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

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87 records · Page 5
All sourcesNASA NTRSDOE OSTI
NASA NTRS1998

The stability of the RNA bases: implications for the origin of life

High-temperature origin-of-life theories require that the components of the first genetic material are stable. We therefore have measured the half-lives for the decomposition of the nucleobases. They have been found to be short on the geologic time scale. At 100 degreesC, the growth temperatures of the hyperthermophiles, the half-lives are too short to allow for the adequate accumulation of these compounds (t1/2 for A and G approximately 1 yr; U = 12 yr; C = 19 days). Therefore, unless the origin of life took place extremely rapidly (<100 yr), we conclude that a high-temperature origin of life may be possible, but it cannot involve adenine, uracil, guanine, or cytosine. The rates of hydrolysis at 100 degreesC also suggest that an ocean-boiling asteroid impact would reset the prebiotic clock, requiring prebiotic synthetic processes to begin again. At 0 degreesC, A, U, G, and T appear to be sufficiently stable (t1/2 >/= 10(6) yr) to be involved in a low-temperature origin of life. However, the lack of stability of cytosine at 0 degreesC (t1/2 = 17, 000 yr) raises the possibility that the GC base pair may not have been used in the first genetic material unless life arose quickly (<10(6) yr) after a sterilization event. A two-letter code or an alternative base pair may have been used instead.

Non-NASA Center↗
DOE OSTI2020

Antecedent conditions determine the biogeochemical response of coastal soils to seawater exposure

Coastal landscapes are increasingly exposed to seawater due to sea level rise and extreme weather events. The biogeochemical responses of these vulnerable ecosystems are poorly understood, limiting our ability to predict how their role in local and global biogeochemical cycles will shift under future conditions. Here we evaluate how antecedent conditions influence the biogeochemical response of soil to seawater inundation events based on a 42-day laboratory incubation experiment with soils collected from a natural salinity gradient across a coastal floodplain. We quantified influences of seawater inundation on intact soil cores through high-frequency carbon dioxide (CO 2 ) and methane (CH 4 ) gas fluxes measurements as well as ultrahigh resolution characterization of organic matter chemistry and metabolites. Mean CO 2 and CH 4 fluxes were higher after inundation compared to control cores for soils that had low in situ salinity. Soils with low in situ salinity also exhibited significant shifts in organic matter profiles after inundation, with surficial soils (0-7.5 cm) becoming more enriched in phenolic compounds, compared to deeper soils (7.5-15 cm). The number of biochemical transformations inferred from mass spectrometry increased significantly after inundation for soils with low in situ salinity, and a trend of decreasing thermodynamic favorability with increasing salinity was observed, suggesting an increase in microbial activity following inundation. Our results suggest that seawater inundation of low-salinity terrestrial environments can lead to increased microbial activity, preferential depletion of more thermodynamically favorable compounds, and increased soil carbon release. Finally, we conclude that the biogeochemical impacts of future seawater exposure will be modulated by antecedent conditions associated with landscape position within coastal watersheds.

54 ENVIRONMENTAL SCIENCES↗
NASA NTRSDate not supplied

Shoulder Postures in EVA Training in Reduced Gravity Analogues

Shoulder Postures in EVA Training in Reduced Gravity Analogues K. Guhl1, L. Vu2, H. Kim3, S. Rajulu4 1KBR Inc., Houston, TX, 2Aegis Aerospace Inc., Houston, TX, 3Leidos Innovations, Houston, TX, 4NASA Johnson Space Center, Houston, TX. During extravehicular activities (EVAs) and EVA training in both the Neutral Buoyancy Laboratory (NBL) and at the Active Response Gravity Offload System (ARGOS), crewmembers perform a variety of hand-intensive tasks with frequent arm/shoulder repositioning while wearing a pressurized spacesuit. As a result, crewmembers may experience ergonomic stressors such as awkward shoulder postures. The ergonomic shoulder risk is also compounded by limited or restricted shoulder mobility of the spacesuit, extreme work positions such as overhead tasks, and tasks with heavy tools and repetitive motions. Prolonged or frequent shoulder elevation and overhead work, in particular, can lead to excessive stresses and musculoskeletal injuries of the shoulder joints. Future EVA missions, specifically lunar surface EVAs, will also be longer in duration and thus increase the exposure to awkward shoulder postures. In this study, we aimed to assess the ergonomic risk of awkward shoulder postures in simulated lunar surface EVAs by quantifying when and how long the arms are raised above the chest level. We assessed video recordings of pilot lunar EVA simulations (3 lunar trials each in the NBL and at ARGOS and 2 microgravity EVA trials in the NBL). These runs consisted of both training and engineering test objectives. Actual demands for shoulder use varied for different EVA types and analogues, but many EVA runs have common tasks and require similar motion components. A video observation and event logging software was used to document the duration and occurrence of the subject’s arms being raised throughout the video recordings of each EVA run. An arm raised instance was classified as the arm being at 90 degrees or above with relation to gravity for lunar EVA training events and with relation to the body for microgravity EVA training events. Such events included EVA hardware maintenance or heavy geology sampling tool operations. Events where the arm load was partially supported by external objects, like climbing a ladder or leaning against a surface were separately identified and excluded. Statistical analysis was performed to summarize the timing, frequency, and durations of the arm raise events and compared across the different EVA tasks and analogue types. Preliminary observations indicated that the total duration and number of arm raised instances were surprisingly smaller for lunar surface EVA training as compared to microgravity EVA training. The observed difference may be attributed to differing task demands and unique environmental characteristics found in lunar EVAs in comparison to microgravity EVAs. A detailed statistical analysis will be performed between lunar surface EVA training events and microgravity EVA training events in the final submission. Overall, this analysis is expected to provide insight into how ergonomic recommendations can be refined for lunar EVA training with pressurized suits. It may also inform task design and influence suit padding design to better protect crewmembers during future lunar training.

Kaitlyn Lea Guhl↗
DOE OSTI2021

Extreme Molecular Complexity Resulting in a Continuum of Carbonaceous Species in Biomass Burning Tar Balls from Wildfire Smoke

Biomass burning emits a wide range of carbonaceous particles into the atmosphere and has negative impacts on human health and the Earth’s radiative balance. Nonvolatile spherical organic aerosol particles, commonly known as tar balls, represent one of the most abundant particles in aged biomass burning smoke. However, the detailed molecular-level composition of ambient tar balls is largely unknown but critical to access their environmental impacts. Ambient aerosol samples collected during a wildfire event, which were ~90% tar balls by number fraction, were analyzed using ultrahigh resolution Orbitrap Elite mass spectrometry with four complementary ionization modes. Our results show the molecular composition of tar balls to be complex, composed of over 10,000 molecular formulas. Model estimated saturation mass concentrations and relative humidity dependent glass transition temperatures were consistent with low volatility and solid morphology as expected for tar balls. Room-temperature evaporation kinetics showed that these particles were composed of ~90% non-volatile species. The molecular complexity detected here signifies a continuum of carbonaceous species, ranging from C3 to C45 with continuous ranges of oxygenation and hydrogen saturation for each Cn. Approximately 24% of molecular formulas were estimated the be highly aromatic, which could indicate chemical compounds with negative health effects, and which may contribute to visible light absorption. The carbon continuum observed here has significant implications for the molecular characterization of atmospheric organic matter. The level of complexity detected here should not be ignored in future studies and we demonstrate that multiple analytical methods may be required to suitably interpret this complexity on a molecular level.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Simulation of Compound Flooding Using River‐Ocean Two‐Way Coupled E3SM Ensemble on Variable‐Resolution Meshes

Abstract Coastal zone compound flooding (CF) can be caused by the interactive fluvial and oceanic processes, particularly when coastal backwater propagates upstream and interacts with high river discharge. The modeling of CF is limited in existing Earth System Models (ESMs) due to coarse mesh resolutions and one‐way coupled river‐ocean components. In this study, we present a novel multi‐scale coupling framework within the Energy Exascale Earth System Model (E3SM), integrating global atmosphere and land with interactively coupled river and ocean models using different meshes with refined resolutions near the coastline. To evaluate this framework, we conducted ensemble simulations of a CF event (Hurricane Irene in 2011) in a Mid‐Atlantic estuary. The results demonstrate that the novel E3SM configuration can reasonably reproduce river discharge and sea surface height variations. The two‐way river‐ocean coupling improves the representation of coastal backwater effects at the terrestrial‐aquatic interface that are caused by the combined actions of tide and storm surge during the CF event, thus providing a valuable modeling tool for better understanding the river‐estuary‐ocean dynamics in extreme events under climate change. Notably, our results show that the most significant CF impacts occur when the highest storm surge generated by a tropical cyclone meets with a moderate river discharge. This study highlights the state‐of‐the‐art advancements developed within E3SM for simulating multi‐scale coastal processes.

54 ENVIRONMENTAL SCIENCES↗
NASA NTRS2018

Flood Hazard Assessment from Storm Tides, Rain and Sea Level Rise for a Tidal River Estuary

Cities and towns along the tidal Hudson River are highly vulnerable to flooding through the combination of storm tides and high streamflows, compounded by sea level rise. Here a three-dimensional hydrodynamic model, validated by comparing peak water levels for 76 historical storms, is applied in a probabilistic flood hazard assessment. In simulations, the model merges streamflows and storm tides from tropical cyclones (TCs), offshore extratropical cyclones (ETCs) and inland "wet extratropical" cyclones (WETCs). The climatology of possible ETC and WETC storm events is represented by historical events (1931-2013), and simulations include gauged streamflows and inferred ungauged streamflows (based on watershed area) for the Hudson River and its tributaries. The TC climatology is created using a stochastic statistical model to represent a wider range of storms than is contained in the historical record. TC streamflow hydrographs are simulated for tributaries spaced along the Hudson, modeled as a function of TC attributes (storm track, sea surface temperature, maximum wind speed) using a statistical Bayesian approach. Results show WETCs are important to flood risk in the upper tidal river (e.g., Albany, New York), ETCs are important in the estuary (e.g., New York City) and lower tidal river, and TCs are important at all locations due to their potential for both high surge and extreme rainfall. The raising of floods by sea level rise is shown to be reduced by approximately 30-60 percent at Albany due to the dominance of streamflow for flood risk. This can be explained with simple channel flow dynamics, in which increased depth throughout the river reduces frictional resistance, thereby reducing the water level slope and the upriver water level.

Tidal river↗
DOE OSTI2022

Anticipating water distribution service outages from increasing temperatures

With projected temperature increases and extreme events due to climate change for many regions of the world, characterizing the impacts of these emerging hazards on water distribution systems is necessary to identify and prioritize adaptation strategies for ensuring reliability. To aid decision-making, new insights are needed into how water distribution system reliability to climate-driven heat will change, and the proactive maintenance strategies available to combat failures. To this end, we present the model Perses, a framework that joins a water distribution network hydraulic solver with reliability models of physical assets or components to estimate temperature increase-driven failures and resulting service outages in the long term. A theoretical case study is developed using Phoenix, Arizona temperature profiles, a city with extreme temperatures and a rapidly expanding infrastructure. By end-of-century under hotter futures there are projected to be 1%–5% more pump failures, 2%–5% more PVC pipe failures, and 3%–7% more iron pipe failures (RCP 4.5–8.5) than a baseline historical temperature profile. Service outages, which constitute inadequate pressure for domestic and commercial use are projected to increase by 16%–26% above the baseline under maximum temperature conditions. The exceedance of baseline failures, when compounded across a large metro region, reveals potential challenges for budgeting, management, and maintenance. An exploration of the mitigation potential of adaptation strategies shows that expedited repair times are capable of offsetting the additional outages from climate change, but will come with a cost.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2023

Dielectrics Under Extreme Electric Fields: In Situ Studies on Nanoscale Mechanisms (Final Technical Report)

The lack of materials that can function reliably under extreme electric fields is a critical roadblock to achieving higher energy efficiency and extended service lifetime of devices in electricity generation, transmission, and consumption. Materials typically fail at two or three orders of magnitude below their theoretical dielectric breakdown strength. Identifying the origins of premature dielectric breakdown using state-of-the-art characterization tools will, therefore, enable the design and discovery of transformational materials capable of approaching their intrinsic limits. The vast improvement in the resolution power of imaging tools, combined with the recently developed in situ electric biasing technique, has made high resolution observations of dielectric breakdown as it happens possible. The overall goal of the project is to directly image the dynamic processes of defect formation, accumulation, and interaction with preexisting defects (e.g., dislocations, domain walls, and grain boundaries in crystalline dielectric films) under electric fields up to 1,000 MV/m with a temporal resolution better than 5 microseconds. Using the newly acquired, custom-made Hysitron PI95 transmission electron microscopy (TEM) specimen holder, in situ TEM observations of breakdown at the sub nanometer resolution will be made on representative dielectric compounds with progressive complexities: the linear dielectric SiO 2 , CuO, and TiO 2 , the ferroelectric BaTiO 3 nanocrystals and nanocubes. Through direct observation of the breakdown event at high spatial and temporal resolutions, the nanoscale mechanisms for the failure of dielectrics under intense electric fields will be identified. The results of the project will be applied to the design and processing of new dielectric materials with higher efficiency, improved reliability, and a prolonged lifetime. Such new dielectrics are urgently needed for modernizing energy infrastructures.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗
DOE OSTI2023

Understanding the compound flood risk along the coast of the contiguous United States

Abstract. Compound flooding is a type of flood event caused by multiple flood drivers. The associated risk has usually been assessed using statistics-based analyses or hydrodynamics-based numerical models. This study proposes a compound flood (CF) risk assessment (CFRA) framework for coastal regions in the contiguous United States (CONUS). In this framework, a large-scale river model is coupled with a global ocean reanalysis dataset to (a) evaluate the CF exposure related to the coastal backwater effects on river basins, and (b) generate spatially distributed data for analyzing the CF hazard using a bivariate statistical model of river discharge and storm surge. The two kinds of risk are also combined to achieve a holistic understanding of the continental-scale CF risk. The estimated CF risk shows remarkable inter- and intra-basin variabilities along the CONUS coast with more variabilities in the CF hazard over the US west and Gulf coastal basins. Different risk assessment methods present significantly different patterns in a few key regions such as the San Francisco Bay area, the lower Mississippi River, and Puget Sound. Our results highlight the need to weigh different CF risk measures and avoid using single statistics-based or hydrodynamics-based CFRAs. Uncertainty sources in these CFRAs include the use of gauge observations, which cannot account for the flow physics or resolve the spatial variability of risks, and underestimations of the flood extremes and the dependence of CF drivers in large-scale models, highlighting the importance of understanding the CF risks for developing a more robust CFRA.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2024

Deciphering the Role of Total Water Storage Anomalies in Mediating Regional Flooding

Regional floods result from various flood generation mechanisms. Traditional analyses mainly link flooding to extreme rainfall, with limited input from soil moisture. Total water storage (TWS) is a holistic measure of basin wetness, including additional storage components from surface water, snow, and groundwater. Utilizing a new 5-day Gravity Recovery and Climate Experiment and its Follow On (GRACE(-FO)) data set, we investigated the linkage between short-term TWS anomaly (TWSA) and regional flooding. The 5-day TWSA solutions revealed flood signals missed by monthly TWSA solutions. Global basins exhibit distinct storage-discharge co-evolution patterns, offering new insights into flood mechanisms and propensity. Our bivariate event analyses show the annual maximum river discharges co-occur more often with the TWSA maxima than with precipitation in many basins. Further analyses revealed TWSA's time-lagged effect on river discharge, particularly in basins susceptible to floods triggered by saturation-excess runoff. The 5-day TWSA provides a new source of information for enhancing global flood preparedness.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2025

Impact of El Niño‐Southern Oscillation and Madden‐Julian Oscillation on the US Puget Sound Regional Hydroclimate

El Niño-Southern Oscillation (ENSO) and Madden-Julian Oscillation (MJO) are two major modes of climate variability with global hydroclimate impacts. However, their impacts often depend on the local climate and geography, resulting in large regional differences. In this study, we examined the connection of ENSO and MJO to the hydroclimate conditions and extremes in the Puget Sound (PS) basin located in the US Pacific Northwest coast. The results indicate that ENSO significantly modulates the cold season temperature and temperature-mediated hydrologic processes. El Niño cold seasons feature less snow accumulation and intensified surface runoff, even if the precipitation amount is similar to La Niña cold seasons. Therefore, El Niño causes more snow drought (in the form of compound dry and warm snow drought) and shifts the surface runoff seasonality by reducing runoff in the subsequent warm season. MJO phases 6–7 trigger more extreme precipitation, temperature, snowmelt, and runoff in the PS region at 0–9–day lags, and such connections are robust regardless of how the ENSO signals are removed. Meanwhile, MJO modulates large-scale extreme weather systems (e.g., atmospheric rivers) with significant enhancement during phases 6–7. ENSO impacts have intensified in the 2001–2020 period, whereas MJO impacts showed some phase shift in this period. This study reveals ENSO and MJO phases 6–7 as useful predictors of the PS hydroclimate anomalies/extremes at seasonal and daily scales, respectively. Utilizing these findings holds the potential to improve regional water resources prediction and management.

ENSO↗
NASA NTRS2000

Growth of Megaspherulites In a Rhyolitic Vitrophyre

Megaspherulites occur in the middle zone of a thick sequence of rhyolitic vitrophyre that occupies a small, late Eocene to early Oligocene volcanic-tectonic basin near Silver Cliff, Custer County, Colorado. Diameters of the megaspherulites range from 0.3 m to over 3.66 m, including a clay envelope. The megaspherulites are compound spherulites. consisting of an extremely large number (3.8 x 10(exp 9) to 9.9 x 10(exp 9)) of individual growth cones averaging 3 mm long by 1.25 mm wide at their termination. They are holocrystalline, very fine- to fine-grained, composed of disordered to ordered sanidine (orthoclase) and quartz, and surrounded by a thin K-feldspar, quartz rich rind, an inner clay layer with mordenite, and an outer clay layer composed wholly of 15 A montmorillonite. Whole rock analyses of the megaspherulites show a restricted composition from their core to their outer edge, with an average analyses of 76.3% SiO2, 0.34% CaO, 2.17% Na2O, 6.92% K2O, 0.83% H2O+ compared to the rhyolitic vitrophyre from which they crystallize with 71.07% SiO2, 0.57% CaO, 4.06% Na2O,4.l0% K2O, and 6.40% H2O+. The remaining oxides of Fe2O3 (total Fe), A12O3, MnO,MgO, TiO2, P2O5, Cr2O3, and trace elements show uniform distribution between the megaspherulites and the rhyolitic vitrophyre. Megaspherulite crystallization began soon after the rhyolitic lava ceased to flow as the result of sparse heterogeneous nucleation, under nonequilibrium conditions, due to a high degree of undercooling, delta T. The crystals grow with a fibrous habit which is favored by a large delta T ranging between 245 C and 295 C, despite lowered viscosity, and enhanced diffusion due to the high H2O content, ranging between 5% and 7%. Therefore, megaspherulite growth proceeded in a diffusion controlled manner, where the diffusion, rate lags behind the crystal growth rate at the crystal-liquid interface, restricting fibril lengths and diameters to the 10 micron to 15 micron and 3 micron and 8 micron ranges respectively. Once diffusion reestablishes itself at the crystallization front, a new nucleation event occurs at the terminated tips of the fibril cones and a new cone begins to develop with a similar orientation (small angle branching) to the earlier cones. During crystallization, these fibril cones impinge upon each other, resulting in fibril cone-free areas. These cone-free areas consist of coarser, fine-grained phases, dominated by quartz, which crystallized from the melt as it accumulated between the crystallizing K-feldspar fibrils of the cones. The anhydrous nature of the disordered to ordered sanidine (orthoclase) and quartz, suggests that water in the vitrophyre moved ahead of the crystallization front, resulting in a water rich fluid being enriched in Si, K, Na, Mg, Ca, Sr, Ba, and Y. The clay layers associated with the megaspherulites are therefore, the result of the deuteric alteration between the fractionated water and the vitrophyre, as indicated by the presence of the minerals mordenite and montmorillonite. This silica rich fluid also resulted in the total silicification of the megaspherulites within the upper 3 m of the vitrophyre.

Smith, Robert K.↗
DOE OSTI2025

Probing the Sustainable Reduction of CO 2 , N 2 and NO 3 to Fuels and Chemicals using Non-Traditional Porphyrinoid Catalysts

For the last several decades, numerous strategies have been proposed to be able to interconvert electricity and commodity fuels for transportation and other applications. Even as solar and wind energy become more widely available, these renewable energy sources are not always available where the population is most dense or during peak times of energy demand. One plausible solution to the issue of electricity storage and transport is to use electricity to drive the formation of high-energy compounds and chemical fuels. As a result, the electrochemical conversion of CO 2 into chemical fuels has received major attention as a multi-pronged approach for electricity coversion, storage, and transport. Similar strategies are also attractive for conversion of N 2 and NO x into value added compounds such as ammonia. Metalloporphyrin and metallocorrole complexes are comprised of aromatic tetrapyrrole scaffolds and have been extensively studied as homogeneous catalysts for critical catalytic processes like the electrochemical CO 2 reduction reaction (eCO 2 RR) to generate CO as feedstock for the Fischer–Tropsch process to generate a variety of hydrocarbons as chemical fuels. Despite their significance and impact, efficiently driving such catalytic reduction processes is challenging for multiple reasons. Such processes require multiple-electron transfer events, as opposed to single-electron redox chemistry that forms high-energy singly-reduced intermediates. In addition, these electron transfer events must be coupled to proton-transfer steps and avoid application of high overpotentials where proton (H + ) reduction to generate H 2 (as well as other side-reactions) can lower the selectivity and energy efficiency of the eCO 2 RR process. Certain Fe(III) aromatic tetrapyrroles (e.g., porphyrins and corroles) have been reported to overcome these challenges, but are often difficult to synthesize and modify, and have a tendency to support single-electron redox chemistry at the metal as opposed to multielectron redox involving the ligand and metal in concert. Other families of tetrapyrroles in which all four meso-carbons are reduced (i.e., sp 3 -hybridized) are also known in the literature. These non-aromatic tetrapyrroles are known as porphyrinogens and support multi-electron redox chemistry which has been elaborated by several groups, prompting researchers to consider whether these scaffolds may improve the kinetics and efficiencies of multi-electron steps attendant to activation of thermodynamically stable small-molecule substrates such as CO 2 , N 2 , NO 3 − , and NO 2 − . Although porphyrinogens support multi-electron redox properties, the four sp 3 -hybridized meso-carbons inherent to the tetrapyrrole core completely disrupt π-conjugation between pyrrolic units, which compromises the photochemical properties of porphyrinogens in comparison to that of traditional porphyrinoids. Moreover, the highly reducing nature of porphyrinogens predisposes these platforms to extreme air and water sensitivity. Accordingly, such metalated porphyrinogens are often pyrophoric and/or incompatible with many common organic solvents (CH 2 Cl 2 , CHCl 3 , CH 3 CN, EtOAc, etc.). Hence, reports of efficient small-molecule activation or catalysis supported by porphyrinogens have been limited. To overcome the instability of porphyrinogens while retaining the scaffold’s attractive multi-electron redox properties, we have directed attention to establishing less-well studied groups of non-aromatic tetrapyrroles (i.e., phlorins, biladienes, and isocorroles). These non-traditional tetrapyrroles each contain just a single sp 3 -hybridized meso-carbon, which ablates the platforms aromaticity but still provides an extended π-framework. In addition to developing innovative platforms that may be used to sustainably generate value-added chemicals, fuels, and ammonia via either photo- or electrocatalytic approaches our work also has significantly broadened our understanding of how to prepare and modulate the properties of non-aromatic tetrapyrroles for other applications. Our efforts entailed a synergistic partnership and active collaborations with Drs. David C. Grills and Mehmed Z. Ertem (both of Brookhaven National Lab) to better characterize isocorroles (and related non-aromatic tetrapyrroles) using a variety of advanced spectroscopic and theoretical methods. Our combined efforts have shown that the combination of properties that isocorroles (and related tetrapyrroles) provide results in good chemical stability paired with unique redox and photochemical characteristics that are not typically supported by simple and/or unadorned aromatic tetrapyrroles. Beside redox chemistry, the photochemistry of isocorroles and other non-aromatic tetrapyrroles containing one sp 3 -hybridized meso-carbon is also appealing due to their absorption in the long-visible to near-IR regions, which are essential for photocatalysis and related applications that benefit from direct excitation at these wavelengths. The results reported vastly improve our understanding of non-aromatic tetrapyrrole synthesis, properties and utility for activation of small molecule substrates such as O 2 and CO 2 in the presence of weak cationic organic acids.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Anthropogenic extremely low volatility organics (ELVOCs) Govern the Growth of Molecular Clusters over the Southern Great Plains during the Springtime

New particle formation (NPF) and growth govern cloud condensation nuclei (CCN) concentrations in many regions. The mechanisms governing the nucleation of molecular clusters vary substantially in different regions of the atmosphere. Additionally, the growth of these clusters from ~2 to 20 nm sizes is often governed by the availability of extremely low volatility organic vapours (ELVOCs). While the pathways to ELVOC formation from the oxidation of biogenic monoterpenes with ozone is better understood, the chemical and mechanistic pathways for ELVOC formation from oxidation of anthropogenic organics are not well understood. We integrate measurements and three-dimensional regional model simulations with the Weather Research and Forecasting Model coupled to chemistry (WRF-Chem) to understand the processes governing new particle formation and growth and secondary organic aerosol (SOA) formation during the Holistic Interactions of Shallow Clouds, Aerosols and Land Ecosystems (HI-SCALE) field campaign at the Southern Great Plains (SGP) observatory in Oklahoma, and contrast it with a site within the Bankhead National Forest (BNF), Alabama in Southeast USA, where 5-year long measurements will begin in 2024. Simulations show that nucleation rates are at least an order of magnitude higher at SGP compared to BNF during the springtime days (April 28 and May 14, 2016), largely due to lower H2SO4 concentrations at BNF, which are needed for nucleation. In addition, the larger CS at BNF (compared to SGP) increase the loss of molecular clusters by coagulation to pre-existing particles. Among the 8 different nucleation mechanisms in WRF-Chem, we find that the amine+H2SO4 nucleation mechanism dominates at the SGP site, while the pure organic ion induced nucleation mechanism dominates over BNF. Through various WRF-Chem sensitivity simulations, we find that anthropogenic ELVOCs are critical for explaining the growth of newly formed particles and the resulting number size distribution observed near the surface at the SGP site during the daytime. In addition, we show that treating organic particles as semisolid, with strong diffusion-limited uptake of organic vapours, brings model predictions into closer agreement with the observed evolution of particle size distribution. Simulations also predict that anthropogenic SOA, formed by the oxidation of aromatic volatile organic compounds (VOCs), is the dominant organic aerosol component at SGP, while biogenic SOA dominates particle composition at the BNF site in Southeast USA on these days.

Shrivastava, ManishKumar B.↗
DOE OSTI2024

Anticipating how rain-on-snow events will change through the 21st century: lessons from the 1997 new year’s flood event

The California-Nevada 1997 New Year’s flood was an atmospheric river (AR)-driven rain-on-snow (RoS) event and remains the costliest in their history. The joint occurrence of saturated soils, rainfall, and snowmelt generated inundation throughout northern California-Nevada. Although AR RoS events are projected to occur more frequently with climate change, the warming sensitivity of their flood drivers across scales remains understudied. We leverage the regionally refined mesh capabilities of the Energy Exascale Earth System Model (RRM-E3SM) to recreate the 1997 New Year’s flood with horizontal grid spacings of 3.5 km across California, with forecast lead times of up to 4 days, and across six warming levels ranging from pre-industrial conditions to +3.5° C. We describe the sensitivity of the flood drivers to warming including AR duration and intensity, precipitation phase, intensity and efficiency, snowpack mass and energy changes, and runoff efficiency. Our findings indicate current levels of climate change negligibly influence the flood drivers. At warming levels ≥ 1.7° C, AR hazard potential increases, snowpack nonlinearly decreases, antecedent soil moisture decreases (except where the snowline retreats), and runoff decreases (except in the southern Sierra Nevada where antecedent snowpack persists). Storm total precipitation increases, but at rates below warming-induced increases in saturation-specific humidity. Warming intensifies short-duration, high-intensity rainfall, particularly where snowfall-to-rainfall transitions occur. This study highlights the nonlinear tradeoffs in 21st-century RoS flood hazards with warming and provides water management and infrastructure investment adaptation considerations.

54 ENVIRONMENTAL SCIENCES↗