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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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At least 865 records · Page 48

Entrainment versus Dilution in Tropical Deep Convection

Abstract The distinction between entrainment and dilution is investigated with cloud-resolving simulations of deep convection in a tropical environment. A method for estimating the rate of dilution by entrainment and detrainment is presented and calculated for a series of bubble simulations with a range of initial radii. Entrainment generally corresponds to dilution of convection, but the two quantities are not well correlated. Core dilution by entrainment is significantly reduced by the presence of a shell of moist air around the core. Dilution by entrainment also increases with increasing updraft velocity but only for sufficiently strong updrafts. Entrainment contributes significantly to the total net dilution, but detrainment and the various source/sink terms play large roles depending on the variable in question. Detrainment has a concentrating effect on average that balances out the dilution by entrainment. The experiments are also used to examine whether entrainment or dilution scale with cloud radius. The results support a weak negative relationship for dilution but not for entrainment. The sensitivity to resolution is briefly discussed. A toy Lagrangian thermal model is used to demonstrate the importance of the cloud shell as a thermodynamic buffer to reduce the dilution of the core by entrainment. The results suggest that explicit cloud heterogeneity may be a useful consideration for future convective parameterization development.

54 ENVIRONMENTAL SCIENCES↗

Mapping Stellar Surfaces. II. An Interpretable Gaussian Process Model for Light Curves

The use of Gaussian processes (GPs) as models for astronomical time series data sets has recently become almost ubiquitous, given their ease of use and flexibility. In particular, GPs excel at marginalization over the stellar signal when the variability due to starspots is treated as a nuisance, as in exoplanet transit modeling. However, these effective models are less useful in cases where the starspot signal is of primary interest, since it is not obvious how the parameters of the GP relate to physical parameters like the spot size, contrast, and latitudinal distribution. Instead, it is common practice to explicitly model the effect of individual starspots on the light curve and attempt to infer their properties via optimization or posterior inference. Unfortunately, this process is ill-posed and often computationally intractable when applied to stars with more than a few spots and/or to ensembles of many stars. Here we derive a closed-form expression for a GP that describes the light curve of a rotating, evolving stellar surface conditioned on a given distribution of starspot sizes, contrasts, and latitudes. We demonstrate that this model is correctly calibrated, allowing one to robustly infer physical parameters of interest from one or more light curves, including the typical spot radii and latitudes. Our GP has far-ranging implications for understanding the variability and magnetic activity of stars from light curves and radial velocity measurements, as well as for modeling correlated noise in exoplanet searches. Our implementation is efficient, user-friendly, and open-source, available in the package starry-process.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Bayesian Inference of High-density Nuclear Symmetry Energy from Radii of Canonical Neutron Stars

The radius R 1.4 of neutron stars (NSs) with a mass of 1.4 M ⊙ has been extracted consistently in many recent studies in the literature. Using representative R 1.4 data, we infer high-density nuclear symmetry energy E sym (ρ) and the associated nucleon specific energy E 0 (ρ) in symmetric nuclear matter (SNM) within a Bayesian statistical approach using an explicitly isospin-dependent parametric equation of state (EOS) for nucleonic matter. We found the following. (1) The available astrophysical data can already significantly improve our current knowledge about the EOS in the density range of ρ 0 - 2.5ρ 0 . In particular, the symmetry energy at twice the saturation density ρ 0 of nuclear matter is determined to be E sym (2ρ 0 )=${39.2}_{-8.2}^{+12.1}$ MeV at a 68% confidence level. (2) A precise measurement of R 1.4 alone with a 4% 1σ statistical error but no systematic error will not greatly improve the constraints on the EOS of dense neutron-rich nucleonic matter compared to what we extracted from using the available radius data. (3) The R 1.4 radius data and other general conditions, such as the observed NS maximum mass and causality condition, introduce strong correlations for the high-order EOS parameters. Consequently, the high-density behavior of E sym (ρ) inferred depends strongly on how the high-density SNM EOS E 0 (ρ) is parameterized, and vice versa. (4) Finally, the value of the observed maximum NS mass and whether it is used as a sharp cutoff for the minimum maximum mass or through a Gaussian distribution significantly affects the lower boundaries of both E 0 (ρ) and E sym (ρ) only at densities higher than about 2.5ρ 0 .

79 ASTRONOMY AND ASTROPHYSICS↗

Studying the effects of overlapping objects in dark energy

Observing the clustering of galaxies allows us to calculate cosmological parameters necessary for understanding dark energy. However, as the density of observed objects increases, the probability of these objects blending likewise increases, causing multiple galaxies to be observed as one. This affects the inferred values of parameters such as the galaxy bias (b) and the matter energy density (ΩM). To see whether the bias from incorrectly inferring the galaxy count is significant, we compare the correlation functions in simulated data for “true” and “observed” data sets with one-to-one and multiple-to-one correspondences, respectively. For each data set, we create two correlation functions: one “measured” function directly relying on the galaxies’ positions using the TreeCorr python library, and one “model” derived mathematically from the galaxies’ power spectrum using the Cosmological Core Library (CCL). By minimizing the residual between these two functions, we compute the ideal values for b and ΩM across the various possible redshifts that position the galaxies in three dimensional space. This minimization is done with an Markov chain Monte Carlo (MCMC) estimate that finds one value of ΩM and ten values for b corresponding to the ten redshift bins ranging from z = 0.2 to z = 1.2. We find that neither b nor ΩM is particularly affected by inclusion of blended galaxies. Though there is room for improvement, the data suggests that the fluctuations we found are a result of noise or limitations on the modeling rather than blending explicitly.

79 ASTRONOMY AND ASTROPHYSICS↗

Factorization connecting continuum & lattice TMDs

Transverse-momentum-dependent parton distribution functions (TMDs) can be studied from first principles by a perturbative matching onto lattice-calculable quantities: so-called lattice TMDs, which are a class of equal-time correlators that includes quasi-TMDs and TMDs in the Lorentz-invariant approach. We introduce a general correlator that includes as special cases these two Lattice TMDs and continuum TMDs, like the Collins scheme. Then, to facilitate the derivation of a factorization relation between lattice and continuum TMDs, we construct a new scheme, the Large Rapidity (LR) scheme, intermediate between the Collins and quasi-TMDs. The LR and Collins schemes differ only by an order of limits, and can be matched onto one another by a multiplicative kernel. We show that this same matching also holds between quasi and Collins TMDs, which enables us to prove a factorization relation between these quantities to all orders in α s . Our results imply that there is no mixing between various quark flavors or gluons when matching Collins and quasi TMDs, making the lattice calculation of individual flavors and gluon TMDs easier than anticipated. We cross-check these results explicitly at one loop and discuss implications for other physical-to-lattice scheme factorizations.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Understanding how microbiomes influence the systems they inhabit

Translating the ever-increasing wealth of information on microbiomes (environment, host, or built environment) to advance the understanding of system-level processes is proving to be an exceptional research challenge. One reason for this challenge is that relationships between characteristics of microbiomes and the system-level processes they influence are often evaluated in the absence of a robust conceptual framework and reported without elucidating the underlying causal mechanisms. The reliance on correlative approaches limits the potential to expand the inference of a single relationship to additional systems and advance the field. We propose that research focused on how microbiomes influence the systems they inhabit should work within a common framework and target known microbial processes that contribute to the system-level processes of interest. Here we identify three distinct categories of microbiome characteristics (microbial processes, microbial community properties, and microbial membership) and propose a framework to empirically link each of these categories to each other and the broader system level processes they affect. We posit that it is particularly important to distinguish microbial community properties that can be predicted from constituent taxa (community aggregated traits) from and those properties that are currently unable to be predicted from constituent taxa (emergent properties). Existing methods in microbial ecology can be applied to more explicitly elucidate properties within each of these categories and connect these three categories of microbial characteristics with each other. We view this proposed framework, gleaned from a breadth of research on environmental microbiomes and ecosystem processes, as a promising pathway with the potential to advance discovery and understanding across a broad range of microbiome science.

Hall, Ed K.↗

Uncertainty Quantification Framework for Predicting Material Response with Large Number of Parameters: Application to Creep Prediction in Ferritic-Martensitic Steels Using Combined Crystal Plasticity and Grain Boundary Models

This paper presents an uncertainty quantification (UQ) framework for the physics-based model prediction of material response with a large number of parameters. The application problem presented in this work is that of predicting creep in Grade 91 steel at 600°C. The material response is defined with a physically based microstructural model with constitutive equations emulating several observed phenomena in Grade 91 and embodied into an explicit geometry mesoscale finite element model for prior austenite grains and grain boundaries. Creep within the grains and in grain boundaries are represented by crystal plasticity for dislocation motion and a physics-based model for cavity growth and nucleation, respectively. The creep behavior of this material is influenced by several parameters, some of which have a wide range of variation based on experimental data. UQ combined with microstructural modeling can discover the core microstructural causes of experimental variability, leading to improved materials with lower variability in critical long-term material properties. In this study, we investigate the model's uncertainty to identify material properties that may be modified during production to increase creep life and analyze different components of the crystal plasticity model for improvements. For this purpose, a quantity of interest is defined as time to minimum creep rate, which correlates well to the creep failure of the material. A deep neural network model was trained and validated to be used as a surrogate for the finite element model. Then, a variance-based sensitivity analysis is performed on the surrogate model to find the Sobol indices of the input parameters in respect to the output quantity of interest. The Sobol indices are used to reduce the dimensionality of the model. Generalized polynomial chaos expansion is used on the reduced basis models to propagate the uncertainty from the input parameters to the quantity of interest using the deep neural network surrogate model. These results are benchmarked against uncertainty propagation using Monte Carlo simulations. In conclusion, the UQ performed through the reduced basis model captures almost all the uncertainty in the model with significantly fewer simulations, making it possible to perform the UQ directly via simulations with the finite element model rather than surrogate machine-learned models.

36 MATERIALS SCIENCE↗

Insights into enhanced sodium ion storage mechanism in Fe 3 S 4 : The coupling of surface chemistry, microstructural regulation and 3D electronic transport

Sodium ion batteries (SIBs) are considered a potential energy storage technology due to their low cost and the abundance of sodium resources. Numerous strategies have been made to address the remaining challenges such as low electronic conductivity, huge volume change, and sluggish sodium ions kinetics. In spite of impressive advances, a comprehensive understanding of the microstructure-stability correlation remains elusive. Here, the three-dimensional (3D) Fe 3 S 4 flower-like hierarchical materials constructed from two-dimensional (2D) nanosheet building units were synthesized via a facile and cost-effective method. Instead of materials synthesis and performance evaluation, more attentions have been paid on the underlying coupling mechanism between microstructure design, surface chemistry and 3D electronic/ionic transport pathways. It found that the thin and stable SEI layer generated by ether-based electrolytes contributes to the stable surface chemistry and fast interfacial Na + ion transport, while 3D hierarchical structure enables short diffusion distance, volume change accomodation as well as stabilizing SEI layer. Taking advantage of the inherent high electronic conductivity in Fe 3 S 4 , we have demonstrated the paramount importance of the synergistic strategy to improve the stability of SIBs through X-ray nanotomography. In conclusion, this work explicitly illuminate the electrochemical stability mechanisms of 3D hierarchitectures and resolves new strategies to rational design SIBs anodes.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

A reduced order model to analytically infer atmospheric CO 2 concentration from stomatal and climate data

To address questions related to the acceleration or deceleration of the global hydrological cycle or links between the carbon and water cycles over land, reliable data for past climatic conditions based on proxies are required. In particular, the reconstruction of palaeoatmospheric CO 2 content (C a ) is needed to assist the separation of natural from anthropogenic C a variability and to explore phase relations between C a and air temperature T a time series. Both T a and C a are needed to fingerprint anthropogenic signatures in vapor pressure deficit, a major driver used to explain acceleration or deceleration phases in the global hydrological cycle. Current approaches to C a reconstruction rely on a robust inverse correlation between measured stomatal density in leaves (ν) of many plant taxa and C a . There are two methods that exploit this correlation: The first uses calibration curves obtained from extant species assumed to represent the fossil taxa, thereby restricting the suitable taxa to those existing today. The second is a hybrid eco-hydrological/physiological approach that determines C a with the aid of systems of equations based on quasi-instantaneous leaf-gas exchange theories and fossil stomatal data collected along with other measured leaf anatomical traits and parameters. In this contribution, a reduced order model (ROM) is proposed that derives C a from a single equation incorporating the aforementioned stomatal data, basic climate (e.g. temperature), estimated biochemical parameters of assimilation and isotope data. The usage of the ROM is then illustrated by applying it to isotopic and anatomical measurements from three extant species. The ROM derivation is based on a balance between the biochemical demand and atmospheric supply of CO 2 that leads to an explicit expression linking stomatal conductance to internal CO 2 concentration (C i ) and C a . The resulting expression of stomatal conductance from the carbon economy of the leaf is then equated to another expression derived from water vapor gas diffusion that includes anatomical traits. When combined with isotopic measurements for long-term C i /C a , C a can be analytically determined and is interpreted as the time-averaged C a that existed over the life-span of the leaf. Key advantages of the proposed ROM are: 1) the usage of isotopic data provides constraints on the reconstructed atmospheric CO 2 concentration from ν, 2) the analytical form of this approach permits direct links between parameter uncertainties and reconstructed C a , and 3) the time-scale mismatch between the application of instantaneous leaf-gas exchange expressions constrained with longer-term isotopic data is reconciled through averaging rules and sensitivity analysis. The latter point was rarely considered in prior reconstruction studies that combined models of leaf-gas exchange and isotopic data to reconstruct C a from ν. The proposed ROM is not without its limitations given the need to a priori assume a parameter related to the control on photosynthetic rate. Our work here further explores immanent constraints for the aforementioned photosynthetic parameter.

54 ENVIRONMENTAL SCIENCES↗

Ising model of cardiac thin filament activation with nearest-neighbor cooperative interactions

We have developed a model of cardiac thin filament activation using an Ising model approach from equilibrium statistical physics. This model explicitly represents nearest-neighbor interactions between 26 troponin/tropomyosin units along a one-dimensional array that represents the cardiac thin filament. With transition rates chosen to match experimental data, the results show that the resulting force-pCa (F-pCa) relations are similar to Hill functions with asymmetries, as seen in experimental data. Specifically, Hill plots showing (log(F/(1-F)) vs. log [Ca]) reveal a steeper slope below the half activation point (Ca(50)) compared with above. Parameter variation studies show interplay of parameters that affect the apparent cooperativity and asymmetry in the F-pCa relations. The model also predicts that Ca binding is uncooperative for low [Ca], becomes steeper near Ca(50), and becomes uncooperative again at higher [Ca]. The steepness near Ca(50) mirrors the steep F-pCa as a result of thermodynamic considerations. The model also predicts that the correlation between troponin/tropomyosin units along the one-dimensional array quickly decays at high and low [Ca], but near Ca(50), high correlation occurs across the whole array. This work provides a simple model that can account for the steepness and shape of F-pCa relations that other models fail to reproduce.

Evaluation Studies↗

A fast reduced model for a shell-and-tube based latent heat thermal energy storage heat exchanger and its application for cost optimal design by nonlinear programming

Numerical simulation of latent heat thermal energy storage (LHTES) systems plays a fundamental role in studying the physical process and guiding the engineering design. Discretization of the PDEs describing the nonlinear solidification/melting process of phase change materials (PCMs) leads to a large-scale complex dynamics system, where the system behavior depends on a set of parameters. In a design setting, repeated model evaluations are required over the set of parameters results in significant computational burden. In this paper, an explicit analytic solution was built for the propagation of the solidification front in a cylindrical coordinate. The analytic solution approach is further employed to develop a low computational reduced model (RM) as a module for a shell-and-tube based LHTES heat exchanger. The levelized Cost of Energy (LCOE) is used as a design metric and the RM model is used to apply system-level constraints in the nonlinear programming formulation that facilitates efficient global optimal design of the PCM properties, flow conditions and tube geometries. The use of LCOE as the design metric prevents over design of the heat transfer rate and also establishes a fair ground for evaluation of different thermal storage technologies and their integrated applications with other systems. Optimal results showed that a higher effectiveness results in a higher LCOE; the velocity of the HTF and the length of the channel are highly correlated with each other; both larger PCM latent energy and conductivity result in lower LCOE.

25 ENERGY STORAGE↗

Performance of wave function and Green's function methods for non-equilibrium many-body dynamics

Theoretical descriptions of the non-equilibrium dynamics of quantum many-body systems essentially employ either (i) explicit treatments, relying on the truncation of the expansion of the many-body wave function, (ii) compressed representations of the many-body wave function, or (iii) evolution of an effective (downfolded) representation through Green's functions. In this work, we select representative cases of each of the methods and address how these complementary approaches capture the dynamics driven by intense field perturbations to non-equilibrium states. Under strong driving, the systems are characterized by strong entanglement of the single-particle density matrix and natural populations approaching those of a strongly interacting equilibrium system. We generate a representative set of results that are numerically exact and form a basis for a critical comparison of the distinct families of methods. We demonstrate that the compressed formulation based on similarity-transformed Hamiltonians (coupled-cluster approach) is practically exact in weak fields and, hence, weakly or moderately correlated systems. Coupled cluster, however, struggles for strong driving fields, under which the system exhibits strongly correlated behavior, as measured by the von Neumann entropy of the single-particle density matrix. The dynamics predicted by Green's functions in the (widely popular) G W approximation are less accurate, but improve significantly upon the mean-field results in the strongly driven regime. Published by the American Physical Society 2025

Reeves, Cian C. (ORCID:0009000642581845)↗

Risk Importance Ranking of Fire Data Parameters to Enhance Fire PRA Model Realism

Fire is historically and analytically a significant contributor to nuclear power plant risk. The level of fire risk and the methods, tools and data for modeling this risk is highly debated by experts. One area of debate is the input data used in fire modeling and how to deal with this data’s high uncertainty. This report outlines initial work performed for determining the key parameters causing this uncertainty and how it propagates into nuclear power plant models. This research paves the way for the development of methods to reduce fire data uncertainty used in modeling. The Nuclear Regulatory Commission has mandated that nuclear power plants perform fire risk modeling. However, there are several issues with the current risk modeling implementation that affect the results. Approved modeling methods can be overly conservative and often do not match plant experience. Also, the data used in the modeling can have high uncertainties and is influenced by expert judgement. To evaluate input data uncertainty, researchers performed an initial review of several fire experiments done at Sandia National Laboratories. Uncertainties for fire data can come from many sources, such as experiment design constraints, environmental conditions, or other plant-specific aspects. There are many different significant and insignificant parameters driving the uncertainty. Additionally, the uncertainty of the different input data used in the fire modeling could have a significant or insignificant effect on the entire plant risk. A four-step methodology was developed to perform Integrated Probabilistic Risk Assessment Importance Ranking. A demonstration case using these steps was set up and three of the four steps were completed in fiscal year (FY) 2019 and the fourth step done FY 2020. These steps are: 1. The qualitative analysis of potential sources was conducted with the following items identified for the demonstration. • Maximum heat release rate • Time to maximum heat release rate • Duration of max heat release rate • Time to decay • Thermal conductivity of concrete • Specific heat of concrete • Density of concrete • Cable jacket thickness 2. A quantitative characterization of dominant sources of uncertainty was performed. A list of distributions and determined values of the dominant sources is shown in Appendix A. 3. A quantitative screening of the potential sources of uncertainty using Morris Elementary Effects Analysis was completed. An experimental model using the physics-based fire modeling tool Fire Dynamics Simulator was developed and coupled with the Risk Analysis Virtual Environment. The Morris analysis identified at least two parameters that can be eliminated as significant contributors (specific heat of concrete and cable jacket thickness). 4. Global importance measure (Global IM) analysis to generate a comprehensive ranking based on their influence on the plant risk. In this research, a moment-independent Global IM is used since it can address (a) uncertainty in the input parameters of the fire model, (b) uncertainty in the risk outputs, and (c) non-linearity and interactions among input parameters in the fire model, more accurately than the correlation-based and variance-based global methods. The observations from the research showed that, depending on the initial and boundary conditions of the fire scenarios, fire-induced damage could have a very small probability and could be dominated by the tail of the uncertainty distribution; hence, the accuracy of the correlation-based and variance-based methods is questionable. The moment-independent Global IM analysis in this research provides a better understanding of how experimental uncertainty data affects industry’s plant models and where improvements in that data will have the largest benefit for improving fire modeling accuracy in causing core damage. Among the five unscreened parameters obtained from the Morris EE analysis, the Global IM analysis results for the case study indicated that max heat release rate and fire location are the most important parameters. The report also outlines benefits of using a unified computational platform that integrates the underlying simulations (e.g., a fire progression model), quantitative screening (using the Morris EE method), and the Global IM analysis. A unified platform can (i) facilitate the ranking of input parameters considering multiple key fire scenarios simultaneously, rather than considering one scenario at a time, (ii) contribute to more explicit and accurate treatment of dependencies at multiple levels of Fire PRA, (iii) facilitate the sampling-based uncertainty quantification for Fire PRA, and (iv) help generating both “industry-wide” and "plant-specific" ranking of uncertainty sources in Fire PRA. Future research should be done to include additional parameters such as detection/suppression or cable fire spread. Adding a PRA software such as SAPHIRE to the RAVEN platform would help with plant model integration and improve treatment of fire-induced dependency. The I-PRA risk importance ranking methodology offered in this report can provide valuable information for efficiently (a) enhancing the realism of Fire PRA for existing plants and (b) supporting the development of Dynamic Fire PRA for advanced reactors and new plants.

97 MATHEMATICS AND COMPUTING↗

Improved pseudopotential transferability for magnetic and electronic properties of binary manganese oxides from DFT + U + J calculations

In this work, we employ the fully anisotropic DFT+U+J approach with the PBEsol functional to investigate ground-state magnetic and electronic properties of bulk binary manganese oxides: MnO, Mn 3 O 4 , α-Mn 2 O 3 , and β-MnO 2 , in order of increasing Mn valence. The computed crystal structures, noncollinear magnetic ground states, and corresponding electronic structures are in good agreement with the experimental data and hybrid functional calculations available in the literature. We take into account the nonlinear core-valence interaction in our Mn pseudopotential designed by ourselves, as it has been proven to be important for transition-metal systems. Although the Hubbard U term is capable by itself of opening a band gap, the explicitly defined exchange parameter J plays an important role in improving the detailed electronic and noncollinear magnetic structure profiles. Appropriate band gaps are obtained with U values smaller than those used in previously reported calculations. Our results suggest that pseudopotential design together with DFT+U+J enables the acquisition of accurate properties of complex magnetic systems using a nonhybrid density functional.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Gap between holographic and quantum mechanical extreme rays of the subadditivity cone

We show via explicit construction that for six or more parties, there exist extreme rays of the subadditivity cone that can be realized by quantum states, but not by holographic states. This is a counterexample to a conjecture first formulated in Hernández-Cuenca et al. [The holographic entropy cone from marginal independence, J. High Energy Phys. 09 (2022) 190.], and implies the existence of deep holographic constraints that restrict the allowed patterns of independence among various subsystems beyond the universal quantum mechanical restrictions.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Improvement and performance evaluation of the perturbation source method for an exact Monte Carlo perturbation calculation in fixed source problems

This paper presents improvement and performance evaluation of the “perturbation source method”, which is one of the Monte Carlo perturbation techniques. The formerly proposed perturbation source method was first-order accurate, although it is known that the method can be easily extended to an exact perturbation method. A transport equation for calculating an exact flux difference caused by a perturbation is solved. A perturbation particle representing a flux difference is explicitly transported in the perturbed system, instead of in the unperturbed system. The source term of the transport equation is defined by the unperturbed flux and the cross section (or optical parameter) changes. The unperturbed flux is provided by an “on-the-fly” technique during the course of the ordinary fixed source calculation for the unperturbed system. A set of perturbation particle is started at the collision point in the perturbed region and tracked until death. For a perturbation in a smaller portion of the whole domain, the efficiency of the perturbation source method can be improved by using a virtual scattering coefficient or cross section in the perturbed region, forcing collisions. Performance is evaluated by comparing the proposed method to other Monte Carlo perturbation methods. Numerical tests performed for a particle transport in a two-dimensional geometry reveal that the perturbation source method is less effective than the correlated sampling method for a perturbation in a larger portion of the whole domain. However, for a perturbation in a smaller portion, the perturbation source method outperforms the correlated sampling method. The efficiency depends strongly on the adjustment of the new virtual scattering coefficient or cross section. - Highlights: • A Monte Carlo perturbation method known as “perturbation source method” is examined. • The method outperforms other perturbation methods when the perturbed region is small. • The efficiency depends on virtual scatterings added by a user-specified parameter.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Impact of isoprene and HONO chemistry on ozone and OVOC formation in a semirural South Korean forest

Rapid urbanization and economic development in East Asia in past decades has led to photochemical air pollution problems such as excess photochemical ozone and aerosol formation. Asian megacities such as Seoul, Tokyo, Shanghai, Guangzhou, and Beijing are surrounded by densely forested areas, and recent research has consistently demonstrated the importance of biogenic volatile organic compounds (VOCs) from vegetation in determining oxidation capacity in the suburban Asian megacity regions. Uncertainties in constraining tropospheric oxidation capacity, dominated by hydroxyl radical, undermine our ability to assess regional photochemical air pollution problems. We present an observational data set of CO, NO x , SO 2 , ozone, HONO, and VOCs (anthropogenic and biogenic) from Taehwa research forest (TRF) near the Seoul metropolitan area in early June 2012. The data show that TRF is influenced both by aged pollution and fresh biogenic volatile organic compound emissions. With the data set, we diagnose HO x (OH, HO 2 , and RO 2 ) distributions calculated using the University of Washington chemical box model (UWCM v2.1) with near-explicit VOC oxidation mechanisms from MCM v3.2 (Master Chemical Mechanism). Uncertainty from unconstrained HONO sources and radical recycling processes highlighted in recent studies is examined using multiple model simulations with different model constraints. The results suggest that (1) different model simulation scenarios cause systematic differences in HO x distributions, especially OH levels (up to 2.5 times), and (2) radical destruction (HO 2 + HO 2 or HO 2 + RO 2 ) could be more efficient than radical recycling (RO 2 + NO), especially in the afternoon. Implications of the uncertainties in radical chemistry are discussed with respect to ozone–VOC–NO x sensitivity and VOC oxidation product formation rates. Overall, the NO x limited regime is assessed except for the morning hours (8 a.m. to 12 p.m. local standard time), but the degree of sensitivity can significantly vary depending on the model scenarios. The model results also suggest that RO 2 levels are positively correlated with oxygenated VOCs (OVOCs) production that is not routinely constrained by observations. These unconstrained OVOCs can cause higher-than-expected OH loss rates (missing OH reactivity) and secondary organic aerosol formation. The series of modeling experiments constrained by observations strongly urge observational constraint of the radical pool to enable precise understanding of regional photochemical pollution problems in the East Asian megacity region.

54 ENVIRONMENTAL SCIENCES↗

Linking Hydrology and Dissolved Organic Matter Characteristics in a Subtropical Wetland: A Long-Term Study of the Florida Everglades

Dissolved organic matter (DOM) acts as an important biogeochemical component of aquatic ecosystems that controls nutrient cycling, influences water quality, and links terrestrial and oceanic carbon pools, yet long-term studies of how changing environmental drivers alter its abundance and composition are rare. Using a ten-year, spatially explicit dataset from Everglades National Park (ENP), a globally significant wetland, we investigated the relationships between DOM quality/quantity and hydrologic/climatic drivers along two contrasting marsh-estuarine transects based on generalized linear modeling and a cumulative sums analysis. Analyses revealed distinct spatial, seasonal, and interannual patterns in variability of DOC and optical properties. Landscape-scale seasonal patterns showed an enrichment in microbial-like and protein-like DOM during the dry season relative to the wet season. We found that, while some compositional constituents varied with the solar calendar, responsive to temperature and photoperiod, others varied with the hydrologic calendar. Independent water level and discharge effects indicated strong hydrologic control on DOM quality that differed between the two transects, evidencing differences in their connectivity to areas of high agricultural activity. Across all sites, a significant long-term increasing trend in the fluorescence index was observed, associated with a positive correlation with precipitation and also potential changes in agricultural inputs, with other features associated with drought and hurricanes. Lastly, the cumulative sums analysis revealed differences between the two transects in the sensitivity of DOM composition to decreased water levels associated with 30-year climate scenarios, with the less hydrologically dynamic transect exhibiting greater potential sensitivity.

54 ENVIRONMENTAL SCIENCES↗