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At least 631 records · Page 35

The Tropospheric Wind Lidar Technology Experiment (TWiLiTE): An Airborne Direct Detection Doppler Lidar Instrument Development Program

Global measurement of tropospheric winds is a key measurement for understanding atmospheric dynamics and improving numerical weather prediction. Global wind profiles remain a high priority for the operational weather community and also for a variety of research applications including studies of the global hydrologic cycle and transport studies of aerosols and trace species. In addition to space based winds, a high altitude airborne system flown on UAV or other advanced platforms would be of great interest for studying mesoscale dynamics and hurricanes. The Tropospheric Wind Lidar Technology Experiment (TWiLiTE) project was selected in 2005 by the NASA Earth Sun Technology Office as part of the Instrument Incubator Program. TWiLiTE will leverage significant research and development investments in key technologies made in the past several years. The primary focus will be on integrating these sub-systems into a complete molecular direct detection Doppler wind lidar system designed for autonomous operation on a high altitude aircraft, such as the NASA WB57, so that the nadir viewing lidar will be able to profile winds through the full troposphere. TWiLiTE is a collaboration involving scientists and technologists from NASA Goddard, NOAA ESRL, Utah State University Space Dynamics Lab and industry partners Michigan Aerospace Corporation and Sigma Space Corporation. NASA Goddard and it's partners have been at the forefront in the development of key lidar technologies (lasers, telescopes, scanning systems, detectors and receivers) required to enable spaceborne global wind lidar measurement. The TWiLiTE integrated airborne Doppler lidar instrument will be the first demonstration of a airborne scanning direct detection Doppler lidar and will serve as a critical milestone on the path to a fixture spaceborne tropospheric wind system. The completed system will have the capability to profile winds in clear air from the aircraft altitude of 18 h to the surface with 250 m vertical resolution and less than 2 meters per second velocity accuracy. The instrument design, technologies and predicted performance will be presented.

Gentry, Bruce↗

Quantifying Species Populations in Multivalent Borohydride Electrolytes

Multivalent batteries represent an important beyond Li-ion energy storage concept. The prospect of calcium batteries, in particular, has emerged recently due to novel electrolyte demonstrations, especially that of a ground-breaking combination of the borohydride salt Ca(BH 4 ) 2 dissolved in tetrahydrofuran. Recent analysis of magnesium and calcium versions of this electrolyte led to the identification of divergent speciation pathways for Mg 2+ and Ca 2+ despite identical anions and solvents, owing to differences in cation size and attendant flexibility of coordination. To test these proposed speciation equilibria and develop a more quantitative understanding thereof, we have applied pulsed-field-gradient nuclear magnetic resonance and dielectric relaxation spectroscopy to study these electrolytes. Additionally, concentration-dependent variation in anion diffusivities and solution dipole relaxations, interpreted with the aid of molecular dynamics simulations, confirms these divergent Mg 2+ and Ca 2+ speciation pathways. These results provide a more quantitative description of the electroactive species populations. We find that these species are present in relatively small quantities, even in the highly active Ca(BH 4 ) 2 /tetrahydrofuran electrolyte. This finding helps interpret previous characterizations of metal deposition efficiency and morphology control and thus provides important fundamental insight into the dynamic properties of multivalent electrolytes for next-generation batteries.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Riverine bacterioplankton and phytoplankton assembly along an environmental gradient induced by urbanization

In the Anthropocene, human activities are intensifying stresses on biological communities across ecosystems. Knowledge on how environmental changes influence microbial community dynamics is crucial but currently limited. Here we unraveled ecological processes generating distribution patterns of bacterioplankton and phytoplankton communities in a river draining an urbanizing watershed in southern China. In this ecosystem, longitudinal environmental heterogeneity and directional flow potentially have counteracting effects on planktonic community assembly. Using simultaneously multiple approaches, we showed that the observed compositional patterns result from an interplay of stochastic and deterministic processes, indicating that dispersal via fluvial connectivity could not override local selective pressures. Successional shifts in the relative importance of the above processes were associated with trends in climatic factors. High diversity was observed at the intermediate levels of ecological processes alongside intense inter-species interactions maintained by a few keystone taxa. Altogether, interactions between climatic conditions, landscape and hydrology control plankton community dynamics.

54 ENVIRONMENTAL SCIENCES↗

Structural evidence for a dynamic metallocofactor during N 2 reduction by Mo-nitrogenase

The enzyme nitrogenase uses a suite of complex metallocofactors to reduce dinitrogen (N 2 ) to ammonia. Mechanistic details of this reaction remain sparse. We report a 1.83-angstrom crystal structure of the nitrogenase molybdenum-iron (MoFe) protein captured under physiological N 2 turnover conditions. This structure reveals asymmetric displacements of the cofactor belt sulfurs (S2B or S3A and S5A) with distinct dinitrogen species in the two αβ dimers of the protein. The sulfur-displaced sites are distinct in the ability of protein ligands to donate protons to the bound dinitrogen species, as well as the elongation of either the Mo–O5 (carboxyl) or Mo–O7 (hydroxyl) distance that switches the Mo-homocitrate ligation from bidentate to monodentate. These results highlight the dynamic nature of the cofactor during catalysis and provide evidence for participation of all belt-sulfur sites in this process.

Science & Technology - Other Topics↗

Reviving the carbon sink: The influence of moderate wind disturbance in a secondary temperate mixed forest

Global forests are increasingly exposed to climate-driven perturbations, which may in turn alter their climate mitigation potential. As tropical cyclones expand poleward due to climate warming, wind disturbances in temperate forests have become increasingly frequent. The consequences of moderate wind disturbances remain poorly understood, hindering efforts to quantify their role in the global carbon cycle. Here, we used 16 years of continuous eddy covariance and biometric measurements to investigate the impacts of moderate wind disturbances on the structure and carbon sink dynamics of a temperate forest in Northeast China. Following Typhoon Maysak in 2020, the mortality of large trees (particularly the aging pioneer species) increased ninefold, whereas that of small trees decreased by nearly half. Both stand basal area and leaf area index were reduced between 2019 and 2023, with aging pioneer tree species being more vulnerable than mid-to-late species to wind disturbances. Shifts in species composition altered the environmental sensitivity of forest carbon sink function. Unexpectedly, wind disturbances reversed the declining trends in net ecosystem production and ecosystem carbon use efficiency of this secondary forest. A novel composite structural indicator—the standardized leaf area index (the maximum leaf area supported by per basal area of the stand)—provided robust predictions (R 2 > 0.4) of carbon sink dynamics throughout the study period. The selective removal of less efficient pioneer trees accelerated succession and reversed the aging-related decline in forest carbon sink strength and carbon use efficiency. In conclusion, these findings highlight the potential role of moderate wind disturbances in enhancing forest carbon sink function and offer a framework for understanding, assessing, and predicting forest carbon dynamics under increasing disturbance frequencies driven by climate change.

Carbon sink↗

Increased water availability at various timescales has different effects on stomatal closure point in isohydric piñon pine and anisohydric juniper

Abstract Stomatal Closure Point (SCP) has commonly been used to describe drought response strategies in plants, with isohydric species maintaining relatively high, constant SCP compared to anisohydric species that can lower SCP with increasing drought severity. However, there is evidence that, within these groups, SCP may respond dynamically to environmental conditions. Here, we explored how increasing water availability affects SCP in classically isohydric piñon pine and anisohydric one-seed or Utah juniper at various spatial- (i.e., from branch, to tree, to ecosystem) and temporal- (i.e., hours to decades) scales. Our results show that short-term increases in water availability decreased SCP in isohydric piñon pine, making it more anisohydric, while short-term rehydration had no effect on SCP in anisohydric juniper. Increasing mean annual precipitation, on the other hand, increased SCP in both species. Our findings are consistent with documented differences in the use of ABA to control stomata in iso- and aniso-hydric species on short timescales, and with structural acclimation in both species at long timescales. These results illustrate that the local environment plays a large role in determining SCP.

Kraklow, Vachel↗

Dynamic Features of Cu-Ceria Interface under CO 2 Hydrogenation to Methanol

It is generally accepted that metal–support interaction is very important for the hydrogenation of CO 2 to methanol, but little has been revealed about the feature of interfacial active sites under real reaction conditions since there are only limited techniques that can be applied under high-pressure conditions. Here, in this work, by combining multiple in situ and operando techniques on a model Cu/ceria catalyst, we have tracked Cu and ceria sites for methanol formation. Under the reaction condition, it is found that upon reaching the reaction temperature, oxidized Cu species in the as-synthesized catalyst immediately change into metallic Cu species. Following this, it is the gradual formation of methanol, the changing rate of which coincides with the formation of a unique Ce 3+ species. The combined experimental results and density functional theory (DFT) calculations have determined that the formed Ce 3+ sites driven by the reaction conditions are bound to hydrides, adsorbed carbonate species, and interfacial active Cu sites. The Cu-ceria interaction in this complex moiety is weak and can be easily disturbed with reaction environment variations, leading to dynamic changes at the interface upon the hydrogenation of active carbonate intermediates, which are precursors for the formation of methanol. The formation of this unique Cu–Ce 3+ interface and its dynamicity lead to an increase of methanol selectivity from less than 20% to 60%. These results suggest that reactant-derived species (H – and carbonate in this work) can be essential components of the active center with the functions of manipulating the metal−oxide interaction and directing reaction pathways.

CO2 hydrogenation to methanol↗

Extension of the Viscous Collision Limiting Direct Simulation Monte Carlo Technique to Multiple Species

There are many flows fields that span a wide range of length scales where regions of both rarefied and continuum flow exist and neither direct simulation Monte Carlo (DSMC) nor computational fluid dynamics (CFD) provide the appropriate solution everywhere. Recently, a new viscous collision limited (VCL) DSMC technique was proposed to incorporate effects of physical diffusion into collision limiter calculations to make the low Knudsen number regime normally limited to CFD more tractable for an all-particle technique. This original work had been derived for a single species gas. The current work extends the VCL-DSMC technique to gases with multiple species. Similar derivations were performed to equate numerical and physical transport coefficients. However, a more rigorous treatment of determining the mixture viscosity is applied. In the original work, consideration was given to internal energy non-equilibrium, and this is also extended in the current work to chemical non-equilibrium.

Liechty, Derek S.↗

Dehydration-Driven Ion Aggregation and the Onset of Gelation in ZnCl2 Solution

A minimal model of ionic aggregation in concentrated ZnCl2 is developed, guided by molecular dynamics simulations with a machine-learned potential. It explicitly incorporates solvent-site depletion, correlated chloride binding, and allows for loops within Zn–Cl clusters. Dehydration drives two coordination-controlled structural changes: a crossover at Z=2 from predominantly isolated Zn-containing species to Cl-bridged clusters and the onset of gelation near Z≈3. The model reproduces the concentration-dependent trends observed in the molecular dynamics simulations with two fitted parameters, while the cluster-size distribution at the highest concentration is consistent with three-dimensional percolation scaling over the accessible range of cluster sizes.

25 ENERGY STORAGE↗

Experimental Studies of the Distribution of Minor Constituents and Dynamic Processes in the Atmosphere

Minor constituents play an important role in atmospheric chemistry and serve as tracers in transport and mixing studies in tropospheric-stratospheric exchange processes. Measurements of trace gases are essential to an understanding of the mechanisms by which minor constituents originating in the troposphere, both naturally occurring and anthropogenic, reach the stratosphere. Many of these gases are sources of species directly involved in the chemistry of ozone depletion in the stratosphere and ozone generation in the troposphere. Some contribute to the warming of the atmosphere. Data on tracer distributions are important in the development of models for predicting photochemical effects in the stratosphere and troposphere. Data on atmospheric dynamics are important for the development of models for predicting the transport of photochemical species and for characterizing the nature of stratospheric motions.

Goodman, Jindra↗

Remote Sensing-Informed Zonation for Understanding Snow, Plant and Soil Moisture Dynamics within a Mountain Ecosystem

In the headwater catchments of the Rocky Mountains, plant productivity and its dynamics are largely dependent upon water availability, which is influenced by changing snowmelt dynamics associated with climate change. Understanding and quantifying the interactions between snow, plants and soil moisture is challenging, since these interactions are highly heterogeneous in mountainous terrain, particularly as they are influenced by microtopography within a hillslope. Recent advances in satellite remote sensing have created an opportunity for monitoring snow and plant dynamics at high spatiotemporal resolutions that can capture microtopographic effects. In this study, we investigate the relationships among topography, snowmelt, soil moisture and plant dynamics in the East River watershed, Crested Butte, Colorado, based on a time series of 3-meter resolution PlanetScope normalized difference vegetation index (NDVI) images. To make use of a large volume of high-resolution time-lapse images (17 images total), we use unsupervised machine learning methods to reduce the dimensionality of the time lapse images by identifying spatial zones that have characteristic NDVI time series. We hypothesize that each zone represents a set of similar snowmelt and plant dynamics that differ from other identified zones and that these zones are associated with key topographic features, plant species and soil moisture. We compare different distance measures (Ward and complete linkage) to understand the effects of their influence on the zonation map. Results show that the identified zones are associated with particular microtopographic features; highly productive zones are associated with low slopes and high topographic wetness index, in contrast with zones of low productivity, which are associated with high slopes and low topographic wetness index. The zones also correspond to particular plant species distributions; higher forb coverage is associated with zones characterized by higher peak productivity combined with rapid senescence in low moisture conditions, while higher sagebrush coverage is associated with low productivity and similar senescence patterns between high and low moisture conditions. In addition, soil moisture probe and sensor data confirm that each zone has a unique soil moisture distribution. This cluster-based analysis can tractably analyze high-resolution time-lapse images to examine plant-soil-snow interactions, guide sampling and sensor placements and identify areas likely vulnerable to ecological change in the future.

54 ENVIRONMENTAL SCIENCES↗

Transcriptome Dynamics of the Inflorescence in Reciprocally Formed Allopolyploid Tragopogon miscellus (Asteraceae)

Polyploidy is an important evolutionary mechanism and is prevalent among land plants. Most polyploid species examined have multiple origins, which provide genetic diversity and may enhance the success of polyploids. In some polyploids, recurrent origins can result from reciprocal crosses between the same diploid progenitors. Although great progress has been made in understanding the genetic consequences of polyploidy, the genetic implications of reciprocal polyploidization remain poorly understood, especially in natural polyploids. Tragopogon (Asteraceae) has become an evolutionary model system for studies of recent and recurrent polyploidy. Allotetraploid T. miscellus has formed reciprocally in nature with resultant distinctive floral and inflorescence morphologies (i.e., short- vs. long-liguled forms). In this study, we performed comparative inflorescence transcriptome analyses of reciprocally formed T. miscellus and its diploid parents, T. dubius and T. pratensis. In both forms of T. miscellus, homeolog expression of ~70% of the loci showed vertical transmission of the parental expression patterns (i.e., parental legacy), and ~20% of the loci showed biased homeolog expression, which was unbalanced toward T. pratensis. However, 17.9% of orthologous pairs showed different homeolog expression patterns between the two forms of T. miscellus. No clear effect of cytonuclear interaction on biased expression of the maternal homeolog was found. In terms of the total expression level of the homeologs studied, 22.6% and 16.2% of the loci displayed non-additive expression in short- and long-liguled T. miscellus, respectively. Unbalanced expression level dominance toward T. pratensis was observed in both forms of T. miscellus. Significantly, genes annotated as being involved in pectin catabolic processes were highly expressed in long-liguled T. miscellus relative to the short-liguled form, and the majority of these differentially expressed genes were transgressively down-regulated in short-liguled T. miscellus. Given the known role of these genes in cell expansion, they may play a role in the differing floral and inflorescence morphologies of the two forms. In summary, the overall inflorescence transcriptome profiles are highly similar between reciprocal origins of T. miscellus. However, the dynamic homeolog-specific expression and non-additive expression patterns observed in T. miscellus emphasize the importance of reciprocal origins in promoting the genetic diversity of polyploids.

54 ENVIRONMENTAL SCIENCES↗

Plant‐Induced Changes Mediate Belowground Carbon Cycling in an Experimentally Warmed Peatland

Warming and elevated atmospheric CO 2 profoundly impact peatland ecosystems, particularly through changes in plant species composition. Plants regulate the initial input of organic compounds to peatland belowground systems, controlling the availability of electron donors and electron acceptors that fuel microbially mediated organic matter decomposition to CO 2 and CH 4 . However, explicit links between porewater CO 2 and CH 4 dynamics and plant-derived chemical compounds remain relatively undefined. In a whole ecosystem warming experiment, we investigated how warming affects plant leaf chemical composition and species assemblages, and how the alteration of leaf-derived organic compounds supplied to the subsurface impacts belowground CO 2 and CH 4 production. While earlier studies at our site found no temperature-dependent changes in CH 4 production pathways, our extended timeseries has revealed increased acetoclastic methanogenesis at higher temperatures in certain peat depths, correlated with elevated porewater phenolics. These changes appear driven by the observed increased plant productivity and altered vegetation inputs, which accelerate decomposition and fuel CH 4 production through enhanced substrate availability. In conclusion, we observed warming-induced changes in molecular composition both between and within plant species, suggesting that plant-mediated controls on belowground carbon processing are more complex than previously recognized.

Wilson, Rachel M. [Florida State Univ., Tallahasse↗

The final piece of the Triangle of U: Evolution of the tetraploid Brassica carinata genome

Abstract Ethiopian mustard (Brassica carinata) is an ancient crop with remarkable stress resilience and a desirable seed fatty acid profile for biofuel uses. Brassica carinata is one of six Brassica species that share three major genomes from three diploid species (AA, BB, and CC) that spontaneously hybridized in a pairwise manner to form three allotetraploid species (AABB, AACC, and BBCC). Of the genomes of these species, that of B. carinata is the least understood. Here, we report a chromosome scale 1.31-Gbp genome assembly with 156.9-fold sequencing coverage for B. carinata, completing the reference genomes comprising the classic Triangle of U, a classical theory of the evolutionary relationships among these six species. Our assembly provides insights into the hybridization event that led to the current B. carinata genome and the genomic features that gave rise to the superior agronomic traits of B. carinata. Notably, we identified an expansion of transcription factor networks and agronomically important gene families. Completion of the Triangle of U comparative genomics platform has allowed us to examine the dynamics of polyploid evolution and the role of subgenome dominance in the domestication and continuing agronomic improvement of B. carinata and other Brassica species.

Biochemistry & Molecular Biology↗

Temporal change in chromatin accessibility predicts regulators of nodulation in Medicago truncatula

Symbiotic associations between bacteria and leguminous plants lead to the formation of root nodules that fix nitrogen needed for sustainable agricultural systems. Symbiosis triggers extensive genome and transcriptome remodeling in the plant, yet an integrated understanding of the extent of chromatin changes and transcriptional networks that functionally regulate gene expression associated with symbiosis remains poorly understood. In particular, analyses of early temporal events driving this symbiosis have only captured correlative relationships between regulators and targets at mRNA level. Here, we characterize changes in transcriptome and chromatin accessibility in the model legume Medicago truncatula, in response to rhizobial signals that trigger the formation of root nodules. We profiled the temporal chromatin accessibility (ATAC-seq) and transcriptome (RNA-seq) dynamics of M. truncatula roots treated with bacterial small molecules called lipo-chitooligosaccharides that trigger host symbiotic pathways of nodule development. Using a novel approach, dynamic regulatory module networks, we integrated ATAC-seq and RNA-seq time courses to predict cis-regulatory elements and transcription factors that most significantly contribute to transcriptomic changes associated with symbiosis. Regulators involved in auxin (IAA4-5, SHY2), ethylene (EIN3, ERF1), and abscisic acid (ABI5) hormone response, as well as histone and DNA methylation (IBM1), emerged among those most predictive of transcriptome dynamics. RNAi-based knockdown of EIN3 and ERF1 reduced nodule number in M. truncatula validating the role of these predicted regulators in symbiosis between legumes and rhizobia. Our transcriptomic and chromatin accessibility datasets provide a valuable resource to understand the gene regulatory programs controlling the early stages of the dynamic process of symbiosis. The regulators identified provide potential targets for future experimental validation, and the engineering of nodulation in species is unable to establish that symbiosis naturally.

59 BASIC BIOLOGICAL SCIENCES↗

Excited State Dynamics of a Conformationally Fluxional Copper Coordination Complex

The conversion of solar energy into chemical fuel represents a capstone goal of the 21st century and has the potential to supply terawatts of power in a globally distributed manner. However, the disparate time scales of photodriven charge separation (~fs) and steps in chemical reactions (~μs) represent an inherent bottleneck in solar-to-fuels technology. Here to address this discrepancy, we are developing earth-abundant coordination complexes that undergo light-induced conformational rearrangements such that charge separation (CS) is hastened, while charge recombination (CR) is slowed. To these ends, we report the preparation and characterization of a new series of conformationally fluxional copper coordination complexes that contain a twisted intramolecular charge transfer (TICT) fluorophore as part of their ligand scaffold. Structural and spectroscopic characterization of the Cu(I) and Cu(II) complexes formed with these ligands in their ground states establish oxidation state-dependent conformational dynamicity, while time-resolved emission and transient absorption spectroscopies define the photopysical parameters of photo-induced excited states. Building on initial reports with a related set of molecules, the improved ligand design presented here greatly simplifies the observed photophysics, effectively shutting down unwanted ligand-centered excited states previously observed. Finally, time-dependent density functional theory (TDDFT) analyses reveal an unusual metal-to-TICT electronic transition only reported once before, and though the formation of a CS state is not observed directly through experiments, TDDFT geometry optimizations in the excited states support the formation of transient Cu(II) CS species, lending credence to the potential success of our approach. These studies establish a clear model for the excited state dynamics at play in proof-of-concept systems and clarify key design parameters for future optimizations toward achieving long-lived CS via photoinduced conformational gating.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Catalytic Resonance Theory: Forecasting the Flow of Programmable Catalytic Loops

Chemical transformations on catalyst surfaces occur through series and parallel reaction pathways. These complex networks and their behavior can be most simply evaluated through a three-species surface reaction loop (A* to B* to C* to A*) that is internal to the overall chemical reaction. Application of an oscillating dynamic catalyst to this reactive loop has been shown to exhibit one of three types of behavior: (1) a positive net flux of molecules about the loop in the clockwise direction, (2) a negative net flux of molecules about the loop in the counterclockwise direction, or (3) negligible flux of molecules about the loop at the limit cycle of reaction. Three-species surface loops were simulated with microkinetic modeling to assess the reaction loop behavior resulting from a catalytic surface oscillating between two or more catalyst surface energy states. Selected input parameters for the simulations spanned an 11-dimensional parameter space using 127 688 different parameter combinations. Their converged limit cycle solutions were analyzed for their loop turnover frequencies, the majority of which were found to be approximately zero. Classification and regression machine learning models were trained to predict the sign and magnitude of the loop turnover frequency and successfully performed above accessible baselines. Notably, the classification models exhibited a baseline weighted F1 score of 0.49, whereas trained models achieved weighted F1 scores of 0.94 and 0.96 when trained on the parameters used to define the simulations and derived rate constants, respectively. The trained models successfully predicted catalytic loop behavior, and interpretation of these models revealed all input parameters to be important for the prediction and performance of each model.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Persistence and Plasticity in Conifer Water–Use Strategies

The selective use of seasonal precipitation by vegetation is critical to understanding the residence time and flow path of water in watersheds, yet there are limited datasets to test how climate alters these dynamics. Here, we use measurements of the seasonal cycle of tree ring δ 18 O for two widespread conifer species in the Rocky Mountains of North America to provide a multi-decadal depiction of the seasonal origins of forest water use. The results show that while the conifer tree stands had a dominant preference for use of snowmelt, there were multi-annual periods over the last four decades when use of summer precipitation was preferential. Utilization of summer rain emerged during years with increased snowfall and tree growth, suggesting that summer rain enhanced the transpiration stream only during the periods of highest water use. We hypothesize this could be explained through shallowing of the root profile during wetter periods and/or through the influence of changing water table depths on the residence time of summer precipitation in the root zone. We suggest the tree ring proxy approach used here could be applied in other watersheds to provide critical insight into the temporal dynamics of plant water use that could not be inferred from short measurement campaigns. Furthermore, these data on the seasonal origins of forest water are critical for understanding forest vulnerability to drought, the processes that affect precipitation pathways and residence time in watersheds and the interpretation of tree ring proxy data.

59 BASIC BIOLOGICAL SCIENCES↗