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At least 361 records · Page 20

Interannual variability of spring and summer monsoon growing season carbon exchange at a semiarid savanna over nearly two decades

Eddy covariance measurements of land-atmosphere energy, carbon, and water exchange now span multiple decades at some sites, supporting an improved understanding of flux interannual variability (IAV) and its ecophysiological and physical controls. Most eddy covariance IAV studies have focused on temperate forest ecosystems, where carbon fluxes are large and flux records are longest – but also where IAV is much lower than in dryland regions, which have been identified as an essential driver of the trend and variability in the global terrestrial carbon sink. In this study, we leveraged 19 years of continuous micrometeorological measurements at the AmeriFlux US-SRM mesquite savanna site in southern Arizona, USA to quantify the IAV, trends, and drivers of carbon fluxes during the distinct spring and summer growing seasons. We also assessed the ability of modern satellite and land surface models to capture the IAV of seasonal water and carbon fluxes. Annual net ecosystem production (NEP) was small and highly variable (23 +/- 64 gC m –2 yr –1 ). Precipitation and associated measures of water availability determined most of the variability in NEP, largely through their influence on annual and seasonal gross ecosystem productivity (GEP) as opposed to ecosystem respiration (ER). Root-zone soil moisture captured between 73% (spring) and 85% (summer) of GEP variability and between 73% (spring) and 58% (summer) of ER variability. Throughout the study period, soil moisture and greenness increased with associated increases in GEP, ER and NEP. These trends were strongly influenced by very productive and wet summer growing seasons during the last two years, which were characterized by abundant understory grass cover. Typically, less than half of the variability in growing season GEP and evapotranspiration was captured by satellite-based estimates and land surface model simulations with local site forcing and calibration, highlighting the ongoing utility of long-term datasets to support careful model testing and improvement.

54 ENVIRONMENTAL SCIENCES↗

Bypassing the Energy Functional in Density Functional Theory: Direct Calculation of Electronic Energies from Conditional Probability Densities

Density functional calculations can fail for want of an accurate exchange-correlation approximation. The energy can instead be extracted from a sequence of density functional calculations of conditional probabilities (CP DFT). Simple CP approximations yield usefully accurate results for two-electron ions, the hydrogen dimer, and the uniform gas at all temperatures. CP DFT has no self-interaction error for one electron, and correctly dissociates H2, both major challenges. For warm dense matter, classical CP DFT calculations can overcome the convergence problems of Kohn-Sham DFT.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

JAX-CanVeg: A Differentiable Land Surface Model

Land surface models consider the exchange of water, energy, and carbon along the soil-canopy-atmosphere continuum, which is challenging to model due to their complex interdependency and associated challenges in representing and parameterizing them. Differentiable modeling provides a new opportunity to capture these complex interactions by seamlessly hybridizing process-based models with deep neural networks (DNNs), benefiting both worlds, that is, the physical interpretation of process-based models and the learning power of DNNs. Here, we developed a differentiable land model, JAX-CanVeg. The new model builds on the legacy CanVeg by incorporating advanced functionalities through JAX in the graphic processing unit support, automatic differentiation, and integration with DNNs. We demonstrated JAX-CanVeg's hybrid modeling capability by applying the model at four flux tower sites with varying aridity. To this end, we developed a hybrid version of the Ball-Berry equation that emulates the water stress impact on stomatal closure to explore the capability of the hybrid model in (a) improving the simulations of latent heat fluxes (LE) and net ecosystem exchange (NEE), (b) improving the optimization trade-off when learning observations of both LE and NEE, and (c) benefiting a multi-layer canopy model setup. Our results show that the proposed hybrid model improved the simulations of LE and NEE at all sites, with an improved optimization trade-off over the process-based model. Additionally, the multi-layer canopy set benefited hybrid modeling at some sites. Anchored in differentiable modeling, our study provides a new avenue for modeling land-atmosphere interactions by leveraging the benefits of both data-driven learning and process-based modeling.

54 ENVIRONMENTAL SCIENCES↗

Freshwater Input and Vertical Mixing in the Canada Basin’s Seasonal Halocline: 1975 versus 2006–12

Abstract The Arctic seasonal halocline impacts the exchange of heat, energy, and nutrients between the surface and the deeper ocean, and it is changing in response to Arctic sea ice melt over the past several decades. Here, we assess seasonal halocline formation in 1975 and 2006–12 by comparing daily, May–September, salinity profiles collected in the Canada Basin under sea ice. We evaluate differences between the two time periods using a one-dimensional (1D) bulk model to quantify differences in freshwater input and vertical mixing. The 1D metrics indicate that two separate factors contribute similarly to stronger stratification in 2006–12 relative to 1975: 1) larger surface freshwater input and 2) less vertical mixing of that freshwater. The larger freshwater input is mainly important in August–September, consistent with a longer melt season in recent years. The reduced vertical mixing is mainly important from June until mid-August, when similar levels of freshwater input in 1975 and 2006–12 are mixed over a different depth range, resulting in different stratification. These results imply that decadal changes to ice–ocean dynamics, in addition to freshwater input, significantly contribute to the stronger seasonal stratification in 2006–12 relative to 1975. These findings highlight the need for near-surface process studies to elucidate the impact of lateral processes and ice–ocean momentum exchange on vertical mixing. Moreover, the results may provide insight for improving the representation of decadal changes to Arctic upper-ocean stratification in climate models that do not capture decadal changes to vertical mixing.

54 ENVIRONMENTAL SCIENCES↗

Electronic structure, magnetic properties, and exchange splitting of gadolinium intermetallics

Here, we report here the electronic structure calculations of the magnetic moment, magneto-crystalline anisotropy energy (MAE), and density of states (DOS) of Gd-metal, GdAl 2 , GdAl 3 , GdCo 2 , GdCo 3 , and GdCo 5 . From the DOS, the exchange splitting energy is derived to map ferrimagnetic to paramagnetic phase transition (Curie temperature, T C ). The employed theoretical method here is based on advanced density functional theory, specifically the linearized augmented plane wave method (LAPW) within the local spin density approximation (LSDA), including spin–orbit coupling (SOC) and Hubbard model parameter (U). DOS analysis of both Gd-Al and Gd-Co systems reveals a strong correlation between exchange splitting energy and T C . The Gd-Co system exhibits an enormous exchange splitting energy among Co-3d electrons, vastly overwhelming the vanishing Gd 5d exchange splitting. Finally, these findings suggest that exchange splitting of Co-3d electrons plays a key role in the ground state magnetism and magnetic transition temperatures in these materials.

36 MATERIALS SCIENCE↗

Competitive Sorption of H 2 O and CO 2 in Clay Mineral Interlayers

The first-reported competitive CO 2 –H 2 O sorption isotherms on a naturally occurring expandable clay mineral (saponite) exchanged with Na, K, and Cs at near ambient CO 2 concentrations (1% CO 2 ) are reported by combining ATR-FTIR spectroscopy with gravimetric sorption methods. Little CO 2 sorption was observed at high relative humidity (RH) but increased significantly at low RH. Unlike prior work where CO 2 sorption was reported on samples that were previously subjected to heating and/or evacuation treatment to remove sorbed H 2 O, this study manipulated CO 2 sorption by controlling RH. CO 2 sorption increased in the order Cs- > K- > Na-exchanged saponite and was anticorrelated with the Gibbs energy of hydration of the exchangeable cation. As expected, H 2 O sorption followed the opposite trend, with increased H 2 O sorption occurring in the order Na > K > Cs. The amount of CO 2 sorbed using 1 atm CO 2 (p/p o = 1.0) ranged from 50 to 30 mg CO 2 /g clay and from 1.25 to 0.8 mg CO2 /g clay for 1% CO 2 (p/p o = 0.01) in N 2 . The sensitivity of the ATR-FTIR measurements is demonstrated by detecting the CO 2 stretch of adsorbed CO 2 from air containing 500 ppmv CO 2 . The spectral features of sorbed CO 2 were minimally affected by the nature of the exchangeable cation or variations in H 2 O content. However, the position of the HOH bending band shifted significantly from 1638 to 1610 cm –1 as H 2 O content decreased, reflecting changes in intermolecular hydrogen bonding between H 2 O molecules in the saponite interlayer. The shift in position of the HOH bending band to lower energy was coincident with increased CO 2 sorption. CO 2 sorption in clay mineral interlayers is consistent with sorption on weakly hydrated partially hydrophobic sites found on low charge density smectites and is enhanced by lower RH and by the presence of weakly hydrated exchangeable cations like Cs + or K + . In conclusion, the greatest CO 2 sorption occurs on Cs-saponite because this is the least hydrated cation of the three used in the study and indicates that CO2 sorption occurs on the neutral portion of the siloxane surface.

Johnston, Cliff T. [Purdue Univ., West Lafayette, ↗

Optimizing Control for Efficient Load Shifting with Thermal Energy Storage in Existing HVAC Systems

This project developed the integration of a direct-contact heat exchanger (DCHX) based thermal energy storage (TES) system with a chiller–air handling unit (AHU) plant to evaluate its potential for reducing building energy costs. Detailed physical models of the TES unit, building envelope, and HVAC components were developed alongside simplified control-oriented models to support both high-fidelity simulation and real-time optimization. Two control strategies were implemented and compared: a rule-based control (RBC) aligned with utility time-of-use (ToU) rates, and a model predictive control (MPC) framework leveraging forecasts of building load, weather, and internal gains. Simulation results show that the RBC strategy reduced daily electricity costs by around 30% by shifting cooling production from on-peak to off-peak hours. In contrast, the MPC strategy achieved significantly greater performance, reducing daily operating costs by up to 44% and peak-hour costs by more than 60%. Both strategies maintained indoor thermal comfort within acceptable limits, with MPC further improving load distribution and reducing equipment cycling. The outcomes confirm that TES integration, particularly when coordinated with advanced predictive control, can provide substantial cost savings and on-peak demand reduction. . These findings directly support the U.S. Department of Energy’s goals for grid-interactive efficient buildings and demonstrate the potential of TES-enabled HVAC systems for scalable deployment across the commercial building.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Diurnal cycle of precipitation over the tropics and central United States: intercomparison of general circulation models

Diurnal precipitation is a fundamental mode of variability that climate models have difficulty in accurately simulating. Here, in this work, the diurnal cycle of precipitation (DCP) in participating climate models from the Global Energy and Water Exchanges' DCP project is evaluated over the tropics and central United States. Common model biases such as excessive precipitation over the tropics, too frequent light-to-moderate rain, and the failure to capture propagating convection in the central United States still exist. Over the central United States, the issues of too weak rainfall intensity in climate runs is well improved in their hindcast runs with initial conditions from numerical weather prediction analyses. But the improvement is minimal over the central Amazon. Incorporating the role of the large-scale environment in convective triggering processes helps resolve the phase-locking issue in many models where precipitation often incorrectly peaks near noon due to maximum insolation over land. Allowing air parcels to be lifted above the boundary layer improves the simulation of nocturnal precipitation which is often associated with the propagation of mesoscale systems. Including convective memory in cumulus parameterizations acts to suppress light-to-moderate rain and promote intense rainfall; however, it also weakens the diurnal variability. Simply increasing model resolution (with cumulus parameterizations still used) cannot fully resolve the biases of low-resolution climate models in DCP. The hierarchy modeling framework from this study is useful for identifying the missing physics in models and testing new development of model convective processes over different convective regimes.

58 GEOSCIENCES↗

Improved subseasonal-to-seasonal precipitation prediction of climate models with nudging approach for better initialization of Tibetan Plateau-Rocky Mountain Circumglobal wave train and land surface conditions

Abstract Reliable subseasonal-to-seasonal (S2S) precipitation prediction is highly desired due to the great socioeconomical implications, yet it remains one of the most challenging topics in the weather/climate prediction research area. As part of the Impact of Initialized Land Temperature and Snowpack on Sub-seasonal to Seasonal Prediction (LS4P) project of the Global Energy and Water Exchanges (GEWEX) program, twenty-one climate models follow the LS4P protocol to quantify the impact of the Tibetan Plateau (TP) land surface temperature/subsurface temperature (LST/SUBT) springtime anomalies on the global summertime precipitation. We find that nudging towards reanalysis winds is crucial for climate models to generate atmosphere and land surface initial conditions close to observations, which is necessary for meaningful S2S applications. Simulations with nudged initial conditions can better capture the summer precipitation responses to the imposed TP LST/SUBT spring anomalies at hotspot regions all over the world. Further analyses show that the enhanced S2S prediction skill is largely attributable to the substantially improved initialization of the Tibetan Plateau-Rocky Mountain Circumglobal (TRC) wave train pattern in the atmosphere. This study highlights the important role that initial condition plays in the S2S prediction and suggests that data assimilation technique (e.g., nudging) should be adopted to initialize climate models to improve their S2S prediction.

54 ENVIRONMENTAL SCIENCES↗

Energy balance in the DSSAT-CSM-CROPGRO model

One potential way to improve crop growth models is for the models to predict energy balance and evapotranspiration (ET) from first principles, thus serving as a check on “engineered” ET methodology. In this paper, we present new implementations and the results of an energy balance model (EBL) developed by Jagtap and Jones (1989) and then implemented in DSSAT’s CROPGRO (CG-EBL) model by Pickering et al. (1995) as a linked energy balance-photosynthesis model that has not been field-tested until now. The energy balance code computes evapotranspiration and other energy balance components, as well as a canopy air temperature, based on three sources (sunlit leaves, shaded leaves, soil surface). Model performance was evaluated with measured biomass and energy fluxes from two sites in Nebraska, namely, the US-Ne2 irrigated maize-soybean rotation field and the US-Ne3 rainfed maize-soybean rotation field, which are part of the Ameriflux eddy covariance network (htt ps://ameriflux.lbl.gov/sites). After implementing new aerodynamic resistances and the stomatal conductance model of the Ball–Berry–Leuning, crop growth, evapotranspiration and soil temperature were simulated well by the EBL model. The EBL improved ET predictions slightly over the often-used FAO56 method [Penman–Monteith (Allen et al., 1998)] for 4 of the 5 years evaluated for both irrigated and rainfed conditions. Further, a significant improvement was achieved using EBL for the simulation of soil temperature at the various depths compared to STEMP, the original subroutine in DSSAT for simulating soil temperature. Compared to the other available DSSAT methods, the EBL explicitly simulates the impacts of crop morphology, physiology and management on the crop’s environment and energy and mass exchange, which in turn directly affect the water use and irrigation requirements, phenology, photosynthesis, growth, sterility, and yield of the crop.

54 ENVIRONMENTAL SCIENCES↗

Hourly water-carbon interactions modulate decadal water-use efficiency trends inferred from ecosystem-scale measurements

Plant stomatal conductance regulates photosynthesis and transpiration. This physiological link affects ecosystem responses to microclimate and harmonizes carbon, energy, and water exchanges between the biosphere and atmosphere. The relationship between water losses via transpiration and carbon gains via photosynthesis can be quantified by plant water-use efficiency (WUE). While leaf- and ecosystem-scale observations both suggest rising WUE in recent decades, WUE trends inferred from the ecosystem scale are much larger than those inferred from the leaf scale or implied by theory. The unexpectedly large ecosystem-scale WUE trends complicate interpretation of ecophysiological responses to changing environmental conditions. Here, we analyze ecosystem-scale WUE inferred from 40 FLUXNET sites, each with at least 10 years of measurements. Furthermore, our results demonstrate that observed ecosystem-scale WUE trends are more sensitive to hourly weather conditions than longer-term changes in atmospheric carbon dioxide or vapor pressure deficit. Our analysis shows that Earth System Models participating in CMIP6 did not capture the observed WUE sensitivity to inter-site variability and microclimatic conditions. Collectively, our findings suggest that ecosystem-scale WUE trends reflect water-carbon interactions across multiple temporal scales, and disentangling factors contributing to emergent ecosystem responses is needed to infer ecophysiological relationships and model structures from observations.

54 ENVIRONMENTAL SCIENCES↗

Extreme hydroclimates amplify the biophysical effects of advanced green-up in temperate China

Vegetation phenology modulates climate by altering energy and water exchange between the land and atmosphere. However, how extreme hydroclimatic conditions modify these phenology-climate feedbacks is still poorly understood. Here, in this study, we used a land–atmosphere-coupled Weather Research and Forecasting model to explore the impacts of advanced green-up on air temperature under different hydroclimate conditions across temperate China and to Mechanistic analysis elucidate the underlying biophysical mechanisms. By imposing a 14-day earlier green-up in line with recent satellite observations, we found that under mean climate conditions, an earlier leaf-out induces immediate surface cooling of 0.14 °C during green-up and a lagging 0.02 °C warming during senescence averaged for temperate China. Extremely humid conditions amplify the cooling effects to 0.18 °C during green-up, extending this cooling into the senescence period. Conversely, under extremely arid conditions, earlier green-up cools air temperature by 0.09 °C, and amplified senescence warming to 0.16 °C. Mechanism analysis revealed that evapotranspiration-dominated non-radiative processes drive immediate cooling during green-up while radiation and circulation process dominates the delayed but opposite warming/cooling effects during senescence in extremely arid/humid hydroclimates. Given the projected continuation of warming trends and increased frequency of extreme climatic events, it is imperative to incorporate the biophysical effects of vegetation phenology into local climate adaptation strategies.

54 ENVIRONMENTAL SCIENCES↗

Nematic order driven by superconducting correlations

The interplay of nematicity and superconductivity has been observed in a wide variety of quantum materials. To explore this interplay, we consider a two-dimensional (2D) array of nematogens, local droplets with Z 3 nematicity, coupled to a network of Josephson junction wires. Using finite temperature classical Monte Carlo simulations, we elucidate the phase diagram of this model and show that the development of superconducting correlations and the directional delocalization of Cooper pairs can promote nematogen ordering, resulting in long-range nematic order. We obtain the transport properties of our model within an effective resistor network picture. We discuss these ideas in the context of the 2D electron gas at the (111) KTaO 3 interface and the doped topological insulators Nb x Bi 2 Se 3 and Cu x Bi 2 Se 3 . Overall, our work makes contact with Phil Anderson’s numerous contributions to broken symmetries driven by the saving of kinetic energy, including double exchange ferromagnetism and the interlayer tunneling theory of high Tc csuperconductivity.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

In-situ thermal transport measurement of flowing fluid using modulated photothermal radiometry

In situ thermal transport measurement of flowing fluid could be useful for the characterization and diagnosis of practical thermal systems such as fluid heat exchangers and thermal energy storage systems. Despite abundant reports on the ex-situ thermal conductivity measurement of stagnant fluids, a suitable technique for the thermal conductivity measurement of flowing fluid has been rarely reported. Here, this paper presents the thermal conductivity measurement of flowing fluid within a pipe using a non-contact modulated photothermal radiometry (MPR) technique, where the surface of the pipe is heated by an intensity-modulated laser and the heat diffuses into the fluid with suitable modulation frequency. We design a tube section with small wall thickness suitable for the MPR measurements to maximize the sensitivity of the thermal response to the fluid properties while minimizing the lateral heat spreading effect. Intrinsic thermal conductivity of different fluids was obtained within a proper range of frequency and flow velocity where the forced convection effect is negligible. The forced convection effect became prominent at high flowing velocity and at low modulation frequency, leading to higher effective thermal conductivity of the fluid. It is found that the intrinsic thermal conductivity could be obtained when the flow velocity is less than 100 mm/sec and Re D 1/2 Pr 1/3 < 100 for DI water and Xceltherm oil under the specified experimental conditions, where Re D is the Reynolds number and Pr is the Prandtl number.

42 ENGINEERING↗

Pressure dependent magnetic properties on bulk CrBr 3 single crystals

The van der Waals class of materials offer an approach to two-dimensional magnetism as their spin fluctuations can be tuned upon exfoliation of layers. Moreover, it has recently been shown that spin-lattice coupling and long-range magnetic ordering can be modified with pressure in van der Waals materials. In this work, the magnetic properties of quasi two-dimensional CrBr 3 are reported applying hydrostatic pressure. The application of pressure up to 0.844 GPa shows a 1.77% decrease in saturation magnetization with a decrease in the Curie temperature from 33.05 to 30.41 K. Density functional theory calculations with pressure up to 1 GPa show a reduction in volume and interplanar distance as pressure increases. To further understand the magnetic properties with applied pressure, the magnetocrystalline anisotropy energy (MAE) and exchange coupling parameter (J) are calculated. There is small decrease in MAE and the first nearest neighbor interaction (J 1 ) (U = 2.7 eV and J = 0.7 eV) is increasing with respect to increasing pressure. Overall, CrBr 3 displays ferromagnetic interlayer coupling and the calculated exchange coupling and MAE parameters match well with the observations from the experimental work.

36 MATERIALS SCIENCE↗

Interplay Between Kondo and Magnetic Interactions in Pr 0.75 Gd 0.25 ScGeH

Combined experimental and density functional theory (DFT) study of Pr 0.75 Gd 0.25 ScGe and its hydride (Pr 0.75 Gd 0.25 ScGeH) reveals intricacies of composition-structure-property relationships in those distinctly layered compounds. Hydrogenation of the intermetallic parent, crystalizing in a tetragonal CeScSi-type structure, leads to an anisotropic volume expansion, that is, a(=b) lattice parameter decreases while the lattice expands along the c direction, yielding a net increase of cell volume. DFT calculations predict an antiparallel coupling of localized Gd and Pr magnetic moments in both materials at the ground state. While experiments corroborate this for the parent compound, there is no conclusive experimental proof for the hydride, where Pr moments do not order down to 3 K. DFT results also reveal that rare-earth – hydrogen interactions reduce spin-polarization of the Pr and Gd 5d and Sc 3d states at the Fermi energy, disrupt indirect exchange interactions mediated by conduction electrons, dramatically reduce the magnetic ordering temperature, and open a pseudo-gap in the majority-spin channel. Here, both experiments and theory show evidence of Kondo-like behavior in the hydride in the absence of an applied magnetic field, whereas increasing the field promotes magnetic ordering and suppresses Kondo-like behavior.

36 MATERIALS SCIENCE↗

Quaternized poly(arylene ether benzonitrile) membranes for vanadium redox flow batteries

In this work, a series of quaternized poly (arylene ether benzonitrile)s (QAxCN; x = percent quaternization) were synthesized for the vanadium redox flow battery (VRFB) application. The presence of highly polar nitrile groups incorporated in the quaternized polymer chain provides desirable polymer properties (low water uptake, high dimensional stability and low VO 2+ permeability) without compromising ion conductivity. VRFB single cells using the aforementioned membranes showed excellent performance. As a result, the cell using a 15 μm-thick QA50CN membrane exhibited superior coulombic efficiency (98.2%) and comparable energy efficiency (86.5%) at 40 mA cm -2 compared to the single cell using Nafion-212 with a coulombic efficiency of 95.5% and an energy efficiency of 86.2%. The cell cycling stability and membrane oxidative stability data confirmed that the QAxCN membranes have the potential to replace Nafion membranes for energy storage in VRFB applications.

25 ENERGY STORAGE↗

Spatial Signatures of Electron Correlation in Least-Squares Tensor Hypercontraction

Least Squares Tensor Hypercontraction (LS-THC) has received some attention in recent years as an approach to reduce the significant computational costs of wavefunc- tion based methods in quantum chemistry. However, previous work has demonstrated that the LS-THC factorization performs disproportionately worse in the description of wavefunction components (e.g. cluster amplitudes T 2 ) than Hamiltonian compo- nents (e.g. electron repulsion integrals (pq|rs)). This work develops novel theoretical methods to study the source of these errors in the context of the real-space T 2 kernel, and reports, for the first time, the existence of a “correlation feature” in the errors of the LS-THC representation of the “exchange-like” correlation energy EX and T 2 that is remarkably consistent across ten molecular species, three correlated wavefunctions, and four basis sets. This correlation feature portends the existence of a “pair-point kernel” missing in the usual LS-THC representation of the wavefunction, which critically depends upon pairs of grid points situated close to atoms and with inter-pair distances between one and two Bohr radii. These findings point the way for future LS-THC developments to address these shortcomings.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗