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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 127 records · Page 7
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Simulating the Geological Fate of Terrestrial Organic Matter: Lignin vs Cellulose

While shale gas has become a major source of energy, a more sustainable recovery requires a better understanding of the gas/kerogen matrix interactions. Here, we use replica exchange molecular dynamics to investigate the geological conversion of two important classes of gas-forming constituents of the terrestrial organic matter: lignin and cellulose. In agreement with results from pyrolysis experiments, we show that lignin produces twice as much kerogen and 5 times more methane than cellulose. In addition, while ex-cellulose kerogen is relatively stiff and almost nonporous, ex-lignin kerogen, despite having a very similar composition and bonding, is an order of magnitude more compliant due to the presence of large micropores. The obtained results can potentially improve the nanoscale brick of bottom-up models of shale gas recovery.

58 GEOSCIENCES↗
DOE OSTI2020

Effect of Natural Organic Matter on the Fate of Cadmium During Microbial Ferrihydrite Reduction

Natural organic matter (NOM) is known to affect the microbial reduction and transformation of ferrihydrite, but its implication toward cadmium (Cd) associated with ferrihydrite is not well-known. In this work, we investigated how Cd is redistributed when ferrihydrite undergoes microbial reduction in the presence of NOM. Incubation with Geobacter sulfurreducens showed that both the rate and the extent of reduction of Cd-loaded ferrihydrite were enhanced by increasing concentrations of NOM (i.e., C/Fe ratio). Furthermore, without NOM, only 3–4% of Fe(III) was reduced, but around 61% of preadsorbed Cd was released into solution due to ferrihydrite transformation to lepidocrocite. At high C/Fe ratio (1.6), more than 35% of Fe(III) was reduced, as NOM can facilitate bioreduction by working as an electron shuttle and decreased aggregate size, but only a negligible amount of Cd was released into solution, thus decreasing Cd toxicity and prolonging microbial Fe(III) reduction. No ferrihydrite transformation was observed at high C/Fe ratios using Mössbauer spectroscopy and X-ray diffraction, and X-ray absorption spectroscopy indicated the proportion of Cd-OM bond increased after microbial reduction. This study shows that the presence of NOM leads to less mobilization of Cd under reducing condition possibly by inhibiting ferrihydrite transformation and recapturing Cd through Cd-OM bond.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Surface Processes Control the Fate of Reactive Oxidants Generated by Electrochemical Activation of Hydrogen Peroxide on Stainless-Steel Electrodes

Low-cost stainless-steel electrodes can activate hydrogen peroxide (H 2 O 2 ) by converting it into a hydroxyl radical ( • OH) and other reactive oxidants. At an applied potential of +0.020 V, the stainless-steel electrode produced • OH with a yield that was over an order of magnitude higher than that reported for other systems that employ iron oxides as catalysts under circumneutral pH conditions. Decreasing the applied potential at pH 8 and 9 enhanced the rate of H 2 O 2 loss by shifting the process to a reaction mechanism that resulted in the formation of an Fe(IV) species. Significant metal leaching was only observed under acidic pH conditions (i.e., at pH <6), with the release of dissolved Fe and Cr occurring as the thickness of the passivation layer decreased. Despite the relatively high yield of • OH production under circumneutral pH conditions, most of the oxidants were scavenged by the electrode surface when contaminant concentrations comparable to those expected in drinking water sources were tested. The stainless-steel electrode efficiently removed trace organic contaminants from an authentic surface water sample without contaminating the water with Fe and Cr. With further development, stainless-steel electrodes could provide a cost-effective alternative to other H 2 O 2 activation processes, such as those by ultraviolet light.

42 ENGINEERING↗
DOE OSTI2025

Wildfire Produces Transient Minerals: Speciation, Reactivity, and Fate of Iron and Manganese in Surface Soils Post Wildfire

Wildfire leads to the deposition of an ash layer at the land surface. This material typically has alkaline properties, abundant pyrogenic carbon, and elevated metal concentrations compared to surface soils. Here, we compare ash and surface soils collected three weeks and two years after the Glass Fire (St. Helena, California, USA) to determine how wildfire affects the speciation and reactivity of iron (Fe) and manganese (Mn), two micronutrients that influence many soil processes. Synchrotron-based analyses revealed that wildfire generated stable Fe oxides like maghemite (γ-Fe 2 O 3 ) and hematite (α-Fe 2 O 3 ) that likely derived from surface soil or mineral dust rather than the vegetation, and Mn oxides such as hausmannite (Mn 3 O 4 ) and bixbyite (Mn 2 O 3 ) that derived primarily from aboveground biomass. However, these pyrogenic minerals were absent in soils collected two years after the fire. Their loss from the soil surface may result from a combination of erosion, translocation to deeper soil layers, and chemical weathering. The latter hypothesis is supported by the enhanced mobilization of Fe and Mn from ash upon the addition of pyoverdine, a model biogenic ligand. The increased mobility of micronutrients from fire-derived minerals in ash in response to microbial and root exudation may facilitate postfire soil and vegetation recovery.

bixbyite↗
DOE OSTI2021

Investigation of the Production of Trifluoroacetic Acid from Two Halocarbons, HFC-134a and HFO-1234yf and Its Fates Using a Global Three-Dimensional Chemical Transport Model

Trifluoroacetic acid (TFA), a highly soluble and stable organic acid, is photochemically produced by certain anthropogenically emitted halocarbons such as HFC-134a and HFO-1234yf. Both these halocarbons are used as refrigerants in the automobile industry, and the high global warming potential of HFC-134a has promoted regulation of its use. Industries are transitioning to the use of HFO-1234yf as a more environmentally friendly alternative. In this work, we investigated the environmental effects of this change and found a 33-fold increase in the global burden of TFA from an annual value of 65 tonnes formed from the 2015 emissions of HFC-134a to a value of 2220 tonnes formed from an equivalent emission of HFO-1234yf. The percentage increase in surface TFA concentrations resulting from the switch from HFC-134a to HFO-1234yf remains substantial with an increase of up to 250-fold across Europe. The increase in emissions greater than the current emission scenario of HFO-1234yf is likely to result in significant TFA burden as the atmosphere is not able to disperse and deposit relevant oxidation products. The Criegee intermediate initiated loss process of TFA reduces the surface level atmospheric lifetime of TFA by up to 5 days (from 7 days to 2 days) in tropical forested regions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Electrons and Their Multiple Kinetic Fates in an Ionic Liquid

Ionic liquids (ILs) for electrochemical, nuclear, and solar energy applications operate under harsh conditions, where electrons and transient radical species can form. This communication discusses why anions such as bis(trifluoromethylsulfonyl)imide (Tf 2 N − ) are reduced at the electron-rich electrode whereas in laser photoionization or pulse radiolysis studies, where electrons are ejected from species in the bulk, we often detect long-lived electrons in cavities that interact with IL cations instead. This work argues that bulk excess electrons generated photolytically or radiolytically follow kinetically favored pathways. As such, cavity electrons may not be the most energetically favorable states, but when they form, and they do form, they are kinetically stable. Reduction reactions of anions or electron localization in cavities and subsequent reactions are all expected outcomes. Here we focus on a pyrrolidinium-based IL of the dicyanamide (N(CN) 2 − ) anion because of its large electrochemical window and very low viscosity, which are ideal for energy applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Carbon Accumulation, Flux, and Fate in Stordalen Mire, a Permafrost Peatland in Transition

Abstract Stordalen Mire is a peatland in the discontinuous permafrost zone in arctic Sweden that exhibits a habitat gradient from permafrost palsa, to Sphagnum bog underlain by permafrost, to Eriophorum ‐dominated fully thawed fen. We used three independent approaches to evaluate the annual, multi‐decadal, and millennial apparent carbon accumulation rates (aCAR) across this gradient: seven years of direct semi‐continuous measurement of CO 2 and CH 4 exchange, and 21 core profiles for 210 Pb and 14 C peat dating. Year‐round chamber measurements indicated net carbon balance of −13 ± 8, −49 ± 15, and −91 ± 43 g C m −2 y −1 for the years 2012–2018 in palsa, bog, and fen, respectively. Methane emission offset 2%, 7%, and 17% of the CO 2 uptake rate across this gradient. Recent aCAR indicates higher C accumulation rates in surface peats in the palsa and bog compared to current CO 2 fluxes, but these assessments are more similar in the fen. aCAR increased from low millennial‐scale levels (17–29 g C m −2 y −1 ) to moderate aCAR of the past century (72–81 g C m −2 y −1 ) to higher recent aCAR of 90–147 g C m −2 y −1 . Recent permafrost collapse, greater inundation and vegetation response has made the landscape a stronger CO 2 sink, but this CO 2 sink is increasingly offset by rising CH 4 emissions, dominated by modern carbon as determined by 14 C. The higher CH 4 emissions result in higher net CO 2‐equivalent emissions, indicating that radiative forcing of this mire and similar permafrost ecosystems will exert a warming influence on future climate.

Holmes, M. E.↗
DOE OSTI2024

Nutrient Dynamics in a Coupled Terrestrial Biosphere and Land Model (ELM-FATES-CNP)

We present a representation of nitrogen and phosphorus cycling in the Functionally Assembled Terrestrial Ecosystem Simulator, a demographic vegetation model within the Energy Exascale Earth System land model. This representation is modular, and designed to allow testing of multiple hypothetical approaches for carbon-nutrient coupling in plants. Novel model hypotheses introduced in this work include, (a) the controls on plant acquisition of aqueous mineralized nutrients in the soil and (b) fairly straight forward methods of allocating nutrients to specific plant organs and their losses through live plant turnover as well as litter fluxes generated through plant mortality. This combines the new with pre-existing hypotheses (such as nitrogen fixation and soil decomposition) into a system that can accommodate plant-soil dynamics for a large number of size- and functional-type-resolved plant cohorts within a time-since-disturbance-resolved ecosystem. Root uptake of nutrients is governed by fine root biomass, and plants vary in their fine root biomass allocation in order to balance carbon and nutrient limitations to growth. We test the sensitivity of the model to a wide range of parameter variations and structural representations, and in the context of observations at Barro Colorado Island, Panama. A key model prediction is that plants in the high-light-availability canopy positions allocate more carbon to fine roots than plants in low-light understory environments, given the widely different carbon versus nutrient constraints of these two niches within a given ecosystem. This model provides a basis for exploring carbon-nutrient coupling with vegetation demography within Earth system models.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2026

Iron as a driver of organic carbon fate in permafrost regions

Iron (Fe) and its biogeochemical interactions with organic carbon (OC) exert critical controls over carbon storage and water quality across Arctic and sub-Arctic landscapes. Permafrost thaw affects Fe–organic carbon interactions by exposing thawed material and driving shifts in hydrologic regimes. Here we propose a conceptual framework describing how Fe–OC interactions respond to permafrost thaw and the implications for global carbon cycling. The framework builds on current understanding of hydrologically driven processes that are altered by permafrost thaw, including microbial Fe reduction that influences OC decomposition and carbon emissions; Fe cycling through redox transformations and sulfide oxidation; dissolution and reprecipitation of Fe–OC assemblages; and Fe export to river networks. We put forward four testable hypotheses—on topics from Fe supply to its role in soil OC storage and transfer to rivers—to advance understanding of the coupled environmental controls on pore-scale reactions (that is, microscale reactions at mineral–water–microorganism interfaces) that are central to global Fe–OC cycling. Our framework highlights how soil-profile- and landscape-scale processes, such as hydrologic connectivity and redox dynamics, regulate pore-scale Fe–OC reactions.

Herndon, Elizabeth [ORNL] (ORCID:0000000291945493)↗
DOE OSTI2023

Sources, seasonal cycling, and fate of plutonium in a seasonally stratified and radiologically contaminated pond

Unlike short-term laboratory experiments, studies at sites historically contaminated with radionuclides can provide insight into contaminant migration behavior at environmentally-relevant decadal timescales. One such site is Pond B, a seasonally stratified reservoir within Savannah River Site (SC, USA) has low levels (μBq L –1 ) of plutonium in the water column. Here, we evaluate the origin of plutonium using high-precision isotope measurements, investigate the impact of water column geochemistry on plutonium cycling during different stratification periods, and re-evaluate long-term mass balance of plutonium in the pond. New isotopic data confirm that reactor-derived plutonium overwhelms input from Northern Hemisphere fallout at this site. Two suggested mechanisms for observed plutonium cycling in the water column include: (1) reductive dissolution of sediment-derived Fe(III)-(oxyhydr)oxides during seasonal stratification and (2) plutonium stabilization complexed strongly to Fe(III)-particulate organic matter (POM) complexes. While plutonium may be mobilized to a limited extent by stratification and reductive dissolution, peak plutonium concentrations are in shallow waters and associated with Fe(III)-POM at the inception of stratification. This suggests that plutonium release from sediments during stratification is not the dominant mechanism driving plutonium cycling in the pond. Importantly, our analysis suggests that the majority is retained in shallow sediments and may become increasingly recalcitrant.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2024

A better fate for PVC

Here, a critical component of plastics waste, polyvinyl chloride, is tough to recycle efficiently and sustainably owing to its high chlorine content. Now, research shows how to convert polyvinyl chloride mixed with polypropylene, at room temperature, into chlorine-free hydrocarbons.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Kinetics of the benzyl + HO 2 and benzoxyl + OH barrierless association reactions: fate of the benzyl hydroperoxide adduct under combustion and atmospheric conditions

Radical–radical association reactions are challenging to address theoretically due to difficulties finding the bottleneck that variationally minimizes the reactive flux. For this purpose, the variable reaction coordinate (VRC) formulation of the variational transition state theory (VTST) represents an appropriate tool. Here, we revisited the kinetics of two radical–radical association reactions of importance in combustion modelling and poly-aromatic hydrocarbon (PAH) chemistry by performing VRC calculations: benzyl + HO 2 and benzoxyl + OH, both forming the adduct benzyl hydroperoxide. Our calculated rate constants are significantly lower than those previously reported based on VTST calculations, which results from a more efficient minimization of the reactive flux through the bottleneck achieved by the VRC formulation. Both reactions show different trends in the variation of their rate constants with temperature. We observed that if the pair of single occupied molecular orbitals (SOMOs) of the associating radicals show a similar nature, i.e. similar character, and thereby a small energy gap, a highly stabilized transition state structure is formed as the result of a very efficient SOMO–SOMO overlap, which may cancel out the free energy bottleneck for the formation of the adduct and result in large rate constants with a negative temperature dependence. This is the case of the benzoxyl and OH radical pair, whose SOMOs show O 2p nature with an energy gap of 20.2 kcal mol –1 . On the other hand, the benzyl and HO 2 radical pair shows lower rate constants with a positive temperature dependence due to the larger difference between both SOMOs (a 28.9 kcal mol –1 energy gap) as a consequence of the contribution of the multiple resonance structures of the benzyl radical. The reverse dissociation rate constants were also calculated using multi-structural torsional anharmonicity partition functions, which were not included in previous work, and the results show a much slower dissociation of benzyl hydroperoxide. Our work may help to improve kinetic models of interest in combustion and PAH formation, as well as to gain further understanding of radical–radical association reactions, which are ubiquitous in different environments.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Impact of ceiling fan and room air cleaner on air mixing and fate of particulate matter in a multiroom residence

We are exposed to airborne particles of health concern in residences, and Room Air Cleaners (RACs) can remove these particles. However, they are often limited to treating local air in the room or near vicinity of the device. RAC performance in multi-room residences may be improved by ceiling fan whole-house air mixing with a minor increase in energy use. Here, this study analyzed air quality and energy efficiency from experimental measurements using combinations of ceiling fan and RAC operation. We measured removal rates of tracer gas and particles from ultrafine to 5 µm after their release in the kitchen area of a multiroom test house. Results show that the air mixing by ceiling fans increased ultrafine and > 1 µm particle removal over the baseline – with no ceiling fans and no RAC – suggesting increased deposition onto the ceiling fan blades and house surfaces. Also, ceiling fan mixing increased particle removal in all size bins over the RAC performance with no ceiling fans. The removal rate with ceiling fans and the RAC was greater than the sum of the rates from each operating alone, indicating that synergistic interactions between the ceiling fans and the RAC increased the RAC filtration rate.

63 RADIATION, THERMAL, AND OTHER ENVIRON. POLLUTAN↗