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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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All sourcesNASA NTRSDOE OSTI
DOE OSTI2011

MAIN-BELT COMET 238P/READ REVISITED

We present a series of observations of the return of activity in main-belt comet (MBC) 238P/Read. Using data obtained in 2010 July and August when 238P appeared to be largely inactive, we find best-fit IAU phase function parameters of H = 19.05 {+-} 0.05 mag, corresponding to a nucleus radius of r{sub n} {approx} 0.4 km (assuming an albedo of p{sub R} = 0.05), and G = -0.03 {+-} 0.05. Observations from 2010 September onward show a clear rise in activity, causing both a notable change in visible morphology and increasing photometric excesses beyond what would be expected based on bare nucleus observations. By the end of the observing period reported on here, the dust mass in the coma shows indications of reaching a level comparable to that observed in 2005, but further observations are highly encouraged once 238P again becomes observable from Earth in mid-2011 to confirm whether this level of activity is achieved, or if the comet shows a noticeable drop in activity strength compared with 2005. Comet 238P is now the second MBC (after 133P/Elst-Pizarro) observed to exhibit recurrent activity, providing strong corroboration for the conclusion that it is a true comet whose active episodes are driven by sublimation of volatile ice.

79 ASTRONOMY AND ASTROPHYSICS↗
NASA NTRS2016

Estimation of the Ocean Skin Temperature using the NASA GEOS Atmospheric Data Assimilation System

This report documents the status of the development of a sea surface temperature (SST) analysis for the Goddard Earth Observing System (GEOS) Version-5 atmospheric data assimilation system (ADAS). Its implementation is part of the steps being taken toward the development of an integrated earth system analysis. Currently, GEOS-ADAS SST is a bulk ocean temperature (from ocean boundary conditions), and is almost identical to the skin sea surface temperature. Here we describe changes to the atmosphere-ocean interface layer of the GEOS-atmospheric general circulation model (AGCM) to include near surface diurnal warming and cool-skin effects. We also added SST relevant Advanced Very High Resolution Radiometer (AVHRR) observations to the GEOS-ADAS observing system. We provide a detailed description of our analysis of these observations, along with the modifications to the interface between the GEOS atmospheric general circulation model, gridpoint statistical interpolation-based atmospheric analysis and the community radiative transfer model. Our experiments (with and without these changes) show improved assimilation of satellite radiance observations. We obtained a closer fit to withheld, in-situ buoys measuring near-surface SST. Evaluation of forecast skill scores corroborate improvements seen in the observation fits. Along with a discussion of our results, we also include directions for future work.

AGCM↗
DOE OSTI2018

Bfd, a New Class of [2Fe-2S] Protein That Functions in Bacterial Iron Homeostasis, Requires a Structural Anion Binding Site

Mobilization of iron from bacterioferritin (BfrB) requires specific interactions with a [2Fe-2S] ferredoxin (Bfd). Blocking the BfrB:Bfd interaction results in irreversible iron accumulation in BfrB and iron deficiency in the cytosol. The only known Bfd structure, which was obtained in complex with BfrB (Protein Data Bank entry 4E6K), indicated a new fold and suggested that the stability of Bfd is aided by an anion binding site consisting of R26, R29, and K46. We investigated the Bfd fold using site-directed mutagenesis, X-ray crystallography, and biochemistry in solution. The X-ray structure, which is nearly identical to that of Bfd in the BfrB:Bfd complex, shows that the [2Fe-2S] cluster preorganizes residues at the BfrB:Bfd interface into a structure complementary to the Bfd binding site on BfrB. Studies in solution showed rapid loss of the [2Fe-2S] cluster at a low ionic strength but higher stability with an increasing ionic strength, thus supporting a structural anion binding site. Structures of the R26E and R26E/K46Y mutants are nearly identical to that of Bfd, except for a new network of hydrogen bonds stabilizing the region encompassing the former anion binding site. Here, the stability of the R26E and R26E/K46Y mutants, which is weakly and completely independent of solution ionic strength, respectively, corroborates that Bfd requires an anion binding site. The mutations, which caused only small changes to the strength of the BfrB:Bfd interaction and mobilization of iron from BfrB, indicate that the anion binding site in Bfd serves primarily a structural role.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Reforming EIA systems: A critical review of proposals in Brazil

Environmental Impact Assessment (EIA) systems are under pressure in many countries, driven by a call for efficiency and streamlining. Such a phenomenon is particularly clear in Brazil, where, in the past few years, a number of influential associations put forward documents proposing significant changes to environmental licensing and impact assessment regulations. So far, there is no publicly available information about any initiative towards scrutinizing those proposals. The objective of this study was to critically review the merits and drawbacks of the changes proposed in those documents. The analysis triangulated content analysis, focus group and online survey data. The focus group included ten seasoned Brazilian EIA specialists; the survey, based on Likert-scale and open-ended questions, resulted in 322 valid responses from EIA professionals. Results show that the proposals generally agree that the current EIA system, while playing a key role in mitigating impacts and enhancing project design, needs many changes. Nonetheless, the proposals neither offered solutions to overcome political, technical and budget barriers, nor established a sense of priority of the most urgent issues. Findings from the focus group and the survey signaled that a number of proposed actions might face public outcry, and that those changes that do not depend on legislative action are more likely to be implementable. Previous studies about EIA reform focused mostly on the context of developed countries after changes had taken place. This study, while addressing the perspective of a large developing country in a “before-reform” stage, shows that capacity-building is a key requirement in EIA reform. - Highlights: • Brazil's EIA system is under strong pressure for change. • Findings corroborate ineffectiveness in current system. • There are tensions as to the best approaches to overcome problems. • Exact effects of proposals are uncertain. • Low institutional capacity can play strong role in driving EIA reform.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2016

Selectivity for HCO 2 – over H 2 in the Electrochemical Catalytic Reduction of CO 2 by (POCOP)IrH 2

It has been demonstrated experimentally that electrochemical CO 2 reduction catalyzed by (POCOP)IrH 2 ([C 6 H 3 -2,6-[OP( t Bu) 2 ] 2 ]IrH 2 ) produces formate without significant H 2 . We use first-principles density functional theory (M06) including Poisson–Boltzmann solvation to determine the detailed atomistic mechanism and illuminate strategies for designing formate-selective catalysts. A mechanism involving hydride transfer from Ir III dihydride explains the selectivity for formate over H 2 and is corroborated by reduction potential (irreversible reduction of (POCOP)Ir(H)(NCMe) 2 + at ca. –1.3 V vs NHE, in comparison to –1.31 V vs NHE calculated for one-electron reduction of Ir III (H)(NCMe) 2 + ) and turnover frequency. We find that several thermodynamically favorable pathways exist for the hydrogen evolution reaction (HER) from both Ir III (H) 2 and Ir I –H – but are kinetically hindered, posing computed activation barriers above 25 kcal/mol at pH 7. However, with formate or bicarbonate acting as cocatalyst, the barriers are lowered to 18.8 kcal/mol. The preference of (POCOP)Ir to form a dihydride instead of a dihydrogen adduct also disfavors the HER and facilitates catalyst regeneration. In contrast, substituting cobalt for iridium raises the barrier for hydride transfer to CO 2 by 12.0 kcal/mol and lowers the required reduction potential to –1.65 V vs NHE. Calculated driving forces for hydride transfer from IrI and IrIII intermediates illustrate different strategies for positioning the hydricity relative to the thermodynamic hydricities of H 2 /H + and HCOO – /CO 2 . The data support an approach of selecting a hydricity that is just thermodynamically able to reduce CO 2 . In conclusion, the effect of solvation on calculated driving forces for hydride transfer is also discussed.

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

Association of post-COVID phenotypic manifestations with new-onset psychiatric disease

Acute COVID-19 infection can be followed by diverse clinical manifestations referred to as Post Acute Sequelae of SARS-CoV2 Infection (PASC). Studies have shown an increased risk of being diagnosed with new-onset psychiatric disease following a diagnosis of acute COVID-19. However, it was unclear whether non-psychiatric PASC-associated manifestations (PASC-AMs) are associated with an increased risk of new-onset psychiatric disease following COVID-19. A retrospective electronic health record (EHR) cohort study of 2,391,006 individuals with acute COVID-19 was performed to evaluate whether non-psychiatric PASC-AMs are associated with new-onset psychiatric disease. Data were obtained from the National COVID Cohort Collaborative (N3C), which has EHR data from 76 clinical organizations. EHR codes were mapped to 151 non-psychiatric PASC-AMs recorded 28–120 days following SARS-CoV-2 diagnosis and before diagnosis of new-onset psychiatric disease. Association of newly diagnosed psychiatric disease with age, sex, race, pre-existing comorbidities, and PASC-AMs in seven categories was assessed by logistic regression. There were significant associations between a diagnosis of any psychiatric disease and five categories of PASC-AMs with odds ratios highest for neurological, cardiovascular, and constitutional PASC-AMs with odds ratios of 1.31, 1.29, and 1.23 respectively. Secondary analysis revealed that the proportions of 50 individual clinical features significantly differed between patients diagnosed with different psychiatric diseases. Our study provides evidence for association between non-psychiatric PASC-AMs and the incidence of newly diagnosed psychiatric disease. Significant associations were found for features related to multiple organ systems. This information could prove useful in understanding risk stratification for new-onset psychiatric disease following COVID-19. Prospective studies are needed to corroborate these findings.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2014

The shock-induced star formation sequence resulting from a constant spiral pattern speed

We utilize a suite of multiwavelength data of nine nearby spirals to analyze the shock-induced star formation sequence that may result from a constant spiral pattern speed. The sequence involves tracers as the H I, CO 24 μm, and FUV, where the spiral arms were analyzed with Fourier techniques in order to obtain their azimuthal phases as a function of radius. It was found that only two of the objects, NGC 628 and NGC 5194, present coherent phases resembling the theoretical expectations, as indicated by the phase shifts of CO- 24 μm. The evidence is more clear for NGC 5194 and moderate for NGC 628. It was also found that the phase shifts are different for the two spiral arms. With the exception on NGC 3627, a two-dimensional Fourier analysis showed that the rest of the objects do not exhibit bi-symmetric spiral structures of stellar mass, i.e., grand-design spirals. A phase order inversion indicates a corotation radius of ∼89'' for NGC 628 and ∼202'' for NGC 5194. For these two objects, the CO-Hα phase shifts corroborate the CO-24 μm azimuthal offsets. Also for NGC 5194, the CO-70 μm, CO-140 μm, and CO-250 μm phase shifts indicate a corotation region.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2018

Microstructural analysis of undoped and moderately Sc-doped TiO2 anatase nanoparticles using Scherrer equation and Debye function analysis

Highlights: • UV light sensitive undoped and moderate Sc-doped anatase nanocrystallites were prepared without post-synthesis annealing. • Elongated nanocrystallites were found by Scherrer equation and Debye Function Analysis applied to XRD data and also HRTEM. • 4 at.% Sc doping reduced the amount of Ti vacancies by half. • Doping showed ~0.3% growth of lattice parameters. - Abstract: UV light sensitive undoped and moderate (4 at.%) Sc-doped anatase nanocrystallites were prepared by an efficient and environmentally benign method based on homogeneous hydrolysis of TiOSO{sub 4} and Sc{sub 2}(C{sub 2}O{sub 4}){sub 3.5}H{sub 2}O aqueous solutions using urea as a precipitation agent, without post-synthesis calcination or annealing. X-ray diffraction study of the obtained powders revealed single phase anatase in both samples. Two different methods were applied to estimate the anatase crystallite size and shape from the X-ray diffraction data. The first one is based on the more conventional Scherrer equation (as implanted in GSAS-II program) while the second one is based on Debye function analysis (as implanted in DUBUSSY suite version 2.2), which is considered to be more adequate for nanocrystallites. Although each program has its own shape models, both methods indicated similar results of elongated nanocrystallite geometry for Sc-doped TiO{sub 2}: (i) GSAS-II confirmed ellipsoid shape with equatorial size of 5.1(0) nm and axial size of 6.8(0), (ii) DEBUSSY suite 2.2 showed cylinder shape with diameter of equivalent circle in the ab-plane, D{sub ab} = 4.9(1.0) nm and crystallite length along the c-axis, L{sub c} = 5.4(3.2) nm. For the undoped TiO{sub 2} sample, equatorial size of 5.5(0) nm and axial size of 7.3(0) nm for the ellipsoid shape was determined according to GSAS-II, while D{sub ab} = 5.5(1.3) nm and L{sub c} = 6.0(2.2) nm for the cylinder shape was determined by DEBUSSY suite 2.2. These outcomes were found to corroborate with HRTEM analysis. Doping with 4 at.% Sc caused ~0.3% growth of lattice parameters from a = 3.7979 [4] Å, c = 9.4995 [9] Å for the undoped sample to a = 3.8110 [7] Å, c = 9.5274 [16] Å for the moderately Sc doped sample, while reduction in the Ti vacancies by half was confirmed by both methods. The introducing of Sc as electronically active secondary species into the crystal lattice of TiO{sub 2} can greatly alter its optical absorption. The incorporation of Sc into the crystal lattice of TiO{sub 2} favors the substitution of Ti, as both have approximately the same ionic size, and generates surface oxygen vacancies which can act as trapping center for the photogenerated electrons and reduce the recombination of electron–hole pairs. We can expect Sc doped TiO{sub 2} nanomaterials to have applications as effective photocatalysts for selective photocatalytic oxidation of various environmental organic pollutants.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2020

Urban building energy modeling (UBEM) tools: A state-of-the-art review of bottom-up physics-based approaches

Regulations corroborate the importance of retrofitting existing building stocks or constructing new energy-efficient districts. There is, thus, a need for modeling tools to evaluate energy scenarios to better manage and design cities, and numerous methodologies and tools have been developed. Among them, Urban Building Energy Modelling (UBEM) tools allow the energy simulation of buildings at large scales. Choosing an appropriate UBEM tool, balancing the level of complexity, accuracy, usability, and computing needs, remains a challenge for users. The review focuses on the main bottom-up physics-based UBEM tools, comparing them from a user-oriented perspective. Five categories are used: (i) the required inputs, (ii) the reported outputs, (iii) the exploited workflow, (iv) the applicability of each tool, and (v) the potential users. Moreover, a critical discussion is proposed, focusing on interests and trends in research and development. The results highlighted major differences between UBEM tools that must be considered to choose the proper one for an application. Finally, barriers of adoption of UBEM tools include the needs of a standardized ontology, a common three-dimensional city model, a standard procedure to collect data, and a standard set of test cases. This feeds into future development of UBEM tools to support cities’ sustainability goals.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗
DOE OSTI2011

Effect of Hysteresis on Measurements of Thin-Film Cell Performance

Transient or hysteresis effects in polycrystalline thin film CdS/CdTe cells are a function of pre-measurement voltage bias and whether Cu is introduced as an intentional dopant during back contact fabrication. When Cu is added, the current-density (J) vs. voltage (V) measurements performed in a reverse-to-forward voltage direction will yield higher open-circuit voltage (Voc), up to 10 mV, andsmaller short-circuit current density (Jsc), by up to 2 mA/cm2, relative to scanning voltage in a forward-to-reverse direction. The variation at the maximum power point, Pmax, is however small. The resulting variation in FF can be as large as 3%. When Cu is not added, hysteresis in both Voc and Jsc is negligible however Pmax hysteresis is considerably greater. This behavior corroborates observedchanges in depletion width, Wd, derived from capacitance (C) vs voltage (V) scans. Measured values of Wd are always smaller in reverse-to-forward voltage scans, and conversely, larger in the forward-to-reverse voltage direction. Transient ion drift (TID) measurements performed on Cu-containing cells do not show ionic behavior suggesting that capacitance transients are more likely due toelectronic capture-emission processes. J-V curve simulation using Pspice shows that increased transient capacitance during light-soak stress at 100 degrees C correlates with increased space-charge recombination. Voltage-dependent collection however was not observed to increase with stress in these cells.

14 SOLAR ENERGY↗
NASA NTRS1986

Utilization of ammonium as a nitrogen source: effects of ambient acidity on growth and nitrogen accumulation by soybean

Dry matter accumulation of plants utilizing NH4+ as the sole nitrogen source generally is less than that of plants receiving NO3- unless acidity of the root-zone is controlled at a pH of about 6.0. To test the hypothesis that the reduction in growth is a consequence of nitrogen stress within the plant in response to effects of increased acidity during uptake of NH4+ by roots, nonnodulated soybean plants (Glycine max [L.] Merr. cv Ransom) were grown for 24 days in flowing nutrient culture containing 1.0 millimolar NH4+ as the nitrogen source. Acidities of the culture solutions were controlled at pH 6.1, 5.1, and 4.1 +/- 0.1 by automatic additions of 0.01 N H2SO4 or Ca(OH)2. Plants were sampled at intervals of 3 to 4 days for determination of dry matter and nitrogen accumulation. Rates of NH4+ uptake per gram root dry weight were calculated from these data. Net CO2 exchange rates per unit leaf area were measured on attached leaves by infrared gas analysis. When acidity of the culture solution was increased from pH 6.1 to 5.1, dry matter and nitrogen accumulation were reduced by about 40% within 14 days. Net CO2 exchange rates per unit leaf area, however, were not affected, and the decreased growth was associated with a reduction in rates of appearance and expansion of new leaves. The uptake rates of NH4+ per gram root were about 25% lower throughout the 24 days at pH 5.1 than at 6.1. A further increase in solution acidity from pH 5.1 to 4.1 resulted in cessation of net dry matter production and appearance of new leaves within 10 days. Net CO2 exchange rates per unit leaf area declined rapidly until all viable leaves had abscised by 18 days. Uptake rates of NH4+, which were initially about 50% lower at pH 4.1 than at 6.1 continued to decline with time of exposure until net uptake ceased at 10 days. Since these responses also are characteristic of the sequence of responses that occur during onset and progression of a nitrogen stress, they corroborate our hypothesis.

NASA Discipline Number 61-10↗
NASA NTRS2022

Evaluation of High Mountain Asia-Land Data Assimilation System (version 1) from 2003 to 2016: 2. The impact of assimilating satellite-based snow cover and freeze/thaw observations into a land surface model

This second paper of the two-part series focuses on demonstrating the impact of assimilating satellite-based snow cover and freeze/thaw observations into the hyper-resolution, offline terrestrial modeling system used for the High Mountain Asia (HMA) region from 2003 to 2016. To this end, this study systematically evaluates a total of six sets of 0.01° (∼1 km) model simulations forced by different precipitation forcings, with and without the dual assimilation scheme enabled, at point-scale, basin-scale, and domain-scale. The key variables of interest include surface net shortwave radiation, surface net longwave radiation, skin temperature, near-surface soil temperature, snow depth, snow water equivalent (SWE), and total runoff. First, the point-scale assessment is mainly conducted via evaluating against ground-based measurements. In general, the assimilation enabled estimates are better than no-assimilation counterparts. Second, the basin-scale runoff assessment demonstrates that across three snow-dominated basins, the assimilation enabled experiment yields systematic improvements in all goodness-of-fit statistics through mitigating the negative effects brought by the fixed long-term precipitation correction factors. For example, when forced by the bias-corrected precipitation, the assimilation-enabled experiment improves the bias by 69%, the root-mean-squared error by 30%, and the unbiased root-mean-squared error by 18% (relative to the no-assimilation counterpart). Finally, the domainscale assessment is conducted via evaluating against satellite-based SWE and skin temperature products. Both sets of domain-scale analysis further corroborate the findings in the point-scale evaluations. Overall, this study suggests the benefits of the proposed multi-variate assimilation system in improving the cryospherichydrological process within a land surface model for use in HMA.

Yuan Xue↗
NASA NTRS1993

Mineral and organic matrix interaction in normally calcifying tendon visualized in three dimensions by high-voltage electron microscopic tomography and graphic image reconstruction

To define the ultrastructural accommodation of mineral crystals by collagen fibrils and other organic matrix components during vertebrate calcification, electron microscopic 3-D reconstructions were generated from the normally mineralizing leg tendons from the domestic turkey, Meleagris gallopavo. Embedded specimens containing initial collagen mineralizing sites were cut into 0.5-micron-thick sections and viewed and photographed at 1.0 MV in the Albany AEI-EM7 high-voltage electron microscope. Tomographic 3-D reconstructions were computed from a 2 degree tilt series of micrographs taken over a minimum angular range of +/- 60 degrees. Reconstructions of longitudinal tendon profiles confirm the presence of irregularly shaped mineral platelets, whose crystallographic c-axes are oriented generally parallel to one another and directed along the collagen long axes. The reconstructions also corroborate observations of a variable crystal length (up to 170 nm measured along crystallographic c-axes), the presence of crystals initially in either the hole or overlap zones of collagen, and crystal growth in the c-axis direction beyond these zones into adjacent overlap and other hole regions. Tomography shows for the first time that crystal width varies (30-45 nm) but crystal thickness is uniform (approximately 4-6 nm at the resolution limit of tomography); more crystals are located in the collagen hole zones than in the overlap regions at the earliest stages of tendon mineralization; the crystallographic c-axes of the platelets lie within +/- 15-20 degrees of one another rather than being perfectly parallel; adjacent platelets are spatially separated by a minimum of 4.2 +/- 1.0 nm; crystals apparently fuse in coplanar alignment to form larger platelets; development of crystals in width occurs to dimensions beyond single collagen hole zones; and a thin envelope of organic origin may be present along or just beneath the surfaces of individual mineral platelets. Implicit in the results is that the formation of crystals occurs at different sites and times by independent nucleation events in local regions of collagen. These data provide the first direct visual evidence from 3-D imaging describing the size, shape, orientation, and growth of mineral crystals in association with collagen of a normally mineralizing vertebrate tissue. They support concepts that c-axial crystal growth is unhindered by collage hole zone dimensions, that crystals are organized in the tendon in a series of generally parallel platelets, and that crystal growth in width across collagen fibrils may follow channels or grooves formed by adjacent hole zones in register.

Non-NASA Center↗
DOE OSTI2022

The Microbial Community and Functional Potential in the Midland Basin Reveal a Community Dominated by Both Thiosulfate and Sulfate-Reducing Microorganisms

The Permian Basin is the highest producing oil and gas reservoir in the United States. Hydrocarbon resources in this region are often accessed by unconventional extraction methods, including horizontal drilling and hydraulic fracturing. Despite the importance of the Permian Basin, there is no publicly available microbiological data from this region. We completed an analysis of Permian produced water samples to understand the dynamics present in hydraulically fractured wells in this region. We analyzed produced water samples taken from 10 wells in the Permian region of the Midland Basin using geochemical measurements, 16S rRNA gene sequencing, and metagenomic sequencing. Compared to other regions, we found that Permian Basin produced water was characterized by higher sulfate and lower total dissolved solids (TDS) concentrations, with a median of 1,110 mg/L and 107,000 mg/L. Additionally, geochemical measurements revealed the presence of frac hits, or interwell communication events where an established well is affected by the pumping of fracturing fluid into a new well. The occurrence of frac hits was supported by correlations between the microbiome and the geochemical parameters. Our 16S rRNA gene sequencing identified a produced water microbiome characterized by anaerobic, halophilic, and sulfur reducing taxa. Interestingly, sulfate and thiosulfate reducing taxa including Halanaerobium, Orenia, Marinobacter, and Desulfohalobium were the most prevalent microbiota in most wells. We further investigated the metabolic potential of microorganisms in the Permian Basin with metagenomic sequencing. We recovered 15 metagenome assembled genomes (MAGs) from seven different samples representing 6 unique well sites. These MAGs corroborated the high presence of sulfate and thiosulfate reducing genes across all wells, especially from key taxa including Halanaerobium and Orenia. The observed microbiome composition and metabolic capabilities in conjunction with the high sulfate concentrations demonstrate a high potential for hydrogen sulfide production in the Permian Basin. Additionally, evidence of frac hits suggests the possibility for the exchange of microbial cells and/or genetic information between wells. This exchange would increase the likelihood of hydrogen sulfide production and has implications for the oil and gas industry.

16S RNA↗
NASA NTRS2022

Evaluation of High Mountain Asia-Land Data Assimilation System (version 1) from 2003 to 2016: 2. The impact of assimilating satellite-based snow cover and freeze/thaw observations into a land surface model

This second paper of the two-part series focuses on demonstrating the impact of assimilating satellite-based snow cover and freeze/thaw observations into the hyper-resolution, offline terrestrial modeling system used for the High Mountain Asia (HMA) region from 2003 to 2016. To this end, this study systematically evaluates a total of six sets of 0.01° (∼1 km) model simulations forced by different precipitation forcings, with and without the dual assimilation scheme enabled, at point-scale, basin-scale, and domain-scale. The key variables of interest include surface net shortwave radiation, surface net longwave radiation, skin temperature, near-surface soil temperature, snow depth, snow water equivalent (SWE), and total runoff. First, the point-scale assessment is mainly conducted via evaluating against ground-based measurements. In general, the assimilation enabled estimates are better than no-assimilation counterparts. Second, the basin-scale runoff assessment demonstrates that across three snow-dominated basins, the assimilation enabled experiment yields systematic improvements in all goodness-of-fit statistics through mitigating the negative effects brought by the fixed long-term precipitation correction factors. For example, when forced by the bias-corrected precipitation, the assimilation-enabled experiment improves the bias by 69%, the root-mean-squared error by 30%, and the unbiased root-mean-squared error by 18% (relative to the no-assimilation counterpart). Finally, the domain-scale assessment is conducted via evaluating against satellite-based SWE and skin temperature products. Both sets of domain-scale analysis further corroborate the findings in the point-scale evaluations. Overall, this study suggests the benefits of the proposed multi-variate assimilation system in improving the cryospheric-hydrological process within a land surface model for use in HMA.

Yuan Xue↗
DOE OSTI2025

Comparison of Ce( iv )/Th( iv )-alkynyl complexes and observation of a trans -influence ligand series for Ce( iv )

Organometallic cerium(iv) complexes have been challenging to isolate and characterize due to the strongly oxidizing nature of the cerium(iv) cation. Herein, we report two cerium(iv) alkynyl complexes, [Ce(TriNOx)(C[triple bond, length as m-dash]C-SiMe3)] (1-CeTMS) and [Ce(TriNOx)(C[triple bond, length as m-dash]C-Ph)] (1-CePh) (TriNOx3- = tris(2-tert-butylhydroxylaminato)benzylamine), that include terminal alkyne moieties. The isostructural thorium analogue [Th(TriNOx)(C[triple bond, length as m-dash]C-SiMe3)] (1-ThTMS) was also synthesized and compared with 1-CeTMS in bond distance, 13C-NMR spectra, vibrational spectra and electronic structure. The Ce-C bond distances were 2.501(3) Å for 1-CePh and 2.513(5) Å for 1-CeTMS on the shorter end of the few reported CeIV-C single bonds (2.478(3)-2.705(2) Å), possibly indicating significant Ce 5d- and 4f-orbital involvement. 13C-NMR spectroscopy was also consistent with Ce-C covalency, with significantly deshielded resonances ranging from 185-213 ppm. Such 13C-NMR shifts demonstrate a strong influence from spin-orbit coupling (SOC) effects, corroborated by computational studies. Raman analysis showed ν C[triple bond, length as m-dash]C stretching frequencies of 2000 cm-1 (1-CeTMS) and 2052 cm-1 (1-CePh), indicating the cerium(iv)-alkynyl interaction, compared to the parent HC[triple bond, length as m-dash]CPh (IR = 2105 cm-1 and Raman = 2104 cm-1). L3-edge X-ray absorption measurements revealed a predominant Ce(iv) electronic configuration, and magnetic measurements revealed temperature-independent paramagnetism. Electrochemical studies similarly revealed the electron donating ability of the alkynyl ligands, stronger than either fluoride or imido ligands for the Ce(iv)(TriNOx)-framework, with a cerium(iv/iii) reduction potential of E pc = -1.58 to -1.66 V vs. Fc/Fc+. Evidence for a trans-influence has been observed by evaluating a series including previously reported [CeIV(TriNOx)X]+/0 complexes with axial ligands X = THF, I-, Br-, Cl-, F-, -C[triple bond, length as m-dash]C-Ph, -C[triple bond, length as m-dash]C-SiMe3, -NH(3,5-(CF3)2-Ar), -OSiPh3, -N(M(L))(3,5-(CF3)2-Ar) [M(L) = Li(TMEDA), K(DME)2 or Cs(2,2,2-crypt)]. These data stand in contrast with previous reports of an inverse trans-influence at cerium(iv) and point to differences in involvement of cerium 4f- versus 5d-orbitals in the electronic structures of the complexes.

Yang, Qiaomu↗
DOE OSTI2022

Broad Applicability of Electrochemical Impedance Spectroscopy to the Measurement of Oxygen Nonstoichiometry in Mixed Ion and Electron Conductors

Oxygen non-stoichiometry is a fundamental feature of mixed ion and electron conductors (MIECs). In this work a general electrochemical method for determining non-stoichiometry in thin film MIECs, via measurement of the chemical capacitance, is demonstrated using ceria and ceria-zirconia (Ce 0.8 Zr 0.2 O 2-δ ) as representative materials. A.C. impedance data are collected from both materials at high temperature (750-900 °C) under reducing conditions with oxygen partial pressure (pO 2 ) in the range 10-13 to 10-20 atm. Additional measurements of ceria-zirconia films are made under relatively oxidizing conditions with pO 2 in the range 0.2 to 10 -4 atm and temperatures of 800-900 °C. Under reducing conditions, the impedance spectra are described by a simple circuit in which a resistor is in series with a resistor and capacitor in parallel, and thickness dependent measurements are used to resolve the capacitance into interfacial and chemical terms. Under more oxidizing conditions, the impedance spectra (of Ce 0.8 Zr 0.2 O 2-δ ) reveal an additional diffusional feature, which enables determination of the ionic resistance of the film in addition to the capacitance, and hence the transport properties. A generalized mathematical formalism is presented for recovering the non-stoichiometry from the chemical capacitance, without recourse to defect chemical models. The ceria non-stoichiometry values are in good agreement with literature values determined by thermogravimetric measurements but display considerably less scatter and are collected on considerably shorter timescales. Here, the thermodynamic analysis of Ce 0.8 Zr 0.2 O 2-δ corroborates earlier findings that introduction of Zr into ceria enhances its reducibility.

08 HYDROGEN↗
DOE OSTI2023

Wintertime synoptic patterns of midlatitude boundary layer clouds over the western North Atlantic: Climatology and insights from in-situ ACTIVATE observations

The winter synoptic evolution of the western North Atlantic and its influence on the atmospheric boundary layer is described by means of a regime classification based on Self Organizing Maps applied to 12 year of data (2009-2020). The regimes are classified into categories according to daily 600-hPa geopotential height: dominant ridge, trough to ridge eastward transition (trough-ridge), dominant trough, and ridge to trough eastward transition (ridge-trough). A fifth synoptic regime resembles the winter climatological mean. Coherent changes in sea-level pressure and large-scale winds are in concert with the synoptic regimes: 1) the ridge regime is associated with a well-developed anticyclone; 2) the trough-ridge gives rise to a low pressure center over the ocean, ascents, and northerly winds over the coastal zone; 3) trough is associated with the eastward displacement of a cyclone, coastal subsidence, and northerly winds, all representative characteristics of cold-air outbreaks; 4) the ridge-trough regime features the development of an anticyclone and weak coastal winds. Low clouds are characteristic of the trough regime, with both trough and trough-ridge featuring synoptic maxima in cloud droplet number concentration (N d ). The N d increase is primarily observed near the coast, concomitant with strong surface heat fluxes exceeding by more than 400 W m -2 compared to fluxes further east. Five consecutive days of aircraft observations collected during the ACTIVATE campaign corroborates the climatological characterization, confirming the occurrence of high N d for days identified as trough. This study emphasizes the role of boundary-layer dynamics and aerosol activation and their roles in modulating cloud microphysics.

54 ENVIRONMENTAL SCIENCES↗