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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 685 records · Page 38
All sourcesNASA NTRSDOE OSTI
DOE OSTI2016

Bioadsorption of rare earth elements through cell surface display of lanthanide binding tags

In this study, with the increasing demand for rare earth elements (REEs) in many emerging clean energy technologies, there is an urgent need for the development of new approaches for efficient REE extraction and recovery. As a step toward this goal, we genetically engineered the aerobic bacterium Caulobacter crescentus for REE adsorption through high-density cell surface display of lanthanide binding tags (LBTs) on its S-layer. The LBT-displayed strains exhibited enhanced adsorption of REEs compared to cells lacking LBT, high specificity for REEs, and an adsorption preference for REEs with small atomic radii. Adsorbed Tb 3+ could be effectively recovered using citrate, consistent with thermodynamic speciation calculations that predicted strong complexation of Tb 3+ by citrate. No reduction in Tb 3+ adsorption capacity was observed following citrate elution, enabling consecutive adsorption/desorption cycles. The LBT-displayed strain was effective for extracting REEs from the acid leachate of core samples collected at a prospective rare earth mine. Our collective results demonstrate a rapid, efficient, and reversible process for REE adsorption with potential industrial application for REE enrichment and separation.

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

Vanadium Geochemistry of Oil Sands Fluid Petroleum Coke

Vanadium has previously been linked to elevated toxicity of leachates derived from oil sands petroleum coke. However, geochemical controls on V mobility within coke deposits remain poorly constrained. Detailed examinations of porewater and solid-phase V geochemistry were therefore performed on oil sands fluid petroleum coke deposits in Alberta, Canada. Sample collection focused on both active and reclaimed deposits, which contained more than 3 × 10 7 m 3 of fluid petroleum coke. Dissolved V concentrations were highest (up to 3.0 mg L –1 ) immediately below the water table but decreased rapidly with increasing depth. This trend corresponded to a transition from mildly acidic (pH 6–7) and oxic conditions to mildly alkaline (pH 7–8.5) and anoxic conditions. Scanning electron microscopy (SEM), electron microprobe analysis (EMPA), and micro-X-ray fluorescence (μXRF) mapping revealed coke particles exhibited an internal structure characterized by successive concentric layers. Here, the outer margins of these layers were characterized by elevated V, Fe, Si, and Al concentrations, indicating the presence of inorganic phases. Micro-X-ray absorption near-edge structure (μXANES) spectroscopy revealed that V speciation was dominated by V(IV) porphyrins except at outer margins of layers, where octahedrally coordinated V(III) was a major component. Minor to trace V(V) was also detected within fluid petroleum coke particles.

58 GEOSCIENCES↗
DOE OSTI2017

Aerosol Emissions from Great Lakes Harmful Algal Blooms

In freshwater lakes, harmful algal blooms (HABs) of Cyanobacteria (blue-green algae) produce toxins that impact human health. However, little is known about the chemical species present in lake spray aerosol (LSA) produced from wave-breaking in freshwater HABs. In this study, a laboratory LSA generator produced aerosols from freshwater samples collected from Lake Michigan and Lake Erie during HAB and non-bloom conditions. Particles were analyzed for size and chemical composition by single particle mass spectrometry, electron microscopy, and fluorescence microscopy, with three distinct types of LSA identified with varying levels of organic carbon and biological material associated with calcium salts. LSA autofluorescence increases with blue-green algae concentration, showing that organic molecules of biological origin are incorporated in LSA from HABs. The number fraction of LSA with biological mass spectral markers also increases with particle diameter (greater than 0.5 μm), showing that HABs have size-dependent impacts on aerosol composition. The highest number fraction of LSA enriched in organic carbon were observed in particles less than 0.5 μm in diameter. Understanding the transfer of organic and biogenic material from freshwater to the atmosphere via LSA particles is crucial for determining health and climate effects due to HABs.

Environmental Molecular Sciences Laboratory↗
DOE OSTI2018

Real-Time XANES Measurement of Se Reduction by Zerovalent Iron in a Flow-through Cell, and Accompanying Se Isotope Measurements

An anoxic flow-through cell experiment was conducted to examine mechanisms controlling the real-time reduction of selenate (Se(VI)) by zerovalent iron (ZVI), which is commonly used in permeable reactive barriers to treat dissolved contaminants including Se(VI). Changes in selenium (Se) isotope composition were examined by increasing the influent Se concentration over time, thus changing the proportion of Se removed from solution. At the conclusion of the experiment, an anoxic Se-free solution was pumped through the cell to assess the stability of the reaction products. At all stages, X-ray absorption data were obtained from the solid phase and Se isotope data from the aqueous phase. Reduced Se in the form of adsorbed Se(IV), Fe 2 SeO 4 , Se(0), and iron selenides accumulated on the ZVI over time. A linear regression function was fit to the $δ$ 82/76 Se values of the effluent, yielding an isotopic separation of 9.6‰. A Rayleigh curve was fit to the isotope data from the effluent samples collected during the rinse stage with an effective fractionation of 2.4‰. The results from this experiment can be used to elucidate the effect of multiple concurrent mechanisms on Se isotope behavior.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Long-Term in Situ Reduction in Soil Lead Bioavailability Measured in a Mouse Model

In this study, effects of different treatments on the bioavailability of lead (Pb) in soil from a smelter emission contaminated site in Joplin, Missouri, were evaluated in a mouse model. Similar estimates of relative bioavailability for Pb in untreated or treated soil were obtained in mice and in the well-established juvenile swine model. In the mouse model, treatments that used phosphate (phosphoric acid or triple superphosphate) combined with iron oxide or biosolids compost significantly reduced soil Pb bioavailability. Notably, effects of these remediation procedures were persistent, given that up to 16 years had elapsed between soil treatment and sample collection. Remediation of soils was associated with changes in Pb species present in soil. Differences in Pb species in ingested soil and in feces from treated mice indicated that changes in Pb speciation occurred during transit through the gastrointestinal tract. Use of the mouse model facilitates evaluation of remediation procedures and allows monitoring of the performance of procedures under laboratory and field conditions.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2019

Online, real-time analysis of highly complex processing streams: Quantification of analytes in Hanford tank sample

Processing of hazardous materials is a crucial example of where on-line monitoring can significantly reduce operation risk, cost, and time. This is particularly true in the case of the Hanford site, where nuclear materials from the cold war era are being processed for environmental cleanup efforts. In exceedingly complex streams such as those at Hanford, on-line and real-time monitoring can be a challenge due to complexity of signals. Further obstacles are imposed by the caustic nature of processing streams as well as the radiation damage inflicted on instruments and probes. On-line monitoring based on Raman spectroscopy enables the detection of many Hanford tank species of interest, and was demonstrated here on nine chemical species that comprise the majority of tank waste by volume, including Al(OH)4-, C2O42-, CO32-, CrO42-, NO32-, NO3-, OH-, PO43-, SO42-. Real-time analysis of Raman signal allows for immediate quantification of target analytes and was successfully accomplished through the use of chemometric models. Furthermore, irradiation tests reveal Raman monitoring systems can effectively continue to operate even after receiving 1·107 Rad of gamma dose. The on-line, real-time monitoring system developed here was successfully used to simultaneously quantify nine target analytes in a real samples collected from Hanford tank AP-105.

Lines, Amanda M.↗
DOE OSTI2022

Bimetallic Metal–Organic Framework Fe/Co-MIL-88(NH 2 ) Exhibiting High Peroxidase-like Activity and Its Application in Detection of Extracellular Vesicles

Metal–organic frameworks (MOFs) have many attractive features, including tunable composition, rigid structure, controllable pore size, and large specific surface area, and thus are highly applicable in molecular analysis. Depending on the MOF structure, a high number of un-saturated metal sites can be exposed to catalyze chemical reactions. In the present work, we report that by using both Co(II) and Fe(III) to prepare the MIL-88(NH 2 ) MOF, we can produce the bimetallic MOF that can catalyze the conversion of 3,3', 5,5"-tetramethylbenzidine (TMB) to a color product through reaction with H 2 O 2 at a higher reaction rate than the monometallic Fe-MIL-88(NH 2 ). The Michaelis constants (K m ) of the catalytic reaction for TMB and H 2 O 2 are 3-5 times smaller, and the catalytic constants (k cat ) are 5-10 times higher than those of the horse-radish peroxidase (HRP), supporting ultrahigh peroxidase-like activity. These values are also much more superior to those of the HRP-mimicking MOFs reported previously. Interestingly, the bimetallic MOF can be coupled with glucose oxidase (GOx) to trigger the cascade enzymatic reaction for highly sensitive detection of extracellular vesicles (EVs), a family of important biomarkers. Through conjugation to the aptamer that recognizes the marker protein on EV surface, the MOF can help isolate the EVs from biological matrices, which are subsequently labeled by GOx via antibody recognition. The cascade enzymatic reaction between MOF and GOx enables detection of EVs at a concentration as low as 7.8 × 10 4 particles/ml. Further, the assay can be applied to monitor EV secretion by cultured cells, and also can successfully detect the different EV quantities in the sera samples collected from cancer patients and healthy controls. Overall, we prove that the bimetallic Fe/Co-MIL-88(NH 2 ) MOF, with its high peroxidase-activity and high biocompatibility, is a valuable tool deployable in clinical assays to facility disease diagnosis and prognosis.

36 MATERIALS SCIENCE↗
DOE OSTI2021

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

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

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

Dynamic Responses of Trace Metal Bioaccessibility to Fluctuating Redox Conditions in Wetland Soils and Stream Sediments

Natural aquatic systems undergo fluctuating redox conditions due to microbial activity, varying water saturation levels, and nutrients dynamics. With fluctuating redox conditions, trace metals can mobilize or sequester in response to changes in iron and sulfur speciation and the concentrations and lability of organic carbon. This study examined the effect of redox fluctuations on trace metal mobility in samples collected from two different natural aquatic systems: riparian wetlands and a stream. The wetland soils contained low sulfur and total Fe contents as compared to stream sediments. The mineral composition at both sites was dominated by quartz. We incubated water-saturated soils under three cycles of anoxic-oxic conditions (τanoxic:τoxic = 3) spanning 24 days and monitored the change in dissolved and bioavailable metal concentrations. For both natural systems, reduction of iron oxides under anoxic conditions caused Co and Zn release. In contrast, oxidation of sulfides mobilized Cu under oxic conditions in both sites. In wetland soils, dissolution of Fe (hydr)oxides increased Ni solubility; however, in stream sediments, Ni release occurred when sulfides or organic matter were oxidized. For stream sediments, each subsequent redox cycle increased the bioavailability of trace metals. Redox fluctuations in wetland soils increased bioavailable Zn and Cu and decreased bioavailable Ni and Co. This study illustrates that different trace metals display distinct bioavailability patterns during redox fluctuations in natural environments. The biogeochemical cycling of nutrients in systems with redox fluctuations may be influenced by these trace metal availability patterns in addition to the availability of electron donors and acceptors.

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

Functional Predictor Variables for the Leaching Potential of Arsenic and Selenium from Coal Fly Ash

The release of leachates from intact coal ash impoundments is a concern due to the enrichment and mobilization of toxic elements such as arsenic (As) and selenium (Se). This study aims to explore the intrinsic properties of coal fly ash that correlate with the relative leachability of As and Se. We performed leaching experiments with 52 fly ash samples collected from 15 different U.S. power plants and representing coal feedstocks from the three major domestic regions. We assessed the mobilization potential of As and Se in fly ash based on standardized leaching protocols and performed multivariate and lasso regression analyses to explore correlations of leachable As and Se contents with characteristics such as major element contents, loss on ignition, and pH. The results of regression models indicated that major elements (Fe, Ca, and Al) for a wide range of fly ashes can serve as predictor variables for the leaching potential of As but not for Se. LOI and pH were not important predictive variables in the models. Both regression approaches resulted in relatively strong fits for leachable As (correlation coefficient R 2 = 0.78 for both models) compared to models for leachable Se (R 2 = 0.49). Overall, these results suggest that correlation models combined with on-site elemental analysis with portable analyzers may enable a screening method for leachable As in coal ash.

01 COAL, LIGNITE, AND PEAT↗
DOE OSTI2015

Exploring the Nature of Cellulose Microfibrils

Ultrathin cellulose microfibril fractions were extracted from spruce wood powder using combined delignification, TEMPO-catalyzed oxidation, and sonication processes. Small-angle X-ray scattering of these microfibril fractions in a “dilute” aqueous suspension (concentration 0.077 wt %) revealed that their shape was in the form of nanostrip with 4 nm width and only about 0.5 nm thicknesses. We found that these dimensions were further confirmed by TEM and AFM measurements. The 0.5 nm thickness implied that the nanostrip could contain only a single layer of cellulose chains. At a higher concentration (0.15 wt %), SAXS analysis indicated that these nanostrips aggregated into a layered structure. The X-ray diffraction of samples collected at different preparation stages suggested that microfibrils were delaminated along the (110) planes from the Iβ cellulose crystals. Moreover, the degree of oxidation and solid-state 13 C NMR characterizations indicated that, in addition to the surface molecules, some inner molecules of microfibrils were also oxidized, facilitating the delamination into cellulose nanostrips.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2025

Functionalized Porous Polymer Networks as High-Performance PFAS Adsorbents

Toxic per- and polyfluoroalkyl substances (PFAS) are now found in nearly every water source on the planet. Exposure to these molecules can have negative health consequences, but the low concentration of PFAS relative to other solutes in water makes their removal challenging. Adsorbents offer a promising treatment route, but often exhibit low selectivities and removal capacities, as well as slow kinetics. The performance in these metrics can be improved by chemically optimizing PFAS binding sites and maximizing PFAS-adsorbent interactions. To explore how to achieve this, a porous polymer network solid (PPN-6, also known as PAF-1) was postsynthetically modified with various chemical moieties capable of leveraging unique combinations of electrostatic, hydrogen-bonding, hydrophobic, and fluorophilic interactions with PFAS molecules. Batch adsorption experiments and computational studies revealed that electrostatic and hydrogen-bonding interactions drive short-chain PFAS adsorption, while hydrophobic and fluorophilic interactions improve long-chain PFAS adsorption. In complex water matrices, a combination of electrostatic and fluorophilic interactions led to the greatest total PFAS removal. The best-performing material, functionalized with a fluorinated alkylammonium (PPN-6-FNDMB), selectively adsorbs PFAS with high capacity (up to 4.0 mmol/g) and rapid kinetics (equilibrium reached in <30 s). Furthermore, PPN-6-FNDMB outperforms several commercial adsorbents, achieving near-complete removal of 21 different PFAS from a groundwater sample collected at a US Air Force base. The PFAS could subsequently be desorbed from PPN-6-FNDMB, concentrating them by a factor of over 50 times. The recycled PPN-6-FNDMB could then be reused with minimal losses in long-chain PFAS adsorption capacity over four cycles.

Pezoulas, Ethan R↗
DOE OSTI2012

Discovery, Synthesis, And Structure-Based Optimization of a Series of N-(tert-Butyl)-2-(N-arylamido)-2-(pyridin-3-yl) Acetamides (ML188) as Potent Noncovalent Small Molecule Inhibitors of the Severe Acute Respiratory Syndrome Coronavirus (SARS-CoV) 3CL Protease

A high-throughput screen of the NIH molecular libraries sample collection and subsequent optimization of a lead dipeptide-like series of severe acute respiratory syndrome (SARS) main protease (3CLpro) inhibitors led to the identification of probe compound ML188 (16-(R), (R)-N-(4-(tert-butyl)phenyl)-N-(2-(tert-butylamino)-2-oxo-1-(pyridin-3-yl)ethyl)furan-2-carboxamide, Pubchem CID: 46897844). But, unlike the majority of reported coronavirus 3CLpro inhibitors that act via covalent modification of the enzyme, 16-(R) is a noncovalent SARS-CoV 3CLpro inhibitor with moderate MW and good enzyme and antiviral inhibitory activity. A multicomponent Ugi reaction was utilized to rapidly explore structure–activity relationships within S1', S1, and S2enzyme binding pockets. Moreover, the X-ray structure of SARS-CoV 3CLpro bound with 16-(R) was instrumental in guiding subsequent rounds of chemistry optimization. 16-(R) provides an excellent starting point for the further design and refinement of 3CLpro inhibitors that act by a noncovalent mechanism of action.

Jacobs, Jon↗
DOE OSTI2018

Investigation of Liquid Cloud Microphysical Properties of Deep Convective Systems: 2. Parameterization of Raindrop Size Distribution and its Application for Convective Rain Estimation

The liquid cloud microphysical properties for stratiform rain (SR) have been investigated in Part 1 of this series. Since convective rain (CR) has characteristics in raindrop size distribution (DSD) and precipitation that are distinct from SR, we investigate the CR properties in this study by using 20 hr of CR samples collected by 17 Automatic Parsivel Units disdrometers during the Midlatitude Continental Convective Clouds Experiment over the Atmospheric Radiation Measurement Southern Great Plains site. A full spectrum of DSD is constructed based on a total of 23 size channels (0.321 to 9.785 mm), and both Gamma and Exponential fitted functions are applied to extract the DSD shape parameters. Compared to SR properties, CR has distinct features including broader size range and narrower exponential slope parameter (λ E ). These results indicate that the assumption of constant exponential intercept parameter ( N 0E ) is inappropriate for CR rain rate estimates. Additionally, the subsetting scheme of the CR DSD spectra also has a strong impact on the Gamma/Exponential functions. Therefore, a new CR DSD parameterization scheme is developed by choosing the appropriate spectra subset with the constraint of rain rate and using the constant λ E instead of constant N 0E . With the input of the radar reflectivity at the lowest observed height, the newly calculated CR rain rates match well with the collocated surface rain gauge measurements (127 Mesonet stations and 17 Automatic Parsivel Units), while the rain rates calculated using traditional Z-R relationship are 3–4 times larger, indicating that constant λ E is a better assumption for CR DSD.

58 GEOSCIENCES↗
DOE OSTI2020

Surface Methane Concentrations Along the Mid-Atlantic Bight Driven by Aerobic Subsurface Production Rather Than Seafloor Gas Seeps

Relatively minor amounts of methane, a potent greenhouse gas, are currently emitted from the oceans to the atmosphere, but such methane emissions have been hypothesized to increase as oceans warm. Here, we investigate the source, distribution, and fate of methane released from the upper continental slope of the U.S. Mid-Atlantic Bight, where hundreds of gas seeps have been discovered between the shelf break and ~1,600 m water depth. Using physical, chemical, and isotopic analyses, we identify two main sources of methane in the water column: seafloor gas seeps and in situ aerobic methanogenesis which primarily occurs at 100–200 m depth in the water column. Stable isotopic analyses reveal that water samples collected at all depths were significantly impacted by aerobic methane oxidation, the dominant methane sink in this region, with the average fraction of methane oxidized being 50%. Due to methane oxidation in the deeper water column, below 200 m depth, surface concentrations of methane are influenced more by methane sources found near the surface (0–10 m depth) and in the subsurface (10–200 m depth), rather than seafloor emissions at greater depths.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2022

Latitude, Elevation, and Mean Annual Temperature Predict Peat Organic Matter Chemistry at a Global Scale

Peatlands contain a significant fraction of global soil carbon, but how these reservoirs will respond to the changing climate is still relatively unknown. A global picture of the variations in peat organic matter chemistry will aid our ability to gauge peatland soil response to climate. Here, the goal of this research is to test the hypotheses that (a) peat carbohydrate content, an indicator of soil organic matter reactivity, will increase with latitude and decrease with mean annual temperatures, (b) while peat aromatic content, an indicator of recalcitrance, will vary inversely, and (c) elevation will have a similar effect to latitude. We used Fourier Transform Infrared Spectroscopy to examine variations in the organic matter functional groups of 1034 peat samples collected from 10 to 20, 30–40, and 60–70 cm depths at 165 individual sites across a latitudinal gradient of 79°N–65°S and from elevations of 0–4,773 m. Carbohydrate contents of high latitude peat were significantly greater than peat originating near the equator, while aromatic content showed the opposite trend. For peat from similar latitudes but different elevations, the carbohydrate content was greater and aromatic content was lower at higher elevations. Higher carbohydrate content at higher latitudes indicates a greater potential for mineralization, whereas the chemical composition of low latitude peat is consistent with their apparent relative stability in the face of warmer temperatures. The combination of low carbohydrates and high aromatics at warmer locations near the equator suggests the mineralization of high latitude peat until reaching recalcitrance under a new temperature regime.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2021

Concentration‐Discharge Relationships of Dissolved Rhenium in Alpine Catchments Reveal Its Use as a Tracer of Oxidative Weathering

Abstract Oxidative weathering of sedimentary rocks plays an important role in the global carbon cycle. Rhenium (Re) has been proposed as a tracer of rock organic carbon (OC petro ) oxidation. However, the sources of Re and its mobilization by hydrological processes remain poorly constrained. Here, we examine dissolved Re as a function of water discharge, using samples collected from three alpine catchments that drain sedimentary rocks in Switzerland (Erlenbach and Vogelbach) and Colorado, USA (East River). The Swiss catchments reveal a higher dissolved Re flux in the catchment with higher erosion rates, but have similar [Re]/[Na + ] and [Re]/[SO 4 2− ] ratios, which indicate a dominance of Re from OC petro . Despite differences in rock type and hydro‐climatic setting, the three catchments have a positive correlation between river water [Re]/[Na + ] and [Re]/[SO 4 2− ] and water discharge. We propose that this reflects preferential routing of Re from a near‐surface, oxidative weathering zone. The observations support the use of Re as a proxy to trace rock‐organic carbon oxidation, and suggest it may be a hydrological tracer of vadose zone processes. We apply the Re proxy and estimate CO 2 release by OC petro oxidation of 5.7 +6.6 / −2.0 tC km −2 yr −1 for the Erlenbach. The overall weathering intensity was ∼40%, meaning that the corresponding export of unweathered OC petro in river sediments is large, and the findings call for more measurements of OC petro oxidation in mountains and rivers as they cross floodplains.

54 ENVIRONMENTAL SCIENCES↗