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At least 865 records · Page 48
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Intrinsically Bifunctional and Tunable Tungsten Carbide Catalysts Enable Efficient PVC-Compatible Polyolefin Hydrocracking

Hydrocracking is a promising route for the chemical recycling of polyolefins (PO), converting them into short hydrocarbons over bifunctional catalysts with metal sites for hydrogenation and dehydrogenation, and Brønsted acid sites (BAS) for isomerization and C–C bond cleavage. However, PO feedstocks containing polyvinyl chloride (PVC) can release chlorine (Cl) under reaction conditions, deactivating conventional noble metal/zeolite catalysts. Moreover, the lack of site intimacy and the presence of micropores within conventional catalysts create challenges around the transport of high-molecular-weight, sterically encumbered polymer intermediates. Here, in this study, we report tungsten carbides (W x C) as a novel type of bifunctional catalysts that address these challenges. W/W 2 C phases on W x C offer “metal” sites, and −OH on WO x species introduces BAS in close proximity. The “metal”:BAS ratio can be tuned through carburization temperature, leading to a volcano-shaped activity trend reflecting the requirement for metal–BAS balance. Kinetic data demonstrate that each PO chain undergoes sequential cleavage, while trends in cracking ideality and selectivity follow those in short-alkane hydrocracking. On the per-BAS basis, W x C is more efficient than conventional bifunctional catalysts by more than an order of magnitude, due to enhanced polymer transport. They maintain or show increased activity with 10 wt % PVC in the substrate. This work establishes transition-metal carbides as earth-abundant bifunctional catalysts with unique site proximity and heteroatom compatibility. These features, along with the broad structure space for rational tuning, make them promising options to tackle specific challenges that polymer feedstocks present in hydrocracking.

Nwachukwu, Uchenna C. [Univ. of Akron, OH (United ↗
DOE OSTI2026

Mechanism of Tyrosine-Driven Deprotonation in Photosystem II Revealed by Multiscale Simulations

Photosystem II (PSII) drives light-induced water oxidation via stepwise redox transitions of its oxygen-evolving complex (OEC), a Mn 4 Ca cluster advancing through five intermediate S-states (S 0 –S 4 ). The S 2 → S 3 transition involves a redox event in which a Mn ion donates an electron to the redox-active tyrosine YZ, coupled to deprotonation of an OEC-bound water ligand─yet the underlying coupling mechanism remains unresolved. Time-resolved serial femtosecond crystallography (TR-SFX) has revealed transient electron density shifts near the redox-active tyrosine Y Z , interpreted as sequential oxidation and reduction, with reduction initiating ∼1 μs after excitation and substantially progressed by 30 μs. However, this interpretation conflicts with kinetics from photothermal beam deflection (PBD), time-resolved X-ray absorption spectroscopy (TR-XAS), and electron paramagnetic resonance (EPR), which place electron transfer at 190–400 μs and proton transfer around 30 μs. Here, we reconcile these discrepancies using quantum mechanics/molecular mechanics (QM/MM) and molecular dynamics (MD) simulations. We show that oxidation of P680 and Y Z breaks the symmetry of the nearby hydrogen bonds involving water molecule W4, displacing Y Z and replicating the TR-SFX features of Y Z and Q165 observed at 1 μs. This local perturbation propagates through a hydrogen-bond network, transmitting the electrostatic signal from Y Z to the E65-E312 dyad and triggering redox-coupled deprotonation via the Cl1 channel. By 30 μs, the hydrogen-bond symmetry is restored through deprotonation of W2 (or alternatively W1), reproducing the disappearance of TR-SFX density differences around Y Z and Q165 without requiring Y Z reduction. Our proposed mechanism also gives molecular insights into the O6* density, assigning it to water reorganization rather than a discrete Ca-bound hydroxide species. Here, our results reveal a detailed atomistic mechanism linking Y Z oxidation to long-range proton release and suggest a functional role for the nearby Cl – ion in proton transfer. More broadly, this study underscores the importance of hydrogen-bond dynamics in mediating redox-driven proton transport and demonstrates how integrative simulations can resolve mechanistic ambiguities.

Deprotonation↗
DOE OSTI2026

Engineering Structural Transitions in a Multilevel Molecular Switch via Intermolecular Coupling

Controlling molecular conformations with atomic precision is essential for advancing molecular functional electronics, as well as our understanding of molecular dynamics. While switching between bistable molecular conformers is common in nature, creating systems with multiple, addressable states remains synthetically challenging. Here, we demonstrate a bottom-up strategy in which intermolecular interactions give rise to multilevel functionality within a simple two-molecule assembly. Using low-temperature scanning tunneling microscopy, we show that a pyrrolidine dimer on Cu(100) exhibits six distinct adsorption conformations, exceeding the four expected from two independent bistable units. This unusual complexity arises from the interplay between intermolecular van der Waals attraction and steric repulsion, which reshapes the potential energy landscape and changes a single high-energy transition into a sequential two-step pathway. Each step is driven by low-energy inelastic electron excitations, achieving a switching efficiency an order of magnitude higher than that of the monomer. Here, by tuning the bias voltage and tip–molecule distance, we achieve deterministic control over multiple stable states, establishing a general design principle for on-demand engineering of collective molecular behavior and energy-efficient multilevel molecular devices.

Molecular interactions↗
DOE OSTI2026

Transient Triamidoamine Neptunium(V)–Mono(Imido) Complexes: C–H Activations and Hydrogen Atom Transfer Driven by Effective Nuclear Charge

Metal-mono(imido) linkages have been known for seven decades, and they are found in transition metal, main group, lanthanide, thorium, and uranium complexes. However, transuranium-mono(imido) complexes remain unknown in any scenario. Here, we present evidence for transient neptunium(V)–mono(imido) complexes. Treatment of [Np III (Tren TIPS )] (1, Tren TIPS = {N(CH 2 CH 2 NSiPr i 3 ) 3 } 3– ) with N 3 R (R = SiMe 3 ; 1-adamantyl, Ad) results in N 2 evolution and dark purple solutions consistent with the formation of [Np V (Tren TIPS )(NR)] (3NpNR). However, solutions of 3NpNR rapidly turn orange, where for R = SiMe 3 the isolated 1:1 products are [Np IV (Tren TIPS ){N(H)SiMe 3 }] (4a) and [Np IV (Tren TIPS-2H ){N(H)SiMe 3 }] (4b, Tren TIPS-2H = {N(CH 2 CH 2 NS i Pri 3 ) 2 (NCH 2 CH 2 NSiPr i 2 C[Me]=CH 2 )} 3– ). The latter contains a dehydrogenated-Pr i vinyl functionality accounting for the source of the two amido H atoms. The reaction for R = Ad proceeds similarly, but only [Np IV (Tren TIPS ){N(H)Ad}] (5a) could be unequivocally confirmed, though its isolation suggests generality of the imido-to-amido functional group transformation. Complexes 4a/4b exhibit slow relaxation of their magnetization, adding to the small number of transuranium single ion magnets. Experimental and computational analysis suggests that the amido products are formed by C–H activation and two sequential hydrogen atom transfer reactions involving a three-step proton-coupled electron-transfer sequence of H • radical abstraction, electron transfer, then another H • radical abstraction step. In contrast to transient 3NpNR, the 5f 2 uranium(IV)-imido complex [K(2.2.2-cryptand)][U IV (Tren TIPS )(NSiMe 3 )] (8UNSiMe 3 ) is robust, even in boiling THF, suggesting the transience of 5f 2 3NpNR is not due to the 5f n -count but the increased effective nuclear charge of neptunium vs uranium. This work highlights divergence of uranium- and neptunium-imido stabilities, emphasizing that the latter is an inherently challenging synthetic target.

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

Ion-Electron Coupling-Driven Redox Behavior in Metal–Organic Frameworks

Redox-active metal–organic frameworks (MOFs) have long been proposed as electronic transport platforms, yet the microscopic origin of their conductivity remains debated. A theoretical demonstration reveals charge transport in a Zn(pyrazole–naphthalene diimide (NDI)) MOF arising not from delocalized band-like states but from redox hopping between discrete linker sites. Using ab initio molecular dynamics simulations combined with electronic structure analysis, we established a direct link among electron injection, structural reorganization, and transport. Electron accumulation proceeds sequentially and site-selectively from imide and carbonyl groups of the NDI core progressively involving pyrazole N atoms at higher reduction states, through a hierarchy of redox-active sites. In contrast, Zn nodes remain essentially redox-inactive, which confirms their structural role. Density-of-states analysis corroborates a transport regime dominated by linker-centered states with evolving p-character upon reduction, resulting in dynamically reconfigured conduction networks. Real-time trajectories reveal anisotropic linker-to-linker electron transfer modulated by counterion coordination. This cooperative ion–electron regime emerges from potential energy surface collapse into a single low-barrier transition (ΔG ‡ ≈ 45 meV), where ionic and electronic motions evolve adiabatically on the same free-energy landscape. Elucidating redox conductivity in Zn(pyrazole–NDI) MOFs provides a theoretical framework for use in neuromorphic computing and related technologies.

Charge transfer↗
DOE OSTI2026

Concerted Electron-Ion Transport by Polyacrylonitrile Elucidated with Reactive Deep Learning Potentials

Charge transport in polymers, such as polyacrylonitrile (PAN), is crucial for electronics and energy storage. For instance, PAN can transport cations e.g., Li + , by facilitating dynamic cation-nitrile coordination in batteries. However, little is known regarding the underlying role of complex reactive polymer configurations. Herein, we develop a deep-learning potential, trained on ab initio energies and forces of nonequilibrium reactive PAN configurations, to unravel the kinetics of PAN cyclization initiated by a nucleophile (OH – dissociated from LiOH) attacking the terminal nitrile carbon. We find, based on the reaction free-energetics, rates, and charge analysis, that the nucleophile attack producing the first ring is the rate-limiting step, which subsequently triggers Li + -coupled electron transfer along the PAN backbone, causing ∼10 4 times faster sequential ring-formation of the remaining nitriles. PAN’s extended configurations, where dipolar and H-bonding interactions are minimal, enable such rapid kinetics. By validating our computational findings with IR and NMR experiments, we establish a pathway for designing reactive polymers with enhanced charge transport for energy applications.

Chahal-Crockett, Rajni [Oak Ridge National Laborat↗
DOE OSTI2026

Enhanced Catalytic Dechlorination of Polyvinyl Chloride (PVC) and H2 Production Enabled by Synergistic Gaδ+/Ga0 Active Sites in Liquid Metal Particles

Polyvinyl chloride (PVC) is ubiquitous yet challenging to recycle due to its tendency to thermally decompose above 250 °C, releasing toxic, corrosive chlorinated compounds, and its inability to melt. Here, we report a catalytic strategy for PVC upcycling at 160 °C using gallium liquid metal particles (Ga-LMP) featuring a dynamic Ga-GaOOH core–shell architecture. These catalysts enable concurrent dechlorination and hydrogen evolution, yielding up to 7% H2 (based on initial hydrogen atoms in PVC) along with a highly dechlorinated (>95%) carbonaceous solid and aqueous HCl. Mechanistic investigations combining X-ray photoelectron spectroscopy, infrared spectroscopy, solid-state NMR, inelastic neutron scattering, and ab initio molecular dynamics reveal a synergistic interplay between Gaδ+ sites in the GaOOH shell and metallic Ga0 in the core. Cationic Ga initiates C–Cl bond activation and HCl formation, while progressive reduction of the shell exposes Ga0 sites that promote C–H activation and H2 evolution. Control experiments with a Ga salt and bulk Ga liquid metal confirmed that neither oxidation state alone can achieve both transformations efficiently. This work establishes a dynamic dual-site paradigm for liquid metal catalysis, in which the in situ evolution and coexistence of oxidized and metallic species enable sequential and cooperative bond activation pathways. These findings provide a general design principle for novel liquid metal catalysts that target challenging polymer transformations under mild conditions.

Zingg, Benjamin [ORNL] (ORCID:0009000914530153)↗
DOE OSTI2025

Electrochemical Observation and pH Dependence of All Three Expected Redox Couples in an Extremophilic Bifurcating Electron Transfer Flavoprotein with Fused Subunits

Bifurcating enzymes employ energy from a favorable electron transfer to drive unfavorable transfer of a second electron, thereby generating a more reactive product. They are therefore highly desirable in catalytic systems, for example, to drive challenging reactions such as nitrogen fixation. While most bifurcating enzymes contain air-sensitive metal centers, bifurcating electron transfer flavoproteins (bETFs) employ flavins. However, they have not been successfully deployed on electrodes. Herein, we demonstrate immobilization and expected thermodynamic reactivity of a bETF from a hyperthermophilic archaeon, Sulfolobus acidocaldarius (SaETF). SaETF differs from previously biochemically characterized bETFs in being a single protein, representing a concatenation of the two subunits of known ETFs. However, SaETF retains the chemical properties of heterodimeric bETFs, including possession of two FADs: one that undergoes sequential 1-electron (1e) reductions at high E° and forms an anionic semiquinone, and another that is amenable to lower-E° 2e reduction, including by NADH. We found homologous monomeric ETF genes in archaeal and bacterial genomes, accompanied by genes that also commonly flank heterodimeric ETFs, and SaETF’s sequence conservation is 50% higher with bETFs than with canonical ETFs. Thus, SaETF is best described as a bETF. Our direct electrochemical trials capture reversible redox couples for all three thermodynamically expected redox events. We document electrochemical activity over a range of pH values and reveal a conformational change coupled to proton acquisition that affects the electrochemical activity of the higher-E° FAD. Thus, this well-behaved monomeric bETF opens the door to bioinspired bifurcating devices or bifurcation on a chip.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Applying Multimodal Mass Spectrometry to Image Tumors Undergoing Ferroptosis Following In Vivo Treatment with a Ferroptosis Inducer

Epithelial ovarian cancer (EOC) is the most common form of ovarian cancer. The poor prognosis generally associated with this disease has led to the search for improved therapies such as ferroptosis-inducing agents. Ferroptosis is a form of regulated cell death that is dependent on iron and is characterized by lipid peroxidation. Precise mapping of lipids and iron within tumors exposed to ferroptosis-inducing agents may provide insight into processes of ferroptosis in vivo and ultimately assist in the optimal deployment of ferroptosis inducers in cancer therapy. In this work, we present a method for combining matrix-assisted laser desorption/ionization (MALDI) mass spectrometry imaging (MSI) with secondary ion mass spectrometry (SIMS) to analyze changes in spatial lipidomics and metal composition, respectively, in ovarian tumors following exposure to a ferroptosis inducer. Tumors were obtained by injecting human ovarian cancer tumor-initiating cells into mice, followed by treatment with the ferroptosis inducer erastin. SIMS imaging detected iron accumulation in the tumor tissue, and sequential MALDI-MS imaging of the same tissue section displayed two chemically distinct regions of lipids. Additionally, one region was associated with the iron-rich area detected with SIMS, and the other region encompassed the remainder of the tissue section. Bulk lipidomics confirmed the lipid assignments putatively assigned from the MALDI-MS data. Overall, we demonstrate the ability of multimodal MSI to identify the spatial locations of iron and lipids in the same tissue section and associate these regions with clinical pathology.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2020

The Sensitivity of Hyporheic Exchange to Fractal Properties of Riverbeds

Hyporheic exchange in riverbeds is driven by current-bed topography interactions. Because riverbeds exhibit topographic roughness across scales, from individual grains to bedforms and bars, they can exhibit fractal patterns. This study analyzed the influence of fractal properties of riverbed topography on hyporheic exchange. A set of synthetic fractal riverbeds with different scaling statistics was used as inputs to sequentially coupled numerical simulations of turbulent channel flow and hyporheic flow. In the analysis, the maximum power spectrum (dune size) and the fractal dimension (topographic complexity) were considered as independent variables and we then investigated how interfacial fluxes and hyporheic travel times are functionally related to these variables. As the maximum power spectrum increases (i.e., dune height to flow depth ratio), the average interfacial flux increases logarithmically whereas it increases exponentially with an increase in fractal dimension. Hyporheic exchange is more sensitive to additional roughness (larger fractal dimensions) than to bedform size (larger maximum power). Our results imply that fractal properties of riverbeds are crucial to predicting hyporheic exchange. The predictive relationships we propose could be integrated with reduced complexity, large-scale models. Further, they can also be used to design artificial topographies that target hyporheic ecosystem services.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2020

Performance and Accuracy Implications of Parallel Split Physics-Dynamics Coupling in the Energy Exascale Earth System Atmosphere Model

Simultaneous calculation of atmospheric processes is faster than calculating processes one at a time. This type of parallelism is beneficial or perhaps even necessary to provide good performance on modern supercomputers, which achieve faster performance through increased processor count rather than improved clock speed. The scalability of the Energy Exascale Earth System Model (E3SM) Atmosphere Model (EAM) is limited by the fluid dynamics which scales up to the number of mesh cells in the global mesh. In contrast, the suite of physics parameterizations in EAM is scalable up to the total number of physics columns, which is an order of magnitude greater than the number of mesh cells. A proposed solution to unlocking the greater potential performance from the physics suite is to solve the physics and dynamics in parallel. This work represents a first attempt at parallel splitting of the grid-scale fluid dynamics model and the subgrid-scale physics parameterizations in a global atmosphere model. We will demonstrate that switching to parallel physics-dynamics coupling extends the scalability of the EAM to up to 3 times the previous peak scalability limit and is up to 20% faster than the sequentially split coupling at the highest core counts and the same time step. Decadal simulations of both coupling approaches show very little impact to the model climate. This improved performance does not come without drawbacks, however. Parallel splitting requires a shorter time step and other modifications which largely offset performance gains. A mass fixer is required for conservation. Techniques for mitigating these issues are also discussed.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2020

Data Assimilative Optimization of WSA Source Surface and Interface Radii using Particle Filtering

TheWang-Sheeley-Arge (WSA) model estimates solar wind speed and interplanetary magnetic field polarity in the inner heliosphere using global photospheric magnetic field maps. WSA employs the Potential Field Source Surface (PFSS) and Schatten Current Sheet (SCS) models to determine the Sun's global coronal magnetic field. The PFSS and SCS models are connected through two radial parameters, the source surface and interface radii, which specify the overlap region between the inner SCS and outer PFSS models. Though both radii values are adjustable, they have typically been fixed to 2.5 solar radii. Our work highlights how solar wind predictions improve when the radii are allowed to vary over time. Data assimilation using particle filtering (sequential Monte Carlo) is used to infer optimal values over a fixed time window. Solar wind model predictions and satellite observations are compared with a newly developed quality-of-agreement prediction metric. The agreement metric between the model and observations is assumed to correspond to the probability of the two key WSA model parameters, the source surface and interface radii, where the highest metric value implies the optimal radii.We find that the optimal particle filter values of solar radii can perform twice as well as standard values for an exploratory period during Carrington Rotation 1901, with these values also reducing nonphysical kinking effects seen in solar magnetic field lines. Data assimilation choices of input realization and time frame have implications for variation in the solar wind over time. We present this work's theoretical context and practical applications for prediction accuracy.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2022

Dissipation and Bathymetric Sensitivities in an Unstructured Mesh Global Tidal Model

Abstract The mechanisms and geographic distribution of global tidal dissipation in barotropic tidal models are examined using a high resolution unstructured mesh finite element model. Mesh resolution varies between 2 and 25 km and is especially focused on inner shelves and steep bathymetric gradients. Tidal response sensitivities to bathymetric changes are examined to put into context response sensitivities to frictional processes. We confirm that the Ronne Ice Shelf dramatically affects Atlantic tides but also find that bathymetry in the Hudson Bay system is a critical control. We follow a sequential frictional parameter optimization process and use TPXO9 data‐assimilated tidal elevations as a reference solution. From simulated velocities and depths, dissipation within the global model is estimated and allows us to pinpoint dissipation at high resolution. Boundary layer dissipation is extremely focused with 1.4% of the ocean accounting for 90% of the total. Internal tide friction is much more distributed with 16.7% of the ocean accounting for 90% of the total. Often highly regional dissipation can impact basin‐scale and even ocean wide tides. Optimized boundary layer friction parameters correlate very well with the physical characteristics of the locality with high friction factors associated with energetic tidal regions, deep ocean island chains, and ice covered areas. Global complex M 2 tide errors are 1.94 cm in deep waters. Total global boundary layer and internal tide dissipation are estimated, respectively, at 1.83 and 1.49 TW. This continues the trend in the literature toward attributing more dissipation to internal tides.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2023

Large Ensemble Particle Filter for Spatial Climate Reconstructions Using a Linear Inverse Model

Proxy records that document the last 2000 years of climate provide evidence for the wide range of the natural climate variability from inter-annual to secular timescales not captured by the short window of recent direct observations. Assessing climate models ability to reproduce such natural variations is crucial to understand climate sensitivity and impacts of future climate change. Paleoclimate data assimilation (PDA) offers a powerful way to extend the short instrumental period by optimally combining the physics described by General Circulation Climate Models (GCMs) with information from available proxy records while taking into account their uncertainties. Here we present a new PDA approach based on a sequential importance resampling (SIR) Particle filter (PF) that uses Linear Inverse Modeling (LIM) as an emulator of several CMIP-class GCMs. We examine in a perfect-model framework the skill of the various LIMs to forecast the dynamics of the surface temperatures and provide spatial field reconstructions over the last millennium in a SIR PF. Our results show that the LIMs allow for skillful ensemble forecasts at 1-year lead-time based on GCMs dynamical knowledge with best prediction in the tropics and the North Atlantic. The PDA further provides a set of physically consistent spatial fields allowing robust uncertainty quantification related to climate models biases and proxy spatial sampling. Our results indicate that the LIM yields dynamical memory improving climate variability reconstructions and support the use of the LIM as a GCM-emulator in real reconstruction to propagate large ensembles of particles at low cost in SIR PF.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2022

Equation‐Free Surrogate Modeling of Geophysical Flows at the Intersection of Machine Learning and Data Assimilation

Abstract There is a growing interest in developing data‐driven reduced‐order models for atmospheric and oceanic flows that are trained on data obtained either from high‐resolution simulations or satellite observations. The data‐driven models are non‐intrusive in nature and offer significant computational savings compared to large‐scale numerical models. These low‐dimensional models can be utilized to reduce the computational burden of generating forecasts and estimating model uncertainty without losing the key information needed for data assimilation (DA) to produce accurate state estimates. This paper aims at exploring an equation‐free surrogate modeling approach at the intersection of machine learning and DA in Earth system modeling. With this objective, we introduce an end‐to‐end non‐intrusive reduced‐order modeling (NIROM) framework equipped with contributions in modal decomposition, time series prediction, optimal sensor placement, and sequential DA. Specifically, we use proper orthogonal decomposition (POD) to identify the dominant structures of the flow, and a long short‐term memory network to model the dynamics of the POD modes. The NIROM is integrated within the deterministic ensemble Kalman filter (DEnKF) to incorporate sparse and noisy observations at optimal sensor locations obtained through QR pivoting. The feasibility and the benefit of the proposed framework are demonstrated for the NOAA Optimum Interpolation Sea Surface Temperature (SST) V2 data set. Our results indicate that the NIROM is stable for long‐term forecasting and can model dynamics of SST with a reasonable level of accuracy. Furthermore, the prediction accuracy of the NIROM gets improved by almost one order of magnitude by the DEnKF algorithm.

Pawar, Suraj↗
DOE OSTI2023

Combining Remotely Sensed Evapotranspiration and an Agroecosystem Model to Estimate Center‐Pivot Irrigation Water Use at High Spatio‐Temporal Resolution

Abstract Estimating irrigation water use accurately is critical for sustainable irrigation and studying terrestrial water cycle in irrigated croplands. However, irrigation is not monitored in most places, and current estimations of irrigation water use has coarse spatial and/or temporal resolutions. This study aims to estimate irrigation water use at the daily and field scale through the proposed model‐data fusion framework, which is achieved by particle filtering with two configurations (concurrent, CON, and sequential, SEQ) by assimilating satellite‐based evapotranspiration (ET) observations into an advanced agroecosystem model, ecosys . Two types of experiments using synthetic and real ET observations were conducted to study the efficacy of the proposed framework for estimating irrigation water use at the irrigated fields in eastern and western Nebraska, United States. The experiments using synthetic ET observations indicated that, for two major sources of uncertainties of ET difference between observations and model simulations, which are bias and noise, noise had larger impacts on degrading the estimation performance of irrigation water use than bias. For the experiments using real ET observations, monthly and annual estimations of irrigation water use matched well with farmer irrigation records, with Pearson correlation coefficient ( r ) around 0.80 and 0.50, respectively. Although detecting daily irrigation records was very challenging, our method still gave a good performance with RMSE, BIAS, and r around 2.90, 0.03, and 0.4 mm/d, respectively. Our proposed model‐data fusion framework for estimating irrigation water use at high spatio‐temporal resolution could contribute to regional water management, sustainable irrigation, and better tracking terrestrial water cycle.

Environmental Sciences & Ecology↗
DOE OSTI2023

Active‐Source Seismic Imaging of Fault Re‐Activation and Leakage: An Injection Experiment at the Mt Terri Rock Laboratory, Switzerland

Abstract We conducted a time‐lapse seismic experiment utilizing automated active seismic source and sensor arrays to monitor a reactivated fault within the Opalinus clay formation at the Mont Terri Rock Laboratory (Switzerland), an analog caprock for geologic carbon storage. A series of six brine injections were conducted into the so‐called Main Fault to reactivate it. Seismic instrumentation in five monitoring boreholes on either side of the fault was used to continuously probe changes in P‐wave travel‐times associated with fault displacement and leakage. We performed time‐lapse travel‐time tomography on five hundred sequential data sets; this revealed a zone of decreased P‐wave velocity, up to 16 m/s, during each injection cycle, followed by a velocity increase during shut‐in. These results demonstrate varying elastic property perturbations, both spatially and temporally, along the fault plane during reactivation. We then interpreted these velocity changes in terms of fault dilation induced by pressurized fluids along the fault.

58 GEOSCIENCES↗
DOE OSTI2023

Influence of Vertical Hydrologic Exchange Flow, Channel Flow, and Biogeochemical Kinetics on CH 4 Emissions From Rivers

Abstract CH 4 emissions from inland water are highly uncertain in the current global CH 4 budget, especially for rivers and streams due to sparse measurements and the uncertainty of measurements caused by turbulent water flow. A previous study has revealed that vertical hydrologic exchange flow (VHEF) is the main regulator of CH 4 emissions from riverbed sediments. However, to what extent the understanding obtained from the plot‐scale can be extended to the reach scale and basin scale remains unknown. To address this challenge, we developed a process‐based model to estimate CH 4 flux at the air‐water interface using the attributes available in the national hydrography data set. It calculates the annual mean flux of VHEF, CH 4 production in sediments, and CH 4 transport in the river channel in a sequential manner. Model performance is evaluated by CH 4 efflux observed at the Hanford reach of the Columbia River. We show that reach‐wise sediment hydrologic and biogeochemical conditions estimated from the national hydrography data set could serve as a good indicator of CH 4 emissions from rivers. Aerobic methane oxidation and export to the downstream are the dominant ways of total CH 4 loss for the large lowland river. The hotspots of CH 4 emissions are likely to be at the reaches with fine sediments and slow channel velocity. This study demonstrates the possibility of quantifying CH 4 emissions at the reach scale and the modeling framework has the potential to be extended to the basin scale to improve estimates of CH 4 emissions from lotic inland water.

58 GEOSCIENCES↗