809 research outputs found
Characteristics of STP Pre-2004 Archived KE Basin Sludge Samples Before and After Re-Jarring in the RPL - April 2012
This report describes results of work performed in the Shielded Analytical Laboratory (SAL) at the Pacific Northwest National Laboratory’s (PNNL) Radiochemical Processing Laboratory (RPL) with archive K East (KE) Basin sludge samples obtained before the year 2004, with some of them composited and initially characterized five years ago (Delegard et al. 2011). The previously performed testing included the physical properties determinations for selected samples (settled and particle densities, water and solids concentrations), the pH, as well as identification of crystalline phases by X-ray diffractometry (XRD) for selected samples. Another objective of the previous characterization and testing campaign was to transfer some sludge composites and individual samples into new storage containers to overcome the embrittlement effect which develops in original glass containers as a result of extended exposure to high radiation fields and which increases probability of sample loss
Recommended from our members
Preparation and Characterization of Uranium Oxides in Support of the K Basin Sludge Treatment Project
Uraninite (UO2) and metaschoepite (UO3·2H2O) are the uranium phases most frequently observed in K Basin sludge. Uraninite arises from the oxidation of uranium metal by anoxic water and metaschoepite arises from oxidation of uraninite by atmospheric or radiolytic oxygen. Studies of the oxidation of uraninite by oxygen to form metaschoepite were performed at 21°C and 50°C. A uranium oxide oxidation state characterization method based on spectrophotometry of the solution formed by dissolving aqueous slurries in phosphoric acid was developed to follow the extent of reaction. This method may be applied to determine uranium oxide oxidation state distribution in K Basin sludge. The uraninite produced by anoxic corrosion of uranium metal has exceedingly fine particle size (6 nm diameter), forms agglomerates, and has the formula UO2.004±0.007; i.e., is practically stoichiometric UO2. The metaschoepite particles are flatter and wider when prepared at 21°C than the particles prepared at 50°C. These particles are much smaller than the metaschoepite observed in prolonged exposure of actual K Basin sludge to warm moist oxidizing conditions. The uraninite produced by anoxic uranium metal corrosion and the metaschoepite produced by reaction of uraninite aqueous slurries with oxygen may be used in engineering and process development testing. A rapid alternative method to determine uranium metal concentrations in sludge also was identified
Mitigation of Hydrogen Gas Generation from the Reaction of Uranium Metal with Water in K Basin Sludge and Sludge Waste Forms
Prior laboratory testing identified sodium nitrate and nitrite to be the most promising agents to minimize hydrogen generation from uranium metal aqueous corrosion in Hanford Site K Basin sludge. Of the two, nitrate was determined to be better because of higher chemical capacity, lower toxicity, more reliable efficacy, and fewer side reactions than nitrite. The present lab tests were run to determine if nitrate’s beneficial effects to lower H2 generation in simulated and genuine sludge continued for simulated sludge mixed with agents to immobilize water to help meet the Waste Isolation Pilot Plant (WIPP) waste acceptance drainable liquid criterion. Tests were run at ~60°C, 80°C, and 95°C using near spherical high-purity uranium metal beads and simulated sludge to emulate uranium-rich KW containerized sludge currently residing in engineered containers KW-210 and KW-220. Immobilization agents tested were Portland cement (PC), a commercial blend of PC with sepiolite clay (Aquaset II H), granulated sepiolite clay (Aquaset II G), and sepiolite clay powder (Aquaset II). In all cases except tests with Aquaset II G, the simulated sludge was mixed intimately with the immobilization agent before testing commenced. For the granulated Aquaset II G clay was added to the top of the settled sludge/solution mixture according to manufacturer application directions. The gas volumes and compositions, uranium metal corrosion mass losses, and nitrite, ammonia, and hydroxide concentrations in the interstitial solutions were measured. Uranium metal corrosion rates were compared with rates forecast from the known uranium metal anoxic water corrosion rate law. The ratios of the forecast to the observed rates were calculated to find the corrosion rate attenuation factors. Hydrogen quantities also were measured and compared with quantities expected based on non-attenuated H2 generation at the full forecast anoxic corrosion rate to arrive at H2 attenuation factors. The uranium metal corrosion rates in water alone and in simulated sludge were near or slightly below the metal-in-water rate while nitrate-free sludge/Aquaset II decreased rates by about a factor of 3. Addition of 1 M nitrate to simulated sludge decreased the corrosion rate by a factor of ~5 while 1 M nitrate in sludge/Aquaset II mixtures decreased the corrosion rate by ~2.5 compared with the nitrate-free analogues. Mixtures of simulated sludge with Aquaset II treated with 1 M nitrate had uranium corrosion rates about a factor of 8 to 10 lower than the water-only rate law. Nitrate was found to provide substantial hydrogen mitigation for immobilized simulant sludge waste forms containing Aquaset II or Aquaset II G clay. Hydrogen attenuation factors of 1000 or greater were determined at 60°C for sludge-clay mixtures at 1 M nitrate. Hydrogen mitigation for tests with PC and Aquaset II H (which contains PC) were inconclusive because of suspected failure to overcome induction times and fully enter into anoxic corrosion. Lessening of hydrogen attenuation at ~80°C and ~95°C for simulated sludge and Aquaset II was observed with attenuation factors around 100 to 200 at 1 M nitrate. Valuable additional information has been obtained on the ability of nitrate to attenuate hydrogen gas generation from solution, simulant K Basin sludge, and simulant sludge with immobilization agents. Details on characteristics of the associated reactions were also obtained. The present testing confirms prior work which indicates that nitrate is an effective agent to attenuate hydrogen from uranium metal corrosion in water and simulated K Basin sludge to show that it is also effective in potential candidate solidified K Basin waste forms for WIPP disposal. The hydrogen mitigation afforded by nitrate appears to be sufficient to meet the hydrogen generation limits for shipping various sludge waste streams based on uranium metal concentrations and assumed waste form loadings
Stochastic Approach to Enantiomeric Excess Amplification and Chiral Symmetry Breaking
Stochastic aspects of chemical reaction models related to the Soai reactions
as well as to the homochirality in life are studied analytically and
numerically by the use of the master equation and random walk model. For
systems with a recycling process, a unique final probability distribution is
obtained by means of detailed balance conditions. With a nonlinear
autocatalysis the distribution has a double-peak structure, indicating the
chiral symmetry breaking. This problem is further analyzed by examining
eigenvalues and eigenfunctions of the master equation. In the case without
recycling process, final probability distributions depend on the initial
conditions. In the nonlinear autocatalytic case, time-evolution starting from a
complete achiral state leads to a final distribution which differs from that
deduced from the nonzero recycling result. This is due to the absence of the
detailed balance, and a directed random walk model is shown to give the correct
final profile. When the nonlinear autocatalysis is sufficiently strong and the
initial state is achiral, the final probability distribution has a double-peak
structure, related to the enantiomeric excess amplification. It is argued that
with autocatalyses and a very small but nonzero spontaneous production, a
single mother scenario could be a main mechanism to produce the homochirality.Comment: 25 pages, 6 figure
The Reverend John H. A. Bomberger, Doctor of Divinity; Doctor of Laws 1817-1890: Centenary Volume
Prepared for the one hundredth anniversary of the birth of John Henry Augustus Bomberger, this biographical volume provides details of Dr. Bomberger\u27s life from his early days as a student at Mercersburg through his final years as the first President of Ursinus College. The 273 page book contains photographs and portraits.https://digitalcommons.ursinus.edu/jhabombergercent/1000/thumbnail.jp
Recommended from our members
Uranium Metal Analysis via Selective Dissolution
Uranium metal, which is present in sludge held in the Hanford Site K West Basin, can create hazardous hydrogen atmospheres during sludge handling, immobilization, or subsequent transport and storage operations by its oxidation/corrosion in water. A thorough knowledge of the uranium metal concentration in sludge therefore is essential to successful sludge management and waste process design. The goal of this work was to establish a rapid routine analytical method to determine uranium metal concentrations as low as 0.03 wt% in sludge even in the presence of up to 1000-fold higher total uranium concentrations (i.e., up to 30 wt% and more uranium) for samples to be taken during the upcoming sludge characterization campaign and in future analyses for sludge handling and processing. This report describes the experiments and results obtained in developing the selective dissolution technique to determine uranium metal concentration in K Basin sludge
Scalar ground-state observables in the random phase approximation
We calculate the ground-state expectation value of scalar observables in the
matrix formulation of the random phase approximation (RPA). Our expression,
derived using the quasiboson approximation, is a straightforward generalization
of the RPA correlation energy. We test the reliability of our expression by
comparing against full diagonalization in 0 h-bar omega shell-model spaces. In
general the RPA values are an improvement over mean-field (Hartree-Fock)
results, but are not always consistent with shell-model results. We also
consider exact symmetries broken in the mean-field state and whether or not
they are restored in RPA.Comment: 7 pages, 3 figure
Evidence for short range orbital order in paramagnetic insulating (Al,V)_2O_3
The local structure of (Al_0.06V_0.94)_2O_3 in the paramagnetic insulating
(PI) and antiferromagnetically ordered insulating (AFI) phase has been
investigated using hard and soft x-ray absorption techniques. It is shown that:
1) on a local scale, the symmetry of the vanadium sites in both the PI and the
AFI phase is the same; and 2) the vanadium 3d - oxygen 2p hybridization, as
gauged by the oxygen 1s absorption edge, is the same for both phases, but
distinctly different from the paramagnetic metallic phase of pure V_2O_3. These
findings can be understood in the context of a recently proposed model which
relates the long range monoclinic distortion of the antiferromagnetically
ordered state to orbital ordering, if orbital short range order in the PI phase
is assumed. The measured anisotropy of the x-ray absorption spectra is
discussed in relation to spin-polarized density functional calculations.Comment: 8 pages, 5 figure
- …