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At least 433 records · Page 24

Low-Temperature Pd/Zeolite Passive NO x Adsorbers: Structure, Performance, and Adsorption Chemistry

Pd/zeolite passive NOx adsorber (PNA) materials were prepared with solution ion-exchange between NH4/zeolites (Beta, ZSM-5 and SSZ-13) and PdCl2 solutions. The nature of Pd (dispersion, distribution and oxidation states) in these materials was characterized with Na+ ion-exchange, TEM imaging, CO titration with FTIR and in situ XPS. The NOx trapping and release properties were tested using feeds with different compositions. It is concluded that multiple Pd species coexist in these materials: atomically dispersed Pd in the cationic sites of zeolites, and PdO2 and PdO particles on the external surfaces. While Pd is largely atomically dispersed in ZSM-5, the small pore opening for SSZ-13 inhibits Pd diffusion such that the majority of Pd stays as external surface PdO2 clusters. NOx trapping and release are not simple chemisorption and desorption events, but involve rather complex chemical reactions. In the absence of CO in the feed, cationic Pd(II) sites with oxygen ligands and PdO2 clusters are reduced by NO to Pd(I) and PdO clusters. These reduced sites are the primary NO adsorption sites. In the presence of H2O, the as-formed NO2 desorb immediately. In the presence of CO in the feed, metallic Pd, “naked” Pd2+, and Pd+ sites are responsible for NO adsorption. For Pd adsorption sites with the same oxidation states but in different zeolite frameworks, NO binding energies are not expected to vary greatly. However, NO release temperatures do vary substantially with different zeolite structures. This indicates that NO transport within these materials play an important role in determining release temperatures. Finally, some rational design principles on efficient PNA materials are suggested. The authors gratefully acknowledge the US Department of Energy (DOE), Energy Efficiency and Renewable Energy, Vehicle Technologies Office for the support of this work. The research described in this paper was performed in the Environmental Molecular Sciences Laboratory (EMSL), a national scientific user facility sponsored by the DOE’s Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory (PNNL). PNNL is operated for the US DOE by Battelle. Discussions with Drs. A. Yezerets, J.Y. Luo, K. Kamasamudram and N. Currier Cummins, Inc., and H.Y. Chen from Johnson-Matthey are greatly appreciated.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Ion Mobility Spectrometry Characterization of the Intermediate Hydrogen-Containing Gold Cluster Au7(PPh3)7H52+

We employ ion mobility spectrometry and density functional theory to determine the structure of Au7(PPh3)7H52+ (PPh3 = triphenylphosphine) which was recently identified by high mass resolution mass spectrometry. Experimental ion-neutral collision cross sections represent the momentum transfer between the ionic clusters and gas molecules averaged over the relative thermal velocities of the colliding pair, thereby providing structural insights. Theoretical calculations indicate the geometry of Au7(PPh3)7H52+ is similar to Au7(PPh3)7+, with three hydrogen atoms bridging two gold atoms and two hydrogen atoms forming single Au–H bonds. Collision induced dissociation products observed during IMS experiments reveal that smaller hydrogen containing clusters may be produced through fragmentation of Au7(PPh3)7H52+. Our findings indicate that hydrogen containing species like Au7(PPh3)7H52+ act as intermediates in the formation of larger phosphine ligated gold clusters. These results advance the understanding and ability to control the mechanisms of size selective cluster formation which is necessary for scalable synthesis of clusters with tailored properties. This work was supported by the U.S. Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences. M.A.H. acknowledges support from the DOE Science Undergraduate Laboratory Internship (SULI) program. H.H. acknowledges support from the DOE Office of Workforce Development for Teachers and Scientist (WDTS) under the Visiting Faculty Program (VFP). The efforts of K.A.M. and B.H.C. were supported by the Defense Threat Reduction Agency (Grant No. HDTRA1-14-1-0023). The research was performed using EMSL, a national scientific user facility sponsored by the DOE’s Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory (PNNL). PNNL is operated by Battelle for DOE under Contract DE-AC05-76RL01830.

Ligare, Marshall R.↗

Iron loading effects in Fe/SSZ-13 NH3-SCR catalysts: nature of the Fe-ions and structure-function relationships

Using a traditional aqueous solution ion-exchange method under a protecting atmosphere of N2, a series of Fe/SSZ-13 catalysts with various Fe loadings were synthesized. UV-Vis, EPR and Mössbauer spectroscopies, coupled with temperature programmed reduction and desorption techniques, were used to probe the nature of the Fe sites. The major monomeric and dimeric Fe species are extra-framework [Fe(OH)2]+ and [HO-Fe-O-Fe-OH]2+. Larger oligomers with unknown nuclearity, poorly crystallized Fe2O3 particles, together with isolated Fe2+ ions, are minor Fe-containing moieties. Reaction rate and Fe loading correlations suggest that isolated Fe3+ ions are the active sites for standard SCR while the dimeric sites are the active centers for NO oxidation. NH3 oxidation, on the other hand, is catalyzed by sites with higher nuclearity. A low-temperature standard SCR reaction network is proposed that includes redox cycling of both monomeric and dimeric Fe species, for SCR and NO2 generation, respectively. The authors gratefully acknowledge the US Department of Energy (DOE), Energy Efficiency and Renewable Energy, Vehicle Technologies Program for the support of this work. The research described in this paper was performed at the Environmental Molecular Sciences Laboratory (EMSL), a national scientific user facility sponsored by the DOE’s Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory (PNNL). PNNL is operated for the US DOE by Battelle.

Environmental Molecular Sciences Laboratory↗

Transformation of Active Sites in Fe/SSZ-13 SCR Catalysts during Hydrothermal Aging: A Spectroscopic, Microscopic, and Kinetics Study

Fe/SSZ-13 catalysts (Si/Al = 12, Fe loadings 0.37% and 1.20%) were prepared via solution ion-exchange, and hydrothermally aged at 600, 700 and 800 C. The fresh and aged catalysts were characterized with surface area/pore volume analysis, Mössbauer, solid-state MAS NMR, NO titration FTIR spectroscopies, and TEM and APT imaging. Hydrothermal aging causes dealumination of the catalysts, and transformation of various Fe sites. The latter include conversion of free Fe2+ ions to dimeric Fe(III) species, the agglomeration of isolated Fe-ions to Fe-oxide clusters, and incorporation of Al into the Fe-oxide species. These changes result in complex influences on standard SCR and NO/NH3 oxidation reactions. In brief, mild aging causes catalyst performance enhancement for SCR, while harsh aging at 800 C deteriorates SCR performance. In comparison to Fe/zeolites more prone to hydrothermal degradation, this study demonstrates that via the utilization of highly hydrothermally stable Fe/SSZ-13 catalysts, more accurate correlations between various Fe species and their roles in SCR related chemistries can be made. The authors gratefully acknowledge the US Department of Energy (DOE), Energy Efficiency and Renewable Energy, Vehicle Technologies Office for the support of this work. The research described in this paper was performed in the Environmental Molecular Sciences Laboratory (EMSL), a national scientific user facility sponsored by the DOE’s Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory (PNNL). PNNL is operated for the US DOE by Battelle.

Environmental Molecular Sciences Laboratory↗

Toward Rational Design of Cu/SSZ-13 Selective Catalytic Reduction Catalysts: Implications from Atomic-Level Understanding of Hydrothermal Stability

The hydrothermal stability of Cu/SSZ-13 SCR catalysts has been extensively studied, yet atomic level understanding of changes to the zeolite support and the Cu active sites during hydrothermal aging are still lacking. In this work, via the utilization of spectroscopic methods including solid-state 27Al and 29Si NMR, EPR, DRIFTS, and XPS, together with imaging and elemental mapping using STEM, detailed kinetic analyses, and theoretical calculations with DFT, various Cu species, including two types of isolated active sites and CuOx clusters, were precisely quantified for samples hydrothermally aged under varying conditions. This quantification convincingly confirms the exceptional hydrothermal stability of isolated Cu2+-2Z sites, and the gradual conversion of [Cu(OH)]+-Z to CuOx clusters with increasing aging severity. This stability difference is rationalized from the hydrolysis activation barrier difference between the two isolated sites via DFT. Discussions are provided on the nature of the CuOx clusters, and their possible detrimental roles on catalyst stability. Finally, a few rational design principles for Cu/SSZ-13 are derived rigorously from the atomic-level understanding of this catalyst obtained here. The authors gratefully acknowledge the US Department of Energy (DOE), Energy Efficiency and Renewable Energy, Vehicle Technologies Office for the support of this work. Computing time was granted by a user proposal at the William R. Wiley Environmental Molecular Sciences Laboratory (EMSL) and by the National Energy Research Scientific Computing Center (NERSC). The experimental studies described in this paper were performed in the EMSL, a national scientific user facility sponsored by the DOE’s Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory (PNNL). PNNL is operated for the US DOE by Battelle.

Cu/SSZ-13↗

Using Transient FTIR Spectroscopy to Probe Active Sites and Reaction Intermediates for Selective Catalytic Reduction of NO on Cu/SSZ-13 Catalysts

A Cu/SSZ-13 catalyst containing predominately Z2Cu sites is prepared. Using diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), two non-steady state measurements, (1) continuous NO titration of an NH3 saturated catalyst and (2) intermittent NO on/off during quasi-steady state (i.e., NO perturbation), are conducted to shed light on active sites, reaction intermediates, and possible reaction mechanisms. During continuous NO titration, a strong NH3 inhibition effect is found, where Cu active sites containing NH3 ligands are less active than Cu sites depleted of NH3 ligands. In the NO perturbation experiments, it is demonstrated that NO+NH3 interactions lead to formation of Brønsted acid sites, which further interact with NH3 to form NH4+. Such a finding is fully consistent with a redox SCR mechanism proposed recently (Angew. Chem. Int. Ed. 2014, 53, 11828–11833). Perturbation measurements, using ND3 to replace NH3 in order to distinguish ammonia and nitrate vibrations, further show that NH4NO3 and other surface nitrates are not involved in the SCR process under typical low temperature quasi-steady state conditions. This work was financially supported by the national key research and development program of China (2017YFC0211302 and 2017YFC0211003), the Sino Japanese cooperation project (2016YFE0126600) and the China Postdoctoral Science Foundation (2017M620800). FG and CHFP gratefully acknowledge financial support for their participation from the US Department of Energy (DOE), Energy Efficiency and Renewable Energy, Vehicle Technologies Office. A portion of this work was performed in the Environmental Molecular Sciences Laboratory (EMSL), a national scientific user facility sponsored by the DOE’s Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory (PNNL). PNNL is operated for the US DOE by Battelle.

Cu, SSZ-13, SCR, DRIFTS, transient kinetics, mecha↗

Synthesis and Evaluation of Cu-SAPO-34 Catalysts for Ammonia Selective Catalytic Reduction. 1. Aqueous Solution Ion Exchange

SAPO-34 molecular sieves are synthesized using various structure directing agents (SDAs). Cu-SAPO-34 catalysts are prepared via aqueous solution ion exchange. Catalysts are characterized with surface area/pore volume measurements, temperature programmed reduction (TPR), electron paramagnetic resonance (EPR) and nuclear magnetic resonance (NMR) spectroscopies. Catalytic properties are examined using standard ammonia selective catalytic reduction (NH3-SCR) and ammonia oxidation reactions. During solution ion exchange, different SAPO-34 samples undergo different extent of structural damage via irreversible hydrolysis. Si content within the samples (i.e., Al-O-Si bond density) and framework stress are key factors that affect irreversible hydrolysis. Even using very dilute Cu acetate solutions, it is not possible to generate Cu-SAPO-34 samples with only isolated Cu2+ ions. Small amounts of CuOx species always coexist with isolated Cu2+ ions. Highly active and selective Cu-SAPO-34 catalysts for NH3-SCR are readily generated using this synthesis protocol, even for SAPO-34 samples that degrade substantially during solution ion exchange. High-temperature aging is found to improve the catalytic performance. This is likely due to reduction of intracrystalline mass-transfer limitations via formation of additional porosity in the highly defective SAPO-34 particles formed after ion exchange. The authors gratefully acknowledge the US Department of Energy (DOE), Office of Energy Efficiency and Renewable Energy, Office of Vehicle Technologies for the support of this work. The research described in this paper was performed at the Environmental Molecular Sciences Laboratory (EMSL), a national scientific user facility sponsored by the DOE’s Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory (PNNL). PNNL is operated for the US DOE by Battelle Memorial Institute under contract number DE-AC05-76RL01830.

chabazite↗

Selective Catalytic Reduction over Cu/SSZ-13: Linking Homo- and Heterogeneous Catalysis

Active centers in Cu/SSZ-13 selective catalytic reduction (SCR) catalysts have been recently identified as isolated Cu2+ and [CuII(OH)]+ ions. A redox reaction mechanism has also been established, where Cu-ions cycle between CuI and CuII oxidation states during SCR reaction. While the mechanism for the reduction half-cycle (CuII CuI) is reasonably well understood, that for the oxidation half-cycle (CuI CuII) remains an unsettled debate. Herein we report detailed reaction kinetics on low-temperature standard NH3-SCR, supplemented by DFT calculations, as strong evidence that the low-temperature oxidation half-cycle occurs with the participation of two isolated CuI ions, via formation of a transient [CuI(NH3)2]+-O2-[CuI(NH3)2]+ intermediate. The feasibility of this reaction mechanism is confirmed from DFT calculations, and the simulated energy barrier and rate constants are consistent with experimental findings. Significantly, the low-temperature standard SCR mechanism proposed here provides full consistency with low-temperature SCR kinetics. The authors gratefully acknowledge the US Department of Energy (DOE), Energy Efficiency and Renewable Energy, Vehicle Technologies Office for the support of this work. The research described in this paper was performed in the Environmental Molecular Sciences Laboratory (EMSL), a national scientific user facility sponsored by the DOE’s Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory (PNNL). PNNL is operated for the US DOE by Battelle.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Genesis and Stability of Hydronium Ions in Zeolite Channels

Zeolite-catalyzed reactions are profoundly altered by the presence of water changing the nature of the Brønsted acid site. High resolution solid-state NMR spectroscopy shows how water interacts with zeolite Brønsted acid sites converting them to hydrated hydronium ions over a wide range in temperature and thermodynamic activity of water. A signal at 9 ppm was observed at loadings of 2–9 water molecules per Brønsted acid site, and assigned to hydrated hydronium ions on the basis of chemical shift calculations and the observation of the signal after addition of HClO4. The intensity of 1H-29Si cross-polarization signal first increased and then decreased with increasing water chemical potential. This shows that the hydrogen bonds between water molecules and tetrahedrally coordinated aluminum in zeolite lattices weaken with the formation of hydronium ion-water clusters and increase the mobility of protons. Above 140 °C, however, fast proton exchange between bridging hydroxyl groups and water occur even in the presence of only one water molecule per acid site, suggesting that water acts at higher temperatures as a competitor for zeolite protons rather than as constituent of catalytically active hydronium ions. This work was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences. Portions of the work were performed at the William R. Wiley Environmental Molecular Science Laboratory, a national scientific user facility sponsored by the DOE’s Office of Biological and Environmental Research located at Pacific Northwest National Laboratory, a multiprogram national laboratory operated for DOE by Battelle Memorial Institute. Addi-tional 1H MAS NMR spectra we acquired using a Bruker 600 MHz NMR spectrometer acquired with support from the US Department of Energy, Office of Science, office of Basic Energy Sciences (Pro-ject Number 66628).

Zeolite, Brønsted acid, water, hydronium ion, NMR ↗

A Thermodynamic and Kenetic Study of the Heterolytic Activation of Hydrogen by Frustrated Borane-Amine Lewis Pairs

Calorimetry is used to measure the reaction enthalpies of hydrogen activation by 2,6-lutidine (Lut), 2,2,6,6-tetramethylpiperidine (TMP), N-methyl-2,2,6,6-tetramethylpiperidine (MeTMP) and tri-tert-butylphosphine (TBP) with tris(pentafluorophenyl)borane (BCF). At 6.6 bar H2 the conversion of the Lewis acid Lewis base pair to the corresponding ionic pair in bromobenzene at 294 K was quantitative in under 60 minutes. Integration of the heat release from the reaction of the Frustrated Lewis Pair (FLP) with hydrogen as a function of time yields a relative rate of hydrogenation in addition to the enthalpy of hydrogenation. The half-lives of hydrogenation range from 230 seconds with TMP, ΔHH2 = -31.5(0.2) kcal/mol, to 1400 seconds with Lut, ΔHH2 = -23.4(0.4) kcal/mol. The 11B NMR spectrum of B(C6F5)3 in bromobenzene exhibits three distinct traits depending on the sterics of the Lewis base; (i) in the presence of pyridine, only the dative bond adduct pyridine--B(C6F5)3 is observed, (ii) in the presence of TMP and MeTMP only the free B(C6F5)3 is observed, and (iii) in the presence of Lut both the free B(C6F5)3 and the Lut--B(C6F5)3 adduct appear in equilibrium. A measure of the change in Keq of Lut + B(C6F5)3 <->Lut--B(C6F5)3 as a function of temperature provides thermodynamic properties of the Lewis acid Lewis base adduct, ΔH = -17.9(1.0) kcal/mol and a ΔS = -49.2(2.5) cal/mol K, suggesting the Lut--B(C6F5)3 adduct is more stable in bromobenzene than in toluene. This research was supported by the U.S. Department of Energy’s Basic Energy Sciences, Division of Chemical Sciences, Biosciences and Geosciences. D.M.C. and A.K. acknowledges support by the Laboratory Directed Research and Development program at the Pacific Northwest National Laboratory (PNNL) to perform kinetic analyses of the calorimetry data. The work was performed in part at EMSL, a national scientific user facility sponsored by the DOE Office of Biological and Environmental Research. EMSL is located at Pacific Northwest National Laboratory (PNNL), which is operated by Battelle for DOE.

calorimetry↗

15N2 formation and fast oxygen isotope exchange during pulsed 15N18O exposure of MnOx/CeO2

Pulsing 15N18O onto an annealed 1% Mn16Ox/Ce16O2 catalyst resulted in very fast oxygen isotope exchange and 15N2 formation at 295 K. In the 1st 15N18O pulse, due to the presence of large number of surface oxygen defects, extensive 15N218O and 15N2 formations were observed. In subsequent pulses oxygen isotope exchange dominated as a result of highly labile oxygen in the oxide. We gratefully acknowledge the US Department of Energy (DOE), Office of Energy Efficiency and Renewable Energy/Vehicle Technologies Program for the support of this work. The research described in this paper was performed at the Environmental Molecular Sciences Laboratory (EMSL), a national scientific user facility sponsored by the DOE’s Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory (PNNL). PNNL is operated for the US DOE by Battelle.

Environmental Molecular Sciences Laboratory↗

Characterization of Fe 2+ ions in Fe,H/SSZ-13 zeolites: FTIR spectroscopy of CO and NO probe molecules

The IR spectra of adsorbed CO and NO probe molecules were used to characterize the coordination chemistry of Fe2+ ions in solution ion exchanged Fe,H/SSZ-13 zeolites. The effects of Fe ion exchange levels, as well the sample pre-treatment conditions on the adsorption of these probe molecules were investigated. The ion exchange levels (in the range of the study) did not affect significantly the IR spectra of either probe molecule, the IR features and their intensity ratios were very similar. Experiments with both probe molecules substantiated the presence of two distinct types of Fe2+ ions in cationic positions. We assign these two Fe2+ ions to two distinct cationic positions: Fe2+ in 6R and 8R positions. NO initially adsorbs preferentially onto Fe2+ sites in the 6R position, and then populates sites in the 8R. Fe2+ ions in the 8R positions require the interaction of more than one NO molecule to move them out from their adsorbate-free cationic positions. As soon as they move from their stable positions, they are able to bind to multiple NO molecules, and form mostly tri-nitrosyls. These tri-nitrosyls, however, are only stable in the presence of gas phase NO; under dynamic vacuum they lose one of the NO molecules from their coordination sphere and form stable di-nitrosyls. The adsorption of CO is much weaker on Fe2+ sites than that of NO, and requires cryogenic sample temperatures to initiate CO adsorption. Under the conditions applied in this study, only mono-carbonyl formation was observed. Reduction in H2 at 773 K increased the number of Fe2+ adsorption sites, primarily in the 8R locations. Oxidation by N2O, on the other hand, selectively reduced the adsorption of both CO and NO on the Fe2+ sites in 8R positions. Adsorbed oxygen left behind from the decomposition of N2O at 573 K readily reacted with CO to produce CO2 even at 150 K. The authors gratefully acknowledge the US Department of Energy (DOE), Energy Efficiency and Renewable Energy, Vehicle Technologies Program for the support of this work. The research described in this paper was performed in the Environmental Molecular Sciences Laboratory (EMSL), a national scientific user facility sponsored by the DOE’s Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory (PNNL). PNNL is operated for the US DOE by Battelle.

coordination chemistry of Fe2+ ions↗

TRACER-VOC: Speciated Volatile Organic Compounds at the Tracking Aerosol Convection Interactions Experiment Field Campaign Report

Formation of secondary organic aerosol (SOA) is responsible for the growth of particles into cloud condensation nuclei (CCN)-relevant sizes and accounts for a substantial fraction of aerosol mass in the troposphere. Despite its wide abundance and importance, capturing SOA in regional and climate models is still challenging due to complex chemical transformations involved in production of SOA. Oxidation products of biogenic hydrocarbons, such as isoprene, monoterpenes, and sesquiterpenes account for the largest fraction of SOA mass over the continents. As such, biogenic SOA is an important source of continental CCN, and has been recently shown to nucleate ice in the deposition mode. To better account for the processes involved in SOA formation in global and regional climate models, we need better measurements of sources and transformations of volatile organic compounds (VOCs), the precursors to SOA formation in the atmosphere. Understanding aerosol-deep convection interactions is an important science driver of the Tracking Aerosol Convection Interactions Experiment (TRACER), requiring a characterization of the critical controls on aerosol properties and processes, and how those properties and processes vary spatially and temporally in the Houston area. In that environment, the atmospheric photo-oxidative chemistry that drives the evolution and transformation of aerosol properties and processes is strongly impacted by the emission of VOCs, which have both anthropogenic (e.g., industrial, urban, transportation, biomass burning) and biogenic (e.g., marine) sources in the region. Understanding (and disentangling) the complex role of VOCs in such a heterogenous region requires high-time-resolution, speciated VOC measurements that are spatially resolved. To meet these measurement requirements, the U.S. Department of Energy Atmospheric Radiation Measurement (ARM) user facility’s time-of-flight proton transfer reaction-mass spectrometer (ToF-PTR-MS) was deployed during the TRACER intensive operational period (IOP) from June to September, 2022 at the ancillary site (ANC), which was sited to provide a characterization of the rural atmospheric environment in contrast to the main site.

54 ENVIRONMENTAL SCIENCES↗

A study of the operation of selected national research facilities

The operation of national research facilities was studied. Conclusions of the study show that a strong resident scientific staff is required for successful facility operation. No unique scheme of scientific management is revealed except for the obvious fact that the management must be responsive to the users needs and requirements. Users groups provide a convenient channel through which these needs and requirements are communicated.

Eisner, M.↗

Management of Disused Sealed Sources in Hungary - 13077

Since 1976 the spent and disused radioactive sources arisen in Hungary are stored in a central storage facility called Radioactive Waste Treatment and Disposal Facility operated by Public Limited Company for Radioactive Waste Management. The Facility is responsible for the record keeping, the waste acceptance procedure, the shipment and the storage or disposal (whether a certain source meets the waste acceptance criteria for disposal or not) of sources. Based on the more than 35 year old operation of the facility many experiences have been gathered regarding the technology for long-term storage of sources, the attitude of the users of sources, the evolution of the legislation and the national record keeping system. Recently a new legislation for the security of radioactive materials (including sources) was introduced, first in Central-Europe. It requires special security arrangements from the facility for transport and for storage. Due to the ongoing retrieval of radioactive waste formerly disposed of, partly containing sealed sources, there is a new challenge in the physical inventory control of historical waste. The paper would show the effect of the changes in the legislation system of record keeping or security on the users' attitude for discard of sources and on the management of the sources in the facility. The facility has a unique storage technology (shallow boreholes) in the narrow region. The sealed sources are placed into vertical pipes sunk into the surface. In the beginning, each of the sources were dropped into the pipe directly, recently they are placed in a metal tube first ensuring the retrieval. The lessons learned will be presented. There were several issues to introduce the new security arrangements (partly financially supported by US DOE) for storage and for transportation of sealed sources. These issues are addressed. In the past part of the sealed sources were disposed together with solid radioactive waste packaged in plastic bags. A waste retrieval campaign was fulfilled in 2008 to retrieve the sealed sources. The paper demonstrates the conditions of sealed sources after twenty-year disposal period. As a summary, the paper will share the main experiences of a 35-year old facility, managing radioactive sealed sources in Central Europe. (authors)

07 ISOTOPE AND RADIATION SOURCES↗

Solving The Space Weather Problem: A 15+ Year Roadmap to Revolutionize Space Weather Research, Protect NASA Space Assets, and Enable Robust Operations

The White Paper (WP) describes a roadmap to address the Space Weather (SpWx) problem. It presents a strategic vision of how a community-wide effort could be organized and implemented to enable transformative advancement in SpWx research and ultimately, in applications. We envision a ‘system-of-systems’—an integrated web of SpWx stations and state-ofthe-art modeling facilities to enable a transformative advance in SpWx nowcasting and forecasting (Figure 1). The Space Weather Aggregated Network of Systems (SWANS) will enable space situational awareness for end-users invested in spaceflight operations, infrastructure risk mitigation, and future human endeavors in space exploration while profoundly transforming Heliophysics research.

A Vourrlidas↗

A CONCEPTUAL 3-GEV LANSCE LINAC UPGRADE FOR ENHANCED PROTON RADIOGRAPHY

A conceptual design of a 3-GeV linac upgrade that would enable enhanced proton radiography at the Los Alamos Neutron Science Center (LANSCE) is presented. The upgrade is based on the use of superconducting accelerating cavities to increase the present LANSCE linac output energy from 800 MeV to 3 GeV. The LANSCE linac currently provides negative hydrogen ion (H{sup -}) and proton (H{sup +}) beams to several user facilities that support Isotope Production, NNSA Stockpile Stewardship, and Basic Energy Science programs. Required changes to the front-end, the accelerating structures, and to the RF systems to meet the new performance goals, and changes to the existing beam switchyard to maintain operations for a robust user program are also described.

43 PARTICLE ACCELERATORS↗