurnal and seasonal cycles (R 2 = 0.61 and 0.64 for 90-min- and daily-averaged data), but that SIF signals were more strongly related to downwelling radiation than GPP (R 2 = 0.91 for daily-averaged data). The dependence of SIF on radiation obscured the impact of intraseasonal drought in the SIF timeseries, but drought stress was apparent as a decrease in relative SIF, which exhibited a stronger correlation with GPP (R 2 = 0.56) than other remotely sensed data over the drought period. These results highlight the potential of SIF for detecting stress-induced losses in forest productivity. Additionally, we found that the red:far-red SIF ratio did not exhibit a response to water stress-induced losses in productivity, but was largely driven by seasonal and interannual changes in canopy structure, as well as by synoptic changes in downwelling radiation.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2022

Quantifying Subsurface Flow and Solute Transport in a Snowmelt‐Recharged Hillslope With Multiyear Water Balance

Abstract Quantifying flow and transport from hillslopes is vital for understanding water quantity and quality in rivers, but remains obscure because of limited subsurface measurements. Using measured hydraulic conductivity K profiles and water balance over a single year to calibrate a transmissivity feedback model for a hillslope in the East River watershed (Colorado) proved unsatisfactory for predicting flow over the subsequent years. Well‐constrained field‐scale K were obtained by optimizing subsurface flux predictions over years having large differences in recharge, and by including estimates of interannual transfer of excess snowmelt recharge. Water and solute exports during high snowmelt recharge occur predominantly via shallow groundwater flow through weathered rock and soil because of their enlarged transmissivities under saturated conditions. Conversely, these shallow pathways are less active in snow drought years when the water table remains deeper within the weathering zone. Hillslope soil water monitoring showed that rainfall does not infiltrate deeply during summer and fall months, and revealed water losses consistent with model ET predictions. By combining water table‐dependent fluxes with pore water chemistry in different zones, time‐dependent rates of solute exports become predictable. As an example, calibrated K were combined with dissolved nitrogen concentrations in pore waters to show the snowmelt‐dependence of reactive nitrogen exported from the hillslope, further supporting the recent finding that the weathering zone is the dominant source of reactive nitrogen at this site. Subsurface export predictions can now be obtained for wide ranges of recharge based on measurements of water table elevation and profiles of pore water chemistry.

54 ENVIRONMENTAL SCIENCES↗