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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 1,027 records · Page 57
All sourcesNASA NTRSDOE OSTI
DOE OSTI2010

Mechanism for the abiotic synthesis of uracil via UV-induced oxidation of pyrimidine in pure H{sub 2}O ices under astrophysical conditions

The UV photoirradiation of pyrimidine in pure H{sub 2}O ices has been explored using second-order Moeller-Plesset perturbation theory and density functional theory methods, and compared with experimental results. Mechanisms studied include those starting with neutral pyrimidine or cationic pyrimidine radicals, and reacting with OH radical. The ab initio calculations reveal that the formation of some key species, including the nucleobase uracil, is energetically favored over others. The presence of one or several water molecules is necessary in order to abstract a proton which leads to the final products. Formation of many of the photoproducts in UV-irradiated H{sub 2}O:pyrimidine=20:1 ice mixtures was established in a previous experimental study. Among all the products, uracil is predicted by quantum chemical calculations to be the most favored, and has been identified in experimental samples by two independent chromatography techniques. The results of the present study strongly support the scenario in which prebiotic molecules, such as the nucleobase uracil, can be formed under abiotic processes in astrophysically relevant environments, namely in condensed phase on the surface of icy, cold grains before being delivered to the telluric planets, like Earth.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2010

Sigma Team for Minor Actinide Separation: PNNL FY 2010 Status Report

Work conducted at Pacific Northwest National Laboratory (PNNL) in FY 2010 addressed two lines of inquiry. The two hypotheses put forth were: 1. The extractants from the TRUEX( ) process (CMPO)( ) and from the TALSPEAK( ) process (HDEHP)( ) can be combined into a single process solvent to separate 1) the lanthanides and actinides from acidic high-level waste and 2) the actinides from the lanthanides in a single solvent extraction process. (Note: This combined process will hereafter be referred to as the TRUSPEAK process.) A series of empirical measurements performed (both at PNNL and Argonne National Laboratory) in FY 2009 supported this hypothesis, but also indicated some nuances to the chemistry. Lanthanide/americium separation factors of 12 and higher were obtained with a prototypic TRUSPEAK solvent when extracting the lanthanides from a citrate-buffered DTPA( ) solution. Although the observed separation factors are sufficiently high to design an actinide/lanthanide separation process, a better understanding of the chemistry is expected to lead to improved solvent formulations and improved process performance. Work in FY 2010 focused on understanding the synergistic extraction behavior observed for Nd(III) and Am(III) when extracted into mixtures of CMPO and HDEHP. The interaction between CMPO and HDEHP in dodecane was investigated by 31P NMR spectroscopy, and an adduct of the type CMPO•HDEHP was found to form. The formation of this adduct will reduce the effective extractant concentrations and must be taken into account when modeling metal ion extraction data in this system. Studies were also initiated to determine the Pitzer parameters for Nd(III) in lactate media. 2. Higher oxidation states (e.g., +5 and +6) of Am can be stabilized in solution by complexation with uranophilic ligands, and this chemistry can be exploited to separate Am from Cm. To test this hypothesis, the previously reported stereognostic uranophilic ligands NPB( ) and ETAC(e) were investigated. To assess the potential of these ligands to stabilize pentavalent and hexavalent actinides, stability constants were measured for complexation of these ligands to Nd(III), Np(V), and Pu(VI) in a solvent mixture consisting of 80% methanol/20% water. For comparison, an analogous non-stereognostic ligand, NTA,(f) was also examined. The ligand ETAC showed greater binding affinity for hexavalent Pu versus trivalent Nd by two orders-of-magnitude. Such selectivity was not observed for either NTA or NPB.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2011

Clay-sewage sludge co-pyrolysis. A TG-MS and Py-GC study on potential advantages afforded by the presence of clay in the pyrolysis of wastewater sewage sludge

Wastewater sewage sludge was co-pyrolyzed with a well characterized clay sample, in order to evaluate possible advantages in the thermal disposal process of solid waste. Characterization of the co-pyrolysis process was carried out both by thermogravimetric-mass spectrometric (TG-MS) analysis, and by reactor tests, using a lab-scale batch reactor equipped with a gas chromatograph for analysis of the evolved gas phase (Py-GC). Due to the presence of clay, two main effects were observed in the instrumental characterization of the process. Firstly, the clay surface catalyzed the pyrolysis reaction of the sludge, and secondly, the release of water from the clay, at temperatures of approx. 450-500 deg. C, enhanced gasification of part of carbon residue of the organic component of sludge following pyrolysis. Moreover, the solid residue remaining after pyrolysis process, composed of the inorganic component of sludge blended with clay, is characterized by good features for possible disposal by vitrification, yielding a vitreous matrix that immobilizes the hazardous heavy metals present in the sludge.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2011

Alteration of municipal solid waste incineration bottom ash focusing on the evolution of iron-rich constituents

Municipal solid waste incineration (MSWI) bottom ash contains a considerable amount of Fe-rich constituents. The behaviors of these constituents, such as dissolution and precipitation, are quite important as they regulate the distribution of a series of ions between the liquid (percolated fluid) and solid (ash deposit) phases. This paper studied both fresh and weathered MSWI bottom ash from the mineralogical and geochemical viewpoint by utilizing optical microscopy, scanning electron microscopy/energy dispersive X-ray spectroscopy (SEM/EDX), and powder X-ray diffraction. The analysis results revealed that for the fresh bottom ash, iron preferentially existed in the chemical forms of spinel group (mainly Fe{sub 3}O{sub 4}, and a series of Al- or Ti- substituted varieties), metallic inclusions (including Fe-P, Fe-S, Fe-Cu-Pb), hematite (Fe{sub 2}O{sub 3}) and unburned iron pieces. In the 1-20 years weathered bottom ash collected from a landfill site, interconversions among these Fe-rich constituents were identified. Consequently, numerous secondary products were developed, including goethite ({alpha}-FeOOH), lepidocrocite ({gamma}-FeOOH), hematite, magnetite, wustite (FeO), Fe-Si-rich gel phase. Of all these transformation products, hydrous iron oxides were the most common secondary minerals. Quantitative chemical analysis of these secondary products by SEM/EDX disclosed a strong association between the newly formed hydrous iron oxides and heavy metals (e.g. Pb, Zn, Ni, and Cu). The results of this study suggest that the processes of natural weathering and secondary mineralization contribute to reduction of the potential risks of heavy metals to the surrounding environments.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2013

Fabrication of Pd/Pd-Alloy Films by Surfactant Induced Electroless Plating for Hydrogen Separation from Advanced Coal Gasification Processes

Dense Pd, Pd-Cu and Pd-Ag composite membranes on microporous stainless steel substrate (MPSS) were fabricated by a novel electroless plating (EP) process. In the conventional Pd-EP process, the oxidation-reduction reactions between Pd-complex and hydrazine result in an evolution of NH 3 and N 2 gas bubbles. When adhered to the substrate surface and in the pores, these gas bubbles hinder uniform Pd-film deposition which results in dendrite growth leading to poor film formation. This problem was addressed by introducing cationic surfactant in the electroless plating process known as surfactant induced electroless plating (SIEP). The unique features of this innovation provide control of Pd-deposition rate, and Pd-grain size distribution. The surfactant molecules play an important role in the EP process by tailoring grain size and the process of agglomeration by removing tiny gas bubbles through adsorption at the gas-liquid interface. As a result surfactant can tailor a nanocrystalline Pd, Cu and Ag deposition in the film resulting in reduced membrane film thickness. Also, it produces a uniform, agglomerated film structure. The Pd-Cu and Pd-Ag membranes on MPSS support were fabricated by sequential deposition using SIEP method. The pre- and post-annealing characterizations of these membranes (Pd, Pd-Cu and Pd-Ag on MPSS substrate) were carried out by SEM, EDX, XRD, and AFM studies. The SEM images show significant improvement of the membrane surface morphology, in terms of metal grain structures and grain agglomeration compared to the membranes fabricated by conventional EP process. The SEM images and helium gas-tightness studies indicate that dense and thinner films of Pd, Pd-Cu and Pd-Ag membranes can be produced with shorter deposition time using surfactant. H 2 Flux through the membranes fabricated by SIEP shows large improvement compared to those by CEP with comparable permselectivity. Pd-MPSS composite membrane was subjected to test for long term performance and thermal cycling (573 - 723 - 573 K) at 15 psi pressure drop for 1200 hours. Pd membranes showed excellent hydrogen permeability and thermal stability during the operational period. Under thermal cycling (573 K - 873 K - 573 K), Pd-Cu-MPSS membrane was stable and retained hydrogen permeation characteristics for over three months of operation. From this limited study, we conclude that SIEP is viable method for fabrication of defect-free, robust Pd-alloy membranes for high-temperature H 2 -separation applications.

08 HYDROGEN↗
DOE OSTI2012

Comparison of different procedures to stabilize biogas formation after process failure in a thermophilic waste digestion system: Influence of aggregate formation on process stability

Highlights: Black-Right-Pointing-Pointer Mechanism of process recovery with calcium oxide. Black-Right-Pointing-Pointer Formation of insoluble calcium salts with long chain fatty acids and phosphate. Black-Right-Pointing-Pointer Adsorption of VFAs by the precipitates resulting in the formation of aggregates. Black-Right-Pointing-Pointer Acid uptake and phosphate release by the phosphate-accumulating organisms. Black-Right-Pointing-Pointer Microbial degradation of volatile fatty acids in the aggregates. - Abstract: Following a process failure in a full-scale biogas reactor, different counter measures were undertaken to stabilize the process of biogas formation, including the reduction of the organic loading rate, the addition of sodium hydroxide (NaOH), and the introduction of calcium oxide (CaO). Corresponding to the results of the process recovery in the full-scale digester, laboratory experiments showed that CaO was more capable of stabilizing the process than NaOH. While both additives were able to raise the pH to a neutral milieu (pH > 7.0), the formation of aggregates was observed particularly when CaO was used as the additive. Scanning electron microscopy investigations revealed calcium phosphate compounds in the core of the aggregates. Phosphate seemed to be released by phosphorus-accumulating organisms, when volatile fatty acids accumulated. The calcium, which was charged by the CaO addition, formed insoluble salts with long chain fatty acids, and caused the precipitation of calcium phosphate compounds. These aggregates were surrounded by a white layer of carbon rich organic matter, probably consisting of volatile fatty acids. Thus, during the process recovery with CaO, the decrease in the amount of accumulated acids in the liquid phase was likely enabled by (1) the formation of insoluble calcium salts with long chain fatty acids, (2) the adsorption of volatile fatty acids by the precipitates, (3) the acid uptake by phosphorus-accumulating organisms and (4) the degradation of volatile fatty acids in the aggregates. Furthermore, this mechanism enabled a stable process performance after re-activation of biogas production. In contrast, during the counter measure with NaOH aggregate formation was only minor resulting in a rapid process failure subsequent the increase of the organic loading rate.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2011

Valorisation of forestry waste by pyrolysis in an auger reactor

Pyrolysis of forestry waste has been carried out in an auger reactor to study the influence of operational variables on the reactor performance and the properties of the related products. Pine woodchips were used for the first time as raw material and fed continuously into the reactor. Ten experiments were carried out under inert atmosphere at: (i) different reaction temperature (1073, 973, 873, 823 and 773 K); (ii) different solid residence time (5, 3, 2 and 1.5 min); and (iii) different biomass flow rate (3.9, 4.8 and 6.9 kg/h). Results show that the greatest yields for liquid production (59%) and optimum product characterisation were obtained at the lowest temperature studied (773 K) and applying solid residence times longer than 2 min. Regarding bio-oil properties, GC/MS qualitative identification show that the most abundant compounds are volatile polar compounds, phenols and benzenediols; and very few differences can be observed among the samples regardless of the pyrolysis operating conditions. On the whole, experimental results demonstrate that complete reaction of forest woodchips can be achieved in an auger reactor in most of the experimental conditions tested. Moreover, this study presents the initial steps for the future scaling up of the auger reactor with the aim of converting it into a mobile plant which will be able to remotely process biomass such as energy crops, forestry and agricultural wastes to obtain bio-oil that, in turn, can be used as energy vector to avoid high transport costs.

09 BIOMASS FUELS↗
DOE OSTI2012

Characterization of cellulosic wastes and gasification products from chicken farms

Highlights: Black-Right-Pointing-Pointer The gas chromatography indicated the variable quality of the producer gas. Black-Right-Pointing-Pointer The char had appreciable NPK values, and can be used as a fertiliser. Black-Right-Pointing-Pointer The bio-oil produced was of poor quality, having high moisture content and low pH. Black-Right-Pointing-Pointer Mass and energy balances showed inadequate level energy recovery from the process. Black-Right-Pointing-Pointer Future work includes changing the operating parameters of the gasification unit. - Abstract: The current article focuses on gasification as a primary disposal solution for cellulosic wastes derived from chicken farms, and the possibility to recover energy from this process. Wood shavings and chicken litter were characterized with a view to establishing their thermal parameters, compositional natures and calorific values. The main products obtained from the gasification of chicken litter, namely, producer gas, bio-oil and char, were also analysed in order to establish their potential as energy sources. The experimental protocol included bomb calorimetry, pyrolysis combustion flow calorimetry (PCFC), thermo-gravimetric analyses (TGA), differential scanning calorimetry (DSC), Fourier transform infrared (FT-IR) spectroscopy, Raman spectroscopy, elemental analyses, X-ray diffraction (XRD), mineral content analyses and gas chromatography. The mass and energy balances of the gasification unit were also estimated. The results obtained confirmed that gasification is a viable method of chicken litter disposal. In addition to this, it is also possible to recover some energy from the process. However, energy content in the gas-phase was relatively low. This might be due to the low energy efficiency (19.6%) of the gasification unit, which could be improved by changing the operation parameters.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2010

Lithium ions in the van der Waals gap of Bi{sub 2}Se{sub 3} single crystals

Insertion/extraction of lithium ions into/from Bi{sub 2}Se{sub 3} crystals was investigated by means of cyclic voltammetry. The process of insertion is reflected in the appearance of two bands on voltammograms at {approx}1.7 and {approx}1.5 V, corresponding to the insertion of Li{sup +} ions into octahedral and tetrahedral sites of the van der Waals gap of these layered crystals. The process of extraction of Li{sup +} ions from the gap results in the appearance of four bands on the voltammograms. The bands 1 and 2 at {approx}2.1 and {approx}2.3 V correspond to the extraction of a part of Li{sup +} guest ions from the octahedral and tetrahedrals sites and this extraction has a character of a reversible intercalation/deintercalation process. A part of Li{sup +} ions is bound firmly in the crystal due to the formation of negatively charged clusters of the (LiBiSe{sub 2}.Bi{sub 3}Se{sub 4}{sup -}) type. A further extraction of Li{sup +} ions from the van der Waals gap is associated with the presence of bands 3 and 4 placed at {approx}2.5 and {approx}2.7 V on the voltammograms as their extraction needs higher voltage due to the influence of negative charges localized on these clusters. -- Graphical abstract: Insertion/extraction of lithium ions into/from Bi{sub 2}Se{sub 3} layered crystals was investigated by cyclic voltammetry. The extraction of Li{sup +} results in the appearance of four bands on the voltammograms. The first two bands have a character of a reversible process. A part of Li{sup +} ions is bound firmly in the crystal due to the formation of negatively charged clusters of the (LiBiSe{sub 2}.Bi{sub 3}Se{sub 4}{sup -}) type. Their extraction needs higher voltage due to the negative charge. Display Omitted

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

Effect of Entropic Constraints on the Thermodynamics of Molecular Adsorption in Nano‐Porous Materials

Abstract Gas separation is a critical industrial process that consumes a significant amount of energy due to the widely used techniques that are currently employed. Adsorptive materials—such as metal–organic frameworks (MOFs)—show promise as an energy‐efficient alternative. Of particular current interest are novel, temperature‐dependent separation processes in MOFs, such as the recently reported separation of ternary isomeric hydrocarbon mixtures within one and the same material. However, the mechanisms of these highly desirable separations remain poorly understood. Herein, through a combination of ab initio simulations and statistical mechanics, it is shown that the temperature dependence is the result of a constraint on the guest molecule's entropic degrees of freedom when loaded into the MOF, caused by the fortuitous tight fitting of the guest inside the pore. While the framework applies to all molecular adsorption in porous media, it is essential for the description of large molecules in small pores, which is demonstrated here using the separation of C6 isomers in Ca(H 2 tcpb) as a test case. The developed framework and analysis not only reveal the reason why separation occurs but also predict the temperatures at which it takes place, thus opening the door to newly designed MOFs with tailor‐made precision.

Chemistry↗
DOE OSTI2016

Characterization of Sr-90 Drums at the Hanford 618-10 Burial Ground - 16132

The 618-10 Burial Ground on the Hanford Reservation was an early trench waste site used for the disposal of waste from the 300 Area at Hanford. Much of this waste consisted of residues from evaluations of failed fuel as well as various process and separations studies associated with the Department of Energy (DOE) mission which were performed in the 300 Area between March 1954 and September 1963. Historical records indicated that there were also several drums which contained significant quantities of separated Sr-90. Cleanup of the 618-10 burial ground is covered under the Washington Closure Hanford (WCH) contract. Due to the proximity of the 618-10 site to the Columbia River, waste is being removed from the 618-10 site, stabilized, and disposed of into either the Environmental Restoration Disposal Facility (ERDF) if the containers are determined to be LLW or transferred to the Hanford Central Waste Complex (CWC) if the containers are suspected to be TRU waste. In order to determine the correct disposal path, Non Destructive Assay (NDA) must be performed on all of the containers excavated from the trenches. The NDA of these containers is performed using germanium gamma spectroscopy with an In Situ Object Counting System (ISOCS) and with a neutron slab counter. Occasional ISOCS spectra exhibited a characteristic Sr-90/Y-90 Bremsstrahlung continuum. In some cases there were measurable gammas present, however in other cases only the Bremsstrahlung continuum was present. Typically Sr-90 is correlated to Cs-137 as they are normally produced in approximately a 1:1 ratio during the fission process. For some of these drums there was no Cs-137 detectable and therefore no way to quantify the Sr-90. Due to concerns about providing a reasonable and conservative nuclide inventory it was decided to evaluate a technique to utilize data from the Bremsstrahlung continuum to quantify the Sr-90 activity in these drums. The development of the technique combined MCNP modeling and comparison of measured gammas to the continuum for a well-defined waste stream. The final result showed reasonable correlation to the expected scaling factors for many drums, while also providing a reasonable measured value for drums with significantly enhanced Sr-90 concentrations. Ultimately all drums were demonstrated to be within the ERDF waste acceptance criteria. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2011

Reducing volatilization of heavy metals in phosphate-pretreated municipal solid waste incineration fly ash by forming pyromorphite-like minerals

This research investigated the feasibility of reducing volatilization of heavy metals (lead, zinc and cadmium) in municipal solid waste incineration (MSWI) fly ash by forming pyromorphite-like minerals via phosphate pre-treatment. To evaluate the evaporation characteristics of three heavy metals from phosphate-pretreated MSWI fly ash, volatilization tests have been performed by means of a dedicated apparatus in the 100-1000 deg. C range. The toxicity characteristic leaching procedure (TCLP) test and BCR sequential extraction procedure were applied to assess phosphate stabilization process. The results showed that the volatilization behavior in phosphate-pretreated MSWI fly ash could be reduced effectively. Pyromorphite-like minerals formed in phosphate-pretreated MSWI fly ash were mainly responsible for the volatilization reduction of heavy metals in MSWI fly ash at higher temperature, due to their chemical fixation and thermal stabilization for heavy metals. The stabilization effects were encouraging for the potential reuse of MSWI fly ash.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2010

Assessment of the long-term stability of cementitious barriers of radioactive waste repositories by using digital-image-based microstructure generation and reactive transport modelling

Cement-based grout plays a significant role in the design and performance of nuclear waste repositories: used correctly, it can enhance their safety. However, the high water-to-binder ratios, which are required to meet the desired workability and injection ability at early age, lead to high porosity that may affect the durability of this material and undermine its long-term geochemical performance. In this paper, a new methodology is presented in order to help the process of mix design which best meets the compromise between these two conflicting requirements. It involves the combined use of the computer programs CEMHYD3D for the generation of digital-image-based microstructures and CrunchFlow, for the reactive transport calculations affecting the materials so simulated. This approach is exemplified with two grout types, namely, the so-called Standard mix 5/5, used in the upper parts of the structure, and the 'low-pH' P308B, to be injected at higher depths. The results of the digital reconstruction of the mineralogical composition of the hardened paste are entirely logical, as the microstructures display high degrees of hydration, large porosities and low or nil contents of aluminium compounds. Diffusion of solutes in the pore solution was considered to be the dominant transport process. A single scenario was studied for both mix designs and their performances were compared. The reactive transport model adequately reproduces the process of decalcification of the C-S-H and the precipitation of calcite, which is corroborated by empirical observations. It was found that the evolution of the deterioration process is sensitive to the chemical composition of groundwater, its effects being more severe when grout is set under continuous exposure to poorly mineralized groundwater. Results obtained appear to indicate that a correct conceptualization of the problem was accomplished and support the assumption that, in absence of more reliable empirical data, it might constitute a useful tool to estimate the durability of cement-based structures.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2011

Treatment of exhaust fluorescent lamps to recover yttrium: Experimental and process analyses

Highlights: > Recovery of yttrium from spent fluorescent lamps by sulphuric acid leaching. > The use of sulphuric acid allows to reduce calcium dissolutions. > Main contaminant of fluorescent powder are Si, Pb, Ca and Ba. > Hydrated yttrium oxalate, recovered by selective precipitation, is quite pure (>90%). > We have studied the whole process for the treatment of dangerous waste (plant capability). - Abstract: The paper deals with recovery of yttrium from fluorescent powder coming from dismantling of spent fluorescent tubes. Metals are leached by using different acids (nitric, hydrochloric and sulphuric) and ammonia in different leaching tests. These tests show that ammonia is not suitable to recover yttrium, whereas HNO{sub 3} produces toxic vapours. A full factorial design is carried out with HCl and H{sub 2}SO{sub 4} to evaluate the influence of operating factors. HCl and H{sub 2}SO{sub 4} leaching systems give similar results in terms of yttrium extraction yield, but the last one allows to reduce calcium extraction with subsequent advantage during recovery of yttrium compounds in the downstream. The greatest extraction of yttrium is obtained by 20% w/v S/L ratio, 4 N H{sub 2}SO{sub 4} concentration and 90 deg. C. Yttrium and calcium yields are nearly 85% and 5%, respectively. The analysis of variance shows that acid concentration alone and interaction between acid and pulp density have a significant positive effect on yttrium solubilization for both HCl and H{sub 2}SO{sub 4} medium. Two models are empirically developed to estimate yttrium and calcium concentration during leaching. Precipitation tests demonstrate that at least the stoichiometric amount of oxalic acid is necessary to recover yttrium efficiently and a pure yttrium oxalate n-hydrate can be produced (99% grade). The process is economically feasible if other components of the fluorescent lamps (glass, ferrous and non-ferrous scraps) are recovered after the equipment dismantling and valorized, besides the cost that is usually paid to recycling companies for collection, treatment or final disposal of such fluorescent powders.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2013

Verification of the Accountability Method as a Means to Classify Radioactive Wastes Processed Using THOR Fluidized Bed Steam Reforming at the Studsvik Processing Facility in Erwin, Tennessee, USA - 13087

Studsviks' Processing Facility Erwin (SPFE) has been treating Low-Level Radioactive Waste using its patented THOR process for over 13 years. Studsvik has been mixing and processing wastes of the same waste classification but different chemical and isotopic characteristics for the full extent of this period as a general matter of operations. Studsvik utilizes the accountability method to track the movement of radionuclides from acceptance of waste, through processing, and finally in the classification of waste for disposal. Recently the NRC has proposed to revise the 1995 Branch Technical Position on Concentration Averaging and Encapsulation (1995 BTP on CA) with additional clarification (draft BTP on CA). The draft BTP on CA has paved the way for large scale blending of higher activity and lower activity waste to produce a single waste for the purpose of classification. With the onset of blending in the waste treatment industry, there is concern from the public and state regulators as to the robustness of the accountability method and the ability of processors to prevent the inclusion of hot spots in waste. To address these concerns and verify the accountability method as applied by the SPFE, as well as the SPFE's ability to control waste package classification, testing of actual waste packages was performed. Testing consisted of a comprehensive dose rate survey of a container of processed waste. Separately, the waste package was modeled chemically and radiologically. Comparing the observed and theoretical data demonstrated that actual dose rates were lower than, but consistent with, modeled dose rates. Moreover, the distribution of radioactivity confirms that the SPFE can produce a radiologically homogeneous waste form. The results of the study demonstrate: 1) the accountability method as applied by the SPFE is valid and produces expected results; 2) the SPFE can produce a radiologically homogeneous waste; and 3) the SPFE can effectively control the waste package classification. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2011

NON-RACEMIC AMINO ACID PRODUCTION BY ULTRAVIOLET IRRADIATION OF ACHIRAL INTERSTELLAR ICE ANALOGS WITH CIRCULARLY POLARIZED LIGHT

The delivery of organic matter to the primitive Earth via comets and meteorites has long been hypothesized to be an important source for prebiotic compounds such as amino acids or their chemical precursors that contributed to the development of prebiotic chemistry leading, on Earth, to the emergence of life. Photochemistry of inter/circumstellar ices around protostellar objects is a potential process leading to complex organic species, although difficult to establish from limited infrared observations only. Here we report the first abiotic cosmic ice simulation experiments that produce species with enantiomeric excesses (e.e.'s). Circularly polarized ultraviolet light (UV-CPL) from a synchrotron source induces asymmetric photochemistry on initially achiral inter/circumstellar ice analogs. Enantioselective multidimensional gas chromatography measurements show significant e.e.'s of up to 1.34% for ({sup 13}C)-alanine, for which the signs and absolute values are related to the helicity and number of CPL photons per deposited molecule. This result, directly comparable with some L excesses measured in meteorites, supports a scenario in which exogenous delivery of organics displaying a slight L excess, produced in an extraterrestrial environment by an asymmetric astrophysical process, is at the origin of biomolecular asymmetry on Earth. As a consequence, a fraction of the meteoritic organic material consisting of non-racemic compounds may well have been formed outside the solar system. Finally, following this hypothesis, we support the idea that the protosolar nebula has indeed been formed in a region of massive star formation, regions where UV-CPL of the same helicity is actually observed over large spatial areas.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2010

Protective or damage promoting effect of calcium carbonate layers on the surface of cement based materials in aqueous environments

Cement based materials permanently exposed to aggressive aqueous environments are subject to chemical changes affecting their durability. However, this holds also for tap water that is considered to be not aggressive to cementitious materials, although in that case a formation of covering layers of CaCO{sub 3} on the alkaline surfaces is commonly supposed to provide protection against reactive transport processes. Thus, investigations of the structural and chemical properties of the material/water interface were carried out in laboratory experiments and case studies to elucidate the consequences of surface reactions for the durability of cement based materials exposed to tap water. Focused Ion Beam investigations revealed that a protective effect of a CaCO{sub 3} covering layer depends on its structural properties, which are in turn affected by the hydro-chemical conditions during crystallization. Surface precipitation of CaCO{sub 3} can trigger further chemical degradation, if the required calcium is supplied by the pore solution of the material.

36 MATERIALS SCIENCE↗