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At least 667 records · Page 37

TPR investigations on the reducibility of Cu supported on Al{sub 2}O{sub 3}, zeolite Y and SAPO-5

Reducibility of Cu supported on Al{sub 2}O{sub 3}, zeolite Y and silicoaluminophosphate SAPO-5 has been investigated in dependence on the Cu content using a method combining conventional temperature programmed reduction (TPR) by hydrogen with reoxidation in N{sub 2}O followed by a second the so-called surface-TPR (s-TPR). The method enables discrimination and a quantitative estimation of the Cu oxidation states +2, +1 and 0. The quantitative results show that the initial oxidation state of Cu after calcination in air at 400 deg. C, independent on the nature of the support, is predominantly +2. Cu{sup 2+} supported on Al{sub 2}O{sub 3} is quantitatively reduced by hydrogen to metallic Cu{sup 0}. Comparing the TPR of the samples calcined in air and that of samples additionally pre-treated in argon reveals that in zeolite Y and SAPO-5 Cu{sup 2+} cations are stabilized as weakly and strongly forms. In both systems, strongly stabilized Cu{sup 2+} ions are not auto-reduced by pre-treatment in argon at 650 deg. C, but are reduced in hydrogen to form Cu{sup +}. The weakly stabilized Cu{sup 2+} ions, in contrast, may be auto-reduced by pre-treatment in argon at 650 deg. C forming Cu{sup +} but are reduced in hydrogen to metallic Cu{sup 0}. - Graphical Abstract: TPR, TPR-(act), s-TPR and s-TPR-(act) profiles of (1.36)Cu/SAPO-5 (A), (4.55)Cu/SAPO-5 (B) and (9.19)Cu/SAPO-5 (C) samples. The intensities of TCD signals in (A) and (B) are multiplied by 4.5 and 2, respectively. Highlights: > Cu supported on SAPO-5, alumina and zeolite Y was investigated by TPR and s-TPR. > Cu oxidation states can be discriminated and quantitatively determined. > In zeolite Y and SAPO-5 Cu{sup 2+} cations are stabilized at weak and strong forms. > Strongly stabilized Cu{sup 2+} cannot be auto-reduced in argon at 650 deg. C.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Propene Metathesis over Supported Tungsten Oxide Catalysts: A Study of Active Site Formation

A detailed investigation was conducted on the factors influencing the properties of silica-supported tungsten oxide catalysts for propene metathesis. A principal goal of this work was to identify the processes involved in the formation of catalytically active sites. To probe the influence of dispersion, samples were prepared across a range of W loadings using two methods of catalyst preparation: incipient wetness impregnation of amorphous silica and ion exchange of mesoporous SBA-15. The samples were characterized by nitrogen adsorption, UV-vis, Raman, and X-ray absorption spectroscopy (XAS). Catalytic activity was observed to increase with W surface concentration up to the point where WO 3 nanoparticles formed. The catalytic performance of all samples was enhanced 2-fold by pretreatment in He, in comparison to pretreatment in air. In situ characterization of samples pretreated in He by Raman and XAS shows an increase in the relative concentration of isolated dioxo W(6+) species relative to mono-oxo W(6+) species, and in situ XAS data collected during propene metathesis indicated that a similar conversion occurs for air-pretreated samples in the presence of propene. For both air- and He-pretreated catalysts an activation period was observed, during which the activity increased and attained steady-state activity. This period was significantly longer for air-pretreated catalysts and was accompanied by the transient formation of acetone. While acetone was not observed during the much shorter transient of He-pretreated samples, in situ XAS provided evidence of reduction occurring in these samples upon contact with propene. In conclusion, it is also notable that, independent of the manner of catalyst preparation or pretreatment, the rate of propene metathesis is first order in propene and exhibits an activation energy of 200 kJ/mol. A model is proposed to explain why only a fraction of the isolated tungstate species is active for propene metathesis (~5%) and why this fraction increases with increasing concentration of W dispersed on silica.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Airborne Observations of Carbon Dioxide and Methane Emission Ratios from the Yosemite Rim Wildfire, California

This paper presents airborne in situ measurements of carbon dioxide (CO2) and methane (CH4) downwind of an exceptionally large wildfire, the Rim Fire, near Yosemite, California, during two flights. Data analyses are discussed in terms of emission ratios (ER) and emission factors (EF) and are compared to previous studies. CH4 ER’s were 7.5-7.9 parts per billion (ppb) CH4 for every 1 part per million (ppm) of CO2 (ppb CH4 (ppm CO2)(exp.-1)) on 29 August 2013 and 14.2-16.7 ppb CH4 (ppm CO2)(exp. -1) on 10 September 2013. This study measured only CO2 and CH4; however, estimated emission factors (EEF’s) are used as rough estimates of EF’s of CO2 and CH4 and are in close agreement with EF’s reported in previous studies. In the western US, wildfires dominate over prescribed fires, contributing to atmospheric trace gas budgets and regional and local air pollution. Limited sampling of emissions from wildfires means western US emission estimates rely largely on data from prescribed fires, which may not be a suitable proxy for wildfire emissions. Given the magnitude of the Yosemite Rim wildfire, the impacts it had on regional air quality and the limited sampling of wildfire emissions in the western US to date, this study provides a valuable measurement dataset and may have important implications for forestry and regional air quality management.

Yates, Emma L.↗

Investigation of Ion-Irradiated Beryllium Carbide (Be 2 C) for High-Temperature Nuclear Reactor Moderators

Beryllium carbide (Be 2 C) is an attractive alternative to graphite as a moderator material because of its high melting point, moderating efficiency, and theoretical environmental compatibility in MSRs, FHRs and HTGRs. However, its behavior under neutron irradiation is not yet known. Research on otherwise promising beryllium compounds are restricted because of the toxic nature of the material. For this work, a novel experiment was designed to safely irradiate beryllium-containing samples at The Michigan Ion Beam Laboratory (MIBL). Using this new capability, Be 2 C samples were irradiated with 9 MeV C 3+ ions from 2 dpa to 30 dpa, at temperatures up to 500 °C. Samples were characterized to investigate radiation tolerance. No evidence of phase precipitation, dislocation loops, or amorphization was observed up to 30 dpa, suggesting good radiation tolerance. One sample left in air for ~3 months oxidized slowly and lost structural integrity, while a sample kept in argon did not, suggesting that Be 2 C is not suitable for service in moist environments, but maintains its integrity in dry environments.

22 - GENERAL STUDIES OF NUCLEAR REACTORS↗

SR19021 Tritium Aging of Regenerated LANA.75 (Final Project Report)

The Savannah River Tritium Enterprise (SRTE) has used the metal hydride LaNi 4.25 Al 0.75 (LANA.75) in the Tritium Facilities for over two decades. LANA.75 beds store significant quantities of tritium but have a limited service life due to the radiolytic decay of tritium to He-3 within the metal matrix. It has been shown that heating tritium-aged LANA.75 under vacuum can reverse tritium aging effects, eliminating the heel of trapped hydrogen, and restoring the reversible capacity. Additional investigation is needed to ensure there are no unexpected changes to the hydride before this restoration technique is employed in full scale beds in the Tritium Facilities. This project was to be comprised of three distinct scopes: obtain tritium aging data on the sample regenerated in 2018, regenerate a tritium-aged sample at 600 °C, and perform thermal stability testing on a non-tritiated sample. Isotherms were collected on the previously regenerated sample after approximately two years of tritium aging. Isotherms were collected at 80, 100, and 120 °C. As expected, there was a decrease in the plateau pressure, an increase in plateau slope, and a portion of the “heel” of tritium trapped in the metal had been reestablished. Unexpectedly, it appeared that the plateau had shortened at the higher tritium to metal ratios as well. This is typically seen in older samples. The second scope, to regenerate a second tritium-aged LANA.75 sample, was not completed. A Task Technical and Quality Assurance Plan was written and approved, a high temperature test cell was fabricated, several pre-job briefs were held, and the hydride sample was passivated with air. Despite these successes, the hydride sample was not recovered from the legacy test cell. The third scope was to perform thermal stability testing on a “cold” LANA.75 sample. A non-tritiated sample of LANA.75 was held at 750 °C under vacuum for 200 hours to simulate exposure to multiple regeneration evolutions. Hydride isotherm performance, chemical composition, crystallinity, particle size, and morphology are compared between the pre- and post-regeneration samples. No significant changes were observed in composition, crystallinity, or particle size. Comparison of before and after isotherms showed that performance improved rather than deteriorated during the evolution. Scanning Electron Microscopy (SEM) analysis showed small growths on the particle surface after exposure to regeneration conditions. Additional testing will be required to determine the cause of these growths.

07 ISOTOPE AND RADIATION SOURCES↗

Venturi air-jet vacuum ejectors for high-volume atmospheric sampling on aircraft platforms

Documentation of the installation and use of venturi air-jet vacuum ejectors for high-volume atmospheric sampling on aircraft platforms is presented. Information on the types of venturis that are useful for meeting the pumping requirements of atmospheric-sampling experiments is also presented. A description of the configuration and installation of the venturi system vacuum line is included with details on the modifications that were made to adapt a venturi to the NASA Electra aircraft at GSFC, Wallops Flight Facility. Flight test results are given for several venturis with emphasis on applications to the Differential Absorption Carbon Monoxide Measurement (DACOM) system at LaRC. This is a source document for atmospheric scientists interested in using the venturi systems installed on the NASA Electra or adapting the technology to other aircraft.

Hill, Gerald F.↗

Effects of Humidity on Aerosols in Southern Africa during the Biomass Burning Season

Measurements of the aerosol total light scattering coefficient, asp, and the aerosol hemispheric backscatter ratio, p(1), as functions of relative humidity (RH in %) (so-called humidographs) at three wavelengths (450,550, and 700 nm) were obtained in the dry season in southern Africa (1) in ambient air in South Africa, Botswana, Mozambique and Zambia, (2) at various distances downwind in identifiable smoke plumes from biomass fires, and (3) along the southwest coast of Africa. The ratio of sigma(sub sp) at an RH of 80% to that at 30% provides a measure of the effects of RH on sigma(sub sp), and similarly for Beta(1). For the three broad sampling categories given above, and at a wavelength of 550 nm, these ratios varied from 1.42 +/- 0.05 to 2.07 +/- 0.03 for sigma(sub sp), and from 0.69 +/- 0.05 to 0.99 +/- 0.14 for Beta(1). In general, humidographs for the ambient air samples showed a greater dependence on RH than those for smoke from identifiable biomass fires. During a period when dense, aged smoke was transported to the region from the north, the humidographs for sigma(sub sp) for ambient air samples were similar to those for identifiable smoke plume samples just approximately 10- to 50-min old. This suggests that as far as the effects of RH on sigma(sub sp) are concerned the effects of aging of smoke and its mixing with ambient air are realized within less than about an hour.

Magi, Brian I.↗

Vertical profiles of CO and CH4 in the lower and middle troposphere over the Eastern United States January 1978

Samples of tropospheric air were obtained over the Eastern United States during January of 1978. These samples were analyzed by gas chromatography using flame ionization detection to produce vertical profiles of carbon monoxide and methane from the surface to 8 km. The carbon monoxide mixing ratios at 35 deg N and 45 deg N agree with previously published values; however, the mixing ratio at 25 deg N was significantly lower than most published values. The methane mixing ratio was weakly dependent on latitude and has an average value of 1.64 ppm.

Reichle, H. G., Jr.↗

Infrared spectra of crystalline and glassy silicates and application to interstellar dust

The infrared spectra of crystalline minerals predicted in theoretical condensation sequences do not match the astronomical observations. Since the astronomical spectra are a closer match to glassy silicates, the authors undertook a study to measure the infrared spectra of glassy silicates that have compositions similar to silicate minerals predicted in theoretical condensation sequences. The data should support observations aimed at elucidating condensation chemistry in dust forming regions. The authors measured the mass absorption coefficients, from 2.5 to 25 microns, of ground samples of olivine, diopside, and serpentine and also smoke samples that were prepared from these minerals. The smoke samples prepared in this way are predominantly glassy with nearly the same composition as the parent minerals. The crystalline samples consisted of pure olivine ((Fe(0.1)Mg(0.9))(2)SiO(4)), serpentine, diopside. Sample purity was confirmed by x ray diffraction. Each mineral was ground for 10 hours and a measured mass of the powder was mixed with KBr powder for absorption measurements using the method of Borghesi et a. (1985). The smoke samples were prepared from the same samples used for grinding by vaporizing the minerals using pulsed laser radiation in air. The smoke samples formed by condensation of the resulting vapor. The smoke settled onto infrared transparent KRS-5 substrates and onto a quartz crystal microbalance used to obtain mass measurements. A description of the preparation method is given in Stephens (1980). The glassy diopside showed only diffuse electron diffraction peaks and hence was nearly amorphous, while the serpentine smoke showed a weak diffraction pattern corresponding to MgO. The smoke from olivine showed a weak diffraction pattern corresponding to Fe2O3 and/or Fe3O4. The mass absorption coefficients, from 2.5 to 25 microns, of crystalline diopside, olivine, and serpentine and their corresponding smoke samples are shown in figures.

Stephens, John R.↗

Estimating Sampling Biases and Measurement Uncertainties of AIRS-AMSU-A Temperature and Water Vapor Observations Using MERRA Reanalysis

We use MERRA (Modern Era Retrospective-Analysis for Research Applications) temperature and water vapor data to estimate the sampling biases of climatologies derived from the AIRS/AMSU-A (Atmospheric Infrared Sounder/Advanced Microwave Sounding Unit-A) suite of instruments. We separate the total sampling bias into temporal and instrumental components. The temporal component is caused by the AIRS/AMSU-A orbit and swath that are not able to sample all of time and space. The instrumental component is caused by scenes that prevent successful retrievals. The temporal sampling biases are generally smaller than the instrumental sampling biases except in regions with large diurnal variations, such as the boundary layer, where the temporal sampling biases of temperature can be +/- 2 K and water vapor can be 10% wet. The instrumental sampling biases are the main contributor to the total sampling biases and are mainly caused by clouds. They are up to 2 K cold and greater than 30% dry over mid-latitude storm tracks and tropical deep convective cloudy regions and up to 20% wet over stratus regions. However, other factors such as surface emissivity and temperature can also influence the instrumental sampling bias over deserts where the biases can be up to 1 K cold and 10% wet. Some instrumental sampling biases can vary seasonally and/or diurnally. We also estimate the combined measurement uncertainties of temperature and water vapor from AIRS/AMSU-A and MERRA by comparing similarly sampled climatologies from both data sets. The measurement differences are often larger than the sampling biases and have longitudinal variations.

MERRA↗

Diurnal Differences in OLR Climatologies and Anomaly Time Series

AIRS (Atmospheric Infrared Sounder) Version-6 OLR (Outgoing Long-Wave Radiation) matches CERES (Clouds and the Earth's Radiant Energy System) Edition-2.8 OLR very closely on a 1x1 latitude x longitude scale, both with regard to absolute values, and also with regard to anomalies of OLR. There is a bias of 3.5 watts per meter squared, which is nearly constant both in time and space. Contiguous areas contain large positive or negative OLR difference between AIRS and CERES are where the day-night difference of OLR is large. For AIRS, the larger the diurnal cycle, the more likely that sampling twice a day is inadequate. Lower values of OLRclr (Clear Sky OLR) and LWCRF (Longwave Cloud Radiative Forcing) in AIRS compared to CERES is at least in part a result of AIRS sampling over cold and cloudy cases.

Anomaly Time Series↗

Direct in-situ observation of early age void evolution in sustainable cement paste containing fly ash or limestone

This paper uses fast X-ray Computed Tomography (fCT) to study the change in air-filled voids during hydration of portland cement pastes of different water to cement ratios and with fly ash and limestone additives between 30 min and 12 h of hydration with deionized and de-aired water. For the deionized samples, the total volume of the air-filled voids increased during the induction period and decreased as the acceleration period began and finally stayed constant. The samples with 20% replacement of fly ash and 20% replacement of limestone showed the same trends as the OPC samples but with a reduction in the observed air-filled void formation. The air-filled void distribution in these samples changed from a limited number of large voids at the beginning of the measurements to a system with a significantly greater number of uniformly distributed smaller voids. The changes in the air-filled voids were not significant in pastes made with 50% fly ash or with de-aired water in the same testing condition. This might be explained by differences in pore solution chemistry and a reduced amount of dissolved air in the mixing water. A mechanism is proposed for a change in ionic concentration in solution to cause release of the dissolved air within the mixing water.

Cement hydration↗

Investigation of Nano-Mechanical and- Tribological Properties of Hydrogenated Diamond Like Carbon (DLC) Coatings

Abstract Hydrogenated diamond like Carbon (H-DLC) is a promising lubricious coating that attracted a great deal of interest in recent years mainly because of its outstanding tribological properties. In this study, the nano-mechanical and -tribological properties of a range of H-DLC films were investigated. Specifically, four kinds of H-DLC coatings were produced on Si substrates in pure acetylene, pure methane, 25% methane + 75% hydrogen, 50% methane + 50% hydrogen discharge plasmas using a plasma enhanced chemical vapour deposition (PECVD) system. Nano indentation was performed to measure the mechanical properties such as hardness and young's modulus and nanoscartching was performed to investigate the frictional behavior and wear mechanism of the H-DLC samples in open air. Moreover, Vickers indentation method was utilized to assess the fracture toughness of the samples. The results revealed that there is a strong correlation between the mechanical properties (hardness, young's modulus, fracture toughness) and the friction coefficient of DLC coatings and the source gas chemistry. Lower hydrogen to carbon ratio in source gas leads to higher hardness, young's modulus, fracture toughness and lower friction coefficient. Furthermore, lower wear volume of the coated materials was observed when the friction coefficient was lower. It was also confirmed that lower hydrogen content of the DLC coating leads to higher wear resistance under nanoscratch conditions.

Fracture toughness↗

Fate and transport of contaminants at soils sites - 15512

As part of the Soils Activity of the Environmental Management Operations at the NNSA, Nevada Field Office, radionuclide-contaminated Soils sites will undergo regulatory closure in accordance with the 1996 Nevada Federal Facilities Agreement and Consent Order. One closure alternative that has been evaluated for each Soils site has been -closure-in-place- with fencing and posting, along with administrative controls. However, potential disturbance agents for radionuclide-contaminated soils left in place are possible erosion and transport by wind and water. Previous work with radionuclide-contaminated soils has indicated that the highest activity levels of Pu tend to be found in the fine sands, silts, or clays, which are the most likely particle sizes to be transported by wind re-suspension, and by runoff flow events. Monitoring and sampling stations have been deployed at specific Soils sites to collect meteorological data, airborne particulate filter samples, and both suspended and bed-load sediment transport samples during and after runoff flow events, as needed. The primary objective of the air monitoring and sampling stations is to evaluate whether there is wind transport of radionuclide-contaminated soils from Soils sites. The primary objective of the precipitation and runoff flow data collection, as well as both suspended and bed-load sediment sampling, is to determine during which rainfall events (i.e., precipitation return interval, duration, and intensity) radionuclide-contaminated soils are likely to be transported. The NNSS continues to demonstrate compliance with US DOE Order 458.1 for the Radiation Protection of the Public and the Environment, as reported in annual environmental reports. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Idaho National Laboratory Site Environmental Surveillance Program Report: Third Quarter 2023

This report for the third quarter of 2023 contains results from the INL Site environmental surveillance program’s monitoring of the U.S. Department of Energy’s Idaho National Laboratory (INL) Site’s onsite, boundary and offsite location environment, July 1 through September 30, 2023. All sample types (media) and the sampling schedule followed during 2023 are listed in Appendix A. This report contains results for the following sample types: (1) Air, including particulate air filters, charcoal cartridges, and atmospheric moisture; (2) Precipitation; (3) Surface water; (4) Milk; (5) Agricultural; and (6) Large game animal sampling.

54 ENVIRONMENTAL SCIENCES↗