Characterization of Actinides Complexed to Nuclear Fuel Constituents Using ESI-MS

DOE PAGES

McDonald, Luther W.; Campbell, James A.; Vercouter, Thomas; ...

2016-03-01

Electrospray ionization-mass spectrometry (ESI-MS) was tested for its use in monitoring spent nuclear fuel (SNF) constituents including U, Pu, dibutyl phosphate (DBP), and tributyl phosphate (TBP). Both positive and negative ion modes were used to evaluate the speciation of U and Pu with TBP and DBP. Furthermore, apparent stability constants were determined for U complexed to TBP and DBP. In positive ion mode, TBP produced a strong signal with and without complexation to U or Pu, but, in negative ion mode, no TBP, U-TBP, or Pu-TBP complexes were observed. Apparent stability constants were determined for [UO 2(NO 3) 2(TBP) 2],more » [UO 2(NO 3) 2(H 2O)(TBP) 2], and [UO 2(NO 3) 2(TBP) 3]. In contrast DBP, U-DBP, and Pu-DBP complexes were observed in both positive and negative ion modes. Apparent stability constants were determined for the species [UO 2(DBP)], [UO 2(DBP) 3], and [UO 2(DBP) 4]. Analyzing mixtures of U or Pu with TBP and DBP yielded the formation of ternary complexes whose stoichiometry was directly related to the ratio of TBP to DBP. The ESI-MS protocols used in this study will further demonstrate the utility of ESI-MS and its applicability to process control monitoring in SNF reprocessing facilities.« less

Heptavalent Neptunium in a Gas-Phase Complex: (Np VIIO 3 +)(NO 3 –) 2

DOE PAGES

Dau, Phuong D.; Maurice, Remi; Renault, Eric; ...

2016-09-15

A central goal of chemistry is to achieve ultimate oxidation states, including in gas-phase complexes with no condensed phase perturbations. In the case of the actinide elements, the highest established oxidation states are labile Pu(VII) and somewhat more stable Np(VII). We have synthesized and characterized gas-phase AnO 3(NO 3) 2- complexes for An = U, Np, and Pu by endothermic NO 2 elimination from AnO 2(NO 3) 3-. It was previously demonstrated that the PuO 3+ core of PuO 3(NO 3) 2- has a Pu—O• radical bond such that the oxidation state is Pu(VI); it follows that in UO 3(NOmore » 3) 2- it is the stable U(VI) oxidation state. On the basis of the relatively more facile synthesis of NpO 3(NO 3) 2-, a Np(VII) oxidation state is inferred. This interpretation is substantiated by reactivity of the three complexes: NO 2 spontaneously adds to UO 3(NO 3) 2- and PuO 3(NO 3) 2- but not to NpO 3(NO 3) 2-. This unreactive character is attributed to a Np(VII)O 3+ core with three stable Np=O bonds, this in contrast to reactive U—O• and Pu—O• radical bonds. The computed structures and reaction energies for the three AnO 3(NO 3) 2- support the conclusion that the oxidation states are U(VI), Np(VII), and Pu(VI). These results establish the extreme Np(VII) oxidation state in a gas-phase complex, and demonstrate the inherently greater stability of Np(VII) versus Pu(VII).« less

Next-generation purex flowsheets with acetohydroxamic acid as complexant for FBR and thermal-fuel reprocessing

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kumar, Shekhar; Koganti, S.B.

2008-07-01

Acetohydroxamic acid (AHA) is a novel complexant for recycle of nuclear-fuel materials. It can be used in ordinary centrifugal extractors, eliminating the need for electro-redox equipment or complex maintenance requirements in a remotely maintained hot cell. In this work, the effect of AHA on Pu(IV) distribution ratios in 30% TBP system was quantified, modeled, and integrated in SIMPSEX code. Two sets of batch experiments involving macro Pu concentrations (conducted at IGCAR) and one high-Pu flowsheet (literature) were simulated for AHA based U-Pu separation. Based on the simulation and validation results, AHA based next-generation reprocessing flowsheets are proposed for co-processing basedmore » FBR and thermal-fuel reprocessing as well as evaporator-less macro-level Pu concentration process required for MOX fuel fabrication. Utilization of AHA results in significant simplification in plant design and simpler technology implementations with significant cost savings. (authors)« less

Decreased solubilization of Pu(IV) polymers by humic acids under anoxic conditions

NASA Astrophysics Data System (ADS)

Xie, Jinchuan; Lin, Jianfeng; Liang, Wei; Li, Mei; Zhou, Xiaohua

2016-11-01

Pu(IV) polymer has a very low solubility (log[Pu(IV)aq]total = -10.4 at pH 7.2 and I = 0). However, some aspects of their environmental fate remain unclear. Humic acids are able to complex with Pu4+ ions and their dissolved species (<10 kD) in the groundwater (neutral to alkaline pH) may cause solubilization of the polymers. Also, humic acids have the native reducing capacity and potentially reduce the polymeric Pu(IV) to Pu(III)aq (log[Pu(III)aq]total = -5.3 at pH 7.2 and I = 0). Solubilization and reduction of the polymers can enhance their mobility in subsurface environments. Nevertheless, humic acids readily coat the surfaces of metal oxides via electrostatic interaction and ligand exchange mechanisms. The humic coatings are expected to prevent both solubilization and reduction of the polymers. Experiments were conducted under anoxic and slightly alkaline (pH 7.2) conditions in order to study whether humic acids have effects on stability of the polymers. The results show that the polymeric Pu(IV) was almost completely transformed into aqueous Pu(IV) in the presence of EDTA ligands. In contrast, the dissolved humic acids did not solubilize the polymers but in fact decreased their solubility by one order of magnitude. The humic coatings were responsible for the decreased solubilization. Such coatings limited the contact between the polymers and EDTA ligands, especially at the relatively high concentrations of humic acids (>0.57 mg/L). Solubilization of the humic-coated polymers was thus inhibited to a significant extent although EDTA, having the great complexation ability, was present in the humic solutions. Reduction of Pu(IV) polymers by the humic acids was also not observed in the absence of EDTA. In the presence of EDTA, the polymers were partially reduced to Pu(III)aq by the humic acids of 0.57 mg/L and the percentage of Pu(III)aq accounted for 51.7% of the total aqueous Pu. This demonstrates that the humic acids were able to reduce the aqueous Pu(IV), instead of the polymeric Pu(IV). Such a demonstration is supported by the very positive redox potential of aqueous Pu(IV)-EDTA complex: Eho ‧ (PuL24-/PuL25-) = 154.3 mV >>Eh (PuO2 (am) /Pu3+) = -182.7 mV calculated at 10-10 mol/L Pu3+ and pH 7.2. At the higher humic concentrations (>0.57 mg/L), the polymers were reduced to a lesser extent because the much denser humic coatings resulted in lower concentrations of the aqueous Pu(IV). Consequently, humic acids make Pu(IV) polymers pretty stable unless the artificial ligands such as EDTA are present in the groundwater.

Method for selectively reducing plutonium values by a photochemical process

DOEpatents

Friedman, Horace A.; Toth, Louis M.; Bell, Jimmy T.

1978-01-01

The rate of reduction of Pu(IV) to Pu(III) in nitric acid solution containing a reducing agent is enhanced by exposing the solution to 200-500 nm electromagnetic radiation. Pu values are recovered from an organic extractant solution containing Pu(IV) values and U(VI) values by the method of contacting the extractant solution with an aqueous nitric acid solution in the presence of a reducing agent and exposing the aqueous solution to electromagnetic radiation having a wavelength of 200-500 nm. Under these conditions, Pu values preferentially distribute to the aqueous phase and U values preferentially distribute to the organic phase.

Incipient class II mixed valency in a plutonium solid-state compound

NASA Astrophysics Data System (ADS)

Cary, Samantha K.; Galley, Shane S.; Marsh, Matthew L.; Hobart, David L.; Baumbach, Ryan E.; Cross, Justin N.; Stritzinger, Jared T.; Polinski, Matthew J.; Maron, Laurent; Albrecht-Schmitt, Thomas E.

2017-09-01

Electron transfer in mixed-valent transition-metal complexes, clusters and materials is ubiquitous in both natural and synthetic systems. The degree to which intervalence charge transfer (IVCT) occurs, dependent on the degree of delocalization, places these within class II or III of the Robin-Day system. In contrast to the d-block, compounds of f-block elements typically exhibit class I behaviour (no IVCT) because of localization of the valence electrons and poor spatial overlap between metal and ligand orbitals. Here, we report experimental and computational evidence for delocalization of 5f electrons in the mixed-valent PuIII/PuIV solid-state compound, Pu3(DPA)5(H2O)2 (DPA = 2,6-pyridinedicarboxylate). The properties of this compound are benchmarked by the pure PuIII and PuIV dipicolinate complexes, [PuIII(DPA)(H2O)4]Br and PuIV(DPA)2(H2O)3·3H2O, as well as by a second mixed-valent compound, PuIII[PuIV(DPA)3H0.5]2, that falls into class I instead. Metal-to-ligand charge transfer is involved in both the formation of Pu3(DPA)5(H2O)2 and in the IVCT.

Studies on transformations of plutonium-239 and americium-241 in three major Indian soils.

PubMed

Vyas, B N; Mistry, K B

1984-01-13

These studies were carried out to elucidate the behaviour of 239Pu and and 241Am in three major soil groups of India, namely oxisol, vertisol-pellustert and entisol-haplaquent, over extended periods up to 400 days. The influences of soil characteristics, addition of organic matter and the chemical form of the radionuclides added to soils were investigated. A large fraction, ranging from 60 to 90% of the soluble radionuclides added as nitrates, underwent rapid conversion to precipitated hydrous oxides and hydroxides (0.3 M sodium citrate-dithionite extracts). At 3 h after contamination, ion-exchangeable forms (0.1 M MgCl2 extracts) contained low levels of total added Pu (0.7 to 19.1%) and from 0.1 to 2.8% of total Am. These levels decreased further with increasing periods of incubation of up to 400 days. In contrast, on addition of chelated forms of radionuclides (as DTPA and EDTA complexes) up to 85% of total Pu, and about 50% of total Am were associated with 0.1 M MgCl2 extracts 3 h post-contamination and significant amounts were extractable when maintained over extended periods of incubation of up to 400 days. The levels of Pu and Am associated with organic-bound forms (0.1 M NaOH extracts) did not show consistent trends, although in all three soil types the contents of these radionuclides in the insoluble residue fraction (including refractory compounds) generally increased with time of incubation.

Chelation of /sup 238/Pu(IV) in vivo by 3,4,3-LICAM(C): Effects of ligand methylation and pH

DOE Office of Scientific and Technical Information (OSTI.GOV)

Durbin, P.W.; White, D.L.; Jeung, N.L.

1989-06-01

The linear tetracarboxycatecholate ligand, 3,4,3-LICAM(C) N1,N5,N10,N14-tetrakis(2,3-dihydroxy-4-carboxybenzoyl-tetraaza tet radecane, tetra sodium salt) injected within 1 h after injection of Pu(IV) citrate, removes about the same fraction of Pu from animals as CaNa3-DTPA but removes less inhaled Pu than CaNa3-DTPA and leaves a Pu residue in the renal cortex. However, the formation constant of the expected Pu-3,4,3-LICAM(C) complexes are orders of magnitude greater than that of Pu-DTPA, and 3,4,3-LICAM(C) is 100 times more efficient than CaNa3-DTPA for removing Pu from transferrin in vitro. Because the formation constants of their actinide complexes are central to in vivo actinide chelation, ligand design strategies aremore » dominated by the search for ligands with large Pu complex stabilities, and it was necessary to explain the failure of 3,4,3-LICAM(C) to achieve its thermodynamic potential in vivo. All the batches of 3,4,3-LICAM(C) prepared at Berkeley or in France (Euro-LICAM(C)) were found by high-pressure liquid chromatography to be mixtures of the pure ligand (55% in Berkeley preparations, 8.5% in Euro-LICAM(C)) and its four methylesters. A revised synthesis for 3,4,3-LICAM(C) is appended to this report. All of the incompletely hydrolyzed 3,4,3-LICAM(C) preparations and the pure ligand were tested for removal of Pu from mice (238Pu(IV) citrate intravenous, 30 mumol kg-1 of ligand at 1 h, kill at 24 h, radioanalyze tissues and separated excretal). The presence of methylesters did not significantly impair the ability of the ligands to remove Pu from mice, and it did not alter the fraction of injected Pu deposited in kidneys. Temporary elevation (reduction) of plasma and urine pH of mice by 0.5 mL of 0.1 M NaHCO3 (NH4Cl) injected before or simultaneously with pure 3,4,3-LICAM(C) somewhat improved (significantly reduced) Pu excretion but had little influence on Pu deposition in kidneys.« less

Investigation of Pu(IV)-acetohydroxamic acid complex by solvent extraction with di(2-ethylhexyl) phosphoric acid

NASA Astrophysics Data System (ADS)

Brown, M. Alex; Paulenova, Alena; Tkac, Peter

2010-03-01

The stability constant of the Pu(IV)-acetohydroxamic acid complex Pu(AHA)3+ at 1 M ionic strength (pH = 0) has been investigated by method of solvent extraction. Di(2-ethylhexyl) phosphoric acid (HDEHP) was used to extract Pu(IV) from perchloric and nitric acid media at various AHA concentrations. Distribution ratios over a range of ligand concentrations were used in conjunction with graphical methods to obtain logβ1 = 14.3 ± 0.03 in perchloric acid. The stability constant determined from solutions in nitric acid was excluded because of the uncertainty in plutonium speciation.

Coordination Chemistry of Homoleptic Actinide(IV)-Thiocyanate Complexes

DOE PAGES

Carter, Tyler J.; Wilson, Richard E.

2015-09-10

Here, the synthesis, X-ray crystal structure, vibrational and optical spectroscopy for the eight-coordinate thiocyanate compounds, [Et 4N] 4[Pu IV(NCS) 8], [Et 4N] 4[Th IV(NCS) 8], and [Et 4N] 4[Ce III(NCS) 7(H 2O)] are reported. Thiocyanate was found to rapidly reduce plutonium to Pu III in acidic solutions (pH<1) in the presence of NCS –. The optical spectrum of [Et 4N][SCN] containing Pu III solution was indistinguishable from that of aquated Pu III suggesting that inner-sphere complexation with [Et 4N][SCN] does not occur in water. However, upon concentration, the homoleptic thiocyanate complex [Et 4N] 4[Pu IV(NCS) 8] was crystallized when amore » large excess of [Et 4N][NCS] was present. This compound, along with its U IV analogue, maintains inner-sphere thiocyanate coordination in acetonitrile based on the observation of intense ligand-to-metal charge-transfer bands. Spectroscopic and crystallographic data do not support the interaction of the metal orbitals with the ligand π system, but support an enhanced An IV–NCS interaction, as the Lewis acidity of the metal ion increases from Th to Pu.« less

Gas-Phase Coordination Complexes of UVIO{2/2+}, NpVIO{2/2+}, and PuVIO{2/2+} with Dimethylformamide

NASA Astrophysics Data System (ADS)

Rutkowski, Philip X.; Rios, Daniel; Gibson, John K.; van Stipdonk, Michael J.

2011-11-01

Electrospray ionization of actinyl perchlorate solutions in H2O with 5% by volume of dimethylformamide (DMF) produced the isolatable gas-phase complexes, [AnVIO2(DMF)3(H2O)]2+ and [AnVIO2(DMF)4]2+, where An = U, Np, and Pu. Collision-induced dissociation confirmed the composition of the dipositive coordination complexes, and produced doubly- and singly-charged fragment ions. The fragmentation products reveal differences in underlying chemistries of uranyl, neptunyl, and plutonyl, including the lower stability of Np(VI) and Pu(VI) compared with U(VI).

Organic and Aqueous Redox Speciation of Cu(III) Periodate Oxidized Transuranium Actinides

DOE Office of Scientific and Technical Information (OSTI.GOV)

McCann, Kevin; Sinkov, Sergey I.; Lumetta, Gregg J.

A hexavalent group actinide separation process could streamline used nuclear fuel recycle and waste management. The limiting factor to such a process compatible with current fuel dissolution practices is obtaining and maintaining hexavalent Am, in molar nitric acid due to the high reduction potential of the Am(VI)/Am(III) couple (1.68 V vs SCE). Two strong oxidants, sodium bismuthate and Cu(III) periodate, have demonstrated quantitative oxidation of Am under molar acid conditions and better than 50% recovery by diamyl amylphosphonate (DAAP) is possible under these same conditions. This work considers the use of Cu(III) periodate to oxidize Np(V) to Np(VI) and Pu(IV)more » to Pu(VI) and recover these elements by extraction with DAAP. A metal:oxidant ratio of 1:1.2 and 1:3 was necessary to quantitatively oxidize Np(V) and Pu(IV), respectively, to the hexavalent state. Extraction of hexavalent Np, Pu, and Am by 1 M DAAP in n-dodecane was measured using UV-Vis [Pu(VI), Am (VI)] and NIR [Np(VI)]. Distribution values of Am(VI) were found to match previous tracer level studies. The organic phase spectra of Np, Pu, and Am are presented and molar absorptivities are calculated for characteristic peaks. Hexavalent Pu was found to be stable in the organic phase while Np(VI) showed some reduction to Np(V) and Am was present as Am(III), Am(V), and Am(VI) species in aqueous and organic phases during the extraction experiments. These results demonstrate, for the first time, the ability to recover macroscopic amounts of americium that would be present during fuel reprocessing and are the first characterization of Am organic phase oxidation state speciation relevant to a hexavalent group actinide separation process under acidic conditions.« less

Characterization of (241)Pu occurrence, distribution, and bioaccumulation in seabirds from northern Eurasia.

PubMed

Strumińska-Parulska, Dagmara I; Skwarzec, Bogdan

2015-05-01

The paper presents unique data of plutonium (241)Pu study in seabirds from northern Eurasia, permanently or temporally living at the southern Baltic Sea coast. Together, ten marine birds species were examined, as follows: three species that permanently reside at the southern Baltic, four species of wintering birds, and three species of migrating birds; 366 samples were analyzed. The obtained results indicated plutonium was non-uniformly distributed in organs and tissues of analyzed seabirds. The highest (241)Pu content was found in the digestion organs and feathers, the lowest in muscles. Also, the internal radiation doses from (241)Pu were evaluated.

DISTRIBUTION OF ACTINIDES BETWEEN THE AQUEOUS AND ORGANIC PHASES IN THE TALSPEAK PROCESS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rudisill, T.; Kyser, E.

2010-09-02

One objective of the US Department of Energy's Office of Nuclear Energy (DOE-NE) is the development of sustainable nuclear fuel cycles which improve uranium resource utilization, maximize energy generation, minimize waste generation, improve safety, and complement institutional measures limiting proliferation risks. Activities in progress which support this objective include the development of advanced separation technologies to recover the actinides from used nuclear fuels. With the increased interest in the development of technology to allow closure of the nuclear fuel cycle, the TALSPEAK process is being considered for the separation of Am and Cm from the lanthanide fission products in amore » next generation reprocessing plant. However, at this time, the level of understanding associated with the chemistry and the control of the process variables is not acceptable for deployment of the process on an industrial scale. To address this issue, DOE-NE is supporting basic scientific studies focused on the TALSPEAK process through its Fuel Cycle Research and Development (R&D) program. One aspect of these studies is an experimental program at the Savannah River National Laboratory (SRNL) in which temperature-dependent distribution coefficients for the extraction of actinide elements in the TALSPEAK process were measured. The data were subsequently used to calculate conditional enthalpies and entropies of extraction by van't Hoff analysis to better understand the thermodynamic driving forces for the TALSPEAK process. In the SRNL studies, the distribution of Pu(III) in the TALSPEAK process was of particular interest. A small amount of Pu(III) would be present in the feed due to process losses and valence adjustment in prior recovery operations. Actinide elements such as Np and Pu have multiple stable oxidation states in aqueous solutions; therefore the oxidation state for these elements must be controlled in the TALSPEAK process, as the extraction chemistry is dependent upon the actinide's valence. Since our plans included the measurement of Pu(III) distribution coefficients using a Np(V) solution containing small amounts of {sup 238}Pu, it was necessary to demonstrate that the desired oxidation states of Np and Pu are produced and could be stabilized in a buffered lactate solution containing diethylenetriaminepentaacetic (DTPA). The stability of Np(V) and Pu(III) in lactic acid/DTPA solutions was evaluated by ultraviolet-visible (UV-vis) spectroscopy. To perform the evaluation, Np and Pu were added to solutions containing either hydroxylamine nitrate (HAN) or ferrous sulfamate (FS) as the reductant and nominally 1.5 M lactic acid/0.05 M DTPA. The pH of the solution was subsequently adjusted to nominally 2.8 as would be performed in the TALSPEAK process. In the valence adjustment study, we found that it was necessary to reduce Pu to Pu(III) prior to combining with the lactic acid and DTPA. The Pu reduction was performed using either HAN or FS. When FS was used, Np was reduced to Np(IV). The spectroscopic studies showed that Np(V) and Pu(III) are not stable in lactic acid/DTPA solutions. The stability of Np(IV)- and Pu(IV)-DTPA complexes are much greater than the stability of the Np(V)- and Pu(III)-DTPA complexes, and as a result, Np is slowly reduced to Np(IV) and Pu is slowly oxidized to Pu(IV) due to the reduced activity of the more stable complexes. When Np(V) was added to a solution containing a 1.5 M lactic acid/ammonium lactate buffer and 0.05 M DTPA, approximately 50% of the Np was reduced to Np(IV) in the first day. The fraction of Np(V) in the solution continued to diminish with time and was essentially reduced to Np(IV) after one week. When Pu(III) was added to a lactic acid/DTPA solution of the same composition, the spectrum recorded following at least two days after preparation of the solution continued to show some sign of Pu(III). The Pu(III) was completely oxidized to Pu(IV) after 3-4 days. The UV-vis spectroscopy demonstrated that Np(V) and Pu(III) were the predominate valences in the lactic acid/DTPA solution for the better part of a day following solution preparation. Based on these results, we chose to initially add HAN to the actinide tracer solution prepared for the distribution coefficient measurements (to produce Pu(III)) prior to combining with lactic acid and DTPA. The distribution coefficient measurements were expected to be complete in 2-3 h; therefore, Np(V) and Pu(III) valences would predominate in the solution during this time. Prior to adding the HAN to the actinide tracers, we added sufficient Am(III) activity to allow the measurement of distribution coefficients during the extraction experiments. Protactinium (V) distribution coefficients were also measured using the activity which was in secular equilibrium with the {sup 237}Np. The actinide distribution coefficients were measured at pH 2.8 and 3.5 and covered a range of temperatures from nominally 20 to 60 C.« less

Posterior Urethroplasty Complexity and Prognosis Can be Described by a Novel Method: Posterior Urethral Stenosis Score.

PubMed

Wang, Lin; Lv, Xiangguo; Jin, Chongrui; Guo, Hailin; Shu, Huiquan; Fu, Qiang; Sa, Yinglong

2018-02-01

To develop a standardized PU-score (posterior urethral stenosis score), with the goal of using this scoring system as a preliminary predictor of surgical complexity and prognosis of posterior urethral stenosis. We retrospectively reviewed records of all patients who underwent posterior urethral surgery at our institution from 2013 to 2015. The PU-score is based on 5 components, namely etiology (1 or 2 points), location (1-3 points), length (1-3 points), urethral fistula (1 or 2 points), and posterior urethral false passage (1 point). We calculated the score of all patients and analyzed its association with surgical complexity, stenosis recurrence, intraoperative blood loss, erectile dysfunction, and urinary incontinence. There were 144 patients who underwent low complexity urethral surgery (direct vision internal urethrotomy, anastomosis with or without crural separation) with a mean score of 5.1 points, whereas 143 underwent high complexity urethroplasty (anastomosis with inferior pubectomy or urethrorectal fistula repair, perineal or scrotum skin flap urethroplasty, bladder flap urethroplasty) with a mean score of 6.9 points. The increase of PU-score was predictive of higher surgical complexity (P = .000), higher recurrence (P = .002), more intraoperative blood loss (P = .000), and decrease of preoperative (P = .037) or postoperative erectile function (P = .047). However, no association was observed between PU-score and urinary incontinence (P = .213). The PU-score is a novel and meaningful scoring system that describes the essential factors in determining the complexity and prognosis for posterior urethral stenosis. Copyright © 2017. Published by Elsevier Inc.

Heptavalent Actinide Tetroxides NpO 4 – and PuO 4 –: Oxidation of Pu(V) to Pu(VII) by Adding an Electron to PuO 4

DOE PAGES

Gibson, John K.; de Jong, Wibe A.; Dau, Phuong D.; ...

2017-11-14

The highest known actinide oxidation states are Np(VII) and Pu(VII), both of which have been identified in solution and solid compounds. Recently a molecular Np(VII) complex, NpO 3(NO 3) 2-, was prepared and characterized in the gas phase. In accord with the lower stability of heptavalent Pu, no Pu(VII) molecular species has been identified. Reported here are the gas-phase syntheses and characterizations of NpO 4 - and PuO 4 -. Reactivity studies and density functional theory computations indicate the heptavalent metal oxidation state in both. This is the first instance of Pu(VII) in the absence of stabilizing effects due tomore » condensed phase solvation or crystal fields. Here, the results indicate that addition of an electron to neutral PuO 4, which has a computed electron affinity of 2.56 eV, counterintuitively results in oxidation of Pu(V) to Pu(VII), concomitant with superoxide reduction.« less

Heptavalent Actinide Tetroxides NpO 4 – and PuO 4 –: Oxidation of Pu(V) to Pu(VII) by Adding an Electron to PuO 4

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gibson, John K.; de Jong, Wibe A.; Dau, Phuong D.

The highest known actinide oxidation states are Np(VII) and Pu(VII), both of which have been identified in solution and solid compounds. Recently a molecular Np(VII) complex, NpO 3(NO 3) 2-, was prepared and characterized in the gas phase. In accord with the lower stability of heptavalent Pu, no Pu(VII) molecular species has been identified. Reported here are the gas-phase syntheses and characterizations of NpO 4 - and PuO 4 -. Reactivity studies and density functional theory computations indicate the heptavalent metal oxidation state in both. This is the first instance of Pu(VII) in the absence of stabilizing effects due tomore » condensed phase solvation or crystal fields. Here, the results indicate that addition of an electron to neutral PuO 4, which has a computed electron affinity of 2.56 eV, counterintuitively results in oxidation of Pu(V) to Pu(VII), concomitant with superoxide reduction.« less

Interaction of aerobic soil bacteria with plutonium(VI)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Panak, Petra J.; Nitsche, Heino

2000-08-22

We studied the interaction of Pu(VI) with Pseudomonas stutzeri ATCC 17588 and Bacillus sphaericus ATCC 14577, representatives of the main aerobic groups of soil bacteria present in the upper soil layers. The accumulation studies have shown that these soil bacteria accumulate high amounts of Pu(VI). The sorption efficiency toward Pu(VI) decreased with increasing biomass concentration due to increased agglomeration of the bacteria resulting in a decreased total surface area and number of available complexing groups. Spores of Bacillus sphaericus showed a higher biosorption than the vegetative cells at low biomass concentration which decreased significantly with increasing biomass concentration. At highermore » biomass concentrations (> 0.7 g/L), the vegetative cells of both strains and the spores of B. sphaericus showed comparable sorption efficiencies. Investigations on the pH dependency of the biosorption and extraction studies with 0.01 M EDTA solution have shown that the biosorption of plutonium is a reversible process and the plutonium is bound by surface complexation. Optical absorption spectroscopy showed that one third of the initially present Pu(VI) was reduced to Pu(V) after 24 hours. Kinetic studies and solvent extraction to separate different oxidation states of Pu after contact with the biomass provided further information on the yield and the kinetics of the bacteria-mediated reduction. Long-term studies showed that also 16% of Pu(IV) was formed after one month. The comparison of the amount of Pu(IV) formed during that time period with literature data of the Pu(V) disproportionation, indicated that the Pu(IV) seemed to be rather the result of the disproportionation of the formed Pu(V) than of a further microbial reduction.« less

What Matters: Quantity or Quality of Pornography Use? Psychological and Behavioral Factors of Seeking Treatment for Problematic Pornography Use.

PubMed

Gola, Mateusz; Lewczuk, Karol; Skorko, Maciej

2016-05-01

Pornography has become popular with Internet technology. For most people, pornography use (PU) is entertainment; for some, it can result in seeking treatment for out-of-control behavior. Previous studies have suggested that PU can influence sexual behaviors, but the direct relation between frequency of PU and treatment-seeking behaviors has not been examined. To investigate whether individuals seeking treatment as a consequence of their problematic PU do so because of their quantity of pornography consumption or because of more complex psychological and behavioral factors related to PU, such as the severity of negative symptoms associated with PU and/or subjective feeling of loss of control over one's behavior. A survey study was conducted of 569 heterosexual Caucasian men 18 to 68 years old, including 132 seeking treatment for problematic PU (referred by psychotherapists after their initial visit). The main outcome measures were self-reported PU, its negative symptoms, and actual treatment-seeking behavior. We tested models explaining sources of seeking treatment for problematic PU with negative symptoms associated with PU and additional factors (eg, onset and number of years of PU, religiosity, age, dyadic sexual activity, and relationship status). Seeking treatment was significantly, yet weakly, correlated solely with the frequency of PU (r = 0.21, P < .05) and this relation was significantly mediated by negative symptoms associated with PU (strong, nearly full mediation effect size; k(2) = 0.266). The relation between PU and negative symptoms was significant and mediated by self-reported subjective religiosity (weak, partial mediation; k(2) = 0.066) in those not seeking treatment. Onset of PU and age appeared to be insignificant. Our model was fairly fitted (comparative fit index = 0.989; root mean square error of approximation = 0.06; standardized root mean square residual = 0.035) and explained 43% of the variance in treatment-seeking behavior (1% was explained by frequency of PU and 42% was explained by negative symptoms associated with PU). Negative symptoms associated with PU more strongly predict seeking treatment than mere quantity of pornography consumption. Thus, treatment of problematic PU should address qualitative factors, rather than merely mitigating the frequency of the behavior, because frequency of PU might not be a core issue for all patients. Future diagnostic criteria for problematic PU should consider the complexity of this issue. Copyright © 2016 International Society for Sexual Medicine. Published by Elsevier Inc. All rights reserved.

Whole-Organism Concentration Ratios for Plutonium in Wildlife from Past US Nuclear Research Data

DOE Office of Scientific and Technical Information (OSTI.GOV)

johansen, M.; Kamboj; Kuhne, W.

Whole-organism concentration ratios (CR{sub wo-media}) for plutonium (Pu) in wildlife were calculated using data from the broad range of organism types and environmental settings of the US nuclear research program. Original sources included site-specific reports and scientific journal articles typically from 1960s to 80s research. Most of the calculated CR{sub wo-media} values are new to existing data sets, and, for some wildlife categories, serve to fill gaps or add to sparse data including those for terrestrial reptile; freshwater bird, crustacean and zooplankton; and marine crustacean and zooplankton. Ratios of Pu concentration in the whole-organism to that in specific tissues andmore » organs are provided here for a range of freshwater and marine fish. The CR{sub wo-media} values in fish living in liquid discharge ponds were two orders of magnitude higher than those for similar species living in lakes receiving Pu from atmospheric fallout, suggesting the physico-chemical form of the source Pu can dominate over other factors related to transfer, such as organism size and feeding behavior. Small rodent data indicated one to two order of magnitude increases when carcass, pelt, and gastrointestinal tract were included together in the whole-organism calculation compared to that for carcass alone. Only 4% of Pu resided in the carcass of small rodents compared to 75% in the gastrointestinal tract and 21% in the pelt.« less

Modulation of electronic structures of bases through DNA recognition of protein.

PubMed

Hagiwara, Yohsuke; Kino, Hiori; Tateno, Masaru

2010-04-21

The effects of environmental structures on the electronic states of functional regions in a fully solvated DNA·protein complex were investigated using combined ab initio quantum mechanics/molecular mechanics calculations. A complex of a transcriptional factor, PU.1, and the target DNA was used for the calculations. The effects of solvent on the energies of molecular orbitals (MOs) of some DNA bases strongly correlate with the magnitude of masking of the DNA bases from the solvent by the protein. In the complex, PU.1 causes a variation in the magnitude among DNA bases by means of directly recognizing the DNA bases through hydrogen bonds and inducing structural changes of the DNA structure from the canonical one. Thus, the strong correlation found in this study is the first evidence showing the close quantitative relationship between recognition modes of DNA bases and the energy levels of the corresponding MOs. Thus, it has been revealed that the electronic state of each base is highly regulated and organized by the DNA recognition of the protein. Other biological macromolecular systems can be expected to also possess similar modulation mechanisms, suggesting that this finding provides a novel basis for the understanding for the regulation functions of biological macromolecular systems.

Application of a canine 238Pu dosimetry model to human bioassay data

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hickman, Jr., A. W.

1991-08-01

Associated with the use of 2 238Pu in thermoelectric power sources for space probes and power supplies for cardiac devices is the potential for human exposure to 238Pu, primarily by inhalation. In the event of human internal exposure, a means is needed for assessing the level of intake and calculating radiation doses. Several bioassay/dosimetry models have been developed for 239Pu. However, results from studies with laboratory animals have indicated that the biokinetics, and therefore the descriptive models, of 238Pu are significantly different from those for 239Pu. A canine model accounting for these differences has been applied in this work tomore » urinary excretion data from seven humans occupationally exposed to low levels of an insoluble 238Pu compound. The modified model provides a good description of the urinary excretion kinetics observed in the exposed humans. The modified model was also used to provide estimates of the initial intakes of 238Pu for the seven individuals; these estimates ranged from 4.5 nCi (170 Bq) to 87 nCi (3200 Bq). Autopsy data on the amount and distribution of 238Pu retained in the organs may be used in the future to validate or refute both these estimates and the assumptions used to formulate the human model. Modification of the human model to simulate an injection exposure to 239Pu gave patterns of retention in the organs and urinary excretion comparable to those seen previously in humans; further modification of the model using fecal data (unavailable for the subjects of this study) is indicated.« less

Nacre biomimetic design--a possible approach to prepare low infrared emissivity composite coatings.

PubMed

Zhang, Weigang; Xu, Guoyue; Ding, Ruya; Duan, Kaige; Qiao, Jialiang

2013-01-01

Mimicking the highly organized brick-and-mortar structure of nacre, a kind of nacre-like organic-inorganic composite material of polyurethane (PU)/flaky bronze composite coatings with low infrared emissivity was successfully designed and prepared by using PU and flaky bronze powders as adhesives and pigments, respectively. The infrared emissivity and microstructure of the coatings were systematically investigated by infrared emissometer and scanning electron microscopy, respectively, and the cause of low infrared emissivity of the coatings was discussed by using the theories of one-dimensional photonic structure. The results show that the infrared emissivity of the nacre-like PU/flaky bronze composite coatings can be as low as 0.206 at the bronze content of 60 wt. %, and it is significantly lower than the value of PU/sphere bronze composite coatings. Microstructure observation illustrated that the nacre-like PU/flaky bronze composite coatings have similar one-dimensional photonic structural characteristics. The low infrared emissivity of PU/flaky bronze composite coatings is derived from the similar one-dimensional photonic structure in the coatings. Copyright © 2012 Elsevier B.V. All rights reserved.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Xu, C.; Santschi, P; Roberts, K

Relatively recently, inorganic colloids have been invoked to reconcile the apparent contradictions between expectations based on classical dissolved-phase Pu transport and field observations of 'enhanced' Pu mobility (Kersting et al. Nature 1999, 397, 56-59). A new paradigm for Pu transport is mobilization and transport via biologically produced ligands. This study for the first time reports a new finding of Pu being transported, at sub-pM concentrations, by a cutin-like natural substance containing siderophore-like moieties and virtually all mobile Pu. Most likely, Pu is complexed by chelating groups derived from siderophores that are covalently bound to a backbone of cutin-derived soil degradationmore » products, thus revealing the history of initial exposure to Pu. Features such as amphiphilicity and small size make this macromolecule an ideal collector for actinides and other metals and a vector for their dispersal. Cross-linking to the hydrophobic domains (e.g., by polysaccharides) gives this macromolecule high mobility and a means of enhancing Pu transport. This finding provides a new mechanism for Pu transport through environmental systems that would not have been predicted by Pu transport models.« less

Comparative uptake of plutonium from soils by Brassica juncea and Helianthus annuus.

PubMed

Lee, J H; Hossner, L R; Attrep, M; Kung, K S

2002-01-01

Plutonium uptake by Brassica juncea (Indian mustard) and Helianthus annuus (sunflower) from soils with varying chemical composition and contaminated with Pu complexes (Pu-nitrate [239Pu(NO3)4], Pu-citrate [239Pu(C6H5O7)], and Pu-diethylenetriaminepentaacetic acid (Pu-DTPA [239Pu-C14H23O10N3]) was investigated. Sequential extraction of soils incubated with applied Pu was used to determine the distribution of Pu in the various soil fractions. The initial Pu activity levels in soils were 44.40-231.25 Bq g(-1) as Pu-nitrate Pu-citrate, or Pu-DTPA. A difference in Pu uptake between treatments of Pu-nitrate and Pu-citrate without chelating agent was observed only with Indian mustard in acidic Crowley soil. The uptake of Pu by plants was increased with increasing DTPA rates, however, the Pu concentration of plants was not proportionally increased with increasing application rate of Pu to soil. Plutonium uptake from Pu-DTPA was significantly higher from the acid Crowley soil than from the calcareous Weswood soil. The uptake of Pu from the soils was higher in Indian mustard than in sunflower. Sequential extraction of Pu showed that the ion-exchangeable Pu fraction in soils was dramatically increased with DTPA treatment and decreased with time of incubation. Extractability of Pu in all fractions was not different when Pu-nitrate and Pu-citrate were applied to the same soil. More Pu was associated with the residual Pu fraction without DTPA application. Consistent trends with time of incubation for other fractions were not apparent. The ion-exchangeable fraction, assumed as plant-available Pu, was significantly higher in acid soil compared with calcareous soil with or without DTPA treatment. When the calcareous soil was treated with DTPA, the ion-exchangeable Pu was comparatively less influenced. This fraction in the soil was more affected with time of incubation. The lowest extractable Pu was from a pH 6.55 Crockett soil that contained the highest clay compared to the other two soils. Extractable soil Pu was largely affected by soil pH and the amounts of clay, salt, metal oxide, and carbonate.

Experimental geochemistry of Pu and Sm and the thermodynamics of trace element partitioning

NASA Technical Reports Server (NTRS)

Jones, John H.; Burnett, Donald S.

1987-01-01

An experimental study of the partitioning of Pu and Sm between diopside/liquid and whitlockite/liquid supports the hypothesis that Pu behaves as a light rare earth element during igneous processes in reducing environments. D-Pu/D-Sm is found to be about 2 for both diopsidic pyroxene and whitlockite, and the amount of fractionation would be decreased further if Pu were compared to Ce or Nd. Data indicate that temperature, rather than melt composition, is the most important control on elemental partitioning, and that P2O5 in aluminosilicate melts serves as a complexing agent for the actinides and lanthanides.

Speciation and Bioavailability Measurements of Environmental Plutonium Using Diffusion in Thin Films.

PubMed

Cusnir, Ruslan; Steinmann, Philipp; Christl, Marcus; Bochud, François; Froidevaux, Pascal

2015-11-09

The biological uptake of plutonium (Pu) in aquatic ecosystems is of particular concern since it is an alpha-particle emitter with long half-life which can potentially contribute to the exposure of biota and humans. The diffusive gradients in thin films technique is introduced here for in-situ measurements of Pu bioavailability and speciation. A diffusion cell constructed for laboratory experiments with Pu and the newly developed protocol make it possible to simulate the environmental behavior of Pu in model solutions of various chemical compositions. Adjustment of the oxidation states to Pu(IV) and Pu(V) described in this protocol is essential in order to investigate the complex redox chemistry of plutonium in the environment. The calibration of this technique and the results obtained in the laboratory experiments enable to develop a specific DGT device for in-situ Pu measurements in freshwaters. Accelerator-based mass-spectrometry measurements of Pu accumulated by DGTs in a karst spring allowed determining the bioavailability of Pu in a mineral freshwater environment. Application of this protocol for Pu measurements using DGT devices has a large potential to improve our understanding of the speciation and the biological transfer of Pu in aquatic ecosystems.

Concentration and purification of plutonium or thorium

DOEpatents

Hayden, John A.; Plock, Carl E.

1976-01-01

In this invention a first solution obtained from such as a plutonium/thorium purification process or the like, containing plutonium (Pu) and/or thorium (Th) in such as a low nitric acid (HNO.sub.3) concentration may have the Pu and/or Th separated and concentrated by passing an electrical current from a first solution having disposed therein an anode to a second solution having disposed therein a cathode and separated from the first solution by a cation permeable membrane, the Pu or Th cation permeating the cation membrane and forming an anionic complex within the second solution, and electrical current passage affecting the complex formed to permeate an anion membrane separating the second solution from an adjoining third solution containing disposed therein an anode, thereby effecting separation and concentration of the Pu and/or Th in the third solution.

Culture on electrospun polyurethane scaffolds decreases atrial natriuretic peptide expression by cardiomyocytes in vitro.

PubMed

Rockwood, Danielle N; Akins, Robert E; Parrag, Ian C; Woodhouse, Kimberly A; Rabolt, John F

2008-12-01

The function of the mammalian heart depends on the functional alignment of cardiomyocytes, and controlling cell alignment is an important consideration in biomaterial design for cardiac tissue engineering and research. The physical cues that guide functional cell alignment in vitro and the impact of substrate-imposed alignment on cell phenotype, however, are only partially understood. In this report, primary cardiac ventricular cells were grown on electrospun, biodegradable polyurethane (ES-PU) with either aligned or unaligned microfibers. ES-PU scaffolds supported high-density cultures and cell subpopulations remained intact over two weeks in culture. ES-PU cultures contained electrically-coupled cardiomyocytes with connexin-43 localized to points of cell:cell contact. Multi-cellular organization correlated with microfiber orientation and aligned materials yielded highly oriented cardiomyocyte groupings. Atrial natriuretic peptide, a molecular marker that shows decreasing expression during ventricular cell maturation, was significantly lower in cultures grown on ES-PU scaffolds than in those grown on tissue culture polystyrene. Cells grown on aligned ES-PU had significantly lower steady state levels of ANP and constitutively released less ANP over time indicating that scaffold-imposed cell organization resulted in a shift in cell phenotype to a more mature state. We conclude that the physical organization of microfibers in ES-PU scaffolds impacts both multi-cellular architecture and cardiac cell phenotype in vitro.

Structures of plutonium coordination compounds: A review of past work, recent single crystal x-ray diffraction results, and what we're learning about plutonium coordination chemistry

NASA Astrophysics Data System (ADS)

Neu, M. P.; Matonic, J. H.; Smith, D. M.; Scott, B. L.

2000-07-01

The compounds we have isolated and characterized include plutonium(III) and plutonium(IV) bound by ligands with a range of donor types and denticity (halide, phosphine oxide, hydroxamate, amine, sulfide) in a variety of coordination geometries. For example, we have obtained the first X-ray structure of Pu(III) complexed by a soft donor ligand. Using a "one pot" synthesis beginning with Pu metal strips and iodine in acetonitrile and adding trithiacyclononane we isolated the complex, PuI3(9S3)(MeCN)2 (Figure 1). On the other end of the coordination chemistry spectrum, we have obtained the first single crystal structure of the Pu(IV) hexachloro anion (Figure 2). Although this species has been used in plutonium purification via anion exchange chromatography for decades, the bond distances and exact structure were not known. We have also characterized the first plutonium-biomolecule complex, Pu(IV) bound by the siderophore desferrioxamine E.In this presentation we will review the preparation, structures, and importance of previously known coordination compounds and of those we have recently isolated. We will show the coordination chemistry of plutonium is rich and varied, well worth additional exploration.

Performance of innovative PU-foam and natural fiber-based composites for the biofiltration of a mixture of volatile organic compounds by a fungal biofilm.

PubMed

Gutiérrez-Acosta, O B; Arriaga, S; Escobar-Barrios, V A; Casas-Flores, S; Almendarez-Camarillo, A

2012-01-30

The performance of perlite and two innovative carriers that consist of polyurethane (PU) chemically modified with starch; and polypropylene reinforced with agave fibers was evaluated in the biofiltration of a mixture of VOCs composed of hexane, toluene and methyl-ethyl-ketone. At a total organic loading rate of 145 gCm(-3)h(-1) the elimination capacities (ECs) obtained were 145, 24 and 96 gCm(-3)h(-1) for the biofilters packed with the PU, the reinforced polypropylene, and perlite, respectively. Specific maximum biodegradation rates of the mixture, in the biofilters, were 416 mgCg(protein)(-1)  h(-1) for the PU and 63 mgCg(protein)(-1) h(-1) for perlite, which confirms the highest performance of the PU-composite. 18S rDNA analysis from the PU-biofilter revealed the presence of Fusarium solani in its sexual and asexual states, respectively. The modified PU carrier significantly reduced the start-up period of the biofilter and enhanced the EC of the VOCs. Thus, this study gives new alternatives in the field of packing materials synthesis, promoting the addition of easily biodegradable sources to enhance the performance of biofilters. Copyright © 2011 Elsevier B.V. All rights reserved.

Multi-isotopic determination of plutonium (239Pu, 240Pu, 241Pu and 242Pu) in marine sediments using sector-field inductively coupled plasma mass spectrometry.

PubMed

Donard, O F X; Bruneau, F; Moldovan, M; Garraud, H; Epov, V N; Boust, D

2007-03-28

Among the transuranic elements present in the environment, plutonium isotopes are mainly attached to particles, and therefore they present a great interest for the study and modelling of particle transport in the marine environment. Except in the close vicinity of industrial sources, plutonium concentration in marine sediments is very low (from 10(-4) ng kg(-1) for (241)Pu to 10 ng kg(-1) for (239)Pu), and therefore the measurement of (238)Pu, (239)Pu, (240)Pu, (241)Pu and (242)Pu in sediments at such concentration level requires the use of very sensitive techniques. Moreover, sediment matrix contains huge amounts of mineral species, uranium and organic substances that must be removed before the determination of plutonium isotopes. Hence, an efficient sample preparation step is necessary prior to analysis. Within this work, a chemical procedure for the extraction, purification and pre-concentration of plutonium from marine sediments prior to sector-field inductively coupled plasma mass spectrometry (SF-ICP-MS) analysis has been optimized. The analytical method developed yields a pre-concentrated solution of plutonium from which (238)U and (241)Am have been removed, and which is suitable for the direct and simultaneous measurement of (239)Pu, (240)Pu, (241)Pu and (242)Pu by SF-ICP-MS.

Sources and pathways of artificial radionuclides to soils at a High Arctic site.

PubMed

Lokas, E; Bartmiński, P; Wachniew, P; Mietelski, J W; Kawiak, T; Srodoń, J

2014-11-01

Activity concentrations, inventories and activity ratios of (137)Cs, (238)Pu, (239 + 240)Pu and (241)Am in soil profiles were surveyed in the dry tundra and the adjoining proglacial zones of glaciers at a High Arctic site on Svalbard. Vertical profiles of radionuclide activities were determined in up to 14-cm-thick soil sequences. Additionally, soil properties (pH, organic matter, texture, mineral composition and sorption capacity) were analyzed. Results obtained in this study revealed a large range of activity concentrations and inventories of the fallout radionuclides from the undetectable to the uncommonly high levels (inventories of 30,900 ± 940, 47 ± 6, 886 ± 80 and 296 ± 19 Bq/m(2) for (137)Cs, (238)Pu, (239 + 240)Pu and (241)Am, respectively) found in two profiles from the proglacial zone. Concentration of these initially airborne radionuclides in the proglacial zone soils is related to their accumulation in cryoconites that have a large ability to concentrate trace metals. The cryoconites develop on the surface of glaciers, and the material they accumulate is deposited on land surface after the glaciers retreat. The radionuclide inventories in the tundra soils, which effectively retain radionuclides due to high organic matter contents, were comparable to the global fallout deposition for this region of the world. The (238)Pu/(239 + 240)Pu activity ratios for tundra soils suggested global fallout as the dominant source of Pu. The (238)Pu/(239 + 240)Pu and (239 + 240)Pu/(137)Cs activity ratios in the proglacial soils pointed to possible contributions of these radionuclides from other, unidentified sources.

Millable polyurethane/organoclay nanocomposites: preparation, characterization, and properties.

PubMed

Siliani, M; López-Manchado, M A; Valentín, J L; Arroyo, M; Marcos, A; Khayet, M; Villaluenga, J P G

2007-02-01

Novel millable polyurethane (PU)/organoclay nanocomposites have been successfully prepared by conventional transformation techniques. One natural (C6A) and two organically modified (C15A and C30B) montmorillonites have been used as clays for preparing PU nanocomposites. The optimum dispersion of nanofiller at a nanometer scale in PU matrix was confirmed by X-ray diffraction patterns and transmission electron microscopy. A substantial improvement of the PU properties by addition of only a small amount of organoclay was observed. It is worthy to note that the organoclays show a different interfacial interaction with the PU matrix, which was reflected in different macroscopic properties. Thus, C30B organoclay seems to react with PU chains to form covalent bonds, while C15A only interacts physically with PU chains. Mechanical and barrier properties are analyzed.

Theory of Photoemission in Actinides

DOE Office of Scientific and Technical Information (OSTI.GOV)

Svane, Axel

2008-07-01

A theory is presented which describes the photoemission spectra of actinide compounds starting from the atomic limit of isolated actinide ions. The multiplets of the ion are calculated and an additional term is introduced to describe the interaction with the sea of conduction electrons. This leads to complex mixed-valent ground states, which describes well the rich spectrum observed for PuSe. In particular, the three-peak feature, which is often seen in Pu and Pu compounds in the vicinity of the Fermi level originates from f{sup 6} {yields} f{sup 5} emission. The theory is further applied to PuSb, PuCoGa{sub 5} and Am.more » (author)« less

Colloidal cutin-like substances cross-linked to siderophore decomposition products mobilizing plutonium from contaminated soils.

PubMed

Xu, C; Santschi, P H; Zhong, J Y; Hatcher, P G; Francis, A J; Dodge, C J; Roberts, K A; Hung, C C; Honeyman, B D

2008-11-15

Relatively recently, inorganic colloids have been invoked to reconcile the apparent contradictions between expectations based on classical dissolved-phase Pu transport and field observations of "enhanced" Pu mobility (Kersting et al. Nature 1999, 397, 56-59). A new paradigm for Pu transport is mobilization and transport via biologically produced ligands. This study for the first time reports a new finding of Pu being transported, at sub-pM concentrations, by a cutin-like natural substance containing siderophore-like moieties and virtually all mobile Pu. Most likely, Pu is complexed by chelating groups derived from siderophores that are covalently bound to a backbone of cutin-derived soil degradation products, thus revealing the history of initial exposure to Pu. Features such as amphiphilicity and small size make this macromolecule an ideal collector for actinides and other metals and a vector for their dispersal. Cross-linking to the hydrophobic domains (e.g., by polysaccharides) gives this macromolecule high mobility and a means of enhancing Pu transport. This finding provides a new mechanism for Pu transport through environmental systems that would not have been predicted by Pu transport models.

PuPHOS: a synthetically useful chiral bidentate ligand for the intermolecular Pauson-Khand reaction.

PubMed

Verdaguer, Xavier; Lledó, Agustí; López-Mosquera, Cristina; Maestro, Miguel Angel; Pericàs, Miquel A; Riera, Antoni

2004-11-12

Here we describe the synthesis and use of the Pulegone-derived bidentate P,S ligands PuPHOS and CyPuPHOS in the intermolecular Pauson-Khand reaction. Ligand exchange reaction of hexacarbonyldicobalt-alkyne complexes with PuPHOS provides a diasteromeric mixture of complexes (up to 4.5:1) from which the major isomers can be conveniently separated by simple crystallization. An isomerization-crystallization sequence of the original mixture results in a dynamic resolution that allows the preparation of the pure major Co(2)(mu-TMSC(2)H)(CO)(4)-PuPHOS (15a) in a multigram scale. Pauson-Khand reaction of 15a with norbornadiene provided, for the first time, the corresponding enone 18 with up to 93% yield and 97% ee. The use of (+)-18 as a surrogate of chiral cyclopentadienone is also demonstrated. Copper-catalyzed Michael addition of a Grignard reagent followed by removal of the TMS group with TBAF were the most reliable methods to transform (+)-18 into valuable starting materials 20a-e for the enantioselective synthesis of cyclopentenoid systems.

Triplet-Triplet Annihilation Photon Upconversion in Polymer Thin Film: Sensitizer Design.

PubMed

Jiang, Xinpeng; Guo, Xinyan; Peng, Jiang; Zhao, Dahui; Ma, Yuguo

2016-05-11

Efficient visible-to-UV photon upconversion via triplet-triplet annihilation (TTA) is accomplished in polyurethane (PU) films by developing new, powerful photosensitizers fully functional in the solid-state matrix. These rationally designed triplet sensitizers feature a bichromophoric scaffold comprising a tris-cyclometalated iridium(III) complex covalently tethered to a suitable organic small molecule. The very rapid intramolecular triplet energy transfer from the former to the latter is pivotal for achieving the potent sensitizing ability, because this process out-competes the radiative and nonradiative decays inherent to the metal complex and produces long-lived triplet excitons localized with the acceptor moiety readily available for intermolecular transfer and TTA. Nonetheless, compared to the solution state, the molecular diffusion is greatly limited in solid matrices, which even creates difficulty for the Dexter-type intramolecular energy transfer. This is proven by the experimental results showing that the sensitizing performance of the bichromophoric molecules strongly depends on the spatial distance separating the donor (D) and acceptor (A) units and that incorporating a longer linker between the D and A evidently curbs the TTA upconversion efficiency in PU films. Using a rationally optimized sensitizer structure in combination with 2,7-di-tert-butylpyrene as the annihilator/emitter, the doped polyurethane (PU) films demonstrate effective visible-to-UV upconverted emission signal under noncoherent-light irradiation, attaining an upconversion quantum yield of 2.6%. Such quantum efficiency is the highest value so far reported for the visible-to-UV TTA systems in solid matrices.

Reduction of the "burst release" of copper ions from copper-based intrauterine devices by organic inhibitors.

PubMed

Alvarez, Florencia; Schilardi, Patricia L; de Mele, Monica Fernández Lorenzo

2012-01-01

The copper intrauterine device is a contraceptive method that is based on the release of copper ions from a copper wire. Immediately after insertion, the dissolution of copper in the uterine fluid is markedly higher ("burst release") than that necessary for contraception action, leading to a variety of harmful effects. Pretreatments with organic compounds [thiourea (TU) and purine (PU), 10(-4)-10(-2) M concentration range, 1- and 3-h immersion times] were tested. The dissolution of copper with and without pretreatments in TU and PU solutions was analyzed by conventional electrochemical techniques and surface analysis. Pretreatments in PU solutions reduced the initial corrosion rate of copper in simulated uterine solutions, with inhibitory efficiencies that depend on the PU concentration and on the immersion time assayed. Inhibitory efficiency values higher than 98% for pretreatments with ≥10(-3) M PU were found. Conversely, after TU pretreatments, a high copper release was measured. It was concluded that 10(-3) M PU pretreatment is a promising strategy able to reduce the "burst release" of copper and to ensure contraceptive action. Copyright © 2012 Elsevier Inc. All rights reserved.

Coordination and Hydrolysis of Plutonium Ions in Aqueous Solution using Car-Parrinello Molecular Dynamics Free Energy Simulations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Odoh, Samuel O.; Bylaska, Eric J.; De Jong, Wibe A.

Car-Parrinello molecular dynamics (CPMD) simulations have been used to examine the hydration structures, coordination energetics and the first hydrolysis constants of Pu3+, Pu4+, PuO2+ and PuO22+ ions in aqueous solution at 300 K. The coordination numbers and structural properties of the first shell of these ions are in good agreement with available experimental estimates. The hexavalent PuO22+ species is coordinated to 5 aquo ligands while the pentavalent PuO2+ complex is coordinated to 4 aquo ligands. The Pu3+ and Pu4+ ions are both coordinated to 8 water molecules. The first hydrolysis constants obtained for Pu3+ and PuO22+ are 6.65 and 5.70more » respectively, all within 0.3 pH units of the experimental values (6.90 and 5.50 respectively). The hydrolysis constant of Pu4+, 0.17, disagrees with the value of -0.60 in the most recent update of the Nuclear Energy Agency Thermochemical Database (NEA-TDB) but supports recent experimental findings. The hydrolysis constant of PuO2+, 9.51, supports the experimental results of Bennett et al. (Radiochim. Act. 1992, 56, 15). A correlation between the pKa of the first hydrolysis reaction and the effective charge of the plutonium center was found.« less

Biodegradation of PuEDTA and Impacts on Pu Mobility

DOE Office of Scientific and Technical Information (OSTI.GOV)

Xun, Luying; Bolton, Jr., Harvey

Ethylenediaminetetraacetate (EDTA) and nitrilotriacetate (NTA) are synthetic chelating agents, which can form strong water-soluble complexes with radionuclides and metals and has been used to decontaminate and process nuclear materials. Synthetic chelating agents were co-disposed with radionuclides (e.g., 60Co, Pu) and heavy metals enhancing their transport in the subsurface. An understanding of EDTA biodegradation is essential to help mitigate enhanced radionuclide transport by EDTA. The objective of this research is to develop fundamental data on factors that govern the biodegradation of radionuclide-EDTA. These factors include the dominant EDTA aqueous species, the biodegradation of various metal-EDTA complexes, the uptake of various metal-EDTAmore » complexes into the cell, the distribution and mobility of the radionuclide during and after EDTA biodegradation, and the enzymology and genetics of EDTA biodegradation.« less

Soy-based UV resistant polyurethane pultruded composites.

DOT National Transportation Integrated Search

2012-02-01

Aliphatic polyurethane (PU) nanocomposites were synthesized using organically modified nanoclays. X-Ray diffraction results : confirmed good exfoliation of nanoclay particles in the PU resin system. With the addition of just 1% of nanoclay in the bas...

Effect of equilibration time on Pu desorption from goethite

DOE PAGES

Wong, Jennifer C.; Zavarin, Mavrik; Begg, James D.; ...

2015-01-28

Strongly sorbing ions such as plutonium may become irreversibly bound to mineral surfaces over time implicates near- and far-field transport of Pu. Batch adsorption–desorption data were collected as a function of time and pH to study the surface stability of Pu on goethite. Pu(IV) was adsorbed to goethite over the pH range 4.2 to 6.6 for different periods of time (1, 6, 15, 34 and 116 d). Moreover, following adsorption, Pu was leached from the mineral surface with desferrioxamine B (DFOB), a complexant capable of effectively competing with the goethite surface for Pu. The amount of Pu desorbed from the goethitemore » was found to vary as a function of the adsorption equilibration time, with less Pu removed from the goethite following longer adsorption periods. This effect was most pronounced at low pH. Logarithmic desorption distribution ratios for each adsorption equilibration time were fit to a pH-dependent model. Model slopes decreased between 1 and 116 d adsorption time, indicating that overall Pu(IV) surface stability on goethite surfaces becomes less dependent on pH with greater adsorption equilibration time. The combination of adsorption and desorption kinetic data suggest that non-redox aging processes affect Pu sorption behavior on goethite.« less

Pacific Northwest Laboratory annual report for 1976 to the ERDA Assistant Administrator for Environment and Safety. Part 1. Biomedical Sciences

DOE Office of Scientific and Technical Information (OSTI.GOV)

Thompson, R.C.

1977-05-01

Separate abstracts were prepared for individual sections of this publication. In addition to research reports the publication also contains organization charts, author index, and appendixes showing data on selected parameters relative to life-span dose-effect studies with inhaled /sup 239/PuO/sub 2/, /sup 238/PuO/sub 2/, and /sup 239/Pu in beagles. (HLW)

Biotic and Abiotic Reduction and Solubilization of Pu(IV)O2•xH2O(am) as Affected by Anthraquinone-2,6-disulfonate (AQDS) and Ethylenediaminetetraacetate (EDTA)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Plymale, Andrew E.; Bailey, Vanessa L.; Fredrickson, Jim K.

2012-01-24

In the presence of hydrogen (H{sub 2}), the synthetic chelating agent ethylenediaminetetraacetate (EDTA), and the electron shuttle anthraquinone-2,6-disulfonate (AQDS), the dissimilatory metal-reducing bacteria (DMRB) Shewanella oneidensis and Geobacter sulfurreducens both reductively solubilized 100% of added 0.5 mM plutonium (IV) hydrous oxide (Pu(IV)O{sub 2} {lg_bullet} xH{sub 2}O{sub (am)}) in {approx}24 h at pH 7 in a non-complexing buffer. In the absence of AQDS, bioreduction was much slower ({approx}22 days) and less extensive ({approx}83-94%). In the absence of DMRB but under comparable conditions, 89% (without AQDS) to 98% (with AQDS) of added 0.5 mM PuO{sub 2} {lg_bullet} xH{sub 2}O{sub (am)} was reductivelymore » solubilized over 418 days. Under comparable conditions but in the absence of EDTA, <0.001% of the 0.5 mM PuO{sub 2} {lg_bullet} xH{sub 2}O{sub (am)} was solubilized, with or without bacteria. However, Pu(aq) increased by as much as an order of magnitude in some EDTA-free treatments, both biotic and abiotic, and increases in solubility were associated with the production of both Pu(OH)3(am) and Pu(III)(aq). Incubation with DMRB in the absence of EDTA increased the polymeric and crystalline content of the PuO{sub 2} {lg_bullet} xH{sub 2}O{sub (am)} and also decreased Pu solubility in 6-N HCl. Results from an in vitro assay demonstrated electron transfer to PuO{sub 2} {lg_bullet} xH{sub 2}O{sub (am)} from the S. oneidensis outer-membrane c-type cytochrome MtrC, and EDTA increased the oxidation of MtrC by PuO{sub 2} {lg_bullet} xH{sub 2}O{sub (am)}. Our results suggest that PuO{sub 2} {lg_bullet} xH{sub 2}O{sub (am)} biotic and abiotic reduction and solubilization may be important in anoxic, reducing environments, especially where complexing ligands and electron shuttling compounds are present.« less

Effect of chemical pollution on forms of 137Cs, 90Sr and 239,240Pu in arctic soil studied by sequential extraction.

PubMed

Puhakainen, M; Riekkinen, I; Heikkinen, T; Jaakkola, T; Steinnes, E; Rissanen, K; Suomela, M; Thørring, H

2001-01-01

The aim of the present study was to determine the forms of 137Cs, 90Sr and 239,240Pu occurring in different soil horizons using sequential extraction of samples taken from four sites located along a pollution gradient from the copper-nickel smelter at Monchegorsk in the Kola Peninsula, Russia, and from a reference site in Finnish Lapland in 1997. A selective sequential-leaching procedure was employed using a modification of the method of Tessier, Cambell and Bisson ((1979). Analytical Chemistry, 51, 844-851). For 137Cs the organic (O) and uppermost mineral (E1) layer were studied, for 90Sr and 239,240Pu only the uppermost organic layer (Of). The fraction of 137Cs occurring in readily exchangeable form in the organic layer was about 50% at the reference site and decreased as a function of pollution, being 15% at the most polluted site in the Kola Peninsula. There was a clear positive correlation in the O layer between the distance from the smelter and the percentage of 137Cs extracted in the readily exchangeable fraction (Spearman correlation rsp = 0.7805, p = 0.0001), whereas in the E1 layer no correlation was evident. The distribution of 90Sr in the Of layer was similar at all sites, with the highest amounts occurring in exchangeable form and bound to organic matter, whereas stable Sr showed a somewhat different distribution with the highest amount in the oxide fraction. Most of the 239,240Pu was bound to organic matter. Chemical pollution affected the exchangeable fraction of 239,240Pu, which was about 1% at the most polluted site and 4-6% at the other sites.

Plutonium interaction studies with the Mont Terri Opalinus Clay isolate Sporomusa sp. MT-2.99: changes in the plutonium speciation by solvent extractions.

PubMed

Moll, Henry; Cherkouk, Andrea; Bok, Frank; Bernhard, Gert

2017-05-01

Since plutonium could be released from nuclear waste disposal sites, the exploration of the complex interaction processes between plutonium and bacteria is necessary for an improved understanding of the fate of plutonium in the vicinity of such a nuclear waste disposal site. In this basic study, the interaction of plutonium with cells of the bacterium, Sporomusa sp. MT-2.99, isolated from Mont Terri Opalinus Clay, was investigated anaerobically (in 0.1 M NaClO 4 ) with or without adding Na-pyruvate as an electron donor. The cells displayed a strong pH-dependent affinity for Pu. In the absence of Na-pyruvate, a strong enrichment of stable Pu(V) in the supernatants was discovered, whereas Pu(IV) polymers dominated the Pu oxidation state distribution on the biomass at pH 6.1. A pH-dependent enrichment of the lower Pu oxidation states (e.g., Pu(III) at pH 6.1 which is considered to be more mobile than Pu(IV) formed at pH 4) was observed in the presence of up to 10 mM Na-pyruvate. In all cases, the presence of bacterial cells enhanced removal of Pu from solution and accelerated Pu interaction reactions, e.g., biosorption and bioreduction.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Scott, B.R.; Muggenburg, B.A.; Welsh, C.A.

The alpha emitter plutonium-238 ({sup 238}Pu), which is produced in uranium-fueled, light-water reactors, is used as a thermoelectric power source for space applications. Inhalation of a mixed oxide form of Pu is the most likely mode of exposure of workers and the general public. Occupational exposures to {sup 238}PuO{sub 2} have occurred in association with the fabrication of radioisotope thermoelectric generators. Organs and tissue at risk for deterministic and stochastic effects of {sup 238}Pu-alpha irradiation include the lung, liver, skeleton, and lymphatic tissue. Little has been reported about the effects of inhaled {sup 238}PuO{sub 2} on peripheral blood cell countsmore » in humans. The purpose of this study was to investigate hematological responses after a single inhalation exposure of Beagle dogs to alpha-emitting {sup 238}PuO{sub 2} particles and to extrapolate results to humans.« less

COMPLEX FLUORIDES OF PLUTONIUM AND AN ALKALI METAL

DOEpatents

Seaborg, G.T.

1960-08-01

A method is given for precipitating alkali metal plutonium fluorides. such as KPuF/sub 5/, KPu/sub 2/F/sub 9/, NaPuF/sub 5/, and RbPuF/sub 5/, from an aqueous plutonium(IV) solution by adding hydrogen fluoride and alkali-metal- fluoride.

PU/SS EUTECTIC ASSESSMENT IN 9975 PACKAGINGS IN A STORAGE FACILITY DURING EXTENDED FIRE

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gupta, N.

2012-03-26

In a radioactive material (RAM) packaging, the formation of eutectic at the Pu/SS (plutonium/stainless steel) interface is a serious concern and must be avoided to prevent of leakage of fissile material to the environment. The eutectic temperature for the Pu/SS is rather low (410 C) and could seriously impact the structural integrity of the containment vessel under accident conditions involving fire. The 9975 packaging is used for long term storage of Pu bearing materials in the DOE complex where the Pu comes in contact with the stainless steel containment vessel. Due to the serious consequences of the containment breach atmore » the eutectic site, the Pu/SS interface temperature is kept well below the eutectic formation temperature of 410 C. This paper discusses the thermal models and the results for the extended fire conditions (1500 F for 86 minutes) that exist in a long term storage facility and concludes that the 9975 packaging Pu/SS interface temperature is well below the eutectic temperature.« less

DFT+U Study of Chemical Impurities in PuO 2

DOE PAGES

Hernandez, Sarah C.; Holby, Edward F.

2016-05-24

In this paper, we employ density functional theory to explore the effects of impurities in the fluorite crystal structure of PuO 2. The impurities that were considered are known impurities that exist in metallic δ-phase Pu, including H, C, Fe, and Ga. These impurities were placed at various high-symmetry sites within the PuO 2 structure including an octahedral interstitial site, an interstitial site with coordination to two neighboring O atoms, an O substitutional site, and a Pu substitutional site. Incorporation energies were calculated to be energetically unfavorable for all sites except the Pu substitutional site. When impurities were placed inmore » a Pu substitutional site, complexes incorporating the impurities and O formed within the PuO 2 structure. The observed defect-oxygen structures were OH, CO 3, FeO 5, and GaO 3. The presence of these defects led to distortion of the surrounding O atoms within the structure, producing long-range disorder of O atoms. In contrast, perturbations of Pu atoms had a relatively short-range effect on the relaxed structures. These effects are demonstrated via radial distribution functions for O and Pu vacancies. Calculated electronic structure revealed hybridization of the impurity atom with the O valence states and a relative decrease in the Pu 5f states. Minor differences in band gaps were observed for the defected PuO 2 structures containing H, C, and Ga. Finally, Fe-containing structures, however, were calculated to have a significantly decreased band gap, where the implementation of a Hubbard U parameter on the Fe 3d orbitals will maintain the calculated PuO 2 band gap.« less

Fabrication of Functional Polyurethane/Rare Earth Nanocomposite Membranes by Electrospinning and Its VOCs Absorption Capacity from Air

PubMed Central

Ge, Jun Cong; Choi, Nag Jung

2017-01-01

Volatile organic compounds (VOCs) are a source of air pollution and are harmful to both human health and the environment. In this study, we fabricated polyurethane/rare earth (PU/RE) composite nanofibrous membranes via electrospinning with the aim of removing VOCs from air. The morphological structure of PU/RE nanofibrous mats was investigated using field emission scanning electron microscopy (FE-SEM), fourier transform infrared spectroscopy (FTIR), and X-ray diffraction (XRD) experimental analyses. A certain amount of RE (up to 50 wt. % compared to PU pellets) nanoparticles (NPs) could be loaded on/into PU fibers. The tensile strength of PU/RE nanofibrous membranes decreased slightly with the increasing RE powder content. The PU nanofiber containing 50 wt. % RE powder had the smallest fiber diameter of 356 nm; it also showed the highest VOC absorption capacity compared with other composite membranes, having an absorption capacity about three times greater than pure PU nanofibers. In addition, all of the PU/RE nanofibrous membranes readily absorbed styrene the most, followed by xylene, toluene, benzene and chloroform. Therefore, the PU/RE nanofibrous membrane can play an important role in removing VOCs from the air, and its development prospects are impressive because they are emerging materials. PMID:28336894

An equivalent n-source for WGPu derived from a spectrum-shifted PuBe source

NASA Astrophysics Data System (ADS)

Ghita, Gabriel; Sjoden, Glenn; Baciak, James; Walker, Scotty; Cornelison, Spring

2008-04-01

We have designed, built, and laboratory-tested a unique shield design that transforms the complex neutron spectrum from PuBe source neutrons, generated at high energies, to nearly exactly the neutron signature leaking from a significant spherical mass of weapons grade plutonium (WGPu). This equivalent "X-material shield assembly" (Patent Pending) enables the harder PuBe source spectrum (average energy of 4.61 MeV) from a small encapsulated standard 1-Ci PuBe source to be transformed, through interactions in the shield, so that leakage neutrons are shifted in energy and yield to become a close reproduction of the neutron spectrum leaking from a large subcritical mass of WGPu metal (mean energy 2.11 MeV). The utility of this shielded PuBe surrogate for WGPu is clear, since it directly enables detector field testing without the expense and risk of handling large amounts of Special Nuclear Materials (SNM) as WGPu. Also, conventional sources using Cf-252, which is difficult to produce, and decays with a 2.7 year half life, could be replaced by this shielded PuBe technology in order to simplify operational use, since a sealed PuBe source relies on Pu-239 (T½=24,110 y), and remains viable for more than hundreds of years.

Plutonium 238/239 Decorporation Model

DTIC Science & Technology

2014-10-01

distribution in tissue compartments over time with and without treatment, excretion rates, and radiation doses to critical organs. Calculations from...kPa) pound- mass -foot2 (moment of inertia) 4.214 011 x E – 2 kilogram-meter2 (kg*m2) pound- mass /foot3 1.601 846 x E + 1 kilogram/m3 (kg/m3) rad...45 Figure 21. Acute Doses to Critical Organs from Pu-238 and Pu-239 Over 90 Days ................... 46 Figure 22. Doses

Anaerobic Biotransformation and Mobility of Pu and of Pu-EDTA

DOE Office of Scientific and Technical Information (OSTI.GOV)

Xun, Luying

2009-11-20

The enhanced mobility of radionuclides by co-disposed chelating agent, ethylenediaminetetraacetate (EDTA), is likely to occur only under anaerobic conditions. Our extensive effort to enrich and isolate anaerobic EDTA-degrading bacteria has failed. Others has tried and also failed. To explain the lack of anaerobic biodegradation of EDTA, we proposed that EDTA has to be transported into the cells for metabolism. A failure of uptake may contribute to the lack of EDTA degradation under anaerobic conditions. We demonstrated that an aerobic EDTA-degrading bacterium strain BNC1 uses an ABC-type transporter system to uptake EDTA. The system has a periplasmic binding protein that bindmore » EDTA and then interacts with membrane proteins to transport EDTA into the cell at the expense of ATP. The bind protein EppA binds only free EDTA with a Kd of 25 nM. The low Kd value indicates high affinity. However, the Kd value of Ni-EDTA is 2.4 x 10^(-10) nM, indicating much stronger stability. Since Ni and other trace metals are essential for anaerobic respiration, we conclude that the added EDTA sequestrates all trace metals and making anaerobic respiration impossible. Thus, the data explain the lack of anaerobic enrichment cultures for EDTA degradation. Although we did not obtain an EDTA degrading culture under anaerobic conditions, our finding may promote the use of certain metals that forms more stable metal-EDTA complexes than Pu(III)-EDTA to prevent the enhanced mobility. Further, our data explain why EDTA is the most dominant organic pollutant in surface waters, due to the lack of degradation of certain metal-EDTA complexes.« less

Recovery of 238PuO2 by Molten Salt Oxidation Processing of 238PuO2 Contaminated Combustibles (Part II)

NASA Astrophysics Data System (ADS)

Remerowski, Mary Lynn; Dozhier, C.; Krenek, K.; VanPelt, C. E.; Reimus, M. A.; Spengler, D.; Matonic, J.; Garcia, L.; Rios, E.; Sandoval, F.; Herman, D.; Hart, R.; Ewing, B.; Lovato, M.; Romero, J. P.

2005-02-01

Pu-238 heat sources are used to fuel radioisotope thermoelectric generators (RTG) used in space missions. The demand for this fuel is increasing, yet there are currently no domestic sources of this material. Much of the fuel is material reprocessed from other sources. One rich source of Pu-238 residual material is that from contaminated combustible materials, such as cheesecloth, ion exchange resins and plastics. From both waste minimization and production efficiency standpoints, the best solution is to recover this material. One way to accomplish separation of the organic component from these residues is a flameless oxidation process using molten salt as the matrix for the breakdown of the organic to carbon dioxide and water. The plutonium is retained in the salt, and can be recovered by dissolution of the carbonate salt in an aqueous solution, leaving the insoluble oxide behind. Further aqueous scrap recovery processing is used to purify the plutonium oxide. Recovery of the plutonium from contaminated combustibles achieves two important goals. First, it increases the inventory of Pu-238 available for heat source fabrication. Second, it is a significant waste minimization process. Because of its thermal activity (0.567 W per gram), combustibles must be packaged for disposition with much lower amounts of Pu-238 per drum than other waste types. Specifically, cheesecloth residues in the form of pyrolyzed ash (for stabilization) are being stored for eventual recovery of the plutonium.

Recovery of 238PuO2 by Molten Salt Oxidation Processing of 238PuO2 Contaminated Combustibles (Part II)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Remerowski, Mary Lynn; Dozhier, C.; Krenek, K.

2005-02-06

Pu-238 heat sources are used to fuel radioisotope thermoelectric generators (RTG) used in space missions. The demand for this fuel is increasing, yet there are currently no domestic sources of this material. Much of the fuel is material reprocessed from other sources. One rich source of Pu-238 residual material is that from contaminated combustible materials, such as cheesecloth, ion exchange resins and plastics. From both waste minimization and production efficiency standpoints, the best solution is to recover this material. One way to accomplish separation of the organic component from these residues is a flameless oxidation process using molten salt asmore » the matrix for the breakdown of the organic to carbon dioxide and water. The plutonium is retained in the salt, and can be recovered by dissolution of the carbonate salt in an aqueous solution, leaving the insoluble oxide behind. Further aqueous scrap recovery processing is used to purify the plutonium oxide. Recovery of the plutonium from contaminated combustibles achieves two important goals. First, it increases the inventory of Pu-238 available for heat source fabrication. Second, it is a significant waste minimization process. Because of its thermal activity (0.567 W per gram), combustibles must be packaged for disposition with much lower amounts of Pu-238 per drum than other waste types. Specifically, cheesecloth residues in the form of pyrolyzed ash (for stabilization) are being stored for eventual recovery of the plutonium.« less

Rigid palm oil-based polyurethane foam reinforced with diamine-modified montmorillonite nanoclay

NASA Astrophysics Data System (ADS)

Haziq Dzulkifli, Mohd; Yazid Yahya, Mohd; Majid, Rohah A.

2017-05-01

This paper presents work on organically-modified montmorillonite (MMT) nanoclay embedded in rigid palm oil-based polyurethane (PU) foam. MMT was modified with organic surfactant diamino propane (DAP). PU foam was fabricated in closed mold, and the amount of DAP-MMT was varied in each foam formulation. The obtained foam was tested for its microstructure and morphology. Appearance of peaks from infra-red spectra corresponding to N-H, C=O, and C-N confirms the formation of PU networks. Scanning electron microscopy (SEM) revealed fine, closed-cellular structure at low clay loading; increasing DAP-MMT content induced larger cell sizes with blowholes. X-ray diffraction (XRD) indicates fully-exfoliated clays at 1 wt. % and partial-exfoliation at 3 wt. % clay loading, suggesting clumping of clays as DAP-MMT content increased.

On the multi-reference nature of plutonium oxides: PuO22+, PuO2, PuO3 and PuO2(OH)2.

PubMed

Boguslawski, Katharina; Réal, Florent; Tecmer, Paweł; Duperrouzel, Corinne; Gomes, André Severo Pereira; Legeza, Örs; Ayers, Paul W; Vallet, Valérie

2017-02-08

Actinide-containing complexes present formidable challenges for electronic structure methods due to the large number of degenerate or quasi-degenerate electronic states arising from partially occupied 5f and 6d shells. Conventional multi-reference methods can treat active spaces that are often at the upper limit of what is required for a proper treatment of species with complex electronic structures, leaving no room for verifying their suitability. In this work we address the issue of properly defining the active spaces in such calculations, and introduce a protocol to determine optimal active spaces based on the use of the Density Matrix Renormalization Group algorithm and concepts of quantum information theory. We apply the protocol to elucidate the electronic structure and bonding mechanism of volatile plutonium oxides (PuO 3 and PuO 2 (OH) 2 ), species associated with nuclear safety issues for which little is known about the electronic structure and energetics. We show how, within a scalar relativistic framework, orbital-pair correlations can be used to guide the definition of optimal active spaces which provide an accurate description of static/non-dynamic electron correlation, as well as to analyse the chemical bonding beyond a simple orbital model. From this bonding analysis we are able to show that the addition of oxo- or hydroxo-groups to the plutonium dioxide species considerably changes the π-bonding mechanism with respect to the bare triatomics, resulting in bent structures with a considerable multi-reference character.

Determination of Plutonium Isotope Ratios at Very Low Levels by ICP-MS using On-Line Electrochemically Modulated Separations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liezers, Martin; Lehn, Scott A; Olsen, Khris B

2009-10-01

Electrochemically modulated separations (EMS) are shown to be a rapid and selective means of extracting and concentrating Pu from complex solutions prior to isotopic analysis by inductively coupled plasma mass spectrometry (ICP-MS). This separation is performed in a flow injection mode, on-line with the ICP-MS. A three-electrode, flow-by electrochemical cell is used to accumulate Pu at an anodized glassy carbon electrode by redox conversion of Pu(III) to Pu (IV&VI). The entire process takes place in 2% v/v (0.46M) HNO 3. No redox chemicals or acid concentration changes are required. Plutonium accumulation and release is redox dependent and controlled by themore » applied cell potential. Thus large transient volumetric concentration enhancements can be achieved. Based on more negative U(IV) potentials relative to Pu(IV), separation of Pu from uranium is efficient, thereby eliminating uranium hydride interferences. EMS-ICP-MS isotope ratio measurement performance will be presented for femtogram to attogram level plutonium concentrations.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fred J. Molz, III

To better understand longer-term vadose zone transport in southeastern soils, field lysimeter experiments were conducted at the Savannah River Site (SRS) near Aiken, SC, in the 1980s. Each of the three lysimeters analyzed herein contained a filter paper spiked with different Pu solutions, and they were left exposed to natural environmental conditions (including the growth of annual weed grasses) for 11 years. The resulting Pu activity measurements from each lysimeter core showed anomalous activity distributions below the source, with significant migration of Pu above the source. Such results are not explainable by adsorption phenomena alone. A transient variably saturated flowmore » model with root water uptake was developed and coupled to a soil reactive transport model. Somewhat surprisingly, the fully transient analysis showed results nearly identical to those of a much simpler steady flow analysis performed previously. However, all phenomena studied were unable to produce the upward Pu transport observed in the data. This result suggests another transport mechanism such as Pu uptake by roots and upward transport due to transpiration. Thus, the variably saturated flow and reactive transport model was extended to include uptake and transport of Pu within the root xylem, along with computational methodology and results. In the extended model, flow velocity in the soil was driven by precipitation input along with transpiration and drainage. Water uptake by the roots determined the flow velocity in the root xylem, and this along with uptake of Pu in the transpiration stream drove advection and dispersion of the two Pu species in the xylem. During wet periods with high potential evapotranspiration, maximum flow velocities through the xylem would approached 600 cm/hr, orders of magnitude larger that flow velocities in the soil. Values for parameters and the correct conceptual viewpoint for Pu transport in plant xylem was uncertain. This motivated further experiments devoted to Pu uptake by corn roots and xylem transport. Plants were started in wet paper wrapped around each corn seed. When the tap roots were sufficiently long, the seedlings were transplanted to a soil container with the tap root extending out the container bottom. The soil container was then placed over a nutrient solution container, and the solution served as an additional medium for root growth. To conduct an uptake study, a radioactive substance, such as Pu complexed with the bacterial siderophore DFOB, was added to the nutrient solution. After a suitable elapsed time, the corn plant was sacrificed, cut into 10 cm lengths, and the activity distribution measured. Experimental results clarified the basic nature of Pu uptake and transport in corn plants, and resulting simulations suggested that each growing season Pu in the SRS lysimeters would move into the plant shoots and be deposited on the soil surface during the Fall dieback. Subsequent isotope ratio analyses showed that this did happen. OVERALL RESULTS AND CONCLUSIONS - (1) Pu transport downward from the source is controlled by advection, dispersion and adsorption, along with surface-mediated REDOX reactions. (2) Hysteresis, extreme root distribution functions, air-content dependent oxidation rate constants, and large evaporation rates from the soil surface were not able to explain the observed upward migration of Pu. (3) Small amounts of Pu uptake by plant roots and translocation in the transpiration stream creates a realistic mechanism for upward Pu migration (4) Realistic xylem cross-sectional areas imply high flow velocities under hot, wet conditions. Such flow velocities produce the correct shape for the observed activity distributions in the top 20 cm of the lysimeter soil. (5) Simulations imply that Pu should have moved into the above-ground grass tissue each year during the duration of the experiments, resulting in an activity residual accumulating on the soil surface. An isotope ratio analysis showed that the observed surface Pu residue was from the buried sources, not atmospheric fallout. (6) The plant experiments indicate a Pu-DFOB velocity in the corn xylem of at least 174 cm/hr, much higher than ionic Pu in soil. Thus, Pu complexation with chelating agents is probably what led to the observed enhanced uptake and mobility in grasses. (7) Plant experiments show that the uptake of Fe-DFOB, Pu-DFOB and the resulting distributions are very similar. This supports the hypothesis that plant and bacterial iron-seeking chemistry mistakes Pu for Fe.« less

Seismic and Infrasound Recordings from Kilauea Volcano: Volcanic Tremor, Lava Outbreaks, and Fissure Eruptions

NASA Astrophysics Data System (ADS)

Fee, D.; Garces, M.; Orr, T.

2007-12-01

The continuous effusion from the Pu'u 'O'o crater complex, the active vent of Kilauea Volcano, Hawaii, produced nearly continuous tremor for years. Recently this tremor was recorded by two infrasound arrays, one at 12.5 km and one at 2.5 km, as well as a broadband seismometer at the closer array. These recordings exhibit significant temporal changes. A sharp, complex spectral peak of ~0.6 Hz is present in nearly the entire dataset, and tends to bifurcate and shift frequency over time. Although the seismic wavefield at Kilauea is complex and path effects appear to play a significant role, this spectral peak is also weakly manifested in the seismic recordings. Array processing of the infrasonic data reveals an abundance of broadband signal as well. Most of the signal appears to originate from the main crater region. However, the 2.5 km array detected the presence of a skylight with growing hornitos ~400 m south of Pu'u 'O'o on the active lava tube system. On June 19th, 2007, the magmatic system at Pu'u 'O'o changed. An intrusion of magma reached the surface 6 km west of the crater complex. The timing and location of the lava outbreak were determined acoustically using array processing. Two distinct acoustic pulses were recorded from the correct azimuth, both exhibiting harmonics. The 7/21 fissure eruption also produced clear infrasound signals. The onset of the fissure eruption east of P'u' 'O'o was apparent beginning around midnight on 7/21 and was focused between ~1.5-5 Hz. Although the fissure eruption continued to produce infrasound, the character of the recorded signal changes over time. A third infrasound array was placed closer to P'u' 'O'o and the fissure to help further constrain the eruption. More detailed results on acoustic signals from the Father's Day Intrusion and Fissure eruption will be presented.

A nurse-led approach to preventing pressure ulcers.

PubMed

Yap, Tracey L; Kennerly, Susan M

2011-01-01

This article discusses a nurse-led multidisciplinary approach that care providers can use to reduce pressure ulcers (PUs) within their organizations. Given the current understanding of PU etiology and prevention, evidence-based prevention protocols and pressure-relief strategies serve as critical foundational principles that must be applied to significantly influence PU prevalence and incidence. Because nursing plays an important role in rehabilitation facility management, nurses' expertise, leadership, and knowledge make nursing the most appropriate discipline to design protocols, implement innovative solutions, and lead the charge for PU prevention.

Biotic and abiotic reduction and solubilization of Pu(IV)O₂•xH₂O(am) as affected by anthraquinone-2,6-disulfonate (AQDS) and ethylenediaminetetraacetate (EDTA).

PubMed

Plymale, Andrew E; Bailey, Vanessa L; Fredrickson, James K; Heald, Steve M; Buck, Edgar C; Shi, Liang; Wang, Zheming; Resch, Charles T; Moore, Dean A; Bolton, Harvey

2012-02-21

This study measured reductive solubilization of plutonium(IV) hydrous oxide (Pu(IV)O(2)·xH(2)O((am))) with hydrogen (H(2)) as electron donor, in the presence or absence of dissimilatory metal-reducing bacteria (DMRB), anthraquinone-2,6-disulfonate (AQDS), and ethylenediaminetetraacetate (EDTA). In PIPES buffer at pH 7 with excess H(2), Shewanella oneidensis and Geobacter sulfurreducens both solubilized <0.001% of 0.5 mM Pu(IV)O(2)·xH(2)O((am)) over 8 days, with or without AQDS. However, Pu((aq)) increased by an order of magnitude in some treatments, and increases in solubility were associated with production of Pu(III)((aq)). The solid phase of these treatments contained Pu(III)(OH)(3(am)), with more in the DMRB treatments compared with abiotic controls. In the presence of EDTA and AQDS, PuO(2)·xH(2)O((am)) was completely solubilized by S. oneidensis and G. sulfurreducens in ∼24 h. Without AQDS, bioreductive solubilization was slower (∼22 days) and less extensive (∼83-94%). In the absence of DMRB, EDTA facilitated reductive solubilization of 89% (without AQDS) to 98% (with AQDS) of the added PuO(2)·xH(2)O((am)) over 418 days. An in vitro assay demonstrated electron transfer to PuO(2)·xH(2)O((am)) from the S. oneidensis outer-membrane c-type cytochrome MtrC. Our results (1) suggest that PuO(2)·xH(2)O((am)) reductive solubilization may be important in reducing environments, especially in the presence of complexing ligands and electron shuttles, (2) highlight the environmental importance of polynuclear, colloidal Pu, (3) provide additional evidence that Pu(III)-EDTA is a more likely mobile form of Pu than Pu(IV)-EDTA, and (4) provide another example of outer-membrane cytochromes and electron-shuttling compounds facilitating bioreduction of insoluble electron acceptors in geologic environments.

Distribution and migration of 239+240Pu in abiotic components of the Black Sea ecosystems during the post-Chernobyl period.

PubMed

Tereshchenko, N N; Gulin, S B; Proskurnin, V Yu

2018-08-01

Distribution of 239,240 Pu in abiotic components (water and bottom sediment) of the Black Sea ecosystems was studied during the post-Chernobyl period at different offshore and near-shore locations. The trends of these radionuclides accumulation by sediments were analyzed. The spatial-temporal changes in the 239,240 Pu distribution as well as effective half-life for these radionuclides in the Black Sea surface water in deep-sea area are presented. The estimations of the average annual removal fluxes of the 239,240 Pu into the bottom sediments were obtained. The Black Sea sediments were characterized by a higher 239,240 Pu concentration factor (C f  ≈ n·10 4 -n·10 6 ) and radiocapacity factor (F( 239,240 Pu) was about 99.9% on the shelf, 94.5-99.1% on deep-sea basin for silty and 94.6-98.9% on the shelf for sandy bottom sediments) as compared with C f and F for 137 Cs and 90 Sr. Silty bottom sediments play the role of 239,240 Pu main depot in the Black Sea ecosystem. The studied radioecological characteristics of Pu allowed us to define the type of plutonium biogeochemical behavior in the Black Sea as a pedotropic one. The results of this complex radioecological monitoring of 239+240 Pu contamination in the Black Sea and their analysis makes it possible to understand the plutonium redistribution pathways which will enable to carry out the tracing of its migration within the ecosystems. Copyright © 2017 Elsevier Ltd. All rights reserved.

Real time studies of Elastic Moduli Pu Aging using Resonant Ultrasound Spectroscopy

NASA Astrophysics Data System (ADS)

Maiorov, Boris

Elastic moduli are fundamental thermodynamic susceptibilities that connect directly to thermodynamics, electronic structure and give important information about mechanical properties. To determine the time evolution of the elastic properties in 239Pu and it Ga alloys, is imperative to study its phase stability and self-irradiation damage process. The most-likely sources of these changes include a) ingrowth of radioactive decay products like He and U, b) the introduction of radiation damage, c) δ-phase instabilities towards α-Pu or to Pu3Ga. The measurement of mechanical resonance frequencies can be made with extreme precision and used to compute the elastic moduli without corrections giving important insight in this problem. Using Resonant Ultrasound Spectroscopy, we measured the time dependence of the mechanical resonance frequencies of fine-grained polycrystalline δ-phase 239Pu, from 300K up to 480K. At room temperature, the shear modulus shows an increase in time (stiffening), but the bulk modulus decreases (softening). These are the first real-time measurements of room temperature aging of the elastic moduli, and the changes are consistent with elastic moduli measurements performed on 44 year old δ-Pu. As the temperature is increased, the rate of change increases exponentially, with both moduli becoming stiffer with time. For T>420K an abrupt change in the time dependence is observed indicating that the bulk and shear moduli have opposite rates of change. Our measurements provide a basis for ruling out the decomposition of δ-Pu towards α-Pu or Pu3Ga, and indicate a complex defect-related scenario from which we are gathering important clues.

PuReD-MCL: a graph-based PubMed document clustering methodology.

PubMed

Theodosiou, T; Darzentas, N; Angelis, L; Ouzounis, C A

2008-09-01

Biomedical literature is the principal repository of biomedical knowledge, with PubMed being the most complete database collecting, organizing and analyzing such textual knowledge. There are numerous efforts that attempt to exploit this information by using text mining and machine learning techniques. We developed a novel approach, called PuReD-MCL (Pubmed Related Documents-MCL), which is based on the graph clustering algorithm MCL and relevant resources from PubMed. PuReD-MCL avoids using natural language processing (NLP) techniques directly; instead, it takes advantage of existing resources, available from PubMed. PuReD-MCL then clusters documents efficiently using the MCL graph clustering algorithm, which is based on graph flow simulation. This process allows users to analyse the results by highlighting important clues, and finally to visualize the clusters and all relevant information using an interactive graph layout algorithm, for instance BioLayout Express 3D. The methodology was applied to two different datasets, previously used for the validation of the document clustering tool TextQuest. The first dataset involves the organisms Escherichia coli and yeast, whereas the second is related to Drosophila development. PuReD-MCL successfully reproduces the annotated results obtained from TextQuest, while at the same time provides additional insights into the clusters and the corresponding documents. Source code in perl and R are available from http://tartara.csd.auth.gr/~theodos/

COMPLEXITY IN ECOLOGICAL SYSTEMS

EPA Science Inventory

The enormous complexity of ecosystems is generally obvious under even the most cursory examination. In the modern world, this complexity is further augmented by the linkage of ecosystems to economic and social systems through the human use of the environment for technological pu...

Preparation and Sound Absorption Properties of a Barium Titanate/Nitrile Butadiene Rubber–Polyurethane Foam Composite with Multilayered Structure

PubMed Central

Jiang, Xueliang; Yang, Zhen; Wang, Zhijie; Zhang, Fuqing; You, Feng

2018-01-01

Barium titanate/nitrile butadiene rubber (BT/NBR) and polyurethane (PU) foam were combined to prepare a sound-absorbing material with an alternating multilayered structure. The effects of the cell size of PU foam and the alternating unit number on the sound absorption property of the material were investigated. The results show that the sound absorption efficiency at a low frequency increased when decreasing the cell size of PU foam layer. With the increasing of the alternating unit number, the material shows the sound absorption effect in a wider bandwidth of frequency. The BT/NBR-PU foam composites with alternating multilayered structure have an excellent sound absorption property at low frequency due to the organic combination of airflow resistivity, resonance absorption, and interface dissipation. PMID:29565321

Preparation and Sound Absorption Properties of a Barium Titanate/Nitrile Butadiene Rubber-Polyurethane Foam Composite with Multilayered Structure.

PubMed

Jiang, Xueliang; Yang, Zhen; Wang, Zhijie; Zhang, Fuqing; You, Feng; Yao, Chu

2018-03-22

Barium titanate/nitrile butadiene rubber (BT/NBR) and polyurethane (PU) foam were combined to prepare a sound-absorbing material with an alternating multilayered structure. The effects of the cell size of PU foam and the alternating unit number on the sound absorption property of the material were investigated. The results show that the sound absorption efficiency at a low frequency increased when decreasing the cell size of PU foam layer. With the increasing of the alternating unit number, the material shows the sound absorption effect in a wider bandwidth of frequency. The BT/NBR-PU foam composites with alternating multilayered structure have an excellent sound absorption property at low frequency due to the organic combination of airflow resistivity, resonance absorption, and interface dissipation.

Minimum pickup velocity ( U pu) of nanoparticles in gas-solid pneumatic conveying

NASA Astrophysics Data System (ADS)

Anantharaman, Aditya; van Ommen, J. Ruud; Chew, Jia Wei

2015-12-01

This paper is the first systematic study of the pneumatic conveying of nanoparticles. The minimum pickup velocity, U pu, of six nanoparticle species of different materials [i.e., silicon dioxide (SiO2), aluminum oxide (Al2O3), and titanium dioxide (TiO2)] and surfaces (i.e., apolar and polar) was determined by the weight loss method. Results show that (1) due to relative lack of hydrogen bonding, apolar nanoparticles had higher mass loss values at the same velocities, mass loss curves with accentuated S-shaped profiles, and lower U pu values, (2) among the three species, SiO2, which has the lowest Hamaker coefficient, exhibited the greatest discrepancy between apolar and polar surfaces with respect to both mass loss curves and U pu values, (3) U mf,polar/ U mf,apolar was between 1 and 3.5 times that of U pu,polar/ U pu,apolar due to greater extents of hydrogen bonding associated with U mf, (4) U pu values were at least an order-of-magnitude lower than that expected from the well-acknowledged U pu correlation (Kalman et al., Powder Technol 160:103-113, 2005) due to agglomeration, (5) although nanoparticles should be categorized as Zone III (Kalman et al. 2005) (or Geldart group C, Powder Technol 7:285-292, 1973), the nanoparticles, and primary and complex agglomerates agreed more with the Zone I (or Geldart group B) correlation.

Analysis of $sup 239$Pu and $sup 241$Am in NAEG large-sized bovine samples

DOE Office of Scientific and Technical Information (OSTI.GOV)

Major, W.J.; Lee, K.D.; Wessman, R.A.

Methods are described for the analysis of environmental levels of $sup 239$Pu and $sup 241$Am in large-sized bovine samples. Special procedure modifications to overcome the complexities of sample preparation and analyses and special techniques employed to prepare and analyze different types of bovine samples, such as muscle, blood, liver, and bone are discussed. (CH)

Development of a Self-Consistent Model of Plutonium Sorption: Quantification of Sorption Enthalpy and Ligand-Promoted Dissolution

DOE Office of Scientific and Technical Information (OSTI.GOV)

Powell, Brian; Kaplan, Daniel I; Arai, Yuji

2016-12-29

This university lead SBR project is a collaboration lead by Dr. Brian Powell (Clemson University) with co-principal investigators Dan Kaplan (Savannah River National Laboratory), Yuji Arai (presently at the University of Illinois), Udo Becker (U of Michigan) and Rod Ewing (presently at Stanford University). Hypothesis: The underlying hypothesis of this work is that strong interactions of plutonium with mineral surfaces are due to formation of inner sphere complexes with a limited number of high-energy surface sites, which results in sorption hysteresis where Pu(IV) is the predominant sorbed oxidation state. The energetic favorability of the Pu(IV) surface complex is strongly influencedmore » by positive sorption entropies, which are mechanistically driven by displacement of solvating water molecules from the actinide and mineral surface during sorption. Objectives: The overarching objective of this work is to examine Pu(IV) and Pu(V) sorption to pure metal (oxyhydr)oxide minerals and sediments using variable temperature batch sorption, X-ray absorption spectroscopy, electron microscopy, and quantum-mechanical and empirical-potential calculations. The data will be compiled into a self-consistent surface complexation model. The novelty of this effort lies largely in the manner the information from these measurements and calculations will be combined into a model that will be used to evaluate the thermodynamics of plutonium sorption reactions as well as predict sorption of plutonium to sediments from DOE sites using a component additivity approach.« less

/sup 239/Pu contamination in snakes inhabiting the Rocky Flats Plant site

DOE Office of Scientific and Technical Information (OSTI.GOV)

Geiger, R.A.; Winsor, T.F.

1975-01-01

For approximately four years studies have been under way at the Rocky Flats plant to determine contamination patterns and concentrations of Pu in the biota. Contamination of the Rocky Flats environs has resulted from at least three incidents, a September 1957 fire, a May 1969 fire, and leaking barrels containing plutonium-laden cutting oil. The latter incident was considered by far the major source of the plutonium contamination. Results are reported from a study conducted to determine whether snake tissues of the area contained detectable amounts of /sup 239/Pu and, if so, at what concentrations. Eastern yellow-bellied racers (Coluber constrictor flaviventris,more » bullsnakes (Pituophis melanoleucus sayi, and prairie rattlesnakes (Crotalus viridis viridis, were collected for /sup 239/Pu bioassay of lung, liver, and bone tissues. Snakes were captured using drift fences terminating in funnel traps and by opportunistic sampling. Results led to the conclusion that snakes are not an important organism in the redistribution of /sup 239/Pu. (CH)« less

Participatory Pedagogy in an Open Educational Course: Challenges and Opportunities

ERIC Educational Resources Information Center

Andersen, Renate; Ponti, Marisa

2014-01-01

This article presents an empirical study of an open educational course in an online peer-to-peer university (P2PU). P2PU is a nonprofit organization offering free educational opportunities. Focus is on how peers are part of creating course content in a Web 2.0 environment. Massive open online courses (MOOCs) have evolved into two different…

Flexible magnetic polyurethane/Fe2O3 nanoparticles as organic-inorganic nanocomposites for biomedical applications: Properties and cell behavior.

PubMed

Shahrousvand, Mohsen; Hoseinian, Monireh Sadat; Ghollasi, Marzieh; Karbalaeimahdi, Ali; Salimi, Ali; Tabar, Fatemeh Ahmadi

2017-05-01

Nowadays, the discovery of cell behaviors and their responses in communication with the stem cell niches and/or microenvironments are one of the major topics in tissue engineering and regenerative medicine. In this study, incorporated organic-inorganic polyurethane (PU) nanocomposites were prepared for better understanding of cell signaling and the effect of magnetite nanoparticles on cell proliferation and cell responses. The properties of PU-IONs were evaluated by fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), atomic-force microscopy (AFM), differential scanning calorimetry (DSC), X-ray diffraction (XRD) and electrochemical impedance spectroscopy (EIS). The presence of the iron oxide nanoparticles (IONs) affects on the properties of polyurethane nanocomposites such as bulk morphology, mechanical, electrochemical, and biological properties. The electrical conductivity and hydrophilicity of PU-IONs were improved by increasing the magnetite nanoparticles; therefore water absorption, biodegradation and cell viability were changed. The biocompatibility of PU-IONs was investigated by MTT assay, cell attachment and cell staining. According to the results, the magnetite polyurethane nanocomposites could be a potential choice for cell therapy and tissue engineering, especially nerve repair. Copyright © 2016 Elsevier B.V. All rights reserved.

Comparison of plutonium systemic distribution in rats and dogs with published data in humans.

PubMed

Melo, Dunstana R; Weber, Waylon; Doyle-Eisele, Melanie; Guilmette, Raymond A

2014-11-01

This manuscript compares the behavior of monomeric (239)Pu(4+)-citrate injected intravenously in rats and dogs with a comparison of available humans' data. The experimental design for these two studies consisted of eight groups sacrificed at predetermined time-points post exposure. All organs and tissues as well as daily urinary and fecal excretion were analyzed. Liver and skeleton were the organs with the highest (239)Pu uptake in both species; 76% in dogs and 70% in rats at 24 hours (h) post IV administration. By the end of the study (28 days, d), the activity in skeleton and liver was 85% in dogs and 65% in rats. The urinary excretion function seems to be similar for rats, dogs and humans but the daily fecal to urinary excretion ratio differs between species. A rapid clearance from the liver of rats was observed compared to dogs. Skeleton-to-liver ratios are variable between species. Urinary and fecal excretion patterns for dogs are consistent with human data, indicating that dogs seem to represent better the (239)Pu behavior in humans. The data confirm that the better animal model to evaluate the efficacy of (239)Pu chelating compounds is the canine model.

Accumulation of atmospheric radionuclides and heavy metals in cryoconite holes on an Arctic glacier.

PubMed

Łokas, Edyta; Zaborska, Agata; Kolicka, Małgorzata; Różycki, Michał; Zawierucha, Krzysztof

2016-10-01

Surface of glaciers is covered by mineral and organic dust, together with microorganisms forming cryoconite granules. Despite fact that glaciers and ice sheets constitute significance part of land surface, reservoir of freshwater, and sites of high biological production, the knowledge on the cryoconite granules still remain unsatisfactory. This study presents information on radionuclide and heavy metal contents in cryoconites. Cryoconites collected from the Hans Glacier in SW Spitsbergen reveal high activity concentrations of anthropogenic ((238,239,240)Pu, (137)Cs, (90)Sr) and natural ((210)Pb) radionuclides. The (238)Pu/(239+240)Pu activity ratios in these cryoconites significantly exceed the mean global fallout ratio (0.025). The (238)Pu/(239+240)Pu ranged from 0.064 to 0.118. The (239+240)Pu/(137)Cs varied from 0.011 ± 0.003 to 0.030 ± 0.007. Such activity ratios as observed in these cryoconites were significantly higher than the values characterizing global fallout, pointing to possible contributions of these radionuclides from other sources. Heavy metals (Pb, Cd, Cu, Zn, Fe, and Mn) in cryoconites exceed both UCC concentrations and local rocks' concentrations, particularly for cadmium. The concentration ratios of stable lead isotopes ((206)Pb/(207)Pb, (208)Pb/(206)Pb) were determined to discriminate between the natural and anthropogenic sources of Pb in cryoconites and to confirm the strong anthropogenic contribution to heavy metal deposition in the Arctic. In investigated cryoconite holes, two groups of invertebrates, both extremophiles, Tardigrada and Rotifera were detected. Our study indicate that cryoconites are aggregates of mineral and organic substances on surfaces of glaciers are able to accumulate large amounts of airborne pollutants bound to extracellular polymeric substances secreted by microorganisms. Copyright © 2016 Elsevier Ltd. All rights reserved.

Transport of Intrinsic Plutonium Colloids in Saturated Porous Media

NASA Astrophysics Data System (ADS)

Zhou, D.; Abdel-Fattah, A.; Boukhalfa, H.; Ware, S. D.; Tarimala, S.; Keller, A. A.

2011-12-01

Actinide contaminants were introduced to the subsurface environment as a result of nuclear weapons development and testing, as well as for nuclear power generation and related research activities for defense and civilian applications. Even though most actinide species were believed to be fairly immobile once in the subsurface, recent studies have shown the transport of actinides kilometers away from their disposal sites. For example, the treated liquid wastes released into Mortandad Canyon at the Los Alamos National Laboratory were predicted to travel less than a few meters; however, plutonium and americium have been detected 3.4 km away from the waste outfall. A colloid-facilitated mechanism has been suggested to account for this unexpected transport of these radioactive wastes. Clays, oxides, organic matters, and actinide hydroxides have all been proposed as the possible mobile phase. Pu ions associated with natural colloids are often referred to as pseudo-Pu colloids, in contrast with the intrinsic Pu colloids that consist of Pu oxides. Significant efforts have been made to investigate the role of pseudo-Pu colloids, while few studies have evaluated the environmental behavior of the intrinsic Pu colloids. Given the fact that Pu (IV) has extremely low solubility product constant, it can be inferred that the transport of Pu in the intrinsic form is highly likely at suitable environmental conditions. This study investigates the transport of intrinsic Pu colloids in a saturated alluvium material packed in a cylindrical column (2.5-cm Dia. x 30-cm high) and compares the results to previous data on the transport of pseudo Pu colloids in the same material. A procedure to prepare a stable intrinsic Pu colloid suspension that produced consistent and reproducible electrokinetic and stability data was developed. Electrokinetic properties and aggregation stability were characterized. The Pu colloids, together with trillium as a conservative tracer, were injected into the column at a flow rate of ~ 6 mL/hr. Despite that the Pu intrinsic colloids are positively charged while the alluvium grain surfaces are negatively charged under the current experimental conditions, about 30% of the Pu colloids population transported through the column and broke through earlier than trillium. Our previous experiments in the same column have shown a highly unretarded transport of the negatively charged pseudo Pu colloids (Pu sorbed onto smectite colloids) and complete retardation of the dissolved Pu. The enhanced transport of Pu colloids was explained by the effective pore volume concept. Combining the results of these two experiments, it is concluded that the intrinsic Pu colloids transported in the column by adsorbing onto the background clay colloids due to electrostatic repulsion.

Synthesis and X-ray Crystallography of [Mg(H2O)6][AnO2(C2H5COO)3]2 (An = U, Np, or Pu).

PubMed

Serezhkin, Viktor N; Grigoriev, Mikhail S; Abdulmyanov, Aleksey R; Fedoseev, Aleksandr M; Savchenkov, Anton V; Serezhkina, Larisa B

2016-08-01

Synthesis and X-ray crystallography of single crystals of [Mg(H2O)6][AnO2(C2H5COO)3]2, where An = U (I), Np (II), or Pu (III), are reported. Compounds I-III are isostructural and crystallize in the trigonal crystal system. The structures of I-III are built of hydrated magnesium cations [Mg(H2O)6](2+) and mononuclear [AnO2(C2H5COO)3](-) complexes, which belong to the AB(01)3 crystallochemical group of uranyl complexes (A = AnO2(2+), B(01) = C2H5COO(-)). Peculiarities of intermolecular interactions in the structures of [Mg(H2O)6][UO2(L)3]2 complexes depending on the carboxylate ion L (acetate, propionate, or n-butyrate) are investigated using the method of molecular Voronoi-Dirichlet polyhedra. Actinide contraction in the series of U(VI)-Np(VI)-Pu(VI) in compounds I-III is reflected in a decrease in the mean An═O bond lengths and in the volume and sphericity degree of Voronoi-Dirichlet polyhedra of An atoms.

The role of surfaces, chemical interfaces, and disorder on plutonium incorporation in pyrochlores

DOE PAGES

Perriot, Romain; Dholabhai, Pratik P.; Uberuaga, Blas P.

2016-07-27

Pyrochlores, a class of complex oxides with formula A 2B 2O 7, are one of the candidates for nuclear waste encapsulation, due to the natural occurrence of actinide-bearing pyrochlore minerals and laboratory observations of high radiation tolerance. In this work, we use atomistic simulations to determine the role of surfaces, chemical interfaces, and cation disorder on the plutonium immobilization properties of pyrochlores as a function of pyrochlore chemistry. We find that both Pu 3+ and Pu 4+ segregate to the surface for the four low-index pyrochlore surfaces considered, and that the segregation energy varies with the chemistry of the compound.more » We also find that pyrochlore/pyrochlore bicrystals A 2B 2O 7/A 2'B 2'O 7 can be used to immobilize Pu 3+ and Pu 4+ either in the same or separate phases of the compound, depending on the chemistry of the material. Finally, we find that Pu 4+ segregates to the disordered phase of an order/disorder bicrystal, driven by the occurrence of local oxygen-rich environments. However, Pu 3+ is weakly sensitive to the oxygen environment, and therefore only slightly favors the disordered phase. This behavior suggests that, at some concentration, Pu incorporation can destabilize the pyrochlore structure. Together, these results provide new insight into the ability of pyrochlore compounds to encapsulate Pu and suggest new considerations in the development of waste forms based on pyrochlores. Particularly, the phase structure of a multi-phase pyrochlore composite can be used to independently getter decay products based on their valence and size.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Perriot, Romain; Dholabhai, Pratik P.; Uberuaga, Blas P.

Pyrochlores, a class of complex oxides with formula A 2B 2O 7, are one of the candidates for nuclear waste encapsulation, due to the natural occurrence of actinide-bearing pyrochlore minerals and laboratory observations of high radiation tolerance. In this work, we use atomistic simulations to determine the role of surfaces, chemical interfaces, and cation disorder on the plutonium immobilization properties of pyrochlores as a function of pyrochlore chemistry. We find that both Pu 3+ and Pu 4+ segregate to the surface for the four low-index pyrochlore surfaces considered, and that the segregation energy varies with the chemistry of the compound.more » We also find that pyrochlore/pyrochlore bicrystals A 2B 2O 7/A 2'B 2'O 7 can be used to immobilize Pu 3+ and Pu 4+ either in the same or separate phases of the compound, depending on the chemistry of the material. Finally, we find that Pu 4+ segregates to the disordered phase of an order/disorder bicrystal, driven by the occurrence of local oxygen-rich environments. However, Pu 3+ is weakly sensitive to the oxygen environment, and therefore only slightly favors the disordered phase. This behavior suggests that, at some concentration, Pu incorporation can destabilize the pyrochlore structure. Together, these results provide new insight into the ability of pyrochlore compounds to encapsulate Pu and suggest new considerations in the development of waste forms based on pyrochlores. Particularly, the phase structure of a multi-phase pyrochlore composite can be used to independently getter decay products based on their valence and size.« less

Simulation of Flow and Long-Term Plutonium (Pu) Transport in the Vadose Zone at the Savannah River National Laboratory (SRNL)

NASA Astrophysics Data System (ADS)

Demirkanli, I.; Molz, F. J.; Kaplan, D. I.; Fjeld, R. A.; Serkiz, S. M.

2006-05-01

An improved understanding of flow and radionuclide transport in vadose zone sediments is fundamental to all types of future planning involving radioactive materials. One way to obtain such understanding is to perform long-term experimental studies of Pu transport in complex natural systems. With this in mind, a series of field experiments were initiated at the SRNL in the early 1980s. Lysimeters containing sources of different Pu oxidation states were placed in the shallow subsurface and left open to the natural environment for 2 to 11 years. At the end of the experiments, Pu activities were measured along vertical cores obtained from the lysimeters. Pu distributions were anomalous in nature, with transport from oxidized Pu sources being less than expected, and a small fraction of Pu from reduced sources moving more. Laboratory studies with lysimeter sediments suggested that surface-mediated, oxidation/reduction (redox) reactions could be responsible for the anomalous behavior, and this hypothesis is tested by performing both steady-state and transient Pu transport simulations that include retardation along with first-order redox reactions on mineral surfaces. Based on the simulations, we conclude that the surface-mediated, redox hypothesis is consistent with the observed downward Pu activity profiles in the experiments, and such profiles are captured well by a steady-state, net downward, flow model. (Discussion is presented as to why a steady model appears to work in a highly transient flow environment.) The redox model explains how Pu(V/VI) sources release activity that moves downward more slowly than expected based on adsorptive retardation alone, and how Pu(III/IV) sources result in a small fraction of activity that moves downward more rapidly than expected. The calibrated parameter values were robust and relatively well-defined throughout all four sets of simulations. Pu(V/VI) (i.e., oxidized Pu)retardation factors were about 15, and reduced Pu(III/IV) retardation factors were about 10,000. For these values, ko (1st order oxidation rate) averaged 2.4x10-7/hr with a standard deviation of 1.6x10-7, and kr (reduction rate)was 7.1x10-4/hr with a standard deviation of 1.6x10-4. Preliminary transient flow simulations showed a very slight increase in the fitted reaction rate constants, but otherwise reproduced the steady-state results. To date, neither approach is able to simulate the observed Pu movement above the source.

Solvation of actinide salts in water using a polarizable continuum model.

PubMed

Kumar, Narendra; Seminario, Jorge M

2015-01-29

In order to determine how actinide atoms are dressed when solvated in water, density functional theory calculations have been carried out to study the equilibrium structure of uranium plutonium and thorium salts (UO2(2+), PuO2(2+), Pu(4+), and Th(4+)) both in vacuum as well as in solution represented by a conductor-like polarizable continuum model. This information is of paramount importance for the development of sensitive nanosensors. Both UO2(2+) and PuO2(2+) ions show coordination number of 4-5 with counterions replacing one or two water molecules from the first coordination shell. On the other hand, Pu(4+), has a coordination number of 8 both when completely solvated and also in the presence of chloride and nitrate ions with counterions replacing water molecules in the first shell. Nitrates were found to bind more strongly to Pu(IV) than chloride anions. In the case of the Th(IV) ion, the coordination number was found to be 9 or 10 in the presence of chlorides. Moreover, the Pu(IV) ion shows greater affinity for chlorides than the Th(IV) ion. Adding dispersion and ZPE corrections to the binding energy does not alter the trends in relative stability of several conformers because of error cancelations. All structures and energetics of these complexes are reported.

Fabrication of 12% {sup 240}Pu calorimetry standards

DOE Office of Scientific and Technical Information (OSTI.GOV)

Long, S.M.; Hildner, S.; Gutierrez, D.

1995-08-01

Throughout the DOE complex, laboratories are performing calorimetric assays on items containing high burnup plutonium. These materials contain higher isotopic range and higher wattages than materials previously encountered in vault holdings. Currently, measurement control standards have been limited to utilizing 6% {sup 240}Pu standards. The lower isotopic and wattage value standards do not complement the measurement of the higher burnup material. Participants of the Calorimetry Exchange (CALEX) Program have identified the need for new calorimetric assay standards with a higher wattage and isotopic range. This paper describes the fabrication and verification measurements of the new CALEX standard containing 12% {supmore » 240}Pu oxide with a wattage of about 6 to 8 watts.« less

Synthesis and characterisation of PuPO4 - a potential analytical standard for EPMA actinide quantification

NASA Astrophysics Data System (ADS)

Wright, K. E.; Popa, K.; Pöml, P.

2018-01-01

Transmutation nuclear fuels contain weight percentage quantities of actinide elements, including Pu, Am and Np. Because of the complex spectra presented by actinide elements using electron probe microanalysis (EPMA), it is necessary to have relatively pure actinide element standards to facilitate overlap correction and accurate quantitation. Synthesis of actinide oxide standards is complicated by their multiple oxidation states, which can result in inhomogeneous standards or standards that are not stable at atmospheric conditions. Synthesis of PuP4 results in a specimen that exhibits stable oxidation-reduction chemistry and is sufficiently homogenous to serve as an EPMA standard. This approach shows promise as a method for producing viable actinide standards for microanalysis.

Ustur whole body case 0269: demonstrating effectiveness of i.v. CA-DTPA for Pu.

PubMed

James, A C; Sasser, L B; Stuit, D B; Glover, S E; Carbaugh, E H

2007-01-01

This whole body donation case (USTUR Registrant) involved a single acute inhalation of an acidic Pu(NO3)4 solution in the form of an aerosol 'mist'. Chelation treatment with intravenously (i.v.) Ca-EDTA was initiated on the day of the intake, and continued intermittently over 6 months. After 2.5 y with no further treatment, a course of i.v. Ca-DTPA was administered. A total of 400 measurements of 239+240Pu excreted in urine were recorded; starting on the first day (both before and during the initial Ca-EDTA chelation) and continuing for 37 y. This sampling included all intervals of chelation. In addition, 91 measurements of 239+240Pu-in-feces were recorded over this whole period. The Registrant died about 38 y after the intake, at age 79 y, with extensive carcinomatosis secondary to adenocarcinoma of the prostate gland. At autopsy, all major soft tissue organs were harvested for radiochemical analyses of their 238Pu, 239+240Pu and 241Am content. Also, all types of bone (comprising about half the skeleton) were harvested for radiochemical analyses, as well as samples of skin, subcutaneous fat and muscle. This comprehensive data set has been applied to derive 'chelation-enhanced' transfer rates in the ICRP Publication 67 plutonium biokinetic model, representing the behaviour of blood-borne and tissue-incorporated plutonium during intervals of therapy. The resulting model of the separate effects of i.v. Ca-EDTA and Ca-DTPA chelation shows that the therapy administered in this case succeeded in reducing substantially the long-term burden of plutonium in all body organs, except for the lungs. The calculated reductions in organ content at the time of death are approximately 40% for the liver, 60% for other soft tissues (muscle, skin, glands, etc.), 50% for the kidneys and 50% for the skeleton. Essentially, all of the substantial reduction in skeletal burden occurred in trabecular bone. This modelling exercise demonstrated that 3-y-delayed Ca-DTPA therapy was as effective as promptly administered Ca-EDTA.

USTUR WHOLE BODY CASE 0269: DEMONSTRATING EFFECTIVENESS OF I.V. CA-DTPA FOR PU

DOE Office of Scientific and Technical Information (OSTI.GOV)

James, Anthony C.; Sasser , Lyle B.; Stuit, Dorothy B.

2008-01-28

This whole body donation case (USTUR Registrant) involved a single acute inhalation of an acidic Pu(NO3)4 solution in the form of an aerosol ‘mist.’ Chelation treatment with i.v. Ca-EDTA was initiated on the day of the intake, and continued intermittently over 6 months. After 2½ years with no further treatment, a course of i.v. Ca-DTPA was administered. A total of 400 measurements of 239+240Pu excreted in urine were recorded; starting on the first day (both before and during the initial Ca-EDTA chelation), and continuing for 37 years. This sampling included all intervals of chelation. In addition, 91 measurements of 239+240Pu-in-fecesmore » were recorded over this whole period. The Registrant died about 38 years after the intake, at age 79 y, with extensive carcinomatosis secondary to adenocarcinoma of the prostate gland. At autopsy, all major soft tissue organs were harvested for radiochemical analyses of their 238Pu, 239+240Pu and 241Am content. Also, all types of bone (comprising about half the skeleton) were harvested for radiochemical analyses, as well as samples of skin, subcutaneous fat and muscle. This comprehensive dataset has been applied to derive ‘chelation-enhanced’ transfer rates in the ICRP Publication 67 plutonium biokinetic model, representing the behaviour of blood-borne and tissue-incorporated plutonium during intervals of therapy. The resulting model of the separate effects of i.v. Ca-EDTA and Ca-DTPA chelation shows that the therapy administered in this case succeeded in reducing substantially the long-term burden of plutonium in all body organs, except for the lungs. The calculated reductions in organ content at the time of death are approximately 40% for the liver, 60% for other soft tissues (muscle, skin, glands, etc.), 50% for the kidneys, and 50% for the skeleton. Essentially all of the substantial reduction in skeletal burden occurred in trabecular bone. This modeling exercise demonstrated that 3-y-delayed Ca-DTPA therapy was as effective as promptly administered Ca-EDTA.« less

Estimates of (239+240)Pu inventories in Gdańsk Bay and Gdańsk basin.

PubMed

Skwarzec, Bogdan; Strumińska, Dagmara I; Prucnal, Małgorzata

2003-01-01

This paper presents and discusses the results of (239+240)Pu determinations in different components of Gdańsk bay and Gdańsk basin ecosystem, as well as estimated sources and inventories of plutonium in these basins. The total plutonium (239+240)Pu activities deposited in Gdańsk bay and Gdańsk basin sediments are 1.18 TBq and 3.77 TBq, respectively. Two rivers, the Vistula and Neman rivers, and atmospheric fallout were distinguished as the main sources of plutonium in these basins. In seawater (with suspended matter included) there is about 2.33 GBq (239+240)Pu (0.2% of total activity) in Gdańsk bay and 9.92 GBq (239+240)Pu (0.3% of total activity) in Gdańsk basin. In both cases, 56% of (239+240)Pu is associated with suspended matter. Organisms contain 3.81 MBq in Gdańsk bay and 7.45 MBq (239+240)Pu in Gdańsk basin. From this value in Gdańsk bay 82.1% of plutonium is associated with zoobenthos, 13.6% with phytobenthos, 1.6% with phytoplankton, 1.5% with zooplankton and 1.2% with fish. In Gdańsk basin, 83.2% is associated with zoobenthos, 7.5% with phytobenthos, 3.6% with phytoplankton, 3.2% with zooplankton and 2.5% with fish.

A two-arm cluster randomized control trial to determine the effectiveness of a pressure ulcer prevention bundle for critically ill patients.

PubMed

Tayyib, Nahla; Coyer, Fiona; Lewis, Peter A

2015-05-01

This study tested the effectiveness of a pressure ulcer (PU) prevention bundle in reducing the incidence of PUs in critically ill patients in two Saudi intensive care units (ICUs). A two-arm cluster randomized experimental control trial. Participants in the intervention group received the PU prevention bundle, while the control group received standard skin care as per the local ICU policies. Data collected included demographic variables (age, diagnosis, comorbidities, admission trajectory, length of stay) and clinical variables (Braden Scale score, severity of organ function score, mechanical ventilation, PU presence, and staging). All patients were followed every two days from admission through to discharge, death, or up to a maximum of 28 days. Data were analyzed with descriptive correlation statistics, Kaplan-Meier survival analysis, and Poisson regression. The total number of participants recruited was 140: 70 control participants (with a total of 728 days of observation) and 70 intervention participants (784 days of observation). PU cumulative incidence was significantly lower in the intervention group (7.14%) compared to the control group (32.86%). Poisson regression revealed the likelihood of PU development was 70% lower in the intervention group. The intervention group had significantly less Stage I (p = .002) and Stage II PU development (p = .026). Significant improvements were observed in PU-related outcomes with the implementation of the PU prevention bundle in the ICU; PU incidence, severity, and total number of PUs per patient were reduced. Utilizing a bundle approach and standardized nursing language through skin assessment and translation of the knowledge to practice has the potential to impact positively on the quality of care and patient outcome. © 2015 Sigma Theta Tau International.

Structure and Bonding Investigation of Plutonium Peroxocarbonate Complexes Using Cerium Surrogates and Electronic Structure Modeling.

PubMed

Sweet, Lucas E; Corbey, Jordan F; Gendron, Frédéric; Autschbach, Jochen; McNamara, Bruce K; Ziegelgruber, Kate L; Arrigo, Leah M; Peper, Shane M; Schwantes, Jon M

2017-01-17

Herein, we report the synthesis and structural characterization of K 8 [(CO 3 ) 3 Pu] 2 (μ-η 2 -η 2 -O 2 ) 2 ·12H 2 O. This is the second Pu-containing addition to the previously studied alkali-metal peroxocarbonate series M 8 [(CO 3 ) 3 A] 2 (μ-η 2 -η 2 -O 2 ) 2 ·xH 2 O (M = alkali metal; A = Ce or Pu; x = 8, 10, 12, or 18), for which only the M = Na analogue has been previously reported when A = Pu. The previously reported crystal structure for Na 8 [(CO 3 ) 3 Pu] 2 (μ-η 2 -η 2 -O 2 ) 2 ·12H 2 O is not isomorphous with its known Ce analogue. However, a new synthetic route to these M 8 [(CO 3 ) 3 A] 2 (μ-η 2 -η 2 -O 2 ) 2 ·12H 2 O complexes, described below, has produced crystals of Na 8 [(CO 3 ) 3 Ce] 2 (μ-η 2 -η 2 -O 2 ) 2 ·12H 2 O that are isomorphous with the previously reported Pu analogue. Via this synthetic method, the M = Na, K, Rb, and Cs salts of M 8 [(CO 3 ) 3 Ce] 2 (μ-η 2 -η 2 -O 2 ) 2 ·xH 2 O have also been synthesized for a systematic structural comparison with each other and the available Pu analogues using single-crystal X-ray diffraction, Raman spectroscopy, and density functional theory calculations. The Ce salts, in particular, demonstrate subtle differences in the peroxide bond lengths, which correlate with Raman shifts for the peroxide O p -O p stretch (O p = O atoms of the peroxide bridges) with each of the cations studied: Na + [1.492(3) Å/847 cm -1 ], Rb + [1.471(1) Å/854 cm -1 ], Cs + [1.474(1) Å/859 cm -1 ], and K + [1.468(6) Å/870 cm -1 ]. The trends observed in the O p -O p bond distances appear to relate to supermolecular interactions between the neighboring cations.

One-step fabrication of multifunctional composite polyurethane spider-web-like nanofibrous membrane for water purification.

PubMed

Pant, Hem Raj; Kim, Han Joo; Joshi, Mahesh Kumar; Pant, Bishweshwar; Park, Chan Hee; Kim, Jeong In; Hui, K S; Kim, Cheol Sang

2014-01-15

A stable silver-doped fly ash/polyurathene (Ag-FA/PU) nanocomposite multifunctional membrane is prepared by a facile one-step electrospinning process using fly ash particles (FAPs). Colloidal solution of PU with FAPs and Ag metal precursor was subjected to fabricate nanocomposite spider-web-like membrane using electrospinning process. Presence of N,N-dimethylformamide (solvent of PU) led to reduce silver nitrate into Ag NPs. Incorporation of Ag NPs and FAPs through electrospun PU fibers is proven through electron microscopy and spectroscopic techniques. Presence of these NPs on PU nanofibers introduces several potential physicochemical properties such as spider-web-like nano-neeting for NPs separation, enhanced absorption capacity to remove carcinogenic arsenic (As) and toxic organic dyes, and antibacterial properties with reduce bio-fouling for membrane filter application. Preliminary observations used for above-mentioned applications for water treatment showed that it will be an economically and environmentally friendly nonwoven matrix for water purification. This simple approach highlights new avenues about the utilization of one pollutant material to control other pollutants in scalable and inexpensive ways. Copyright © 2013 Elsevier B.V. All rights reserved.

FCRD Advanced Reactor (Transmutation) Fuels Handbook

DOE Office of Scientific and Technical Information (OSTI.GOV)

Janney, Dawn Elizabeth; Papesch, Cynthia Ann

2016-09-01

Transmutation of minor actinides such as Np, Am, and Cm in spent nuclear fuel is of international interest because of its potential for reducing the long-term health and safety hazards caused by the radioactivity of the spent fuel. One important approach to transmutation (currently being pursued by the DOE Fuel Cycle Research & Development Advanced Fuels Campaign) involves incorporating the minor actinides into U-Pu-Zr alloys, which can be used as fuel in fast reactors. U-Pu-Zr alloys are well suited for electrolytic refining, which leads to incorporation rare-earth fission products such as La, Ce, Pr, and Nd. It is, therefore, importantmore » to understand not only the properties of U-Pu-Zr alloys but also those of U-Pu-Zr alloys with concentrations of minor actinides (Np, Am) and rare-earth elements (La, Ce, Pr, and Nd) similar to those in reprocessed fuel. In addition to requiring extensive safety precautions, alloys containing U, Pu, and minor actinides (Np and Am) are difficult to study for numerous reasons, including their complex phase transformations, characteristically sluggish phasetransformation kinetics, tendency to produce experimental results that vary depending on the histories of individual samples, rapid oxidation, and sensitivity to contaminants such as oxygen in concentrations below a hundred parts per million. Although less toxic, rare-earth elements such as La, Ce, Pr, and Nd are also difficult to study for similar reasons. Many of the experimental measurements were made before 1980, and the level of documentation for experimental methods and results varies widely. It is, therefore, not surprising that little is known with certainty about U-Pu-Zr alloys, particularly those that also contain minor actinides and rare-earth elements. General acceptance of results commonly indicates that there is only a single measurement for a particular property. This handbook summarizes currently available information about U, Pu, Zr, Np, Am, La, Ce, Pr, and Nd and alloys of two or three of these elements. It contains information about phase diagrams and related information (including phases and phase transformations); heat capacity, entropy, and enthalpy; thermal expansion; and thermal conductivity and diffusivity. In addition to presenting information about materials properties, the handbook attempts to provide information about how well the property is known and how much variation exists between measurements. Although it includes some results from models, its primary focus is experimental data. The Handbook is organized in two sections: one with information about the U-Pu-Zr ternary and one with information about other elements and binary and vi ternary alloys in the U-Np-Pu-Am-La-Ce-Pr-Nd-Zr system. Within each section, information about elements is presented first, followed by information about binary alloys, then information about ternary alloys. The order in which the elements in each alloy are mentioned follows the order in the first sentence of this paragraph. Much of the information on the U-Pu-Zr system repeats information from the FCRD Transmutation Fuels Handbook 2015. Most of the other data has been published elsewhere (although scattered throughout numerous references, some quite obscure); however, some data from Idaho National Laboratory is presented here for the first time. As the FCRD programmatic mission evolves, future editions of this handbook will begin to include other advanced reactor fuel designs and compositions. Hence, the title of the handbook will transition to the Advanced Reactor Fuels Handbook.« less

Synthesis and 3D printing of biodegradable polyurethane elastomer by a water-based process for cartilage tissue engineering applications.

PubMed

Hung, Kun-Che; Tseng, Ching-Shiow; Hsu, Shan-Hui

2014-10-01

Biodegradable materials that can undergo degradation in vivo are commonly employed to manufacture tissue engineering scaffolds, by techniques including the customized 3D printing. Traditional 3D printing methods involve the use of heat, toxic organic solvents, or toxic photoinitiators for fabrication of synthetic scaffolds. So far, there is no investigation on water-based 3D printing for synthetic materials. In this study, the water dispersion of elastic and biodegradable polyurethane (PU) nanoparticles is synthesized, which is further employed to fabricate scaffolds by 3D printing using polyethylene oxide (PEO) as a viscosity enhancer. The surface morphology, degradation rate, and mechanical properties of the water-based 3D-printed PU scaffolds are evaluated and compared with those of polylactic-co-glycolic acid (PLGA) scaffolds made from the solution in organic solvent. These scaffolds are seeded with chondrocytes for evaluation of their potential as cartilage scaffolds. Chondrocytes in 3D-printed PU scaffolds have excellent seeding efficiency, proliferation, and matrix production. Since PU is a category of versatile materials, the aqueous 3D printing process developed in this study is a platform technology that can be used to fabricate devices for biomedical applications. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

AFS-2 FLOWSHEET MODIFICATIONS TO ADDRESS THE INGROWTH OF PU(VI) DURING METAL DISSOLUTION

DOE Office of Scientific and Technical Information (OSTI.GOV)

Crapse, K.; Rudisill, T.; O'Rourke, P.

2014-07-02

In support of the Alternate Feed Stock Two (AFS-2) PuO{sub 2} production campaign, Savannah River National Laboratory (SRNL) conducted a series of experiments concluding that dissolving Pu metal at 95°C using a 6–10 M HNO{sub 3} solution containing 0.05–0.2 M KF and 0–2 g/L B could reduce the oxidation of Pu(IV) to Pu(VI) as compared to dissolving Pu metal under the same conditions but at or near the boiling temperature. This flowsheet was demonstrated by conducting Pu metal dissolutions at 95°C to ensure that PuO{sub 2} solids were not formed during the dissolution. These dissolution parameters can be used formore » dissolving both Aqueous Polishing (AP) and MOX Process (MP) specification materials. Preceding the studies reported herein, two batches of Pu metal were dissolved in the H-Canyon 6.1D dissolver to prepare feed solution for the AFS-2 PuO{sub 2} production campaign. While in storage, UV-visible spectra obtained from an at-line spectrophotometer indicated the presence of Pu(VI). Analysis of the solutions also showed the presence of Fe, Ni, and Cr. Oxidation of Pu(IV) produced during metal dissolution to Pu(VI) is a concern for anion exchange purification. Anion exchange requires Pu in the +4 oxidation state for formation of the anionic plutonium(IV) hexanitrato complex which absorbs onto the resin. The presence of Pu(VI) in the anion feed solution would require a valence adjustment step to prevent losses. In addition, the presence of Cr(VI) would result in absorption of chromate ion onto the resin and could limit the purification of Pu from Cr which may challenge the purity specification of the final PuO{sub 2} product. Initial experiments were performed to quantify the rate of oxidation of Pu(IV) to Pu(VI) (presumed to be facilitated by Cr(VI)) as functions of the HNO{sub 3} concentration and temperature in simulated dissolution solutions containing Cr, Fe, and Ni. In these simulated Pu dissolutions studies, lowering the temperature from near boiling to 95 °C reduced the oxidation rate of Pu(IV) to Pu(VI). For 8.1 M HNO{sub 3} simulated dissolution solutions, at near boiling conditions >35% Pu(VI) was present in 50 h while at 95 °C <10% Pu(VI) was present at 50 h. At near boiling temperatures, eliminating the presence of Cr and varying the HNO{sub 3} concentration in the range of 7–8.5 M had little effect on the rate of conversion of Pu(IV) to Pu(VI). HNO{sub 3} oxidation of Pu(IV) to Pu(VI) in a pure solution has been reported previously. Based on simulated dissolution experiments, this study concluded that dissolving Pu metal at 95°C using a 6 to 10 M HNO{sub 3} solution 0.05–0.2 M KF and 0–2 g/L B could reduce the rate of oxidation of Pu(IV) to Pu(VI) as compared to near boiling conditions. To demonstrate this flowsheet, two small-scale experiments were performed dissolving Pu metal up to 6.75 g/L. No Pu-containing residues were observed in the solutions after cooling. Using Pu metal dissolution rates measured during the experiments and a correlation developed by Holcomb, the time required to completely dissolve a batch of Pu metal in an H-Canyon dissolver using this flowsheet was estimated to require nearly 5 days (120 h). This value is reasonably consistent with an estimate based on the Batch 2 and 3 dissolution times in the 6.1D dissolver and Pu metal dissolution rates measured in this study and by Rudisill et al. Data from the present and previous studies show that the Pu metal dissolution rate decreases by a factor of approximately two when the temperature decreased from boiling (112 to 116°C) to 95°C. Therefore, the time required to dissolve a batch of Pu metal in an H-Canyon dissolver at 95°C would likely double (from 36 to 54 h) and require 72 to 108 h depending on the surface area of the Pu metal. Based on the experimental studies, a Pu metal dissolution flowsheet utilizing 6–10 M HNO{sub 3} containing 0.05–0.2 M KF (with 0–2 g/L B) at 95°C is recommended to reduce the oxidation of Pu(IV) to Pu(VI) as compared to near boiling conditions. The time required to completely dissolve a batch of Pu metal will increase, however, by approximately a factor of two as compared to initial dissolutions at near boiling (assuming the KF concentration is maintained at nominally 0.1 M). By lowering the temperature to 95°C under otherwise the same operating parameters as previous dissolutions, the Pu(VI) concentration should not exceed 15% after a 120 h heating cycle. Increasing the HNO{sub 3} concentration and lowering Pu concentration are expected to further limit the amount of Pu(VI) formed.« less

Ultra-small plutonium oxide nanocrystals: an innovative material in plutonium science.

PubMed

Hudry, Damien; Apostolidis, Christos; Walter, Olaf; Janssen, Arne; Manara, Dario; Griveau, Jean-Christophe; Colineau, Eric; Vitova, Tonya; Prüssmann, Tim; Wang, Di; Kübel, Christian; Meyer, Daniel

2014-08-11

Apart from its technological importance, plutonium (Pu) is also one of the most intriguing elements because of its non-conventional physical properties and fascinating chemistry. Those fundamental aspects are particularly interesting when dealing with the challenging study of plutonium-based nanomaterials. Here we show that ultra-small (3.2±0.9 nm) and highly crystalline plutonium oxide (PuO2 ) nanocrystals (NCs) can be synthesized by the thermal decomposition of plutonyl nitrate ([PuO2 (NO3 )2 ]⋅3 H2 O) in a highly coordinating organic medium. This is the first example reporting on the preparation of significant quantities (several tens of milligrams) of PuO2 NCs, in a controllable and reproducible manner. The structure and magnetic properties of PuO2 NCs have been characterized by a wide variety of techniques (powder X-ray diffraction (PXRD), X-ray absorption fine structure (XAFS), X-ray absorption near edge structure (XANES), TEM, IR, Raman, UV/Vis spectroscopies, and superconducting quantum interference device (SQUID) magnetometry). The current PuO2 NCs constitute an innovative material for the study of challenging problems as diverse as the transport behavior of plutonium in the environment or size and shape effects on the physics of transuranium elements. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Radiochemical determination of 237NP in soil samples contaminated with weapon grade plutonium

NASA Astrophysics Data System (ADS)

Antón, M. P.; Espinosa, A.; Aragón, A.

2006-01-01

The Palomares terrestrial ecosystem (Spain) constitutes a natural laboratory to study transuranics. This scenario is partially contaminated with weapon-grade plutonium since the burnout and fragmentation of two thermonuclear bombs accidentally dropped in 1966. While performing radiometric measurements in the field, the possible presence of 237Np was observed through its 29 keV gamma emission. To accomplish a detailed characterization of the source term in the contaminated area using the isotopic ratios Pu-Am-Np, the radiochemical isolation and quantification by alpha spectrometry of 237Np was initiated. The selected radiochemical procedure involves separation of Np from Am, U and Pu with ionic resins, given that in soil samples from Palomares 239+240Pu levels are several orders of magnitude higher than 237Np. Then neptunium is isolated using TEVA organic resins. After electrodeposition, quantification is performed by alpha spectrometry. Different tests were done with blank solutions spiked with 236Pu and 237Np, solutions resulting from the total dissolution of radioactive particles and soil samples. Results indicate that the optimal sequential radionuclide separation order is Pu-Np, with decontamination percentages obtained with the ionic resins ranging from 98% to 100%. Also, the addition of NaNO2 has proved to be necessary, acting as a stabilizer of Pu-Np valences.

Multiscale Speciation of U and Pu at Chernobyl, Hanford, Los Alamos, McGuire AFB, Mayak, and Rocky Flats.

PubMed

Batuk, Olga N; Conradson, Steven D; Aleksandrova, Olga N; Boukhalfa, Hakim; Burakov, Boris E; Clark, David L; Czerwinski, Ken R; Felmy, Andrew R; Lezama-Pacheco, Juan S; Kalmykov, Stepan N; Moore, Dean A; Myasoedov, Boris F; Reed, Donald T; Reilly, Dallas D; Roback, Robert C; Vlasova, Irina E; Webb, Samuel M; Wilkerson, Marianne P

2015-06-02

The speciation of U and Pu in soil and concrete from Rocky Flats and in particles from soils from Chernobyl, Hanford, Los Alamos, and McGuire Air Force Base and bottom sediments from Mayak was determined by a combination of X-ray absorption fine structure (XAFS) spectroscopy and X-ray fluorescence (XRF) element maps. These experiments identify four types of speciation that sometimes may and other times do not exhibit an association with the source terms and histories of these samples: relatively well ordered PuO2+x and UO2+x that had equilibrated with O2 and H2O under both ambient conditions and in fires or explosions; instances of small, isolated particles of U as UO2+x, U3O8, and U(VI) species coexisting in close proximity after decades in the environment; alteration phases of uranyl with other elements including ones that would not have come from soils; and mononuclear Pu-O species and novel PuO2+x-type compounds incorporating additional elements that may have occurred because the Pu was exposed to extreme chemical conditions such as acidic solutions released directly into soil or concrete. Our results therefore directly demonstrate instances of novel complexity in the Å and μm-scale chemical speciation and reactivity of U and Pu in their initial formation and after environmental exposure as well as occasions of unexpected behavior in the reaction pathways over short geological but significant sociological times. They also show that incorporating the actual disposal and site conditions and resultant novel materials such as those reported here may be necessary to develop the most accurate predictive models for Pu and U in the environment.

Capillary Force Lithography for Cardiac Tissue Engineering

PubMed Central

Macadangdang, Jesse; Lee, Hyun Jung; Carson, Daniel; Jiao, Alex; Fugate, James; Pabon, Lil; Regnier, Michael; Murry, Charles; Kim, Deok-Ho

2014-01-01

Cardiovascular disease remains the leading cause of death worldwide1. Cardiac tissue engineering holds much promise to deliver groundbreaking medical discoveries with the aims of developing functional tissues for cardiac regeneration as well as in vitro screening assays. However, the ability to create high-fidelity models of heart tissue has proven difficult. The heart’s extracellular matrix (ECM) is a complex structure consisting of both biochemical and biomechanical signals ranging from the micro- to the nanometer scale2. Local mechanical loading conditions and cell-ECM interactions have recently been recognized as vital components in cardiac tissue engineering3-5. A large portion of the cardiac ECM is composed of aligned collagen fibers with nano-scale diameters that significantly influences tissue architecture and electromechanical coupling2. Unfortunately, few methods have been able to mimic the organization of ECM fibers down to the nanometer scale. Recent advancements in nanofabrication techniques, however, have enabled the design and fabrication of scalable scaffolds that mimic the in vivo structural and substrate stiffness cues of the ECM in the heart6-9. Here we present the development of two reproducible, cost-effective, and scalable nanopatterning processes for the functional alignment of cardiac cells using the biocompatible polymer poly(lactide-co-glycolide) (PLGA)8 and a polyurethane (PU) based polymer. These anisotropically nanofabricated substrata (ANFS) mimic the underlying ECM of well-organized, aligned tissues and can be used to investigate the role of nanotopography on cell morphology and function10-14. Using a nanopatterned (NP) silicon master as a template, a polyurethane acrylate (PUA) mold is fabricated. This PUA mold is then used to pattern the PU or PLGA hydrogel via UV-assisted or solvent-mediated capillary force lithography (CFL), respectively15,16. Briefly, PU or PLGA pre-polymer is drop dispensed onto a glass coverslip and the PUA mold is placed on top. For UV-assisted CFL, the PU is then exposed to UV radiation (λ = 250-400 nm) for curing. For solvent-mediated CFL, the PLGA is embossed using heat (120 °C) and pressure (100 kPa). After curing, the PUA mold is peeled off, leaving behind an ANFS for cell culture. Primary cells, such as neonatal rat ventricular myocytes, as well as human pluripotent stem cell-derived cardiomyocytes, can be maintained on the ANFS2. PMID:24962161

Determination of the activity concentration of a 238 Pu solution by the defined solid angle method utilizing a novel dual diaphragm-detector assembly.

PubMed

Aguiar, Julio C; Galiano, Eduardo; Arenillas, Pablo

2005-08-01

The activity concentration of a (238)Pu solution was measured by the determined solid angle method employing a novel dual diaphragm-detector assembly, which has been previously described. Due to the special requirements of the detector, a new type of source holder was developed, which consisted of sandwiching the radioisotope between two organic films called VYNS. It was experimentally demonstrated that the VYNS films do not absorb alpha particles, but reduce their energy by an average of 22 keV.A mean activity concentration for (238)Pu of 359.10+/-0.8 kBq/g was measured.

Incorporation of amoxicillin-loaded organic montmorillonite into poly(ester-urethane) urea nanofibers as a functional tissue engineering scaffold.

PubMed

Yu, Kui; Zhu, Tonghe; Wu, Yu; Zhou, Xiangxiang; Yang, Xingxing; Wang, Juan; Fang, Jun; El-Hamshary, Hany; Al-Deyab, Salem S; Mo, Xiumei

2017-03-01

A dual drug-loaded system is a promising alternative for the sustained drug release system and skin tissue engineering. In this study, a natural sodium montmorillonite (Na-MMT) modified by cetyl trimethyl ammonium bromide (CTAB) was prepared as a carrier to load a model drug - amoxicillin (AMX), the modified organic montmorillonite (CTAB-OMMT) loaded with AMX was marked as AMX@CTAB-OMMT and was subsequently incorporated into poly(ester-urethane) urea (PEUU) and gelatin hybrid nanofibers via electrospinning, resulting in a new drug-loaded nanofibrous scaffold (AMX@CTAB-OMMT-PU75). The scanning electron microscopy (SEM) result showed that the fiber morphology did not change after the embedding of AMX@CTAB-OMMT. Meanwhile, there was a significant increase of mechanical properties for PEUU/Gelatin hybrid nanofibers (PU75) after the incorporation of AMX@CTAB-OMMT and CTAB-OMMT. Importantly, AMX@CTAB-OMMT-PU75 nanofibers showed a kind of sustained drug release property which could be justified reasonably for the controlled release of AMX depending on the various application. The sustained release property could be identified roughly by the result of antibacterial test. The anaphylactic reaction test proved that there was no any anaphylactic reaction or inflammation on the back of rat for AMX@CTAB-OMMT-PU75 nanofibers. Consequently, the prepared drug-loaded AMX@CTAB-OMMT-PU75 nanofibrous scaffold is a promising candidate for application in the skin tissue engineering field and controlled drug release system. Copyright © 2016 Elsevier B.V. All rights reserved.

Novel polymer electrolytes based on cationic polyurethane with different alkyl chain length

NASA Astrophysics Data System (ADS)

Liu, Libin; Wu, Xiwen; Li, Tianduo

2014-03-01

A series of comb-like cationic polyurethanes (PUs) were synthesized by quaternizing different bromoalkane (C2H5Br, C8H17Br, and C14H29Br) with polyurethane. Solid polymer electrolytes were prepared by complexes cationic PUs with different content of LiClO4. All the solid polymer electrolytes had sufficient thermal stability as confirmed by TGA and exhibited a single-phase behavior evidenced by DSC results. For these electrolytes, FT-IR spectra indicated the formation of polymer-ion complexes. The ac impedance spectra show that the conductivity of the electrolytes follow the Arrhenius behavior, and ionic conductivity is associated with both the charge migration of ions between coordination sites and transmission between aggregates, as confirmed by FT-IR and SEM. Alkyl quaternary ammonium salts in the polymer backbone are recognized as inherent plasticizers, which make the electrolytes exhibit liquid-like behavior. The plasticizing effect of PU-C8 and PU-C14 electrolytes are more effective than that of PU-C2 electrolyte. Maximum ionic conductivity at room temperature for PU-C8 electrolytes containing 50 wt% LiClO4 reached 1.1 × 10-4 S cm-1. This work provides a new research clue that alkyl quaternary ammonium salts could be used as inherent plasticizers and hence make the system behave like a liquid with high ionic conductivity, while preserving the dimensional stability of the solids.

Primary liver tumors in beagle dogs exposed by inhalation to aerosols of plutonium-238 dioxide

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gillett, N.A.; Muggenburg, B.A.; Mewhinney, J.A.

1988-11-01

Primary liver tumors developed in Beagle dogs exposed by inhalation to aerosols of /sup 238/PuO/sub 2/. Initial deposition of /sup 238/PuO/sub 2/ in the respiratory tract was followed by translocation of a portion of the /sup 238/Pu to the liver and skeleton, which resulted in a large dose commitment and tumor risk to all three tissues. In a population of 144 dogs exposed to /sup 238/PuO/sub 2/, 112 dogs died or were killed 4000 days after /sup 238/Pu exposure, 100 dogs had osteosarcoma, and 28 dogs had lung cancers. At increasing times after exposure, however, liver lesions have become moremore » pronounced. Ten primary liver tumors in nine animals were diagnosed in the dogs dying before 4000 days after exposure. An additional five primary liver tumors in three dogs occurred in 9 animals killed after 4000 days after exposure. The majority of these tumors have been fibrosarcomas. The liver tumors were usually not the cause of death, and rarely metastasized. The occurrence of liver tumors in this study indicates that /sup 238/Pu is an effective hepatic carcinogen. Liver carcinogenesis is assuming an increasing importance in this study at late times after inhalation exposure. These results suggest that the liver may be an important organ at risk for the development of neoplasia in humans at time periods long after inhalation of /sup 238/Pu.« less

Characterization of Hydrogen Interactions with δ-Pu using Electronic Structure Theory

NASA Astrophysics Data System (ADS)

Taylor, Christopher D.; Hernandez, Sarah C.

2012-02-01

The generalized gradient approximation to density functional theory was used to study surface, bulk, defect, and reaction states of hydrogen in δ-Pu. The quasi-disordered anti-ferromagnetic arrangement gave a volume of 24.1 å^3 and a bulk modulus of 48.1 GPa for δ-Pu, in reasonable agreement with the experimental values of 24.9 å^3 and 30-35 GPa. This arrangement was thus subsequently used for all calculations. We have determined that hydrogen interactions with δ-Pu are exothermic in character at all levels ranging from dissociative chemisorption to interstitial absorption, the formation of hydrogen-vacancy complexes, and generation of a hydride phase. The exothermic character of these interactions appears to be the reason for the rapid hydriding reaction, which has been determined experimentally to be essentially a barrierless process. The anionic character is observed to be retained. Our studies also indicate that vacancies do not appear to be strong traps for hydrogen, since the interstitial absorption sites are exothermic in nature. We will propose a scheme by which hydrogen interacts with Pu. Results will be compared with previous studies in the literature where available.

Plutonium isotopes in the atmosphere of Central Europe: Isotopic composition and time evolution vs. circulation factors.

PubMed

Kierepko, Renata; Mietelski, Jerzy W; Ustrnul, Zbigniew; Anczkiewicz, Robert; Wershofen, Herbert; Holgye, Zoltan; Kapała, Jacek; Isajenko, Krzysztof

2016-11-01

This paper reports evidence of Pu isotopes in the lower part of the troposphere of Central Europe. The data were obtained based on atmospheric aerosol fraction samples collected from four places in three countries (participating in the informal European network known as the Ring of Five (Ro5)) forming a cell with a surface area of about 200,000km(2). We compared our original data sets from Krakow (Poland, 1990-2007) and Bialystok (Poland, 1991-2007) with the results from two other locations, Prague (Czech Republic; 1997-2004) and Braunschweig (Germany; 1990-2003) to find time evolution of the Pu isotopes. The levels of the activity concentration for (238)Pu and for ((239+240))Pu were estimated to be a few and some tens of nBqm(-3), respectively. However, we also noted some results were much higher (even about 70 times higher) than the average concentration of (238)Pu in the atmosphere. The achieved complex data sets were used to test a new approach to the problem of solving mixing isotopic traces from various sources (here up to three) in one sample. Results of our model, supported by mesoscale atmospheric circulation parameters, suggest that Pu from nuclear weapon accidents or tests and nuclear burnt-up fuel are present in the air. Copyright © 2016 Elsevier B.V. All rights reserved.

Structural Characterization of Am(III)- and Pu(III)-DOTA Complexes.

PubMed

Audras, Matthieu; Berthon, Laurence; Berthon, Claude; Guillaumont, Dominique; Dumas, Thomas; Illy, Marie-Claire; Martin, Nicolas; Zilbermann, Israel; Moiseev, Yulia; Ben-Eliyahu, Yeshayahu; Bettelheim, Armand; Cammelli, Sebastiano; Hennig, Christoph; Moisy, Philippe

2017-10-16

The complexation of 1,4,7,10-tetrazacyclodecane-1,4,7,10-tetraacetic acid (DOTA) ligand with two trivalent actinides (Am 3+ and Pu 3+ ) was investigated by UV-visible spectrophotometry, NMR spectroscopy, and extended X-ray absorption fine structure in conjunction with computational methods. The complexation process of these two cations is similar to what has been previously observed with lanthanides(III) of similar ionic radius. The complexation takes place in different steps and ends with the formation of a (1:1) complex [(An(III)DOTA)(H 2 O)] - , where the cation is bonded to the nitrogen atoms of the ring, the four carboxylate arms, and a water molecule to complete the coordination sphere. The formation of An(III)-DOTA complexes is faster than the Ln(III)-DOTA systems of equivalent ionic radius. Furthermore, it is found that An-N distances are slightly shorter than Ln-N distances. Theoretical calculations showed that the slightly higher affinity of DOTA toward Am over Nd is correlated with slightly enhanced ligand-to-metal charge donation arising from oxygen and nitrogen atoms.

Analysis of linear energy transfers and quality factors of charged particles produced by spontaneous fission neutrons from 252Cf and 244Pu in the human body.

PubMed

Endo, Akira; Sato, Tatsuhiko

2013-04-01

Absorbed doses, linear energy transfers (LETs) and quality factors of secondary charged particles in organs and tissues, generated via the interactions of the spontaneous fission neutrons from (252)Cf and (244)Pu within the human body, were studied using the Particle and Heavy Ion Transport Code System (PHITS) coupled with the ICRP Reference Phantom. Both the absorbed doses and the quality factors in target organs generally decrease with increasing distance from the source organ. The analysis of LET distributions of secondary charged particles led to the identification of the relationship between LET spectra and target-source organ locations. A comparison between human body-averaged mean quality factors and fluence-averaged radiation weighting factors showed that the current numerical conventions for the radiation weighting factors of neutrons, updated in ICRP103, and the quality factors for internal exposure are valid.

User acceptance of a picture archiving and communication system (PACS) in a Saudi Arabian hospital radiology department

PubMed Central

2012-01-01

Background Compared with the increasingly widespread use of picture archiving and communication systems (PACSs), knowledge concerning users’ acceptance of such systems is limited. Knowledge of acceptance is needed given the large (and growing) financial investment associated with the implementation of PACSs, and because the level of user acceptance influences the degree to which the benefits of the systems for healthcare can be realized. Methods A Technology Acceptance Model (TAM) was used to assess the level of acceptance of the host PACS by staff in the radiology department at King Abdulaziz Medical City (KAMC), Riyadh, Saudi Arabia. A questionnaire survey of 89 PACS users was employed to obtain data regarding user characteristics, perceived usefulness (PU) (6 items), perceived ease of use (PEU) (4 items), a change construct (4 items), and a behavior (acceptance) construct (9 items). Respondents graded each item in each construct using five-point likert scales. Results Surveyed users reported high levels of PU (4.33/5), PEU (4.15/5), change (4.26/5), and acceptance (3.86/5). The three constructs of PU, PEU, and change explained 41 % of the variation in PACS user acceptance. PU was the most important predictor, explaining 38 % of the variation on its own. The most important single item in the explanatory constructs was that users found PACS to have improved the quality of their work in providing better patient care. Technologists had lower acceptance ratings than did clinicians/radiologists, but no influence on acceptance level was found due to gender, age, or length of experience using the PACS. Although not directly measured, there appeared to be no cultural influence on either the level of acceptance or its determinants. Conclusions User acceptance must be considered when an organization implements a PACS, in order to enhance its successful adoption. Health organizations should adopt a PACS that offers all required functions and which is likely to generate high PU on the part of its users, rather than a system that is easy to use. Training/familiarization programs should aim at establishing high levels of PU in all users, particularly technologists. Health organizations are advised to measure all the factors that influence the acceptance of a PACS by their staff, in order to optimize the productivity of the system and realize the potential benefits to the greatest extent possible. PMID:22640490

LAB-SCALE DEMONSTRATION OF PLUTONIUM PURIFICATION BY ANION EXCHANGE, PLUTONIUM (IV) OXALATE PRECIPITATION, AND CALCINATION TO PLUTONIUM OXIDE TO SUPPORT THE MOX FEED MISSION

DOE Office of Scientific and Technical Information (OSTI.GOV)

Crowder, M.; Pierce, R.

2012-08-22

H-Canyon and HB-Line are tasked with the production of PuO{sub 2} from a feed of plutonium metal. The PuO{sub 2} will provide feed material for the MOX Fuel Fabrication Facility. After dissolution of the Pu metal in H-Canyon, the solution will be transferred to HB-Line for purification by anion exchange. Subsequent unit operations include Pu(IV) oxalate precipitation, filtration and calcination to form PuO{sub 2}. This report details the results from SRNL anion exchange, precipitation, filtration, calcination, and characterization tests, as requested by HB-Line1 and described in the task plan. This study involved an 80-g batch of Pu and employed testmore » conditions prototypical of HB-Line conditions, wherever feasible. In addition, this study integrated lessons learned from earlier anion exchange and precipitation and calcination studies. H-Area Engineering selected direct strike Pu(IV) oxalate precipitation to produce a more dense PuO{sub 2} product than expected from Pu(III) oxalate precipitation. One benefit of the Pu(IV) approach is that it eliminates the need for reduction by ascorbic acid. The proposed HB-Line precipitation process involves a digestion time of 5 minutes after the time (44 min) required for oxalic acid addition. These were the conditions during HB-line production of neptunium oxide (NpO{sub 2}). In addition, a series of small Pu(IV) oxalate precipitation tests with different digestion times were conducted to better understand the effect of digestion time on particle size, filtration efficiency and other factors. To test the recommended process conditions, researchers performed two nearly-identical larger-scale precipitation and calcination tests. The calcined batches of PuO{sub 2} were characterized for density, specific surface area (SSA), particle size, moisture content, and impurities. Because the 3013 Standard requires that the calcination (or stabilization) process eliminate organics, characterization of PuO{sub 2} batches monitored the presence of oxalate by thermogravimetric analysis-mass spectrometry (TGA-MS). To use the TGA-MS for carbon or oxalate content, some method development will be required. However, the TGA-MS is already used for moisture measurements. Therefore, SRNL initiated method development for the TGA-MS to allow quantification of oxalate or total carbon. That work continues at this time and is not yet ready for use in this study. However, the collected test data can be reviewed later as those analysis tools are available.« less

3D bioprinting of neural stem cell-laden thermoresponsive biodegradable polyurethane hydrogel and potential in central nervous system repair.

PubMed

Hsieh, Fu-Yu; Lin, Hsin-Hua; Hsu, Shan-Hui

2015-12-01

The 3D bioprinting technology serves as a powerful tool for building tissue in the field of tissue engineering. Traditional 3D printing methods involve the use of heat, toxic organic solvents, or toxic photoinitiators for fabrication of synthetic scaffolds. In this study, two thermoresponsive water-based biodegradable polyurethane dispersions (PU1 and PU2) were synthesized which may form gel near 37 °C without any crosslinker. The stiffness of the hydrogel could be easily fine-tuned by the solid content of the dispersion. Neural stem cells (NSCs) were embedded into the polyurethane dispersions before gelation. The dispersions containing NSCs were subsequently printed and maintained at 37 °C. The NSCs in 25-30% PU2 hydrogels (∼680-2400 Pa) had excellent proliferation and differentiation but not in 25-30% PU1 hydrogels. Moreover, NSC-laden 25-30% PU2 hydrogels injected into the zebrafish embryo neural injury model could rescue the function of impaired nervous system. However, NSC-laden 25-30% PU1 hydrogels only showed a minor repair effect in the zebrafish model. In addition, the function of adult zebrafish with traumatic brain injury was rescued after implantation of the 3D-printed NSC-laden 25% PU2 constructs. Therefore, the newly developed 3D bioprinting technique involving NSCs embedded in the thermoresponsive biodegradable polyurethane ink offers new possibilities for future applications of 3D bioprinting in neural tissue engineering. Copyright © 2015 Elsevier Ltd. All rights reserved.

Increased retention of americium in kidneys as compared with plutonium in an actinide wound contamination model in the rat.

PubMed

Griffiths, Nina M; Coudert, Sylvie; Molina, Thibaut; Wilk, Jean-Claude; Renault, Daniel; Berard, Philippe; Van der Meeren, Anne

2014-11-01

Americium-241 ((241)Am) presents a potential risk for nuclear industry workers associated with reactor decommissioning and aging combustible materials. The purpose of this study was to investigate Am renal retention after actinide contamination by wounding in the rat. Anesthetized rats were contaminated with Mixed Oxide (MOX) (7.1% Plutonium [Pu] by mass and containing 27% Am as % total alpha activity), Pu or Am nitrate following an incision wound of the hind leg. Times of euthanasia ranged from 2 hours to 5 months after contamination. Pu and Am levels were quantified following radiochemistry and alpha-spectrophotometry. Initial data show that over the experimental period the proportion of Am in kidneys as a fraction of total kidney alpha activity was elevated as compared to MOX powder indicating a specific retention in this organ. The percentage of Pu was similar to the powder. After MOX contamination, kidney to liver ratios appeared to increase more markedly for Am (from 0.2 at 7 days to 0.6 at 90 days) as compared with Pu (0.1 at 7 days to 0.2 at 90 days). In accordance with tissue actinide retention the dose from Am to the kidney increases with time. For comparison, the ratio of estimated equivalent doses due to Am to kidney is 1.5-fold greater than for Pu (around 90 versus 60 mSv). After actinide contamination of wounds, Am is concentrated in the kidneys as compared to Pu leading to potential exposure of renal tissue to both alpha particles and gamma radiation.

Development of polyurethane-based passive samplers for ambient monitoring of urban-use insecticides in water.

PubMed

Liao, Chunyang; Richards, Jaben; Taylor, Allison R; Gan, Jay

2017-12-01

Widespread use of insecticides for the control of urban pests such as ants, termites, and spiders has resulted in contamination and toxicity in urban aquatic ecosystems in different regions of the world. Passive samplers are a convenient and integrative tool for in situ monitoring of trace contaminants in surface water. However, the performance of a passive sampler depends closely on its affinity for the target analytes, making passive samplers highly specific to the types of contaminants being monitored. The goal of this study was to develop a passive sampler compatible with a wide range of insecticides, including the strongly hydrophobic pyrethroids and the weakly hydrophobic fipronil and organophosphates. Of six candidate polymeric thin films, polyurethane film (PU) was identified to be the best at enriching the test compounds. The inclusion of stable isotope labeled analogs as performance reference compounds (PRCs) further allowed the use of PU film for pyrethroids under non-equilibrium conditions. The PU sampler was tested in a large aquarium with circulatory water flow, and also deployed at multiple sites in surface streams in southern California. The concentrations of pesticides derived from the PU sampler ranged from 0.5 to 18.5 ng/L, which were generally lower than the total chemical concentration measured by grab samples, suggesting that suspended particles and dissolved organic matter in water rendered them less available. The influence of suspended particles and dissolved organic matter on bioavailability was more pronounced for pyrethroids than for fipronils. The results show that the developed PU film sampler, when coupled with PRCs, may be used for rapid and sensitive in-situ monitoring of a wide range of insecticides in surface water. Copyright © 2017 Elsevier Ltd. All rights reserved.

Scaling the PuNDIT project for wide area deployments

NASA Astrophysics Data System (ADS)

McKee, Shawn; Batista, Jorge; Carcassi, Gabriele; Dovrolis, Constantine; Lee, Danny

2017-10-01

In today’s world of distributed scientific collaborations, there are many challenges to providing reliable inter-domain network infrastructure. Network operators use a combination of active monitoring and trouble tickets to detect problems, but these are often ineffective at identifying issues that impact wide-area network users. Additionally, these approaches do not scale to wide area inter-domain networks due to unavailability of data from all the domains along typical network paths. The Pythia Network Diagnostic InfrasTructure (PuNDIT) project aims to create a scalable infrastructure for automating the detection and localization of problems across these networks. The project goal is to gather and analyze metrics from existing perfSONAR monitoring infrastructures to identify the signatures of possible problems, locate affected network links, and report them to the user in an intuitive fashion. Simply put, PuNDIT seeks to convert complex network metrics into easily understood diagnoses in an automated manner. We present our progress in creating the PuNDIT system and our status in developing, testing and deploying PuNDIT. We report on the project progress to-date, describe the current implementation architecture and demonstrate some of the various user interfaces it will support. We close by discussing the remaining challenges and next steps and where we see the project going in the future.

ADVANCEMENTS IN TIME-SPECTRA ANALYSIS METHODS FOR LEAD SLOWING-DOWN SPECTROSCOPY

DOE Office of Scientific and Technical Information (OSTI.GOV)

Smith, Leon E.; Anderson, Kevin K.; Gesh, Christopher J.

2010-08-11

Direct measurement of Pu in spent nuclear fuel remains a key challenge for safeguarding nuclear fuel cycles of today and tomorrow. Lead slowing-down spectroscopy (LSDS) is an active nondestructive assay method that has the potential to provide independent, direct measurement of Pu and U isotopic mass with an uncertainty lower than the approximately 10 percent typical of today’s confirmatory assay methods. Pacific Northwest National Laboratory’s (PNNL) previous work to assess the viability of LSDS for the assay of pressurized water reactor (PWR) assemblies indicated that the method could provide direct assay of Pu-239 and U-235 (and possibly Pu-240 and Pu-241)more » with uncertainties less than a few percent, assuming suitably efficient instrumentation, an intense pulsed neutron source, and improvements in the time-spectra analysis methods used to extract isotopic information from a complex LSDS signal. This previous simulation-based evaluation used relatively simple PWR fuel assembly definitions (e.g. constant burnup across the assembly) and a constant initial enrichment and cooling time. The time-spectra analysis method was founded on a preliminary analytical model of self-shielding intended to correct for assay-signal nonlinearities introduced by attenuation of the interrogating neutron flux within the assembly.« less

Pu-239 organ specific dosimetric model applied to non-human biota

NASA Astrophysics Data System (ADS)

Kaspar, Matthew Jason

There are few locations throughout the world, like the Maralinga nuclear test site located in south western Australia, where sufficient plutonium contaminate concentration levels exist that they can be utilized for studies of the long-term radionuclide accumulation in non-human biota. The information obtained will be useful for the potential human users of the site while also keeping with international efforts to better understand doses to non-human biota. In particular, this study focuses primarily on a rabbit sample set collected from the population located within the site. Our approach is intended to employ the same dose and dose rate methods selected by the International Commission on Radiological Protection and adapted by the scientific community for similar research questions. These models rely on a series of simplifying assumptions on biota and their geometry; in particular; organisms are treated as spherical and ellipsoidal representations displaying the animal mass and volume. These simplifications assume homogeneity of all animal tissues. In collaborative efforts between Colorado State University and the Australian Nuclear Science and Technology Organisation (ANSTO), we are expanding current knowledge on radionuclide accumulation in specific organs causing organ-specific dose rates, such as Pu-239 accumulating in bone, liver, and lungs. Organ-specific dose models have been developed for humans; however, little has been developed for the dose assessment to biota, in particular rabbits. This study will determine if it is scientifically valid to use standard software, in particular ERICA Tool, as a means to determine organ-specific dosimetry due to Pu-239 accumulation in organs. ERICA Tool is normally applied to whole organisms as a means to determine radiological risk to whole ecosystems. We will focus on the aquatic model within ERICA Tool, as animal organs, like aquatic organisms, can be assumed to lie within an infinite uniform medium. This model would scientifically be valid for radionuclides emitting short-range radiation, as with Pu-239, where the energy is deposited locally. Two MCNPX models have been created and evaluated against ERICA Tool's aquatic model. One MCNPX model replicates ERICA Tool's intrinsic assumptions while the other uses a more realistic animal model adopted by ICRP Publication 108 and ERICA Tool for the organs "infinite" surrounding universe. In addition, the role of model geometry will be analyzed by focusing on four geometry sets for the same organ, including a spherical geometry. ERICA Tool will be compared to MCNPX results within and between each organ geometry set. In addition, the organ absorbed dose rate will be calculated for six rabbits located on the Maralinga nuclear test site as a preliminary test for further investigation. Data in all cases will be compared using percent differences and Student's t-test with respect to ERICA Tool's results and the overall average organ mean absorbed dose rate.

A Clinical Nurse Specialist-Led Interprofessional Quality Improvement Project to Reduce Hospital-Acquired Pressure Ulcers.

PubMed

Fabbruzzo-Cota, Christina; Frecea, Monica; Kozell, Kathryn; Pere, Katalin; Thompson, Tamara; Tjan Thomas, Julie; Wong, Angela

2016-01-01

The purpose of this clinical nurse specialist-led interprofessional quality improvement project was to reduce hospital-acquired pressure ulcers (HAPUs) using evidence-based practice. Hospital-acquired pressure ulcers (PUs) have been linked to morbidity, poor quality of life, and increasing costs. Pressure ulcer prevention and management remain a challenge for interprofessional teams in acute care settings. Hospital-acquired PU rate is a critical nursing quality indicator for healthcare organizations and ties directly with Mount Sinai Hospital's (MSH's) mission and vision, which mandates providing the highest quality care to patients and families. This quality improvement project, guided by the Donabedian model, was based on the Registered Nurses' Association of Ontario Best Practice Guideline Risk Assessment & Prevention of Pressure Ulcers. A working group was established to promote evidence-based practice for PU prevention. Initiatives such as documentation standardization, development of staff education and patient and family educational resources, initiation of a hospital-wide inventory for support surfaces, and procurement of equipment were implemented to improve PU prevention and management across the organization. An 80% decrease in HAPUs has been achieved since the implementation of best practices by the Best Practice Guideline Pressure Ulcer working group. The implementation of PU prevention strategies led to a reduction in HAPU rates. The working group will continue to work on building interprofessional awareness and collaboration in order to prevent HAPUs and promote an organizational culture that supports staff development, teamwork and communication. This quality improvement project is a successful example of an interprofessional clinical nurse specialist-led initiative that impacts patient/family and organization outcomes through the identification and implementation of evidence-based nursing practice.

Dynamics of an unusual cone-building trachyte eruption at Pu`u Wa`awa`a, Hualālai volcano, Hawai`i

NASA Astrophysics Data System (ADS)

Shea, Thomas; Leonhardi, Tanis; Giachetti, Thomas; Lindoo, Amanda; Larsen, Jessica; Sinton, John; Parsons, Elliott

2017-04-01

The Pu`u Wa`awa`a pyroclastic cone and Pu`u Anahulu lava flow are two prominent monogenetic eruptive features assumed to result from a single eruption during the trachyte-dominated early post-shield stage of Hualālai volcano (Hawaíi). Púu Wa`awa`a is composed of complex repetitions of crudely cross-stratified units rich in dark dense clasts, which reversely grade into coarser pumice-rich units. Pyroclasts from the cone are extremely diverse texturally, ranging from glassy obsidian to vesicular scoria or pumice, in addition to fully crystalline end-members. The >100-m thick Pu`u Anahulu flow is, in contrast, entirely holocrystalline. Using field observations coupled with whole rock analyses, this study aimed to test whether the Pu`u Wa`awa`a tephra and Pu`u Anahulu lava flows originated from the same eruption, as had been previously assumed. Crystal and vesicle textures are characterized along with the volatile contents of interstitial glasses to determine the origin of textural variability within Pu`u Wáawáa trachytes (e.g., magma mixing vs. degassing origin). We find that (1) the two eruptions likely originated from distinct vents and magma reservoirs, despite their proximity and similar age, (2) the textural diversity of pyroclasts forming Pu`u Wa`awa`a can be fully explained by variable magma degassing and outgassing within the conduit, (3) the Pu`u Wa`awa`a cone was constructed during explosions transitional in style between violent Strombolian and Vulcanian, involving the formation of a large cone and with repeated disruption of conduit plugs, but without production of large pyroclastic density currents (PDCs), and (4) the contrasting eruption styles of Hawaiian trachytes (flow-, cone-, and PDC-forming) are probably related to differences in the outgassing capacity of the magmas prior to reaching the surface and not in intrinsic compositional or temperature properties. These results further highlight that trachytes are "kinetically faster" magmas compared to dacites or rhyolites, likely degassing and crystallizing more rapidly.

Advances in containment methods and plutonium recovery strategies that led to the structural characterization of plutonium(IV) tetrachloride tris-diphenylsulfoxide, PuCl 4(OSPh 2) 3

DOE PAGES

Schrell, Samantha K.; Boland, Kevin Sean; Cross, Justin Neil; ...

2017-01-18

In an attempt to further advance the understanding of plutonium coordination chemistry, we report a robust method for recycling and obtaining plutonium aqueous stock solutions that can be used as a convenient starting material in plutonium synthesis. This approach was used to prepare and characterize plutonium(IV) tetrachloride tris-diphenylsulfoxide, PuCl 4(OSPh 2) 3, by single crystal X-ray diffraction. The PuCl 4(OSPh 2) 3 compound represents a rare example of a 7-coordinate plutonium(IV) complex. Structural characterization of PuCl 4(OSPh 2) 3 by X-ray diffraction utilized a new containment method for radioactive crystals. The procedure makes use of epoxy, polyimide loops, and amore » polyester sheath to provide a robust method for safely containing and easily handling radioactive samples. Lastly, the described procedure is more user friendly than traditional containment methods that employ fragile quartz capillary tubes. Additionally, moving to polyester, instead of quartz, lowers the background scattering from the heavier silicon atoms.« less

PuLSE: Quality control and quantification of peptide sequences explored by phage display libraries.

PubMed

Shave, Steven; Mann, Stefan; Koszela, Joanna; Kerr, Alastair; Auer, Manfred

2018-01-01

The design of highly diverse phage display libraries is based on assumption that DNA bases are incorporated at similar rates within the randomized sequence. As library complexity increases and expected copy numbers of unique sequences decrease, the exploration of library space becomes sparser and the presence of truly random sequences becomes critical. We present the program PuLSE (Phage Library Sequence Evaluation) as a tool for assessing randomness and therefore diversity of phage display libraries. PuLSE runs on a collection of sequence reads in the fastq file format and generates tables profiling the library in terms of unique DNA sequence counts and positions, translated peptide sequences, and normalized 'expected' occurrences from base to residue codon frequencies. The output allows at-a-glance quantitative quality control of a phage library in terms of sequence coverage both at the DNA base and translated protein residue level, which has been missing from toolsets and literature. The open source program PuLSE is available in two formats, a C++ source code package for compilation and integration into existing bioinformatics pipelines and precompiled binaries for ease of use.

Overview of reductants utilized in nuclear fuel reprocessing/recycling

DOE Office of Scientific and Technical Information (OSTI.GOV)

Patricia Paviet-Hartmann; Catherine Riddle; Keri Campbell

2013-10-01

Most of the aqueous processes developed, or under consideration worldwide for the recycling of used nuclear fuel (UNF) utilize the oxido-reduction properties of actinides to separate them from other radionuclides. Generally, after acid dissolution of the UNF, (essentially in nitric acid solution), actinides are separated from the raffinate by liquid-liquid extraction using specific solvents, associated along the process, with a particular reductant that will allow the separation to occur. For example, the industrial PUREX process utilizes hydroxylamine as a plutonium reductant. Hydroxylamine has numerous advantages: not only does it have the proper attributes to reduce Pu(IV) to Pu(III), but itmore » is also a non-metallic chemical that is readily decomposed to innocuous products by heating. However, it has been observed that the presence of high nitric acid concentrations or impurities (such as metal ions) in hydroxylamine solutions increase the likelihood of the initiation of an autocatalytic reaction. Recently there has been some interest in the application of simple hydrophilic hydroxamic ligands such as acetohydroxamic acid (AHA) for the stripping of tetravalent actinides in the UREX process flowsheet. This approach is based on the high coordinating ability of hydroxamic acids with tetravalent actinides (Np and Pu) compared with hexavalent uranium. Thus, the use of AHA offers a route for controlling neptunium and plutonium in the UREX process by complexant based stripping of Np(IV) and Pu(IV) from the TBP solvent phase, while U(VI) ions are not affected by AHA and remain solvated in the TBP phase. In the European GANEX process, AHA is also used to form hydrophilic complexes with actinides and strip them from the organic phase into nitric acid. However, AHA does not decompose completely when treated with nitric acid and hampers nitric acid recycling. In lieu of using AHA in the UREX + process, formohydroxamic acid (FHA), although not commercially available, hold promises as a replacement for AHA. FHA undergoes hydrolysis to formic acid which is volatile, thus allowing the recycling of nitric acid. Unfortunately, FHA powder was not stable in the experiments we ran in our laboratory. In addition, AHA and FHA also decompose to hydroxylamine which may undergo an autocatalytic reaction. Other reductants are available and could be extremely useful for actinides separation. The review presents the current plutonium reductants used in used nuclear fuel reprocessing and will introduce innovative and novel reductants that could become reducers for future research on UNF separation.« less

Sorption/Desorption Interactions of Plutonium with Montmorillonite

NASA Astrophysics Data System (ADS)

Begg, J.; Zavarin, M.; Zhao, P.; Kersting, A. B.

2012-12-01

Plutonium (Pu) release to the environment through nuclear weapon development and the nuclear fuel cycle is an unfortunate legacy of the nuclear age. In part due to public health concerns over the risk of Pu contamination of drinking water, predicting the behavior of Pu in both surface and sub-surface water is a topic of continued interest. Typically it was assumed that Pu mobility in groundwater would be severely restricted, as laboratory adsorption studies commonly show that naturally occurring minerals can effectively remove plutonium from solution. However, evidence for the transport of Pu over significant distances at field sites highlights a relative lack of understanding of the fundamental processes controlling plutonium behavior in natural systems. At several field locations, enhanced mobility is due to Pu association with colloidal particles that serve to increase the transport of sorbed contaminants (Kersting et al., 1999; Santschi et al., 2002, Novikov et al., 2006). The ability for mineral colloids to transport Pu is in part controlled by its oxidation state and the rate of plutonium adsorption to, and desorption from, the mineral surface. Previously we have investigated the adsorption affinity of Pu for montmorillonite colloids, finding affinities to be similar over a wide range of Pu concentrations. In the present study we examine the stability of adsorbed Pu on the mineral surface. Pu(IV) at an initial concentration of 10-10 M was pre-equilibrated with montmorillonite in a background electrolyte at pH values of 4, 6 and 8. Following equilibration, aliquots of the suspensions were placed in a flow cell and Pu-free background electrolyte at the relevant pH was passed through the system. Flow rates were varied in order to investigate the kinetics of desorption and hence gain a mechanistic understanding of the desorption process. The flow cell experiments demonstrate that desorption of Pu from the montmorillonite surface cannot be modeled as a simple first order process. Furthermore, a pH dependence was observed, with less desorbed at pH 4 compared to pH 8. We suggest the pH dependence is likely controlled by reoxidation of Pu(IV) to Pu(V) and aqueous speciation. We will present models used to describe desorption behavior and discuss the implications for Pu transport. References: Kersting, A.B.; Efurd, D.W.; Finnegan, D.L.; Rokop, D.J.; Smith, D.K.; Thompson J.L. (1999) Migration of plutonium in groundwater at the Nevada Test Site, Nature, 397, 56-59. Novikov A.P.; Kalmykov, S.N.; Utsunomiya, S.; Ewing, R.C.; Horreard, F.; Merkulov, A.; Clark, S.B.; Tkachev, V.V.; Myasoedov, B.F. (2006) Colloid transport of plutonium in the far-field of the Mayak Production Association, Russia, Science, 314, 638-641. Santschi, P.H.; Roberts, K.; Guo, L. (2002) The organic nature of colloidal actinides transported in surface water environments. Environ. Sci. Technol., 36, 3711-3719. This work was funded by U. S. DOE Office of Biological & Environmental Sciences, Subsurface Biogeochemistry Research Program, and performed under the auspices of the U. S. Department of Energy by Lawrence Livermore National Security, LLC under Contract DE-AC52-07NA27344. LLNL-ABS-570161

Continuous Optical 3D Printing of Green Aliphatic Polyurethanes.

PubMed

Pyo, Sang-Hyun; Wang, Pengrui; Hwang, Henry H; Zhu, Wei; Warner, John; Chen, Shaochen

2017-01-11

Photosensitive diurethanes were prepared from a green chemistry synthesis pathway based on methacrylate-functionalized six-membered cyclic carbonate and biogenic amines. A continuous optical 3D printing method for the diurethanes was developed to create user-defined gradient stiffness and smooth complex surface microstructures in seconds. The green chemistry-derived polyurethane (gPU) showed high optical transparency, and we demonstrate the ability to tune the material stiffness of the printed structure along a gradient by controlling the exposure time and selecting various amine compounds. High-resolution 3D biomimetic structures with smooth curves and complex contours were printed using our gPU. High cell viability (over 95%) was demonstrated during cytocompatibility testing using C3H 10T1/2 cells seeded directly on the printed structures.

Comparison of bioreactors with different kinds of submerged packed beds for domestic wastewater treatment.

PubMed

Nacheva, P Mijaylova; Moeller Chávez, G; Bustos, C; Garzón Zúñiga, M A; Hornelas Orozco, Y

2008-01-01

The performance of aerobic submerged packed bed reactors was studied for the treatment of domestic wastewater using different kinds of packing materials with high specific areas (760-1,200 m(2)/m(3)). The tested materials were ceramic spheres, crushed tezontle, grains of high density polyethylene (HDPE), of low density polyethylene (LDPE) and of polypropylene (PP), cubes of polyurethane (PU) and polyethylene tape (SESSIL). The bioreactors were operated in continuous regime, applying organic loads in the range of 0.8-6.0 g COD.m(-2).d(-1). The obtained specific COD removal rates were very similar in all the reactors when they were operated at organic loads up to 2.0 g COD.m(-2).d(-1), after which differences in effectiveness appeared and the best results were determined in the reactors with SESSIL, LDPE and PU. Very low TSS, O&G and turbidity were obtained in all the effluents. The NH(3)-N and TN removals were dependent on the dissolved oxygen (DO) concentration and the removals at DO of 5 mg/l were 84-99% and 61-74% respectively. The best removals were determined in the reactors with PU, SESSIL and LDPE. The reactor with tezontle had also a good performance when operated with loads up to 1.0 g TN.m(-2).d(-1). The best phosphate removals (38-49%) were obtained in the reactors with PU, tezontle, ceramic sheres and SESSIL. (c) IWA Publishing 2008.

Fundamental Chemical Kinetic And Thermodynamic Data For Purex Process Models

DOE Office of Scientific and Technical Information (OSTI.GOV)

Taylor, R.J.; Fox, O.D.; Sarsfield, M.J.

2007-07-01

To support either the continued operations of current reprocessing plants or the development of future fuel processing using hydrometallurgical processes, such as Advanced Purex or UREX type flowsheets, the accurate simulation of Purex solvent extraction is required. In recent years we have developed advanced process modeling capabilities that utilize modern software platforms such as Aspen Custom Modeler and can be run in steady state and dynamic simulations. However, such advanced models of the Purex process require a wide range of fundamental data including all relevant basic chemical kinetic and thermodynamic data for the major species present in the process. Thismore » paper will summarize some of these recent process chemistry studies that underpin our simulation, design and testing of Purex solvent extraction flowsheets. Whilst much kinetic data for actinide redox reactions in nitric acid exists in the literature, the data on reactions in the diluted TBP solvent phase is much rarer. This inhibits the accurate modelization of the Purex process particularly when species show a significant extractability in to the solvent phase or when cycling between solvent and aqueous phases occurs, for example in the reductive stripping of Pu(IV) by ferrous sulfamate in the Magnox reprocessing plant. To support current oxide reprocessing, we have investigated a range of solvent phase reactions: - U(IV)+HNO{sub 3}; - U(IV)+HNO{sub 2}; - U(IV)+HNO{sub 3} (Pu catalysis); - U(IV)+HNO{sub 3} (Tc catalysis); - U(IV)+ Np(VI); - U(IV)+Np(V); - Np(IV)+HNO{sub 3}; - Np(V)+Np(V); Rate equations have been determined for all these reactions and kinetic rate constants and activation energies are now available. Specific features of these reactions in the TBP phase include the roles of water and hydrolyzed intermediates in the reaction mechanisms. In reactions involving Np(V), cation-cation complex formation, which is much more favourable in TBP than in HNO{sub 3}, also occurs and complicates the redox chemistry. Whilst some features of the redox chemistry in TBP appear similar to the corresponding reactions in aqueous HNO{sub 3}, there are notable differences in rates, the forms of the rate equations and mechanisms. Secondly, to underpin the development of advanced single cycle flowsheets using the complexant aceto-hydroxamic acid, we have also characterised in some detail its redox chemistry and solvent extraction behaviour with both Np and Pu ions. We find that simple hydroxamic acids are remarkably rapid reducing agents for Np(VI). They also reduce Pu(VI) and cause a much slower reduction of Pu(IV) through a complex mechanism involving acid hydrolysis of the ligand. AHA is a strong hydrophilic and selective complexant for the tetravalent actinide ions as evidenced by stability constant and solvent extraction data for An(IV), M(III) and U(VI) ions. This has allowed the successful design of U/Pu+Np separation flowsheets suitable for advanced fuel cycles. (authors)« less

137Cs, 239,240Pu and 241Am in boreal forest soil and their transfer into wild mushrooms and berries.

PubMed

Lehto, Jukka; Vaaramaa, Kaisa; Leskinen, Anumaija

2013-02-01

Profiles of podzolic soil from boreal forests were sampled from eight sites in Finland and the distribution of (137)Cs in the soil layers was determined. In addition, (239,240)Pu and (241)Am were determined from two soil profiles taken at one sampling site. Inventories of (137)Cs in the soil profiles varied between 1.7 kBq/m(2) and 42 kBq/m(2), reflecting known variation in (137)Cs fallout from the Chernobyl accident. The highest proportions of the radionuclides were found in the organic layer at a depth of less than 5 cm, which on average contained 47% of (137)Cs, 76% of (239,240)Pu and 79% of (241)Am. In the litter, clearly higher proportions of (137)Cs were found compared to (239,240)Pu and (241)Am, probably indicating its more effective recycling from the organic layer back to the surface. Only very minor proportions of (137)Cs were recorded below 20 cm. The concentration of (137)Cs in the soil profiles could be approximated with a declining logarithmic trend. The activity concentrations of (137)Cs were determined for six wild mushroom species and three wild berry species at two sites, as well as the aggregated transfer factors and the distribution of (137)Cs between their various parts. In addition, (239,240)Pu and (241)Am were determined in one mushroom and three berry species at one site. Very high concentrations of (137)Cs, up to 20 kBq/kg (d.w.), were found in mushrooms, and their transfer factors were between 0.1 m(2)/kg and 1.0 m(2)/kg. In berries, the transfer factors were an order of magnitude lower. (137)Cs accumulated more in the caps of mushrooms and in the fruits of berries than in other parts. Transfer factors for (239,240)Pu and (241)Am were two to three orders of magnitude lower than those of (137)Cs. Copyright © 2012 Elsevier Ltd. All rights reserved.

Advancing Understanding of the +4 Metal Extractant Thenoyltrifluoroacetonate (TTA-); Synthesis and Structure of MIVTTA4 (MIV = Zr, Hf, Ce, Th, U, Np, Pu) and MIII(TTA)4- (MIII = Ce, Nd, Sm, Yb).

PubMed

Cary, Samantha K; Livshits, Maksim; Cross, Justin N; Ferrier, Maryline G; Mocko, Veronika; Stein, Benjamin W; Kozimor, Stosh A; Scott, Brian L; Rack, Jeffrey J

2018-04-02

Thenoyltrifluoroacetone (HTTA)-based extractions represent popular methods for separating microscopic amounts of transuranic actinides (i.e., Np and Pu) from macroscopic actinide matrixes (e.g. bulk uranium). It is well-established that this procedure enables +4 actinides to be selectively removed from +3, + 5, and +6 f-elements. However, even highly skilled and well-trained researchers find this process complicated and (at times) unpredictable. It is difficult to improve the HTTA extraction-or find alternatives-because little is understood about why this separation works. Even the identities of the extracted species are unknown. In addressing this knowledge gap, we report here advances in fundamental understanding of the HTTA-based extraction. This effort included comparatively evaluating HTTA complexation with +4 and +3 metals (M IV = Zr, Hf, Ce, Th, U, Np, and Pu vs M III = Ce, Nd, Sm, and Yb). We observed +4 metals formed neutral complexes of the general formula M IV (TTA) 4 . Meanwhile, +3 metals formed anionic M III (TTA) 4 - species. Characterization of these M(TTA) 4 x- ( x = 0, 1) compounds by UV-vis-NIR, IR, 1 H and 19 F NMR, single-crystal X-ray diffraction, and X-ray absorption spectroscopy (both near-edge and extended fine structure) was critical for determining that Np IV (TTA) 4 and Pu IV (TTA) 4 were the primary species extracted by HTTA. Furthermore, this information lays the foundation to begin developing and understanding of why the HTTA extraction works so well. The data suggest that the solubility differences between M IV (TTA) 4 and M III (TTA) 4 - are likely a major contributor to the selectivity of HTTA extractions for +4 cations over +3 metals. Moreover, these results will enable future studies focused on explaining HTTA extractions preference for +4 cations, which increases from Np IV to Pu IV , Hf IV , and Zr IV .

3D bioprinting: A new insight into the therapeutic strategy of neural tissue regeneration.

PubMed

Hsieh, Fu-Yu; Hsu, Shan-hui

2015-01-01

Acute traumatic injuries and chronic degenerative diseases represent the world's largest unmet medical need. There are over 50 million people worldwide suffering from neurodegenerative diseases. However, there are only a few treatment options available for acute traumatic injuries and neurodegenerative diseases. Recently, 3D bioprinting is being applied to regenerative medicine to address the need for tissues and organs suitable for transplantation. In this commentary, the newly developed 3D bioprinting technique involving neural stem cells (NSCs) embedded in the thermoresponsive biodegradable polyurethane (PU) bioink is reviewed. The thermoresponsive and biodegradable PU dispersion can form gel near 37 °C without any crosslinker. NSCs embedded within the water-based PU hydrogel with appropriate stiffness showed comparable viability and differentiation after printing. Moreover, in the zebrafish embryo neural deficit model, injection of the NSC-laden PU hydrogels promoted the repair of damaged CNS. In addition, the function of adult zebrafish with traumatic brain injury was rescued after implantation of the 3D-printed NSC-laden constructs. Therefore, the newly developed 3D bioprinting technique may offer new possibilities for future therapeutic strategy of neural tissue regeneration.

Transcoding method from H.264/AVC to high efficiency video coding based on similarity of intraprediction, interprediction, and motion vector

NASA Astrophysics Data System (ADS)

Liu, Mei-Feng; Zhong, Guo-Yun; He, Xiao-Hai; Qing, Lin-Bo

2016-09-01

Currently, most video resources on line are encoded in the H.264/AVC format. More fluent video transmission can be obtained if these resources are encoded in the newest international video coding standard: high efficiency video coding (HEVC). In order to improve the video transmission and storage on line, a transcoding method from H.264/AVC to HEVC is proposed. In this transcoding algorithm, the coding information of intraprediction, interprediction, and motion vector (MV) in H.264/AVC video stream are used to accelerate the coding in HEVC. It is found through experiments that the region of interprediction in HEVC overlaps that in H.264/AVC. Therefore, the intraprediction for the region in HEVC, which is interpredicted in H.264/AVC, can be skipped to reduce coding complexity. Several macroblocks in H.264/AVC are combined into one PU in HEVC when the MV difference between two of the macroblocks in H.264/AVC is lower than a threshold. This method selects only one coding unit depth and one prediction unit (PU) mode to reduce the coding complexity. An MV interpolation method of combined PU in HEVC is proposed according to the areas and distances between the center of one macroblock in H.264/AVC and that of the PU in HEVC. The predicted MV accelerates the motion estimation for HEVC coding. The simulation results show that our proposed algorithm achieves significant coding time reduction with a little loss in bitrates distortion rate, compared to the existing transcoding algorithms and normal HEVC coding.

Analysis of plutonium isotope ratios including 238Pu/239Pu in individual U-Pu mixed oxide particles by means of a combination of alpha spectrometry and ICP-MS.

PubMed

Esaka, Fumitaka; Yasuda, Kenichiro; Suzuki, Daisuke; Miyamoto, Yutaka; Magara, Masaaki

2017-04-01

Isotope ratio analysis of individual uranium-plutonium (U-Pu) mixed oxide particles contained within environmental samples taken from nuclear facilities is proving to be increasingly important in the field of nuclear safeguards. However, isobaric interferences, such as 238 U with 238 Pu and 241 Am with 241 Pu, make it difficult to determine plutonium isotope ratios in mass spectrometric measurements. In the present study, the isotope ratios of 238 Pu/ 239 Pu, 240 Pu/ 239 Pu, 241 Pu/ 239 Pu, and 242 Pu/ 239 Pu were measured for individual Pu and U-Pu mixed oxide particles by a combination of alpha spectrometry and inductively coupled plasma mass spectrometry (ICP-MS). As a consequence, we were able to determine the 240 Pu/ 239 Pu, 241 Pu/ 239 Pu, and 242 Pu/ 239 Pu isotope ratios with ICP-MS after particle dissolution and chemical separation of plutonium with UTEVA resins. Furthermore, 238 Pu/ 239 Pu isotope ratios were able to be calculated by using both the 238 Pu/( 239 Pu+ 240 Pu) activity ratios that had been measured through alpha spectrometry and the 240 Pu/ 239 Pu isotope ratios determined through ICP-MS. Therefore, the combined use of alpha spectrometry and ICP-MS is useful in determining plutonium isotope ratios, including 238 Pu/ 239 Pu, in individual U-Pu mixed oxide particles. Copyright © 2016 Elsevier B.V. All rights reserved.

Coordination chemistry of 2,2'-biphenylenedithiophosphinate and diphenyldithiophosphinate with U, Np, and Pu

DOE PAGES

Macor, Joseph A.; Brown, Jessie L.; Cross, Justin Neil; ...

2015-01-01

New members of the dithiophosphinic acid family of potential actinide extractants were prepared: heterocyclic 2,2'-biphenylenedithiophosphinic acids of stoichiometry HS 2P(R 2C 12H 6) (R = H or tBu). The time- and atom-efficient syntheses afforded multigram quantities of pure HS 2P(R 2C 12H 6) in reasonable yields (~60%). These compounds differed from other diaryldithiophosphinic acid extractants in that the two aryl groups were connected to one another at the ortho positions to form a 5-membered dibenzophosphole ring. These 2,2'-biphenylenedithiophosphinic acids were readily deprotonated to form S 2P(R 2C 12H 6) 1- anions, which were crystallized as salts with tetraphenylpnictonium cations (ZPhmore » 4 1+; Z = P or As). Coordination chemistry between [S 2P( tBu 2C 12H 6)] 1- and [S 2P(C 6H 5)2] 1- with U, Np, and Pu was comparatively investigated. The results showed that dithiophosphinate complexes of UIV and NpIV were redox stable relative to those of UIII, whereas reactions involving PuIV gave intractable material. For instance, reactions involving UIV and NpIV generated An[S 2P( tBu 2C 12H 6)] 4 and An[S 2P(C 6H 5) 2] 4 whereas reactions between PuIV and [S 2P(C 6H 5) 2] 1- generated a mixture of products from which we postulated a transient PuIII species based on UV-Vis spectroscopy. However, the trivalent Pu[S 2P(C 6H 5) 2] 3(NC 5H 5) 2 compound is stable and could be isolated from reactions between [S 2P(C 6H 5) 2] 1- and the trivalent PuI 3(NC 5H 5) 4 starting material. Attempts to synthesize analogous trivalent compounds with UIII provided the tetravalent U[S 2P(C 6H 5 )2] 4 oxidation product.« less

Vertical migration of plutonium-239 + -240, americium-241 and caesium-137 fallout in a forest soil under spruce.

PubMed

Bunzl, K; Kracke, W; Schimmack, W

1992-03-01

The vertical activity distributions of fallout 238Pu, 239+240Pu, 241Am, 134Cs and 137Cs in a forest soil (Hapludult) were determined at several locations in a spruce stand separately according to their origin (global fallout or Chernobyl fallout). To determine the rate of migration of these radionuclides in each soil horizon, the observed depth profiles of the radionuclides were evaluated with a compartment model. In the top organic horizons (LOf1 and Of2), the migration rates for all radionuclides from both sources were above 0.5 cm per year. In the Oh horizon the migration rates observed for global fallout Pu, Am and Cs were similar (0.2-0.4 cm per year). Compared with Pu, however, the mobility of Am is slightly, but statistically significantly, enhanced. The highest rate in this layer was found for Chernobyl-derived radiocaesium (2 cm per year). In the layers of the mineral horizon (depth 0-2, 2-5 and 5-10 cm) the observed migration rates were very similar for global fallout Pu (0.08-0.7 cm per year) and Am (0.1-2 cm per year). In comparison, the migration rate of global fallout radiocaesium was about half in each layer. The highest rate was observed again for Chernobyl-derived radiocaesium (0.5-3 cm per year).

Role of natural organic matter on iodine and (239)(,240)Pu distribution and mobility in environmental samples from the northwestern Fukushima Prefecture, Japan.

PubMed

Xu, Chen; Zhang, Saijin; Sugiyama, Yuko; Ohte, Nobuhito; Ho, Yi-Fang; Fujitake, Nobuhide; Kaplan, Daniel I; Yeager, Chris M; Schwehr, Kathleen; Santschi, Peter H

2016-03-01

In order to assess how environmental factors are affecting the distribution and migration of radioiodine and plutonium that were emitted from the Fukushima Dai-ichi Nuclear Power Plant (FDNPP) accident, we quantified iodine and (239,240)Pu concentration changes in soil samples with different land uses (urban, paddy, deciduous forest and coniferous forest), as well as iodine speciation in surface water and rainwater. Sampling locations were 53-63 km northwest of the FDNPP within a 75-km radius, in close proximity of each other. A ranking of the land uses by their surface soil (<4 cm) stable (127)I concentrations was coniferous forest > deciduous forest > urban > paddy, and (239,240)Pu concentrations ranked as deciduous forest > coniferous forest > paddy ≥ urban. Both were quite distinct from that of (134)Cs and (137)Cs: urban > coniferous forest > deciduous forest > paddy, indicating differences in their sources, deposition phases, and biogeochemical behavior in these soil systems. Although stable (127)I might not have fully equilibrated with Fukushima-derived (129)I, it likely still works as a proxy for the long-term fate of (129)I. Surficial soil (127)I content was well correlated to soil organic matter (SOM) content, regardless of land use type, suggesting that SOM might be an important factor affecting iodine biogeochemistry. Other soil chemical properties, such as Eh and pH, had strong correlations to soil (127)I content, but only within a given land use (e.g., within urban soils). Organic carbon (OC) concentrations and Eh were positively, and pH was negatively correlated to (127)I concentrations in surface water and rain samples. It is also noticeable that (127)I in the wet deposition was concentrated in both the deciduous and coniferous forest throughfall and stemfall water, respectively, comparing to the bulk rainwater. Further, both forest throughfall and stemflow water consisted exclusively of organo-iodine, suggesting all inorganic iodine in the original bulk deposition (∼ 28.6% of total iodine) have been completely converted to organo-iodine. Fukushima-derived (239,240)Pu was detectable at a distance ∼ 61 km away, NW of FDNPP. However, it is confined to the litter layer, even three years after the FDNPP accident-derived emissions. Plutonium-239,240 activities were significantly correlated with soil OC and nitrogen contents, indicating Pu may be associated with nitrogen-containing SOM, similar to what has been observed at other locations in the United States. Together, these finding suggest that natural organic matter (NOM) plays a key role in affecting the fate and transport of I and Pu and may warrant greater consideration for predicting long-term stewardship of contaminated areas and evaluating various remediation options in Japan. Copyright © 2016 Elsevier Ltd. All rights reserved.

Distribution and life strategies of two bacterial populations in a eutrophic lake

PubMed

Weinbauer; Hofle

1998-10-01

Monoclonal antibodies and epifluorescence microscopy were used to determine the depth distribution of two indigenous bacterial populations in the stratified Lake Plusssee and characterize their life strategies. Populations of Comamonas acidovorans PX54 showed a depth distribution with maximum abundances in the oxic epilimnion, whereas Aeromonas hydrophila PU7718 showed a depth distribution with maximum abundances in the anoxic thermocline layer (metalimnion), i. e., in the water layer with the highest microbial activity. Resistance of PX54 to protist grazing and high metabolic versatility and growth rate of PU7718 were the most important life strategy traits for explaining the depth distribution of the two bacterial populations. Maximum abundance of PX54 was 16,000 cells per ml, and maximum abundance of PU7718 was 20,000 cells per ml. Determination of bacterial productivity in dilution cultures with different-size fractions of dissolved organic matter (DOM) from lake water indicates that low-molecular-weight (LMW) DOM is less bioreactive than total DOM (TDOM). The abundance and growth rate of PU7718 were highest in the TDOM fractions, whereas those of PX54 were highest in the LMW DOM fraction, demonstrating that PX54 can grow well on the less bioreactive DOM fraction. We estimated that 13 to 24% of the entire bacterial community and 14% of PU7718 were removed by viral lysis, whereas no significant effect of viral lysis on PX54 could be detected. Growth rates of PX54 (0.11 to 0.13 h-1) were higher than those of the entire bacterial community (0.04 to 0.08 h-1) but lower than those of PU7718 (0.26 to 0.31 h-1). In undiluted cultures, the growth rates were significantly lower, pointing to density effects such as resource limitation or antibiosis, and the effects were stronger for PU7718 and the entire bacterial community than for PX54. Life strategy characterizations based on data from literature and this study revealed that the fast-growing and metabolically versatile A. hydrophila PU7718 is an r-strategist or opportunistic population in Lake Plusssee, whereas the grazing-resistant C. acidovorans PX54 is rather a K-strategist or equilibrium population.

Synthesis of palm-based polyurethane-LiClO{sub 4} via prepolymerization

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sien, Jason Wong Chee; School of Biosciences, Taylor’s University, Subang Jaya; Badri, Khairiah Haji

2015-09-25

Palm-based polyurethane (pPU) with varying lithium salt (LiClO{sub 4}) content was synthesized. Higher loading percentage of LiClO{sub 4} in the pPU led to the inhibition of prepolymerization process from taking place. Hydrogen bonded C=O was detected in the FTIR spectrum indicating the hydrogen bonding between the urethane bonds. Ordered complexed C=O was observed in the FTIR spectrum confirming the complex formation between urethane bond and Li{sup +} ion. DSC thermogram showed the increase in the LiClO{sub 4} content could increase the glass transition temperature. SEM micrographs exhibited that more bubbles were formed when the LiClO{sub 4} increased from 10 tomore » 30wt% indicating the reaction between free isocyanate groups with moisture presence in the salt due to the hygroscopic properties of LiClO{sub 4}.« less

3D bioprinting: A new insight into the therapeutic strategy of neural tissue regeneration

PubMed Central

Hsieh, Fu-Yu; Hsu, Shan-hui

2015-01-01

ABSTRACT Acute traumatic injuries and chronic degenerative diseases represent the world’s largest unmet medical need. There are over 50 million people worldwide suffering from neurodegenerative diseases. However, there are only a few treatment options available for acute traumatic injuries and neurodegenerative diseases. Recently, 3D bioprinting is being applied to regenerative medicine to address the need for tissues and organs suitable for transplantation. In this commentary, the newly developed 3D bioprinting technique involving neural stem cells (NSCs) embedded in the thermoresponsive biodegradable polyurethane (PU) bioink is reviewed. The thermoresponsive and biodegradable PU dispersion can form gel near 37°C without any crosslinker. NSCs embedded within the water-based PU hydrogel with appropriate stiffness showed comparable viability and differentiation after printing. Moreover, in the zebrafish embryo neural deficit model, injection of the NSC-laden PU hydrogels promoted the repair of damaged CNS. In addition, the function of adult zebrafish with traumatic brain injury was rescued after implantation of the 3D-printed NSC-laden constructs. Therefore, the newly developed 3D bioprinting technique may offer new possibilities for future therapeutic strategy of neural tissue regeneration. PMID:26709633

Background radioactivity in sediments near Los Alamos, New Mexico.

PubMed

McLin, Stephen G

2004-07-26

River and reservoir sediments have been collected annually by Los Alamos National Laboratory since 1974 and 1979, respectively. These background samples are collected from five river stations and four reservoirs located throughout northern New Mexico and southern Colorado. Analyses include 3H, 90Sr, 137Cs, total U, 238Pu, 239,240Pu, 241Am, gross alpha, gross beta, and gross gamma radioactivity. Surprisingly, there are no federal or state regulatory standards in the USA that specify how to compute background radioactivity values on sediments. Hence, the sample median (or 0.50 quantile) is proposed for this background because it reflects central data tendency and is distribution-free. Estimates for the upper limit of background radioactivity on river and reservoir sediments are made for sampled analytes using the 0.95 quantile (two-tail). These analyses also show that seven of ten analytes from reservoir sediments are normally distributed, or are normally distributed after a logarithmic or square root transformation. However, only three of ten analytes from river sediments are similarly distributed. In addition, isotope ratios for 137Cs/238Pu, 137Cs/239,240Pu, and 239,240Pu/238Pu from reservoir sediments are independent of clay content, total organic carbon/specific surface area (TOC/SSA) and cation exchange capacity/specific surface area (CEC/SSA) ratios. These TOC/SSA and CEC/SSA ratios reflect sediment organic carbon and surface charge densities that are associated with radionuclide absorption, adsorption, and ion exchange reactions on clay mineral structures. These latter ratio values greatly exceed the availability of background radionuclides in the environment, and insure that measured background levels are a maximum. Since finer-grained reservoir sediments contain larger clay-sized fractions compared to coarser river sediments, they show higher background levels for most analytes. Furthermore, radioactivity values on reservoir sediments have remained relatively constant since the early 1980s. These results suggest that clay contents in terrestrial sediments are often more important at concentrating background radionuclides than many other environmental factors, including geology, climate and vegetation. Hence, reservoirs and floodplains represent ideal radionuclide sampling locations because fine-grained materials are more easily trapped here. Ultimately, most of these differences still reflect spatial and temporal variability originating from global atmospheric nuclear weapons testing and disintegration of nuclear-powered satellites upon atmospheric reentry. Copyright 2004 Elsevier B.V.

Infrasonic tremor wavefield of the Pu`u `Ō`ō crater complex and lava tube system, Hawaii, in April 2007

NASA Astrophysics Data System (ADS)

Matoza, Robin S.; Fee, David; GarcéS, Milton A.

2010-12-01

Long-lived effusive volcanism at the Pu`u `Ō`ō crater complex, Kilauea Volcano, Hawaii produces persistent infrasonic tremor that has been recorded almost continuously for months to years. Previous studies showed that this infrasonic tremor wavefield can be recorded at a range of >10 km. However, the low signal power of this tremor relative to ambient noise levels results in significant propagation effects on signal detectability at this range. In April 2007, we supplemented a broadband infrasound array at ˜12.5 km from Pu`u `Ō`ō (MENE) with a similar array at ˜2.4 km from the source (KIPU). The additional closer-range data enable further evaluation of tropospheric propagation effects and provide higher signal-to-noise ratios for studying volcanic source processes. The infrasonic tremor source appears to consist of at least two separate physical processes. We suggest that bubble cloud oscillation in a roiling magma conduit beneath the crater complex may produce a broadband component of the tremor. Low-frequency sound sourced in a shallow magma conduit may radiate infrasound efficiently into the atmosphere due to the anomalous transparency of the magma-air interface. We further propose that more sharply peaked tones with complex temporal evolution may result from oscillatory interactions of a low-velocity gas jet with solid vent boundaries in a process analogous to the hole tone or whistler nozzle. The infrasonic tremor arrives with a median azimuth of ˜67° at KIPU. Additional infrasonic signals and audible sounds originating from the extended lava tube system to the south of the crater complex (median azimuth ˜77°) coincided with turbulent degassing activity at a new lava tube skylight. Our observations indicate that acoustic studies may aid in understanding persistent continuous degassing and unsteady flow dynamics at Kilauea Volcano.

Organic Scintillator Detector Response Simulations with DRiFT

DOE PAGES

Andrews, Madison Theresa; Bates, Cameron Russell; Mckigney, Edward Allen; ...

2016-06-11

Here, this work presents the organic scintillation simulation capabilities of DRiFT, a post-processing Detector Response Function Toolkit for MCNPR output. DRiFT is used to create realistic scintillation detector response functions to incident neutron and gamma mixed- field radiation. As a post-processing tool, DRiFT leverages the extensively validated radiation transport capabilities of MCNPR ®6, which also provides the ability to simulate complex sources and geometries. DRiFT is designed to be flexible, it allows the user to specify scintillator material, PMT type, applied PMT voltage, and quenching data used in simulations. The toolkit's capabilities, which include the generation of pulse shape discriminationmore » plots and full-energy detector spectra, are demonstrated in a comparison of measured and simulated neutron contributions from 252Cf and PuBe, and photon spectra from 22Na and 228Th sources. DRiFT reproduced energy resolution effects observed in EJ-301 measurements through the inclusion of scintillation yield variances, photon transport noise, and PMT photocathode and multiplication noise.« less

Organic scintillator detector response simulations with DRiFT

NASA Astrophysics Data System (ADS)

Andrews, M. T.; Bates, C. R.; McKigney, E. A.; Solomon, C. J.; Sood, A.

2016-09-01

This work presents the organic scintillation simulation capabilities of DRiFT, a post-processing Detector Response Function Toolkit for MCNP® output. DRiFT is used to create realistic scintillation detector response functions to incident neutron and gamma mixed-field radiation. As a post-processing tool, DRiFT leverages the extensively validated radiation transport capabilities of MCNP® 6 , which also provides the ability to simulate complex sources and geometries. DRiFT is designed to be flexible, it allows the user to specify scintillator material, PMT type, applied PMT voltage, and quenching data used in simulations. The toolkit's capabilities, which include the generation of pulse shape discrimination plots and full-energy detector spectra, are demonstrated in a comparison of measured and simulated neutron contributions from 252Cf and PuBe, and photon spectra from 22Na and 228Th sources. DRiFT reproduced energy resolution effects observed in EJ-301 measurements through the inclusion of scintillation yield variances, photon transport noise, and PMT photocathode and multiplication noise.

Time-dependent local and average structural evolution of δ-phase 239Pu-Ga alloys

DOE PAGES

Smith, Alice I.; Page, Katharine L.; Siewenie, Joan E.; ...

2016-08-05

Here, plutonium metal is a very unusual element, exhibiting six allotropes at ambient pressure, between room temperature and its melting point, a complicated phase diagram, and a complex electronic structure. Many phases of plutonium metal are unstable with changes in temperature, pressure, chemical additions, or time. This strongly affects structure and properties, and becomes of high importance, particularly when considering effects on structural integrity over long periods of time [1]. This paper presents a time-dependent neutron total scattering study of the local and average structure of naturally aging δ-phase 239Pu-Ga alloys, together with preliminary results on neutron tomography characterization.

Plutonium Isotopes (239-241Pu) Dissolved in Pacific Ocean Waters Detected by Accelerator Mass Spectrometry: No Effects of the Fukushima Accident Observed.

PubMed

Hain, Karin; Faestermann, Thomas; Fimiani, Leticia; Golser, Robin; Gómez-Guzmán, José Manuel; Korschinek, Gunther; Kortmann, Florian; Lierse von Gostomski, Christoph; Ludwig, Peter; Steier, Peter; Tazoe, Hirofumi; Yamada, Masatoshi

2017-02-21

The concentration of plutonium (Pu) and the isotopic ratios of 240 Pu to 239 Pu and 241 Pu to 239 Pu were determined by accelerator mass spectrometry (AMS) in Pacific Ocean water samples (20 L each) collected in late 2012. The isotopic Pu ratios are important indicators of different contamination sources and were used to identify a possible release of Pu into the ocean by the Fukushima Daiichi Nuclear Power Plant (FDNPP) accident. In particular, 241 Pu is a well-suited indicator for a recent entry of Pu because 241 Pu from fallout of nuclear weapon testings has already significantly decayed. A total of 10 ocean water samples were prepared at the Radiochemie München of the TUM and analyzed at the Vienna Environmental Research Laboratory (VERA). Several samples showed a slightly elevated 240 Pu/ 239 Pu ratio of up to 0.22 ± 0.02 compared to global fallout ( 240 Pu/ 239 Pu = 0.180 ± 0.007), whereas all measured 241 Pu-to- 239 Pu ratios were consistent with nuclear weapon fallout ( 241 Pu/ 239 Pu < 2.4 × 10 -3 ), which means that no impact from the Fukushima accident was detected. From the average 241 Pu-to- 239 Pu ratio of 8 -2 +3 ×10 -4 at a sampling station located at a distance of 39.6 km to FDNPP, the 1-σ upper limit for the FDNPP contribution to the 239 Pu inventory in the water column was estimated to be 0.2%. Pu, with the signature of weapon-grade Pu was found in a single sample collected around 770 km off the west coast of the United States.

Advancing Understanding of the +4 Metal Extractant Thenoyltrifluoroacetonate (TTA –); Synthesis and Structure of M IVTTA 4 (M IV = Zr, Hf, Ce, Th, U, Np, Pu) and M III(TTA) 4 – (M III = Ce, Nd, Sm, Yb)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cary, Samantha K.; Livshits, Maksim; Cross, Justin N.

Thenoyltrifluoroacetone (HTTA)-based extractions represent popular methods for separating microscopic amounts of transuranic actinides (i.e., Np and Pu) from macroscopic actinide matrixes (e.g. bulk uranium). It is well-established that this procedure enables +4 actinides to be selectively removed from +3, + 5, and +6 f-elements. However, even highly skilled and well-trained researchers find this process complicated and (at times) unpredictable. It is difficult to improve the HTTA extraction—or find alternatives—because little is understood about why this separation works. Even the identities of the extracted species are unknown. In addressing this knowledge gap, we report in this paper advances in fundamental understandingmore » of the HTTA-based extraction. This effort included comparatively evaluating HTTA complexation with +4 and +3 metals (M IV = Zr, Hf, Ce, Th, U, Np, and Pu vs M III = Ce, Nd, Sm, and Yb). We observed +4 metals formed neutral complexes of the general formula M IV(TTA) 4. Meanwhile, +3 metals formed anionic M III(TTA) 4 – species. Characterization of these M(TTA) 4 x– (x = 0, 1) compounds by UV–vis–NIR, IR, 1H and 19F NMR, single-crystal X-ray diffraction, and X-ray absorption spectroscopy (both near-edge and extended fine structure) was critical for determining that Np IV(TTA) 4 and Pu IV(TTA) 4 were the primary species extracted by HTTA. Furthermore, this information lays the foundation to begin developing and understanding of why the HTTA extraction works so well. The data suggest that the solubility differences between M IV(TTA) 4 and M III(TTA) 4 – are likely a major contributor to the selectivity of HTTA extractions for +4 cations over +3 metals. Finally and moreover, these results will enable future studies focused on explaining HTTA extractions preference for +4 cations, which increases from Np IV to Pu IV, Hf IV, and Zr IV.« less

Advancing Understanding of the +4 Metal Extractant Thenoyltrifluoroacetonate (TTA –); Synthesis and Structure of M IVTTA 4 (M IV = Zr, Hf, Ce, Th, U, Np, Pu) and M III(TTA) 4 – (M III = Ce, Nd, Sm, Yb)

DOE PAGES

Cary, Samantha K.; Livshits, Maksim; Cross, Justin N.; ...

2018-03-21

Thenoyltrifluoroacetone (HTTA)-based extractions represent popular methods for separating microscopic amounts of transuranic actinides (i.e., Np and Pu) from macroscopic actinide matrixes (e.g. bulk uranium). It is well-established that this procedure enables +4 actinides to be selectively removed from +3, + 5, and +6 f-elements. However, even highly skilled and well-trained researchers find this process complicated and (at times) unpredictable. It is difficult to improve the HTTA extraction—or find alternatives—because little is understood about why this separation works. Even the identities of the extracted species are unknown. In addressing this knowledge gap, we report in this paper advances in fundamental understandingmore » of the HTTA-based extraction. This effort included comparatively evaluating HTTA complexation with +4 and +3 metals (M IV = Zr, Hf, Ce, Th, U, Np, and Pu vs M III = Ce, Nd, Sm, and Yb). We observed +4 metals formed neutral complexes of the general formula M IV(TTA) 4. Meanwhile, +3 metals formed anionic M III(TTA) 4 – species. Characterization of these M(TTA) 4 x– (x = 0, 1) compounds by UV–vis–NIR, IR, 1H and 19F NMR, single-crystal X-ray diffraction, and X-ray absorption spectroscopy (both near-edge and extended fine structure) was critical for determining that Np IV(TTA) 4 and Pu IV(TTA) 4 were the primary species extracted by HTTA. Furthermore, this information lays the foundation to begin developing and understanding of why the HTTA extraction works so well. The data suggest that the solubility differences between M IV(TTA) 4 and M III(TTA) 4 – are likely a major contributor to the selectivity of HTTA extractions for +4 cations over +3 metals. Finally and moreover, these results will enable future studies focused on explaining HTTA extractions preference for +4 cations, which increases from Np IV to Pu IV, Hf IV, and Zr IV.« less

Plutonium isotopes offer an alternative approach to establishing chronological profiles in coarse sediments

NASA Astrophysics Data System (ADS)

Pondell, C.; Kuehl, S. A.; Canuel, E. A.

2016-12-01

There are several methodologies used to determine chronologies for sediments deposited within the past 100 years, including 210Pb and 137Cs radioisotopes and organic and inorganic contaminants. These techniques are quite effective in fine sediments, which generally have a high affinity for metals and organic compounds. However, the application of these chronological tools becomes limited in systems where coarse sediments accumulate. Englebright Lake is an impoundment in northern California where sediment accumulation is characterized by a combination of fine and coarse sediments. This combination of sediment grain size complicated chronological analysis using the more traditional 137Cs chronological approach. This study established a chronology of these sediments using 239+240Pu isotopes. While most of the 249+240Pu activity was measured in the fine grain size fraction (<63 microns), up to 25% of the plutonium activity was detected in the coarse size fractions of sediments from Englebright Lake. Profiles of 239+240Pu were similar to available 137Cs profiles, verifying the application of plutonium isotopes for determining sediment chronologies and expanding the established geochronology for Englebright Lake sediments. This study of sediment accumulation in Englebright Lake demonstrates the application of plutonium isotopes in establishing chronologies in coarse sediments and highlights the potential for plutonium to offer new insights into patterns of coarse sediment accumulation.

Insights into the sonochemical synthesis and properties of salt-free intrinsic plutonium colloids

NASA Astrophysics Data System (ADS)

Dalodière, Elodie; Virot, Matthieu; Morosini, Vincent; Chave, Tony; Dumas, Thomas; Hennig, Christoph; Wiss, Thierry; Dieste Blanco, Oliver; Shuh, David K.; Tyliszcak, Tolek; Venault, Laurent; Moisy, Philippe; Nikitenko, Sergey I.

2017-03-01

Fundamental knowledge on intrinsic plutonium colloids is important for the prediction of plutonium behaviour in the geosphere and in engineered systems. The first synthetic route to obtain salt-free intrinsic plutonium colloids by ultrasonic treatment of PuO2 suspensions in pure water is reported. Kinetics showed that both chemical and mechanical effects of ultrasound contribute to the mechanism of Pu colloid formation. In the first stage, fragmentation of initial PuO2 particles provides larger surface contact between cavitation bubbles and solids. Furthermore, hydrogen formed during sonochemical water splitting enables reduction of Pu(IV) to more soluble Pu(III), which then re-oxidizes yielding Pu(IV) colloid. A comparative study of nanostructured PuO2 and Pu colloids produced by sonochemical and hydrolytic methods, has been conducted using HRTEM, Pu LIII-edge XAS, and O K-edge NEXAFS/STXM. Characterization of Pu colloids revealed a correlation between the number of Pu-O and Pu-Pu contacts and the atomic surface-to-volume ratio of the PuO2 nanoparticles. NEXAFS indicated that oxygen state in hydrolytic Pu colloid is influenced by hydrolysed Pu(IV) species to a greater extent than in sonochemical PuO2 nanoparticles. In general, hydrolytic and sonochemical Pu colloids can be described as core-shell nanoparticles composed of quasi-stoichiometric PuO2 cores and hydrolyzed Pu(IV) moieties at the surface shell.

Insights into the sonochemical synthesis and properties of salt-free intrinsic plutonium colloids

PubMed Central

Dalodière, Elodie; Virot, Matthieu; Morosini, Vincent; Chave, Tony; Dumas, Thomas; Hennig, Christoph; Wiss, Thierry; Dieste Blanco, Oliver; Shuh, David K.; Tyliszcak, Tolek; Venault, Laurent; Moisy, Philippe; Nikitenko, Sergey I.

2017-01-01

Fundamental knowledge on intrinsic plutonium colloids is important for the prediction of plutonium behaviour in the geosphere and in engineered systems. The first synthetic route to obtain salt-free intrinsic plutonium colloids by ultrasonic treatment of PuO2 suspensions in pure water is reported. Kinetics showed that both chemical and mechanical effects of ultrasound contribute to the mechanism of Pu colloid formation. In the first stage, fragmentation of initial PuO2 particles provides larger surface contact between cavitation bubbles and solids. Furthermore, hydrogen formed during sonochemical water splitting enables reduction of Pu(IV) to more soluble Pu(III), which then re-oxidizes yielding Pu(IV) colloid. A comparative study of nanostructured PuO2 and Pu colloids produced by sonochemical and hydrolytic methods, has been conducted using HRTEM, Pu LIII-edge XAS, and O K-edge NEXAFS/STXM. Characterization of Pu colloids revealed a correlation between the number of Pu-O and Pu-Pu contacts and the atomic surface-to-volume ratio of the PuO2 nanoparticles. NEXAFS indicated that oxygen state in hydrolytic Pu colloid is influenced by hydrolysed Pu(IV) species to a greater extent than in sonochemical PuO2 nanoparticles. In general, hydrolytic and sonochemical Pu colloids can be described as core-shell nanoparticles composed of quasi-stoichiometric PuO2 cores and hydrolyzed Pu(IV) moieties at the surface shell. PMID:28256635

Insights into the sonochemical synthesis and properties of salt-free intrinsic plutonium colloids

DOE PAGES

Dalodière, Elodie; Virot, Matthieu; Morosini, Vincent; ...

2017-03-03

Fundamental knowledge on intrinsic plutonium colloids is important for the prediction of plutonium behaviour in the geosphere and in engineered systems. The first synthetic route to obtain salt-free intrinsic plutonium colloids by ultrasonic treatment of PuO 2 suspensions in pure water is reported. Kinetics showed that both chemical and mechanical effects of ultrasound contribute to the mechanism of Pu colloid formation. In the first stage, fragmentation of initial PuO 2 particles provides larger surface contact between cavitation bubbles and solids. Furthermore, hydrogen formed during sonochemical water splitting enables reduction of Pu(IV) to more soluble Pu(III), which then re-oxidizes yielding Pu(IV)more » colloid. A comparative study of nanostructured PuO 2 and Pu colloids produced by sonochemical and hydrolytic methods, has been conducted using HRTEM, Pu LIII-edge XAS, and O K-edge NEXAFS/STXM. Characterization of Pu colloids revealed a correlation between the number of Pu-O and Pu-Pu contacts and the atomic surface-to-volume ratio of the PuO 2 nanoparticles. NEXAFS indicated that oxygen state in hydrolytic Pu colloid is influenced by hydrolysed Pu(IV) species to a greater extent than in sonochemical PuO 2 nanoparticles. In general, hydrolytic and sonochemical Pu colloids can be described as core-shell nanoparticles composed of quasi-stoichiometric PuO 2 cores and hydrolyzed Pu(IV) moieties at the surface shell.« less

Plutonium(IV) and (V) sorption to goethite at sub-femtomolar to micromolar concentrations: Redox transformations and surface precipitation

DOE PAGES

Zhao, Pihong; Begg, James D.; Zavarin, Mavrik; ...

2016-06-06

Here, Pu(IV) and Pu(V) sorption to goethite was investigated over a concentration range of 10 –15–10 –5 M at pH 8. Experiments with initial Pu concentrations of 10 –15 – 10 –8 M produced linear Pu sorption isotherms, demonstrating that Pu sorption to goethite is not concentration-dependent across this concentration range. Equivalent Pu(IV) and Pu(V) sorption Kd values obtained at 1 and 2-week sampling time points indicated that Pu(V) is rapidly reduced to Pu(IV) on the goethite surface. Further, it suggested that Pu surface redox transformations are sufficiently rapid to achieve an equilibrium state within 1 week, regardless of themore » initial Pu oxidation state. At initial concentrations >10 –8 M, both Pu oxidation states exhibited deviations from linear sorption behavior and less Pu was adsorbed than at lower concentrations. NanoSIMS and HRTEM analysis of samples with initial Pu concentrations of 10 –8 – 10 –6 M indicated that Pu surface and/or bulk precipitation was likely responsible for this deviation. In 10 –6 M Pu(IV) and Pu(V) samples, HRTEM analysis showed the formation of a body centered cubic (bcc) Pu 4O 7 structure on the goethite surface, confirming that reduction of Pu(V) had occurred on the mineral surface and that epitaxial distortion previously observed for Pu(IV) sorption occurs with Pu(V) as well.« less

Supercritical fluid extraction and separation of uranium from other actinides.

PubMed

Quach, Donna L; Mincher, Bruce J; Wai, Chien M

2014-06-15

The feasibility of separating U from nitric acid solutions of mixed actinides using tri-n-butylphosphate (TBP)-modified supercritical fluid carbon dioxide (sc-CO2) was investigated. The actinides U, Np, Pu, and Am were extracted into sc-CO2 modified with TBP from a range of nitric acid concentrations, in the absence of, or in the presence of, a number of traditional reducing and/or complexing agents to demonstrate the separation of these metals from U under sc-CO2 conditions. The separation of U from Pu using sc-CO2 was successful at nitric acid concentrations of less than 3M in the presence of acetohydroxamic acid (AHA) or oxalic acid (OA) to mitigate Pu extraction, and the separation of U from Np was successful at nitric acid concentrations of less than 1M in the presence of AHA, OA, or sodium nitrite to mitigate Np extraction. Americium was not well extracted under any condition studied. Copyright © 2014 Elsevier B.V. All rights reserved.

Resolving global versus local/regional Pu sources in the environment using sector ICP-MS

USGS Publications Warehouse

Ketterer, M.E.; Hafer, K.M.; Link, C.L.; Kolwaite, D.; Wilson, Jim; Mietelski, J.W.

2004-01-01

Sector inductively coupled plasma mass spectrometry is a versatile method for the determination of plutonium activities and isotopic compositions in samples containing this element at fallout levels. Typical detection limits for 239+240Pu are 0.1, 0.02 and 0.002 Bq kg -1Pu for samples sizes of 0.5 g, 3 g, and 50 g of soil, respectively. The application of sector ICP-MS-based Pu determinations is demonstrated in studies in sediment chronology, soil Pu inventory and depth distribution, and the provenance of global fallout versus local or regional Pu sources. A sediment core collected from Sloans Lake (Denver, Colorado, USA) exhibits very similar 137Cs and 239+240Pu activity profiles; 240Pu/239Pu atom ratios indicate possible small influences from the Nevada Test Site and/or the Rocky Flats Environmental Technology Site. An undisturbed soil profile from Lockett Meadow (Flagstaff, Arizona, USA) exhibits an exponential decrease in 239+240Pu activity versus depth; 240Pu/239Pu in the top 3 cm is slightly lower than the global fallout range of 0.180 ?? 0.014 due to possible regional influence of Nevada Test Site fallout. The 239??240Pu inventory at Lockett Meadow is 56 ?? 4 Bq m-2, consistent with Northern Hemisphere mid-latitude fallout. Archived NdF3 sources, prepared from Polish soils, demonstrate that substantial 239+240Pu from the 1986 Chernobyl disaster has been deposited in north eastern regions of Poland; compared to global fallout, Chernobyl Pu exhibits higher abundances of 240Pu and 241Pu. The ratios 240Pu/239pu and 241Pu/239Pu co-vary and range from 0.186-0.348 and 0.0029-0.0412, respectively, in forest soils (241Pu/239Pu = 0.2407??[240Pu/239Pu] - 0.0413; r2 = 0.9924). ?? The Royal Society of Chemistry 2004.

Bitstream decoding processor for fast entropy decoding of variable length coding-based multiformat videos

NASA Astrophysics Data System (ADS)

Jo, Hyunho; Sim, Donggyu

2014-06-01

We present a bitstream decoding processor for entropy decoding of variable length coding-based multiformat videos. Since most of the computational complexity of entropy decoders comes from bitstream accesses and table look-up process, the developed bitstream processing unit (BsPU) has several designated instructions to access bitstreams and to minimize branch operations in the table look-up process. In addition, the instruction for bitstream access has the capability to remove emulation prevention bytes (EPBs) of H.264/AVC without initial delay, repeated memory accesses, and additional buffer. Experimental results show that the proposed method for EPB removal achieves a speed-up of 1.23 times compared to the conventional EPB removal method. In addition, the BsPU achieves speed-ups of 5.6 and 3.5 times in entropy decoding of H.264/AVC and MPEG-4 Visual bitstreams, respectively, compared to an existing processor without designated instructions and a new table mapping algorithm. The BsPU is implemented on a Xilinx Virtex5 LX330 field-programmable gate array. The MPEG-4 Visual (ASP, Level 5) and H.264/AVC (Main Profile, Level 4) are processed using the developed BsPU with a core clock speed of under 250 MHz in real time.

Laboratory studies of the diagenesis and mobility of 239,240pu and 137Cs in nearshore sediments

NASA Astrophysics Data System (ADS)

Sholkovitz, Edward R.; Cochran, J. Kirk; Carey, Anne E.

1983-08-01

Controlled laboratory experiments have been used to study the diagenetic chemistry of 239,240Pu 137Cs, and 55Fe. Experiments using Buzzards Bay sediments in small tanks show that sulfate reduction is accompanied by the production of large pore water concentration gradients of alkalinity, phosphate, ammonia and dissolved organic carbon and the formation of subsurface maxima in Fe and Mn. These pore water profiles demonstrate that bacterially-mediated processes of organic matter degradation and redox reactions can be simulated in the laboratory. A vertical profile of 55Fe in pore waters is reported for the first time: it follows the profile of stable Fe and as such has a large (200 dpm/100 kg) subsurface maximum between 2-4 cm depth. Comparison of 55Fe/Fe ratios in sediments and pore waters shows that there is preferential solubilization of 55Fe over stable Fe. The pore water activities of 239,240Pu show no gradients within the large uncertainties of the counting statistics, but are two to four times higher than Buzzards Bay seawater (0.05 dpm/100 kg). The activity of 137Cs in the pore water profile is constant (40 dpm/100 kg) within the large counting uncertainties and is twice that of Buzzards Bay seawater. Cs-137 does not appear to be involved in diagenetic chemistry but may increase in pore waters as a result of ion exchange reactions. Flux estimates based on the pore water data show that remobilization and transport of 239,240 Pu in coastal sediments are not significant processes while the transport of l37Cs may be.

New Insights into Clinical Characteristics of Gilles de la Tourette Syndrome: Findings in 1032 Patients from a Single German Center.

PubMed

Sambrani, Tanvi; Jakubovski, Ewgeni; Müller-Vahl, Kirsten R

2016-01-01

Gilles de la Tourette syndrome (TS) is a complex neuropsychiatric disorder defined by the presence of motor and phonic tics, but often associated with psychiatric comorbidities. The main objective of this study was to explore the clinical presentation and comorbidities of TS. We analyzed clinical data obtained from a large sample (n = 1032; 529 children and 503 adults) of patients with tic disorders from one single German TS center assessed by one investigator. Data was collected with the help of an expert-reviewed semi-structured interview, designed to assess tic severity and certain comorbidities. Group comparisons were carried out via independent sample t-tests and chi-square tests. The main findings of the study are: (1) tic severity is associated with the presence of premonitory urges (PU), copro-, echo-, and paliphenomena and the number of comorbidities, but not age at tic onset; it is higher in patients with comorbid obsessive-compulsive disorder (OCD) than in patients with comorbid attention deficit/hyperactivity disorder (ADHD). (2) PU were found to be highly associated with "not just right experiences" and to emerge much earlier than previously thought alongside with the ability to suppress tics (PU in >60% and suppressibility in >75% at age 8-10 years). (3) Self-injurious behavior (SIB) is highly associated with complex motor tics and coprophenomena, but not with OCD/obsessive-compulsive behavior (OCB). While comorbid ADHD is associated with a lower ability to suppress tics, comorbid depression is associated with sleeping problems. Our results demonstrate that tic severity is not influenced by age at onset. From our data, it is suggested that PU represent a specific type of "not just right experience" that is not a prerequisite for tic suppression. Comorbid ADHD reduces patients' ability of successful tic suppression. Our data suggest that SIB belongs to the coprophenomena spectrum and hence should be conceptualized as a complex tic rather than a compulsion. Finally, this study strongly supports the hypothesis that TS+OCD is a more severe form of TS and that comorbid OCD/OCB, depression, and anxiety belong to the TS spectrum, while ADHD should be better conceptualized as a separate problem.

Uptake and translocation of plutonium in two plant species using hydroponics.

PubMed

Lee, J H; Hossner, L R; Attrep, M; Kung, K S

2002-01-01

This study presents determinations of the uptake and translocation of Pu in Indian mustard (Brassica juncea) and sunflower (Helianthus annuus) from Pu contaminated solution media. The initial activity levels of Pu were 18.50 and 37.00 Bq ml(-1), for Pu-nitrate [239Pu(NO3)4] and for Pu-citrate [239Pu(C6H5O7)+] in nutrient solution. Plutonium-diethylenetriaminepentaacetic acid (DTPA: [239Pu-C14H23O10N3] solution was prepared by adding 0, 5, 10, and 50 microg of DTPA ml(-1) with 239Pu(NO3)4 in nutrient solution. Concentration ratios (CR, Pu concentration in dry plant material/Pu concentration in nutrient solution) and transport indices (Tl, Pu content in the shoot/Pu content in the whole plant) were calculated to evaluate Pu uptake and translocation. All experiments were conducted in hydroponic solution in an environmental growth chamber. Plutonium concentration in the plant tissue was increased with increased Pu contamination. Plant tissue Pu concentration for Pu-nitrate and Pu-citrate application was not correlated and may be dependent on plant species. For plants receiving Pu-DTPA, the Pu concentration was increased in the shoots but decreased in the roots resulting in a negative correlation between the Pu concentrations in the plant shoots and roots. The Pu concentration in shoots of Indian mustard was increased for application rates up to 10 microg DTPA ml(-1) and up to 5 microg DTPA ml(-1) for sunflower. Similar trends were observed for the CR of plants compared to the Pu concentration in the shoots and roots, whereas the Tl was increased with increasing DTPA concentration. Plutonium in shoots of Indian mustard was up to 10 times higher than that in shoots of sunflower. The Pu concentration in the apparent free space (AFS) of plant root tissue of sunflower was more affected by concentration of DTPA than that of Indian mustard.

U, Pu, and Am nuclear signatures of the Thule hydrogen bomb debris.

PubMed

Eriksson, Mats; Lindahl, Patric; Roos, Per; Dahlgaard, Henning; Holm, Elis

2008-07-01

This study concerns an arctic marine environment that was contaminated by actinide elements after a nuclear accident in 1968, the so-called Thule accident In this study we have analyzed five isolated hot particles as well as sediment samples containing particles from the weapon material for the determination of the nuclear fingerprint of the accident. We report that the fissile material in the hydrogen weapons involved in the Thule accident was a mixture of highly enriched uranium and weapon-grade plutonium and that the main fissile material was 235U (about 4 times more than the mass of 239Pu). In the five hot particles examined, the measured uranium atomic ratio was 235U/238U = 1.02 +/- 0.16 and the Pu-isotopic ratios were as follows: 24Pu/239Pu = 0.0551 +/- 0.0008 (atom ratio), 238Pu/239+240Pu = 0.0161 +/- 0.0005 (activity ratio), 241Pu/239+240Pu = 0.87 +/- 0.12 (activity ratio), and 241Am/ 239+240Pu = 0.169 +/- 0.005 (activity ratio) (reference date 2001-10-01). From the activity ratios of 241Pu/241Am, we estimated the time of production of this weapon material to be from the late 1950s to the early 1960s. The results from reanalyzed bulk sediment samples showed the presence of more than one Pu source involved in the accident, confirming earlier studies. The 238Pu/239+240PU activity ratio and the 240Pu/ 239Pu atomic ratio were divided into at least two Pu-isotopic ratio groups. For both Pu-isotopic ratios, one ratio group had identical ratios as the five hot particles described above and for the other groups the Pu isotopic ratios were lower (238Pu/ 239+240PU activity ratio approximately 0.01 and the 240Pu/P239Pu atomic ratio 0.03). On the studied particles we observed that the U/Pu ratio decreased as a function of the time these particles were present in the sediment. We hypothesis that the decrease in the ratio is due to a preferential leaching of U relative to Pu from the particle matrix.

Rapid dating of recent aquatic sediments using Pu activities and 240Pu/239Pu as determined by quadrupole inductively coupled plasma mass spectrometry.

PubMed

Ketterer, Michael E; Watson, Bridgette R; Matisoff, Gerald; Wilsont, Christopher G

2002-03-15

Quadrupole inductively coupled plasma mass spectrometry has been used to rapidly establish the chronology of recent aquatic sediments via measurements of the activities of 239Pu, 240Pu, and the atom ratio 240Pu/239Pu. Following addition of 0.007 Bq of a 242Pu spike isotope, Pu is leached from 3-20 g aliquots of dry-ashed sediments with HNO3. A selective anion exchanger is used to preconcentrate Pu into approximately 2 mL aliquots, which are directly analyzed using a pneumatic nebulizer and double-pass spraychamber operating at 60 microL/min solution uptake rate. The ICPMS data collection is performed for 10 min per sample. The U concentrations were 0.01-0.05 microg/L in the analyzed solutions, and the interference of 238U1H+ upon 239Pu+ was negligible. The method has been applied to determining Pu activities, inventory, and 240Pu/239Pu in a complete sediment core from Old Woman Creek (Huron, OH). The Pu activity profiles, obtained in approximately 6 h of instrumental measurement time, are in agreement with a y spectrometric 137Cs profile. Peak 239+240Pu and 137Cs activities in the core were 1.60 +/- 0.02 and 47.8 +/- 0.8 Bq/kg, respectively; inventories were 108 +/- 2 Bq/m2 239+240Pu and 2710 +/- 40 Bq/m2 137Cs. Detection limits, based upon the analysis of 20 g samples, were 0.004 Bq/kg 239Pu, 0.012 Bq/kg 240Pu, and 0.012 Bq/kg 239+240Pu. 240Pu/239Pu atom ratios of 0.16-0.19 were obtained for all core intervals containing detectable Pu, which indicates that global fallout is the source of these radionuclides.

Plutonium Oxidation State Distribution under Aerobic and Anaerobic Subsurface Conditions for Metal-Reducing Bacteria

NASA Astrophysics Data System (ADS)

Reed, D. T.; Swanson, J.; Khaing, H.; Deo, R.; Rittmann, B.

2009-12-01

The fate and potential mobility of plutonium in the subsurface is receiving increased attention as the DOE looks to cleanup the many legacy nuclear waste sites and associated subsurface contamination. Plutonium is the near-surface contaminant of concern at several DOE sites and continues to be the contaminant of concern for the permanent disposal of nuclear waste. The mobility of plutonium is highly dependent on its redox distribution at its contamination source and along its potential migration pathways. This redox distribution is often controlled, especially in the near-surface where organic/inorganic contaminants often coexist, by the direct and indirect effects of microbial activity. The redox distribution of plutonium in the presence of facultative metal reducing bacteria (specifically Shewanella and Geobacter species) was established in a concurrent experimental and modeling study under aerobic and anaerobic conditions. Pu(VI), although relatively soluble under oxidizing conditions at near-neutral pH, does not persist under a wide range of the oxic and anoxic conditions investigated in microbiologically active systems. Pu(V) complexes, which exhibit high chemical toxicity towards microorganisms, are relatively stable under oxic conditions but are reduced by metal reducing bacteria under anaerobic conditions. These facultative metal-reducing bacteria led to the rapid reduction of higher valent plutonium to form Pu(III/IV) species depending on nature of the starting plutonium species and chelating agents present in solution. Redox cycling of these lower oxidation states is likely a critical step in the formation of pseudo colloids that may lead to long-range subsurface transport. The CCBATCH biogeochemical model is used to explain the redox mechanisms and final speciation of the plutonium oxidation state distributions observed. These results for microbiologically active systems are interpreted in the context of their importance in defining the overall migration of plutonium in the subsurface.

Volcanology Curricula Development Aided by Online Educational Resource

NASA Astrophysics Data System (ADS)

Poland, Michael P.; van der Hoeven Kraft, Katrien J.; Teasdale, Rachel

2011-03-01

Using On-Line Volcano Monitoring Data in College and University Courses: The Volcano Exploration Project: Pu`u `Ō`ō (VEPP); Hawaii Volcanoes National Park, Hawaii, 26-30 July 2010; Volcanic activity is an excellent hook for engaging college and university students in geoscience classes. An increasing number of Internet-accessible real-time and near-real time volcano monitoring data are now available and constitute an important resource for geoscience education; however, relatively few data sets are comprehensive, and many lack background information to aid in interpretation. In response to the need for organized, accessible, and well-documented volcano education resources, the U.S. Geological Survey's Hawaiian Volcano Observatory (HVO), in collaboration with NASA and the University of Hawai`i at Manoa, established the Volcanoes Exploration Project: Pu`u `Ō`ō (VEPP). The VEPP Web site (http://vepp.wr.usgs.gov) is an educational resource that provides access, in near real time, to geodetic, seismic, and geologic data from the active Pu`u `Ō`ō eruptive vent on Kilauea volcano, Hawaii, along with background and context information. A strength of the VEPP site is the common theme of the Pu`u `Ō`ō eruption, which allows the site to be revisited multiple times to demonstrate different principles and integrate many aspects of volcanology.

Volcanology curricula development aided by online educational resource

USGS Publications Warehouse

Poland, Michael P.; Van Der Hoeven, Kraft; Teasdale, R.

2011-01-01

Using On-Line Volcano Monitoring Data in College and University Courses: The Volcano Exploration Project: Pu`u `Ō`ō (VEPP); Hawaii Volcanoes National Park, Hawaii, 26–30 July 2010; Volcanic activity is an excellent hook for engaging college and university students in geoscience classes. An increasing number of Internet-accessible real-time and near–real time volcano monitoring data are now available and constitute an important resource for geoscience education; however, relatively few data sets are comprehensive, and many lack background information to aid in interpretation. In response to the need for organized, accessible, and well-documented volcano education resources, the U.S. Geological Survey's Hawaiian Volcano Observatory (HVO), in collaboration with NASA and the University of Hawai`i at Manoa, established the Volcanoes Exploration Project: Pu`u `Ō`ō (VEPP). The VEPP Web site (http://vepp.wr.usgs.gov) is an educational resource that provides access, in near real time, to geodetic, seismic, and geologic data from the active Pu`u `Ō`ō eruptive vent on Kilauea volcano, Hawaii, along with background and context information. A strength of the VEPP site is the common theme of the Pu`u `Ō`ō eruption, which allows the site to be revisited multiple times to demonstrate different principles and integrate many aspects of volcanology.

Variations in Pu isotopic composition in soils from the Spitsbergen (Norway): Three potential pollution sources of the Arctic region.

PubMed

Łokas, E; Anczkiewicz, R; Kierepko, R; Mietelski, J W

2017-07-01

Although the polar regions have not been industrialised, numerous contaminants originating from human activity are detectable in the Arctic environment. This study reports evidence of 240 Pu/ 239 Pu atomic ratios in the tundra and initial soils from different parts of west and central Spitsbergen and recognizes possible environmental inputs of non-global fallout Pu. The average atomic ratio of 240 Pu/ 239 Pu equal to 0.179 (ranging between 0.129 and 0.201) in tundra soils are comparable to the characteristic ratio for global fallout (0.180). However, the 240 Pu/ 239 Pu atomic ratios in the initial soils from proglacial zone of glaciers change within wide range between 0.1281 and 0.234 with the mean value of 0.169. By combining alpha and mass spectrometry, the three-sources model was used to identify the Pu sources in initial soils. Our study indicated that the main source of Pu is nuclear tests and that a second source with lower Pu ratio may come from weapons grade Pu (unexploded weapons grade Pu ie. material from bomb which didn't undergo nuclear explosions for example for security tests). Additionally, we found samples with high 238 Pu/ 239+240 Pu activity ratios and with typical global fallout 240 Pu/ 239 Pu atomic ratios, which are associated with separate sources of pure 238 Pu from the SNAP-9A satellite burn up in the atmosphere. Copyright © 2017 Elsevier Ltd. All rights reserved.

Sources of plutonium to the tropical Northwest Pacific Ocean (1943-1999) identified using a natural coral archive

NASA Astrophysics Data System (ADS)

Lindahl, Patric; Asami, Ryuji; Iryu, Yasufumi; Worsfold, Paul; Keith-Roach, Miranda; Choi, Min-Seok

2011-03-01

The Pu isotopes, 239Pu and 240Pu, were determined in annually-banded skeletons of an accurately dated (1943-1999) modern coral ( Porites lobata) from Guam Island to identify historical Pu sources to the tropical Northwest Pacific Ocean. Activity concentrations of 239+240Pu and 240Pu/ 239Pu atom ratios were determined in the dated coral bands using multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS). Close-in fallout from the former US Pacific Proving Grounds (PPG) in the Marshall Islands and global fallout were identified as the two main sources. The Guam site was dominated by PPG close-in fallout in the 1950s, with an average 240Pu/ 239Pu atom ratio of 0.315 ± 0.005. In addition, a higher 240Pu/ 239Pu atom ratio (0.456 ± 0.020) was observed that could be attributed to fallout from the "Ivy Mike" thermonuclear detonation in 1952. The atom ratio decreased in the 1960s and 1970s due to increase in the global fallout with a low 240Pu/ 239Pu atom ratio (˜0.18). Recent coral bands (1981-1999) are dominated by the transport of remobilised Pu, with high 240Pu/ 239Pu atom ratios, from the Marshall Islands to Guam Island along the North Equatorial Current (NEC). This remobilised Pu was estimated to comprise 69% of the total Pu in the recent coral bands, although its contribution was variable over time.

Evaluation of phases in Pu-C-O and (U, Pu)-C-O systems by X-ray diffractometry and chemical analysis

NASA Astrophysics Data System (ADS)

Jain, G. C.; Ganguly, C.

1993-12-01

Preparation and characterisation of the carbides of uranium, plutonium and mixed uranium and plutonium form a part of advanced fuel development programs for fast breeder reactors. In the present study, the compositions of the phases of Pu-C-O and (U.Pu)-C-O systems have been determined by chemical analysis and lattice parameter measurement. The carbide samples have been prepared by vacuum carbothermic synthesis of tabletted oxide-graphite powder mixture. Dependence of stoichiometry of Pu 2C 3 phase on the oxygen content of Pu(C,O) phase in Pu(C,O) + Pu 2C 3 phase mixture has been evaluated. Stoichiometry and oxygen solubility of (U 0.3Pu 0.7)(C,O) phase in multiple phase mixture have been determined. Segregation of plutonium in (U,Pu) 2C 3 phase of (U,Pu)(C,O) + (U,Pu) 2C 3 phase mixture and its dependence on the oxygen content of (U,Pu)(C,O) phase have also been determined from the measurement of the lattice parameter of (U,Pu) 2C 3 phase.

Pu-239 and Pu-240 inventories and Pu-240/ Pu-239 atom ratios in the water column off Sanriku, Japan.

NASA Astrophysics Data System (ADS)

Yamada, Masatoshi; Zheng, Jian; Aono, Tatsuo

2013-04-01

A magnitude 9.0 earthquake and subsequent tsunami occurred in the Pacific Ocean off northern Honshu, Japan, on 11 March 2011 which caused severe damage to the Fukushima Dai-ichi Nuclear Power Plant. This accident has resulted in a substantial release of radioactive materials to the atmosphere and ocean, and has caused extensive contamination of the environment. However, no information is available on the amounts of radionuclides such as Pu isotopes released into the ocean at this time. Investigating the background baseline concentration and atom ratio of Pu isotopes in seawater is important for assessment of the possible contamination in the marine environment. Pu-239 (half-life: 24,100 years), Pu-240 (half-life: 6,560 years) and Pu-241 (half-life: 14.325 years) mainly have been released into the environment as the result of atmospheric nuclear weapons testing. The atom ratio of Pu-240/Pu-239 is a powerful fingerprint to identify the sources of Pu in the ocean. The Pu-239 and Pu-240 inventories and Pu-240/Pu-239 atom ratios in seawater samples collected in the western North Pacific off Sanriku before the accident at Fukushima Dai-ichi Nuclear Power Plant will provide useful background baseline data for understanding the process controlling Pu transport and for distinguishing additional Pu sources. Seawater samples were collected with acoustically triggered quadruple PVC sampling bottles during the KH-98-3 cruise of the R/V Hakuho-Maru. The Pu-240/Pu-239 atom ratios were measured with a double-focusing SF-ICP-MS, which was equipped with a guard electrode to eliminate secondary discharge in the plasma and to enhance overall sensitivity. The Pu-239 and Pu-240 concentrations were 2.07 and 1.67 mBq/m3 in the surface water, respectively, and increased with depth; a subsurface maximum was identified at 750 m depth, and the concentrations decreased with depth, then increased at the bottom layer. The total Pu-239+240 inventory in the entire water column (depth interval 0-bottom) was 69.8 Bq/m2. This was significantly higher than the expected cumulative deposition density of atmospheric global fallout. The Pu-240/Pu-239 atom ratios were 0.22 in the surface water and increased gradually with depth reaching 0.26 at the 5000 m depth. The obtained Pu-240/Pu-239 atom ratios were higher than the mean global fallout ratio of 0.18. These high atom ratios proved the existence of close-in tropospheric fallout Pu from the Pacific Proving Grounds in the Marshall Islands.

Miller Cave (23PU2), Fort Leonard Wood, Pulaski County, Missouri: Report of Archaeological Testing and Assessment of Damage

DTIC Science & Technology

1993-01-01

SECURITY CLASSIFICATION AUTHORITY 3. DISTRIBUTION JAVAILABIUITY OF REPORT 2b. DECLASSIFICATION I OWNGRAD)ING SCHEDULE I4. PERFORMING ORGANIZATION ...REPORT NUMBER(S) 5. MONITORING ORGANIZATION REPORT NUMBER(S) RESEARCH REPORT NO. 9 6a. NAME OF PERFORMING ORGANIZATION 6b. OFFICE SYMBOL 7a. NAME OF...MONITORING ORGANIZATION Markman & Associates, Inc.(I plcbe 6c. ADDRESS (City. State. and ZIP Code) 7b. ADDRESS (City. State. and ZIP Code) 824 N. Bl

Porous Nanogold/Polyurethane Scaffolds with Improved Antibiofilm, Mechanical, and Thermal Properties and with Reduced Effects on Cell Viability: A Suitable Material for Soft Tissue Applications.

PubMed

Tamayo, L; Acuña, D; Riveros, A L; Kogan, M J; Azócar, M I; Páez, M; Leal, M; Urzúa, M; Cerda, E

2018-04-25

The use of implants carries on a series of problems, among them infections, poor biocompatibility, high levels of cytotoxicity, and significant mechanical differences between implants and host organs that promote stress shielding effects. These problems indicate that the materials used to make implants must meet essential requirements and high standards for implantations to be successful. In this work, we present the synthesis, characterization and evaluation of the antibiofilm, mechanical, and thermal properties, and cytotoxic effect of a nanocomposite-based scaffold on polyurethane (PU) and gold nanoparticles (AuNPs) for soft tissue applications. The effect of the quantity of AuNPs on the antibacterial activity of nanocomposite scaffolds was evaluated against Staphylococcus epidermidis and Klebsiella spp., with a resulting 99.99% inhibition of both bacteria using a small quantity of nanoparticles. Cytotoxicity was evaluated with the T10 1/2 test against fibroblast cells. The results demonstrated that porous nanogold/PU scaffolds have no toxic effects on fibroblast cells to the 5 day exposition. With respect to mechanical properties, stress-strain curves showed that the compressive modulus and yield strength of PU scaffolds were significantly enhanced by AuNPs (by at least 10 times). This is due to changes in the arrangement of hard segments of PU, which increase the stiffness of the polymer. Thermogravimetric analysis showed that the degradation onset temperature rises with an increase in the quantity of AuNPs. These properties and characteristics demonstrate that porous nanogold/PU scaffolds are suitable material for use in soft tissue implants.

Transcriptome Profile Reveals that Pu-Erh Tea Represses the Expression of Vitellogenin Family to Reduce Fat Accumulation in Caenorhabditis elegans.

PubMed

Xiao, Ru-Yue; Hao, Junjun; Ding, Yi-Hong; Che, Yan-Yun; Zou, Xiao-Ju; Liang, Bin

2016-10-17

Due to misbalanced energy surplus and expenditure, obesity has become a common chronic disorder that is highly associated with many metabolic diseases. Pu-erh tea, a traditional Chinese beverage, has been believed to have numerous health benefits, such as anti-obesity. However, the underlying mechanisms of its anti-obesity effect are yet to be understood. Here, we take the advantages of transcriptional profile by RNA sequencing (RNA-Seq) to view the global gene expression of Pu-erh tea. The model organism Caenorhabditis elegans was treated with different concentrations of Pu-erh tea water extract (PTE, 0 g/mL, 0.025 g/mL, and 0.05 g/mL). Compared with the control, PTE indeed decreases lipid droplets size and fat accumulation. The high-throughput RNA-Sequence technique detected 18073 and 18105 genes expressed in 0.025 g/mL and 0.05 g/mL PTE treated groups, respectively. Interestingly, the expression of the vitellogenin family ( vit-1 , vit-2 , vit-3, vit-4 and vit-5 ) was significantly decreased by PTE, which was validated by qPCR analysis. Furthermore, vit-1(ok2616) , vit-3(ok2348) and vit-5(ok3239) mutants are insensitive to PTE triggered fat reduction. In conclusion, our transcriptional profile by RNA-Sequence suggests that Pu-erh tea lowers the fat accumulation primarily through repression of the expression of vit (vitellogenin) family, in addition to our previously reported (sterol regulatory element binding protein) SREBP-SCD (stearoyl-CoA desaturase) axis.

Comparative study of the fragments' mass and energy characteristics in the spontaneous fussion of 238Pu, 240Pu and 242Pu and in the thermal-neutron-induced fission of 239Pu

NASA Astrophysics Data System (ADS)

Schillebeeckx, P.; Wagemans, C.; Deruytter, A. J.; Barthélémy, R.

1992-08-01

The energy and mass distribution and their correlations have been studied for the spontaneous fission of 238, 240, 242Pu and for the thermal-neutron-induced fission of 239Pu. A comparison of 240Pu(s.f.) and 239Pu(nth,f) shows that the increase in excitation energy mainly results in an increase of the intrinsic excitation energy. A comparison of the results for 238Pu, 240Pu and 242Pu(s.f.) demonstrates the occurence of different fission modes with varying relative probability. These results are discussed in terms of the scission point model as well as in terms of the fission channel model with random neck-rupture.

Humic acids facilitated microbial reduction of polymeric Pu(IV) under anaerobic conditions.

PubMed

Xie, Jinchuan; Liang, Wei; Lin, Jianfeng; Zhou, Xiaohua; Li, Mei

2018-01-01

Flavins and humic substances have been extensively studied with emphasis on their ability to transfer extracellular electrons to insoluble metal oxides. Nevertheless, whether the low-solubility Pu(IV) polymers are microbially reduced to aqueous Pu(III) remains uncertain. Experiments were conducted under anaerobic and slightly alkaline conditions to study the difference between humic acids and flavins to transport extracellular electrons to Pu(IV) polymers. Our study demonstrates that Shewanella putrefaciens was unable to directly reduce polymeric Pu(IV) with a notably low reduction rate (3.4×10 -12 mol/L Pu(III) aq within 144h). The relatively high redox potential of flavins reveals the thermodynamically unfavorable reduction: E h (PuO 2 (am)/Pu 3+ )

Determination of plutonium isotopes (238Pu, 239Pu, 240Pu, 241Pu) in environmental samples using radiochemical separation combined with radiometric and mass spectrometric measurements.

PubMed

Xu, Yihong; Qiao, Jixin; Hou, Xiaolin; Pan, Shaoming; Roos, Per

2014-02-01

This paper reports an analytical method for the determination of plutonium isotopes ((238)Pu, (239)Pu, (240)Pu, (241)Pu) in environmental samples using anion exchange chromatography in combination with extraction chromatography for chemical separation of Pu. Both radiometric methods (liquid scintillation counting and alpha spectrometry) and inductively coupled plasma mass spectrometry (ICP-MS) were applied for the measurement of plutonium isotopes. The decontamination factors for uranium were significantly improved up to 7.5 × 10(5) for 20 g soil compared to the level reported in the literature, this is critical for the measurement of plutonium isotopes using mass spectrometric technique. Although the chemical yield of Pu in the entire procedure is about 55%, the analytical results of IAEA soil 6 and IAEA-367 in this work are in a good agreement with the values reported in the literature or reference values, revealing that the developed method for plutonium determination in environmental samples is reliable. The measurement results of (239+240)Pu by alpha spectrometry agreed very well with the sum of (239)Pu and (240)Pu measured by ICP-MS. ICP-MS can not only measure (239)Pu and (240)Pu separately but also (241)Pu. However, it is impossible to measure (238)Pu using ICP-MS in environmental samples even a decontamination factor as high as 10(6) for uranium was obtained by chemical separation. © 2013 Elsevier B.V. All rights reserved.

Spatial and temporal distribution of Pu in the Northwest Pacific Ocean using modern coral archives.

PubMed

Lindahl, Patric; Andersen, Morten B; Keith-Roach, Miranda; Worsfold, Paul; Hyeong, Kiseong; Choi, Min-Seok; Lee, Sang-Hoon

2012-04-01

Historical (239)Pu activity concentrations and (240)Pu/(239)Pu atom ratios were determined in skeletons of dated modern corals collected from three locations (Chuuk Lagoon, Ishigaki Island and Iki Island) to identify spatial and temporal variations in Pu inputs to the Northwest Pacific Ocean. The main Pu source in the Northwest Pacific is fallout from atmospheric nuclear weapons testing which consists of global fallout and close-in fallout from the former US Pacific Proving Grounds (PPG) in the Marshall Islands. PPG close-in fallout dominated the Pu input in the 1950s, as was observed with higher (240)Pu/(239)Pu atom ratios (>0.30) at the Ishigaki site. Specific fallout Pu contamination from the Nagasaki atomic bomb and the Ivy Mike thermonuclear detonation at the PPG were identified at Ishigaki Island from the (240)Pu/(239)Pu atom ratios of 0.07 and 0.46, respectively. During the 1960s and 1970s, global fallout was the major Pu source to the Northwest Pacific with over 60% contribution to the total Pu. After the cessation of the atmospheric nuclear tests, the PPG again dominated the Pu input due to the continuous transport of remobilised Pu from the Marshall Islands along the North Equatorial Current and the subsequent Kuroshio Current. The Pu contributions from the PPG in recent coral bands (1984 onwards) varied over time with average estimated PPG contributions between 54% and 72% depending on location. Copyright © 2011 Elsevier Ltd. All rights reserved.

The AMchip04 and the processing unit prototype for the FastTracker

NASA Astrophysics Data System (ADS)

Andreani, A.; Annovi, A.; Beretta, M.; Bogdan, M.; Citterio, M.; Alberti, F.; Giannetti, P.; Lanza, A.; Magalotti, D.; Piendibene, M.; Shochet, M.; Stabile, A.; Tang, J.; Tompkins, L.; Volpi, G.

2012-08-01

Modern experiments search for extremely rare processes hidden in much larger background levels. As the experiment`s complexity, the accelerator backgrounds and luminosity increase we need increasingly complex and exclusive event selection. We present the first prototype of a new Processing Unit (PU), the core of the FastTracker processor (FTK). FTK is a real time tracking device for the ATLAS experiment`s trigger upgrade. The computing power of the PU is such that a few hundred of them will be able to reconstruct all the tracks with transverse momentum above 1 GeV/c in ATLAS events up to Phase II instantaneous luminosities (3 × 1034 cm-2 s-1) with an event input rate of 100 kHz and a latency below a hundred microseconds. The PU provides massive computing power to minimize the online execution time of complex tracking algorithms. The time consuming pattern recognition problem, generally referred to as the ``combinatorial challenge'', is solved by the Associative Memory (AM) technology exploiting parallelism to the maximum extent; it compares the event to all pre-calculated ``expectations'' or ``patterns'' (pattern matching) simultaneously, looking for candidate tracks called ``roads''. This approach reduces to a linear behavior the typical exponential complexity of the CPU based algorithms. Pattern recognition is completed by the time data are loaded into the AM devices. We report on the design of the first Processing Unit prototypes. The design had to address the most challenging aspects of this technology: a huge number of detector clusters (``hits'') must be distributed at high rate with very large fan-out to all patterns (10 Million patterns will be located on 128 chips placed on a single board) and a huge number of roads must be collected and sent back to the FTK post-pattern-recognition functions. A network of high speed serial links is used to solve the data distribution problem.

Neutron and gamma-ray energy reconstruction for characterization of special nuclear material

DOE PAGES

Clarke, Shaun D.; Hamel, Michael C.; Di fulvio, Angela; ...

2017-06-30

Characterization of special nuclear material may be performed using energy spectroscopy of either the neutron or gamma-ray emissions from the sample. Gamma-ray spectroscopy can be performed relatively easily using high-resolution semiconductors such as high-purity germanium. Neutron spectroscopy, by contrast, is a complex inverse problem. Here, results are presented for 252Cf and PuBe energy spectra unfolded using a single EJ309 organic scintillator; excellent agreement is observed with the reference spectra. Neutron energy spectroscopy is also possible using a two-plane detector array, whereby time-offlight kinematics can be used. With this system, energy spectra can also be obtained as a function of position.more » Finally, spatial-dependent energy spectra are presented for neutron and gamma-ray sources that are in excellent agreement with expectations.« less

Neutron and gamma-ray energy reconstruction for characterization of special nuclear material

DOE Office of Scientific and Technical Information (OSTI.GOV)

Clarke, Shaun D.; Hamel, Michael C.; Di fulvio, Angela

Characterization of special nuclear material may be performed using energy spectroscopy of either the neutron or gamma-ray emissions from the sample. Gamma-ray spectroscopy can be performed relatively easily using high-resolution semiconductors such as high-purity germanium. Neutron spectroscopy, by contrast, is a complex inverse problem. Here, results are presented for 252Cf and PuBe energy spectra unfolded using a single EJ309 organic scintillator; excellent agreement is observed with the reference spectra. Neutron energy spectroscopy is also possible using a two-plane detector array, whereby time-offlight kinematics can be used. With this system, energy spectra can also be obtained as a function of position.more » Finally, spatial-dependent energy spectra are presented for neutron and gamma-ray sources that are in excellent agreement with expectations.« less

Inconsistencies between 14C and short-lived radionuclides-based sediment accumulation rates: Effects of long-term remineralization.

PubMed

Baskaran, M; Bianchi, T S; Filley, T R

2017-08-01

14 C is the most widely utilized geochronometer to investigate geological, geochemical and geophysical problems over the past 5 decades. Establishment of precise sedimentation rates is crucial for the reconstruction of paleo-climate, -ecological and - environmental studies when extrapolation of sedimentation rates is utilized for time scales beyond the dating range. However, agreement between short-term and long-term sedimentation rates in anthropogenically unperturbed sediment cores has not been shown. Here we show that the AMS 14 C-based long-term mass accumulation rate (MAR) of an organic-rich (>70%) sediment core from Mud Lake, Florida to be ∼5 times lower than the short-term MAR obtained using 239,240 Pu, 137 Cs and excess 210 Pb ( 210 Pb xs ). The measured sediment inventories of 210 Pb xs , 137 Cs and 239,240 Pu are comparable to the atmospheric fallout for the sampling site, indicating very little accelerated sediment erosion over the past several decades. Presence of sharp fallout peaks of 239,240 Pu indicates very little sediment mixing. The penetration depths of 137 Cs and 239,240 Pu were found to be much deeper than expected and this is attributed to their post-depositional mobility. MAR calculated using 14 C-ages in successive layers also indicated decreasing MARs with depth, and was reflective of progressive remineralization. Using first-order kinetics, the sediment remineralization rate was found to be 4.4 × 10 -4 y -1 and propose that over the long-term, remineralization of organic-rich sediment affected the long-term MAR, but not the ratio of 14 C/ 12 C. Thus, the MAR and linear sedimentation rate obtained using 14 C (and other isotope-based methods) could be erroneous, although 14 C ages may not be affected by such remineralization. Long-term remineralization rates of organic matter has a direct bearing on the biogeochemical cycling of elements in aqueous systems and mass balance of elements needs to be taken into consideration. Copyright © 2016 Elsevier Ltd. All rights reserved.

Communications for intelligent transportation systems, successful practices : a cross-cutting study : reaching cost-effective solutions through better decision-making techniques

DOT National Transportation Integrated Search

2000-11-01

In many intelligent transportation systems (ITS) implementations, the telecommunications solution was arrived at without the kind of rigorous examination that would have accompanied similarly significant and complex technical/business choices. The pu...

Exploring the Interaction Natures in Plutonyl (VI) Complexes with Topological Analyses of Electron Density

PubMed Central

Du, Jiguang; Sun, Xiyuan; Jiang, Gang

2016-01-01

The interaction natures between Pu and different ligands in several plutonyl (VI) complexes are investigated by performing topological analyses of electron density. The geometrical structures in both gaseous and aqueous phases are obtained with B3LYP functional, and are generally in agreement with available theoretical and experimental results when combined with all-electron segmented all-electron relativistic contracted (SARC) basis set. The Pu–Oyl bond orders show significant linear dependence on bond length and the charge of oxygen atoms in plutonyl moiety. The closed-shell interactions were identified for Pu-Ligand bonds in most complexes with quantum theory of atoms in molecules (QTAIM) analyses. Meanwhile, we found that some Pu–Ligand bonds, like Pu–OH−, show weak covalent. The interactive nature of Pu–ligand bonds were revealed based on the interaction quantum atom (IQA) energy decomposition approach, and our results indicate that all Pu–Ligand interactions is dominated by the electrostatic attraction interaction as expected. Meanwhile it is also important to note that the quantum mechanical exchange-correlation contributions can not be ignored. By means of the non-covalent interaction (NCI) approach it has been found that some weak and repulsion interactions existed in plutonyl(VI) complexes, which can not be distinguished by QTAIM, can be successfully identified. PMID:27077844

Historical changes in 239Pu and 240Pu sources in sedimentary records in the East China Sea: Implications for provenance and transportation

NASA Astrophysics Data System (ADS)

Wang, Jinlong; Baskaran, Mark; Hou, Xiaolin; Du, Jinzhou; Zhang, Jing

2017-05-01

Concentrations and isotopic compositions of plutonium (Pu) are widely used for its source identification and to determine transport processes of Pu-associated particulate matter and water. We investigated the concentrations of 239Pu and 240Pu and their ratios in a number of sediment samples from the East China Sea (ECS) collected in the summer of 2013 (August 6-28). The 239+240Pu activity concentrations in surface sediment samples were found to range between 0.048 and 0.492 Bq kg-1 and the 240Pu/239Pu atom ratios showed a similar trend as that of the 239, 240Pu activities; the Pu atom ratios ranged from 0.158 to 0.297 and were mostly higher than the mean global fallout value of 0.18. The 239, 240Pu inventories in the ECS varied widely, from 2 to 807 Bq m-2, with the highest values commonly found in the coastal areas. In the Yangtze Estuary, the mean 239+240Pu activity concentration is close to the estimated value of the suspended material from the Yangtze River catchment (0.18 Bq kg-1), and the 240Pu/239Pu atom ratio was found to be ∼0.18, which indicates that the Yangtze River input is the dominant source of Pu for this area. The total annual Yangtze River input of 239+240Pu was estimated to be 2.4 ×1010 Bq, which is small compared to the total amount of 239+240Pu buried, 3.1 ×1013 Bq in the whole ECS. The Pacific Proving Ground input appears to be the dominant source of Pu to the ECS, accounting for 45%-52% of the total inventory. The fractional amount of 239+240Pu scavenged from the total 239+240Pu transported by the Kuroshio Current (KC) and Taiwan Warm Current (TWC) into ECS sediments is estimated to be ∼10%. Our study shows that the 240Pu/239Pu atom ratio is useful not only to obtain a better insight of the biogeochemistry influenced by the KC, but also to trace the long-range transport of other particle-reactive species. Besides, the sedimentation rates obtained based on the penetration depths of 239+240Pu and vertical profiles of excess 210Pb agree within uncertainties, which suggests that 239+240Pu can potentially be used as a chronostratigraphic time marker in the marine environment.

Virgin olive oil blended polyurethane micro/nanofibers ornamented with copper oxide nanocrystals for biomedical applications.

PubMed

Amna, Touseef; Hassan, M Shamshi; Yang, Jieun; Khil, Myung-Seob; Song, Ki-Duk; Oh, Jae-Don; Hwang, Inho

2014-01-01

Recently, substantial interest has been generated in using electrospun biomimetic nanofibers of hybrids, particularly organic/inorganic, to engineer different tissues. The present work, for the first time, introduced a unique natural and synthetic hybrid micronanofiber wound dressing, composed of virgin olive oil/copper oxide nanocrystals and polyurethane (PU), developed via facile electrospinning. The as-spun organic/inorganic hybrid micronanofibers were characterized by scanning electron microscopy (SEM), energy dispersive X-ray analysis, X-ray diffraction, electron probe microanalysis, and transmission electron microscopy. The interaction of cells with scaffold was studied by culturing NIH 3T3 fibroblasts on an as-spun hybrid micronanofibrous mat, and viability, proliferation, and growth were assessed. The 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide assay results and SEM observation showed that the hybrid micronanofibrous scaffold was noncytotoxic to fibroblast cell culture and was found to benefit cell attachment and proliferation. Hence our results suggest the potential utilization of as-spun micronanoscaffolds for tissue engineering. Copper oxide-olive oil/PU wound dressing may exert its positive beneficial effects at every stage during wound-healing progression, and these micronanofibers may serve diverse biomedical applications, such as tissue regeneration, damaged skin treatment, wound healing applications, etc. Conclusively, the fabricated olive oil-copper oxide/PU micronanofibers combine the benefits of virgin olive oil and copper oxide, and therefore hold great promise for biomedical applications in the near future.

U-PuO2, U-PuC, U-PuN cermet fuel for fast reactor

NASA Astrophysics Data System (ADS)

Mishra, Sudhir; Kaity, Santu; Banerjee, Joydipta; Nandi, Chiranjeet; Dey, G. K.; Khan, K. B.

2018-02-01

Cermet fuel combines beneficial properties of both ceramic and metal and attracts global interest for research as a candidate fuel for nuclear reactors. In the present study, U matrix PuC/PuN/PuO2 cermet for fast reactor have been fabricated on laboratory scale by the powder metallurgy route. Characterization of the fuel has been carried out using Dilatometer, Differential Thermal analysis (DTA), X-ray diffractometer and Optical microscope. X ray diffraction study of the fuel reveals presence of different phases. The PuN dispersed cermet was observed to have high solidus temperature as compared to PuC and PuO2 dispersed cermet. Swelling was observed in U matrix PuO2 cermet which also showed higher thermal expansion. Among the three cermets studied, U matrix PuC cermet showed maximum thermal conductivity.

The geometric structures, vibrational frequencies and redox properties of the actinyl coordination complexes ([AnO2(L)n](m); An = U, Pu, Np; L = H2O, Cl-, CO3(2-), CH3CO2(-), OH-) in aqueous solution, studied by density functional theory methods.

PubMed

Austin, Jonathan P; Sundararajan, Mahesh; Vincent, Mark A; Hillier, Ian H

2009-08-14

The geometric and electronic structures of the aqua, chloro, acetato, hydroxo and carbonato complexes of U, Np and Pu in both their (VI) and (V) oxidation states, and in an aqueous environment, have been studied using density functional theory methods. We have obtained micro-solvated structures derived from molecular dynamics simulations and included the bulk solvent using a continuum model. We find that two different hydrogen bonding patterns involving the axial actinyl oxygen atoms are sometimes possible, and may give rise to different An-O bond lengths and vibrational frequencies. These alternative structures are reflected in the experimental An-O bond lengths of the aqua and carbonato complexes. The variation of the redox potential of the uranyl complexes with the different ligands has been studied using both BP86 and B3LYP functionals. The relative values for the four uranium complexes having anionic ligands are in surprisingly good agreement with experiment, although the absolute values are in error by approximately 1 eV. The absolute error for the aqua species is much less, leading to an incorrect order of the redox potentials of the aqua and chloro species.

²³⁹Pu and ²⁴⁰Pu inventories and ²⁴⁰Pu/²³⁹Pu atom ratios in the equatorial Pacific Ocean water column.

PubMed

Yamada, Masatoshi; Zheng, Jian

2012-07-15

The (239+240)Pu concentrations and (240)Pu/(239)Pu atom ratios were determined by alpha spectrometry and inductively coupled plasma mass spectrometry for seawater samples from two stations, one at the equator and the other in the equatorial South Pacific. To better understand the fate of Pu isotopes, this study dealt with the contribution of the close-in fallout Pu from the Pacific Proving Grounds (PPG) in water columns of the Pacific Ocean. The (239)Pu, (240)Pu and (239+240)Pu inventories over the depth interval 0-3000 m at the equator station were 10.4, 8.9 and 19.3 Bq m(-2), respectively. Further, no noticeable difference was observed in (239)Pu, (240)Pu and (239+240)Pu inventories over the depth interval 0-3000 m between the two stations. The total (239+240)Pu inventories were significantly higher than the expected cumulative deposition density of global fallout. Water column (239+240)Pu inventories measured in this study were lower than those reported for comparable stations in the Geochemical Ocean Sections Study, indicating that these inventories have been decreasing at average rates of 0.89 ± 0.07 and 0.16 ± 0.07 Bq m(-2)yr(-1) at the equator and equatorial South Pacific stations, respectively, from 1973 to 1990. The obtained (240)Pu/(239)Pu atom ratios were higher than the mean global fallout ratio of 0.18. These high atom ratios proved the existence of close-in tropospheric fallout Pu from the PPG in the Marshall Islands. The (239+240)Pu inventories originating from the close-in fallout in the entire water column were estimated to be 11.1 Bq m(-2) at the equator station and 7.1 Bq m(-2) at the equatorial South Pacific Ocean station, and the relative percentages of close-in fallout Pu were 40% at the former and 34% at the latter. A significant amount of close-in fallout Pu originating from the PPG has been transported to deep layers below the 1000 m depth in the equatorial Pacific Ocean. Copyright © 2012 Elsevier B.V. All rights reserved.

Electrokinetic remediation of plutonium-contaminated nuclear site wastes: results from a pilot-scale on-site trial.

PubMed

Agnew, Kieran; Cundy, Andrew B; Hopkinson, Laurence; Croudace, Ian W; Warwick, Phillip E; Purdie, Philip

2011-02-28

This paper examines the field-scale application of a novel low-energy electrokinetic technique for the remediation of plutonium-contaminated nuclear site soils, using soil wastes from the Atomic Weapons Establishment (AWE) Aldermaston site, Berkshire, UK as a test medium. Soils and sediments with varying composition, contaminated with Pu through historical site operations, were electrokinetically treated at laboratory-scale with and without various soil pre-conditioning agents. Results from these bench-scale trials were used to inform a larger on-site remediation trial, using an adapted containment pack with battery power supply. 2.4 m(3) (ca. 4t onnes) of Pu-contaminated soil was treated for 60 days at a power consumption of 33 kWh/m(3), and then destructively sampled. Radiochemical data indicate mobilisation of Pu in the treated soil, and migration (probably as a negatively charged Pu-citrate complex) towards the anodic compartment of the treatment cell. Soil in the cathodic zone of the treatment unit was remediated to a level below free-release disposal thresholds (1.7 Bq/g, or <0.4 Bq/g above background activities). The data show the potential of this method as a low-cost, on-site tool for remediation of radioactively contaminated soils and wastes which can be operated remotely on working sites, with minimal disruption to site infrastructure or operations. Copyright © 2010 Elsevier B.V. All rights reserved.

Surface structural conformations of fibrinogen polypeptides for improved biocompatibility.

PubMed

Yaseen, Mohammed; Zhao, Xiubo; Freund, Amy; Seifalian, Alexander M; Lu, Jian R

2010-05-01

This work reports on how incorporation of silica nanocages into poly(urethane) copolymers (PU) affects conformational orientations of adsorbed fibrinogen and how different surfaces subsequently influenced HeLa cell attachment and proliferation. Incorporation of 2 wt% silica nanocages into poly(urethane) (PU4) substantially altered the surface topography of the films and some 50% of the surface was covered with the nanocages due to their preferential exposure. AFM studies revealed the deposition of a dense protein network on the soft polymeric domains of PU4 and much reduced fibrinogen adsorption on the hard nanocage domains. As on the bare SiO(2) control surface, fibrinogen molecules adsorbed on top of the hard nanocages mainly took the dominant trinodular structures in monomeric and dimeric forms. In addition, net positively charged long alpha chains were prone to being hidden beneath the D domains whilst gamma chains predominantly remained exposed. Dynamic interfacial adsorption as probed by spectroscopic ellipsometry revealed fast changes in interfacial conformation induced by electrostatic interactions between different segments of fibrinogen and the surface, consistent with the AFM imaging. On the PU surfaces without nanocage incorporation (PUA), however, adsorbed fibrinogen molecules formed beads-like chain networks, consistent with the structure featured on the soft PU4 domains, showing very different effects of surface chemical nature. Monoclonal antibodies specific to the alpha and gamma chains showed reduced alpha but increased gamma chain binding at the silicon oxide control and PU4 surfaces, whilst on the PUA, C18 and amine surfaces (organic surface controls) the opposite binding trend was detected with alpha chain binding dominant, showing different fibrinogen conformations. Cell attachment studies revealed differences in cell attachment and proliferation, consistent with the different polypeptide conformations on the two types of surfaces, showing a strong preference to the extent of exposure of gamma chains. Crown Copyright 2010. Published by Elsevier Ltd. All rights reserved.

Localized 5f electrons in superconducting PuCoIn₅: consequences for superconductivity in PuCoGa₅.

PubMed

Bauer, E D; Altarawneh, M M; Tobash, P H; Gofryk, K; Ayala-Valenzuela, O E; Mitchell, J N; McDonald, R D; Mielke, C H; Ronning, F; Griveau, J-C; Colineau, E; Eloirdi, R; Caciuffo, R; Scott, B L; Janka, O; Kauzlarich, S M; Thompson, J D

2012-02-08

The physical properties of the first In analog of the PuMGa(5) (M = Co, Rh) family of superconductors, PuCoIn(5), are reported. With its unit cell volume being 28% larger than that of PuCoGa(5), the characteristic spin-fluctuation energy scale of PuCoIn(5) is three to four times smaller than that of PuCoGa(5), which suggests that the Pu 5f electrons are in a more localized state relative to PuCoGa(5). This raises the possibility that the high superconducting transition temperature T(c) = 18.5 K of PuCoGa(5) stems from the proximity to a valence instability, while the superconductivity at T(c) = 2.5 K of PuCoIn(5) is mediated by antiferromagnetic spin fluctuations associated with a quantum critical point.

Transport of (137)Cs, (241)Am and Pu isotopes in the Curonian Lagoon and the Baltic Sea.

PubMed

Lujanienė, G; Remeikaitė-Nikienė, N; Garnaga, G; Jokšas, K; Šilobritienė, B; Stankevičius, A; Šemčuk, S; Kulakauskaitė, I

2014-01-01

Activities of (137)Cs, (241)Am and (239,240)Pu were analyzed with special emphasis on better understanding of radionuclide transport from land via the Neman River estuaries to the Baltic Sea and behavior in the marine environment. Although activity concentrations of (137)Cs in water samples collected the Baltic Sea were almost 100 times higher as compared to the Curonian Lagoon, its activities in the bottom sediments were found to be comparable. Activity (238)Pu/(239,240)Pu and atom (240)Pu/(239)Pu ratios indicated a different contribution of the Chernobyl-originated Pu to the suspended particulate matter (SPM) and bottom sediments. The largest amount of the Chernobyl-derived Pu was found in the smallest suspended matter particles of 0.2-1 μm in size collected in the Klaipeda Strait in 2011-2012. The decrease of characteristic activity (238)Pu/(239,240)Pu and atom (240)Pu/(239)Pu ratios towards the global fallout ones in surface soil and the corresponding increase of plutonium (Pu) ratios in the suspended particulate matter and bottom sediments have indicated that the Chernobyl-derived Pu, primarily deposited on the soil surface, was washed out and transported to the Baltic Sea. Behavior of (241)Am was found to be similar to that of Pu isotopes. Copyright © 2013 Elsevier Ltd. All rights reserved.

Upward movement of plutonium to surface sediments during an 11-year field study.

PubMed

Kaplan, D I; Demirkanli, D I; Molz, F J; Beals, D M; Cadieux, J R; Halverson, J E

2010-05-01

An 11-year lysimeter study was established to monitor the movement of Pu through vadose zone sediments. Sediment Pu concentrations as a function of depth indicated that some Pu moved upward from the buried source material. Subsequent numerical modeling suggested that the upward movement was largely the result of invading grasses taking up the Pu and translocating it upward. The objective of this study was to determine if the Pu of surface sediments originated from atmosphere fallout or from the buried lysimeter source material (weapons-grade Pu), providing additional evidence that plants were involved in the upward migration of Pu. The (240)Pu/(239)Pu and (242)Pu/(239)Pu atomic fraction ratios of the lysimeter surface sediments, as determined by Thermal Ionization Mass Spectroscopy (TIMS), were 0.063 and 0.00045, respectively; consistent with the signatures of the weapons-grade Pu. Our numerical simulations indicate that because plants create a large water flux, small concentrations over multiple years may result in a measurable accumulation of Pu on the ground surface. These results may have implications on the conceptual model for calculating risk associated with long-term stewardship and monitored natural attenuation management of Pu contaminated subsurface and surface sediments. Copyright (c) 2010 Elsevier Ltd. All rights reserved.

Determination of plutonium and its isotopic ratio in marine sediment samples using quadrupole ICP-MS with the shield torch system under normal plasma conditions.

PubMed

Zheng, Jian; Yamada, Masatoshi; Wang, Zhongliang; Aono, Tatsuo; Kusakabe, Masashi

2004-06-01

An analytical method for determining (239)Pu and (240)Pu in marine sediment samples, which uses quadrupole ICP-MS, was developed in this work. A simple anion-exchange chromatography system was employed for the separation and purification of Pu from the sample matrix. A sufficient decontamination factor of 1.4 x 10(4) for U, which interferes with the determination of (239)Pu, was achieved. High sensitivity Pu determination was obtained, which led to an extremely low concentration detection limit of approximately 8 fg/ml (0.019 mBq/ml for (239)Pu; 0.071 mBq/ml for (240)Pu) in a sample solution, or an absolute detection limit of 42 fg in a 5 ml sample solution, by using the shield torch technique. Analytical results for the determination of the (239+240)Pu and the (240)Pu/(239)Pu ratio in IAEA 368 (ocean sediment) reference material indicated that the accuracy of the method was satisfactory. The method developed was successfully applied to a study of Pu behavior in the sediments from Sagami Bay, Japan. The observed high (240)Pu/(239)Pu ratio in the sediment core indicated that there was additional Pu input derived from close-in fallout in addition to the global fallout.

Radiation Chemistry of Acetohydroxamic Acid in the UREX Process

DOE Office of Scientific and Technical Information (OSTI.GOV)

Karraker, D.G.

2002-07-31

The UREX process is being developed to process irradiated power reactor elements by dissolution in nitric acid and solvent extraction by a variation of the PUREX process.1 Rather than recovering both U and Pu, as in Purex, only U will be recovered by solvent extraction, hence the name ''UREX.'' A complexing agent, acetohydroxamic acid (AHA), will be added to the scrub stream to prevent the extraction of Pu(IV) and Np(VI). AHA (CH3C=ONHOH) is decomposed to gaseous products in waste evaporation, so no solid waste is generated by its addition. AHA is hydrolyzed in acid solution to acetic acid and hydroxylaminemore » at a rate dependent on the acid concentration.2-4 The fuel to be processed is ca 40 years cooled, 30,000-50,000 MWD/MT material; although only a few fission products remain, the Pu isotopes and 241Am generate a radiation field estimated to be 2.6E+02R during processing. (see Appendix for calculation.) This study was conducted to determine the effect of this level of radiation on the stability of AHA during processing.« less

Biodegradative Activities of Selected Environmental Fungi on a Polyester Polyurethane Varnish and Polyether Polyurethane Foams

PubMed Central

Álvarez-Barragán, Joyce; Domínguez-Malfavón, Lilianha; Vargas-Suárez, Martín; González-Hernández, Ricardo; Aguilar-Osorio, Guillermo

2016-01-01

ABSTRACT Polyurethane (PU) is widely used in many aspects of modern life because of its versatility and resistance. However, PU waste disposal generates large problems, since it is slowly degraded, there are limited recycling processes, and its destruction may generate toxic compounds. In this work, we isolated fungal strains able to grow in mineral medium with a polyester PU (PS-PU; Impranil DLN) or a polyether PU (PE-PU; Poly Lack) varnish as the only carbon source. Of the eight best Impranil-degrading strains, the six best degraders belonged to the Cladosporium cladosporioides complex, including the species C. pseudocladosporioides, C. tenuissimum, C. asperulatum, and C. montecillanum, and the two others were identified as Aspergillus fumigatus and Penicillium chrysogenum. The best Impranil degrader, C. pseudocladosporioides strain T1.PL.1, degraded up to 87% after 14 days of incubation. Fourier transform infrared (FTIR) spectroscopy analysis of Impranil degradation by this strain showed a loss of carbonyl groups (1,729 cm−1) and N—H bonds (1,540 and 1,261 cm−1), and gas chromatography-mass spectrometry (GC-MS) analysis showed a decrease in ester compounds and increase in alcohols and hexane diisocyanate, indicating the hydrolysis of ester and urethane bonds. Extracellular esterase and low urease, but not protease activities were detected at 7 and 14 days of culture in Impranil. The best eight Impranil-degrading fungi were also able to degrade solid foams of the highly recalcitrant PE-PU type to different extents, with the highest levels generating up to 65% of dry-weight losses not previously reported. Scanning electron microscopy (SEM) analysis of fungus-treated foams showed melted and thinner cell wall structures than the non-fungus-treated ones, demonstrating fungal biodegradative action on PE-PU. IMPORTANCE Polyurethane waste disposal has become a serious problem. In this work, fungal strains able to efficiently degrade different types of polyurethanes are reported, and their biodegradative activity was studied by different experimental approaches. Varnish biodegradation analyses showed that fungi were able to break down the polymer in some of their precursors, offering the possibility that they may be recovered and used for new polyurethane synthesis. Also, the levels of degradation of solid polyether polyurethane foams reported in this work have never been observed previously. Isolation of efficient polyurethane-degrading microorganisms and delving into the mechanisms they used to degrade the polymer provide the basis for the development of biotechnological processes for polyurethane biodegradation and recycling. PMID:27316963

Biodegradative Activities of Selected Environmental Fungi on a Polyester Polyurethane Varnish and Polyether Polyurethane Foams.

PubMed

Álvarez-Barragán, Joyce; Domínguez-Malfavón, Lilianha; Vargas-Suárez, Martín; González-Hernández, Ricardo; Aguilar-Osorio, Guillermo; Loza-Tavera, Herminia

2016-09-01

Polyurethane (PU) is widely used in many aspects of modern life because of its versatility and resistance. However, PU waste disposal generates large problems, since it is slowly degraded, there are limited recycling processes, and its destruction may generate toxic compounds. In this work, we isolated fungal strains able to grow in mineral medium with a polyester PU (PS-PU; Impranil DLN) or a polyether PU (PE-PU; Poly Lack) varnish as the only carbon source. Of the eight best Impranil-degrading strains, the six best degraders belonged to the Cladosporium cladosporioides complex, including the species C. pseudocladosporioides, C. tenuissimum, C. asperulatum, and C. montecillanum, and the two others were identified as Aspergillus fumigatus and Penicillium chrysogenum The best Impranil degrader, C. pseudocladosporioides strain T1.PL.1, degraded up to 87% after 14 days of incubation. Fourier transform infrared (FTIR) spectroscopy analysis of Impranil degradation by this strain showed a loss of carbonyl groups (1,729 cm(-1)) and N-H bonds (1,540 and 1,261 cm(-1)), and gas chromatography-mass spectrometry (GC-MS) analysis showed a decrease in ester compounds and increase in alcohols and hexane diisocyanate, indicating the hydrolysis of ester and urethane bonds. Extracellular esterase and low urease, but not protease activities were detected at 7 and 14 days of culture in Impranil. The best eight Impranil-degrading fungi were also able to degrade solid foams of the highly recalcitrant PE-PU type to different extents, with the highest levels generating up to 65% of dry-weight losses not previously reported. Scanning electron microscopy (SEM) analysis of fungus-treated foams showed melted and thinner cell wall structures than the non-fungus-treated ones, demonstrating fungal biodegradative action on PE-PU. Polyurethane waste disposal has become a serious problem. In this work, fungal strains able to efficiently degrade different types of polyurethanes are reported, and their biodegradative activity was studied by different experimental approaches. Varnish biodegradation analyses showed that fungi were able to break down the polymer in some of their precursors, offering the possibility that they may be recovered and used for new polyurethane synthesis. Also, the levels of degradation of solid polyether polyurethane foams reported in this work have never been observed previously. Isolation of efficient polyurethane-degrading microorganisms and delving into the mechanisms they used to degrade the polymer provide the basis for the development of biotechnological processes for polyurethane biodegradation and recycling. Copyright © 2016, American Society for Microbiology. All Rights Reserved.

Source-dependent and source-independent controls on plutonium oxidation state and colloid associations in groundwater.

PubMed

Buesseler, Ken O; Kaplan, Daniel I; Dai, Minhan; Pike, Steven

2009-03-01

Plutonium (Pu) was characterized for its isotopic composition, oxidation states, and association with colloids in groundwater samples near disposal basins in F-Area of the Savannah River Site and compared to similar samples collected six years earlier. Two sources of Pu were identified, the disposal basins, which contained a 24Pu/l39Pu isotopic signature consistent with weapons grade Pu, and 244Cm, a cocontaminant that is a progenitor radionuclide of 24Pu. 24Pu that originated primarily from 244Cm tended to be appreciably more oxidized (Pu(V/VI)), less associated with colloids (approximately 1 kDa - 0.2 microm), and more mobile than 239Pu, as suggested by our prior studies at this site. This is not evidence of isotope fractionation but rather "source-dependent" controls on 240Pu speciation which are processes that are not at equilibrium, i.e., processes that appear kinetically hindered. There were also "source-independent" controls on 239Pu speciation, which are those processes that follow thermodynamic equilibrium with their surroundings. For example, a groundwater pH increase in one well from 4.1 in 1998 to 6.1 in 2004 resulted in an order of magnitude decrease in groundwater 239Pu concentrations. Similarly, the fraction of 239Pu in the reduced Pu(III/IV) and colloidal forms increased systematically with decreases in redox condition in 2004 vs 1998. This research demonstrates the importance of source-dependent and source-independent controls on Pu speciation which would impact Pu mobility during changes in hydrological, chemical, or biological conditions on both seasonal and decadal time scales, and over short spatial scales. This implies more dynamic shifts in Pu speciation, colloids association, and transport in groundwater than commonly believed.

Analysis of actinides in an ombrotrophic peat core - evidence of post-depositional migration of fallout radionuclides

NASA Astrophysics Data System (ADS)

Quinto, Francesca; Hrnecek, Erich; Krachler, Michael; Shotyk, William; Steier, Peter; Winkler, Stephan R.

2013-04-01

Plutonium (239Pu, 240Pu, 241Pu, 242Pu) and uranium (236U, 238U) isotopes were analyzed in an ombrotrophic peat core from the Black Forest, Germany, representing the last 80 years of atmospheric deposition. The reliable determination of these isotopes at ultra-trace levels was possible using ultra-clean laboratory procedures and accelerator mass spectrometry. The 240Pu/239Pu isotopic ratios are constant along the core with a mean value of 0.19 ±0.02 (N = 32). This result is consistent with the acknowledged average 240Pu/239Pu isotopic ratio from global fallout in the Northern Hemisphere. The global fallout origin of Pu is confirmed by the corresponding 241Pu/239Pu (0.0012 ±0.0005) and 242Pu/239Pu (0.004 ± 0.001) isotopic ratios. The identification of the Pu isotopic composition characteristic for global fallout in peat layers pre-dating the period of atmospheric atom bomb testing (AD 1956 - AD 1980) is a clear evidence of the migration of Pu downwards the peat profile. The maximum of global fallout derived 236U is detected in correspondence to the age/depth layer of maximum stratospheric fallout (AD 1963). This finding demonstrates that the 236U bomb peak can be successfully used as an independent chronological marker complementing the 210Pb dating of peat cores. The profiles of the global fallout derived 236U and 239Pu are compared with those of 137Cs and 241Am. As typical of ombrothrophic peat, the temporal fallout pattern of 137Cs is poorly retained. Similarly like for Pu, post-depositional migration of 241Am in peat layers preceding the era of atmospheric nuclear tests is observed.

DISSOLUTION OF PLUTONIUM METAL IN 8-10 M NITRIC ACID

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rudisill, T. S.; Pierce, R. A.

2012-07-02

The H-Canyon facility will be used to dissolve Pu metal for subsequent purification and conversion to plutonium dioxide (PuO{sub 2}) using Phase II of HB-Line. To support the new mission, the development of a Pu metal dissolution flowsheet which utilizes concentrated (8-10 M) nitric acid (HNO{sub 3}) solutions containing potassium fluoride (KF) is required. Dissolution of Pu metal in concentrated HNO{sub 3} is desired to eliminate the need to adjust the solution acidity prior to purification by anion exchange. The preferred flowsheet would use 8-10 M HNO{sub 3}, 0.015-0.07 M KF, and 0.5-1.0 g/L Gd to dissolve the Pu upmore » to 6.75 g/L. An alternate flowsheet would use 8-10 M HNO{sub 3}, 0.05-0.2 M KF, and 1-2 g/L B to dissolve the Pu. The targeted average Pu metal dissolution rate is 20 mg/min-cm{sup 2}, which is sufficient to dissolve a “standard” 2250-g Pu metal button in 24 h. Plutonium metal dissolution rate measurements showed that if Gd is used as the nuclear poison, the optimum dissolution conditions occur in 10 M HNO{sub 3}, 0.04-0.05 M KF, and 0.5-1.0 g/L Gd at 112 to 116 °C (boiling). These conditions will result in an estimated Pu metal dissolution rate of ~11-15 mg/min-cm{sup 2} and will result in dissolution times of 36-48 h for standard buttons. The recommended minimum and maximum KF concentrations are 0.03 M and 0.07 M, respectively. The data also indicate that lower KF concentrations would yield dissolution rates for B comparable to those observed with Gd at the same HNO{sub 3} concentration and dissolution temperature. To confirm that the optimal conditions identified by the dissolution rate measurements can be used to dissolve Pu metal up to 6.75 g/L in the presence of representative concentrations of Fe and Gd or B, a series of experiments was performed to demonstrate the flowsheets. In three of the five experiments, the offgas generation rate during the dissolution was measured and samples were analyzed for hydrogen gas (H{sub 2}). The use of 10 M HNO{sub 3} containing 0.03-0.05 M KF, 0.5-1.0 g/L Gd, and 1.9 g/L Fe resulted in complete dissolution of the metal in 2.0-3.5 h. When B was used as the neutron poison, 10 M HNO{sub 3} solutions containing 0.05-0.1 M KF, 1.9 g/L Fe, and 1 g/L B resulted in complete dissolution of the metal in 0.75-2.0 h. Dissolution rates estimated using data from the flowsheet demonstrations agreed reasonably well with the measured rates; although, a discrepancy was observed in the Gd system. The presence of 1 g/L Gd or B in the dissolving solution had about the same effect on the dissolution rate. The predominant Pu valence in the dissolving solution was Pu(IV). The concentration of Pu(VI) was evaluated by UV-visible spectroscopy and was estimated to be significantly less than 1 wt %. The offgas generation rates and H{sub 2} concentrations measured in the offgas from experiments performed using 10 M HNO{sub 3} containing 0.05 M KF, 1.9 g/L Fe and either 1 g/L Gd or B were approximately the same. These data support the conclusion that the presence of either 1 g/L Gd or B had the same general effect on the dissolution rate. The calculated offgas generation during the dissolutions was 0.6 mol offgas/mol of Pu. The H{sub 2} concentration measured in the offgas from the dissolution using Gd as the neutron poison was approximately 0.5 vol %. In the B system, the H{sub 2} ranged from nominally 0.8 to 1 vol % which is about the same as measured in the Gd system within the uncertainty of the analysis. The offgas generation rate for the dissolution performed using 10 M HNO{sub 3} containing 0.03 M KF, 0.5 g/L Gd, and 1.9 g/L Fe was approximately a factor of two less than produced in the other dissolutions; however, the concentration of H{sub 2} measured in the offgas was higher. The adjusted concentration ranged from 2.7 to 8.8 vol % as the dissolution proceeded. Higher concentrations of H{sub 2} occur when the Pu dissolution proceeds by a metal/acid reaction rather than nitrate oxidation. The higher H{sub 2} concentration could be attributed to the reduced activity of the fluoride due to complexation with Pu as the dissolution progressed. Dissolution of Pu metal at 20 °C in 10 M HNO{sub 3} containing 0.05 M KF showed that the Pu metal dissolves slowly without any visible gas generation. As the Pu metal dissolves, it forms a more-dense Pu-bearing solution which sank to the bottom of the dissolution vessel. The dissolved Pu did not form a boundary layer around the sample and failed to distribute homogeneously due to minimal (thermally-induced) mixing. This indicates that in the H-Canyon dissolver insert, the Pu will diffuse out of the insert into the bulk dissolver solution where it will disperse. At 35 °C, the Pu metal dissolved without visible gas generation. However, due to thermal currents caused by maintaining the solution at 35 °C, the dissolved Pu distributed evenly throughout the dissolver solution. It did not form a boundary layer around the sample.« less

Sodium hydrogen carbonate as an alternative blowing agent in the preparation of palm-based polyurethane foam

NASA Astrophysics Data System (ADS)

Shakir, Amira Shakim Abdul; Badri, Khairiah Haji; Hua, Chia Chin

2016-11-01

An environmental-friendly blowing agent has been used to fabricate flexible polyurethane (PU) foam. Polyurethane foam was prepared from palm kernel oil-based monoester polyol (PKO-p) via prepolymerization method. Acetone has been used as solvent in this study. The developed polyurethane foam was characterized using tensile, differential scanning calorimetry analysis (DSC), thermogravimetric analysis (TGA), optical microscope and drop shape analyzer. The mechanical properties of the PU-reference (PU-R) and PU-NaHCO3 foam was analyzed by tensile using ASTM D 3574-01. From the results, the elongation of PU- NaHCO3 shows reduction to 26.3 % compared to PU-R. The DSC showed two glass transition temperatures in all samples that belonged to the PU-R and PU-NaHCO3. TGA revealed that the incorporation of sodium hydrogen carbonate into the PU system did not show significant difference as compared to the control PU. The morphology of both PU was investigated using optical microscope. Contact angle has been measured to determine the hydrophobicity of the PU. The PU- NaHCO3 exhibited an increase in contact angle (93.1°).

In vivo canine studies of a Sinkhole valve and vascular graft coated with biocompatible PU-PEO-SO3.

PubMed

Han, D K; Lee, K B; Park, K D; Kim, C S; Jeong, S Y; Kim, Y H; Kim, H M; Min, B G

1993-01-01

PU-PEO-SO3 was applied as a coating material over a newly designed Sinkhole bileaflet PU heart valve and a porous PU vascular graft. Performance and biocompatibility were evaluated using an in vivo canine shunt system between the right ventricle and pulmonary artery. The survival periods in three implantations were 14, 24, and 39 days, during which no mechanical failure occurred in any Sinkhole valve or vascular graft. Scanning electron microscopy (SEM) studies demonstrated much less platelet adhesion and thrombus formation on PU-PEO-SO3 grafts than on PU vascular grafts. Cracks in the valve leaflet were occasionally observed on PU surfaces, but not on PU-PEO-SO3. After a 39 day implantation, calcium deposition on vascular grafts was decreased as compared with valve leaflets, and calcification on PU-PEO-SO3 was much lower than on PU. These results suggest that Sinkhole valves and vascular grafts are promising, and PU-PEO-SO3 as a coating material is more blood compatible, biostable, and calcification resistant in vivo than in untreated PU.

ANALYSIS AND PRODUCTS FROM NHEXAS -- NATIONAL HUMAN EXPOSURE ASSESSMENT SURVEY

EPA Science Inventory

The National Human Exposure Assessment Survey (NHEXAS) was developed as a federal interagency research effort to examine the full range of environmental pollutants and chemicals (volatile organic chemicals, metals, and pesticides) that humans are exposed to in daily life. The pu...

Pu and 137Cs in the Yangtze River estuary sediments: distribution and source identification.

PubMed

Liu, Zhiyong; Zheng, Jian; Pan, Shaoming; Dong, Wei; Yamada, Masatoshi; Aono, Tatsuo; Guo, Qiuju

2011-03-01

Pu isotopes and (137)Cs were analyzed using sector field ICP-MS and γ spectrometry, respectively, in surface sediment and core sediment samples from the Yangtze River estuary. (239+240)Pu activity and (240)Pu/(239)Pu atom ratios (>0.18) shows a generally increasing trend from land to sea and from north to south in the estuary. This spatial distribution pattern indicates that the Pacific Proving Grounds (PPG) source Pu transported by ocean currents was intensively scavenged into the suspended sediment under favorable conditions, and mixed with riverine sediment as the water circulated in the estuary. This process is the main control for the distribution of Pu in the estuary. Moreover, Pu is also an important indicator for monitoring the changes of environmental radioactivity in the estuary as the river basin is currently the site of extensive human activities and the sea level is rising because of global climate changes. For core sediment samples the maximum peak of (239+240)Pu activity was observed at a depth of 172 cm. The sedimentation rate was estimated on the basis of the Pu maximum deposition peak in 1963-1964 to be 4.1 cm/a. The contributions of the PPG close-in fallout Pu (44%) and the riverine Pu (45%) in Yangtze River estuary sediments are equally important for the total Pu deposition in the estuary, which challenges the current hypothesis that the riverine Pu input was the major source of Pu budget in this area.

PREVENTION OF POLYURETHANE OXIDATIVE DEGRADATION WITH PHENOLIC-ANTIOXIDANTS COVALENTLY ATTACHED TO THE HARD SEGMENTS: STRUCTURE FUNCTION RELATIONSHIPS

PubMed Central

Stachelek, Stanley J; Alferiev, Ivan; Ueda, Masako; Eckels, Edward C.; Gleason, Kevin T.; Levy, Robert J

2010-01-01

Oxidative degradation of the polyurethane elastomeric (PU) components greatly reduces the efficacy of PU containing cardiovascular devices. Covalently appending the phenol-based antioxidant, 4-substituted 2,6-di-tert-butylphenol (DBP), to PU hard segments effectively reduced oxidative degradation of the PU in vivo and in vitro in prior studies by our group. In these experiments we analyze the contribution of the tethering molecule to the antioxidant capabilities of the DBP modified PU. Bromoalkylation chemistry was used to link DBP to the hard segment of the polyether polyurethane, Tecothane, via our original linker (PU-DBP), or variants containing side chains with 1 (PU-C-DBP) or 3 (PU-3C-DBP) carbons. Two additional DBP variants were fabricated in which the DBP group was appended to the alkyl chain via an oxygen atom (PU-O-DBP) or an amide linkage in the middle of the tether (PU-NHCO-DBP). All DBP variant films and unmodified control films were subject to oxidative degradation via 15 day immersion in a solution of 20% H2O2 + 0.1 M CoCl2. At the end of the oxidation protocol films were analyzed for the presence of oxidation related endpoints via scanning electron microscopy, contact angle measurements and Fourier transformation infrared spectroscopy (FTIR). All DBP containing variants resisted oxidation damage significantly better than the unmodified control PU. SEM analysis of oxidized PU-C-DBP and PU-O-DBP showed evidence of surface cracking consistent with oxidative degradation of the PU surfaces. Similarly there was a trend in increased ether cross-linking, a marker for oxidative degradation, in PU-C-DBP and PU-NHCO-DBP films. Consistent with these FTIR results, both PU-C-DBP and PU-NHCO-DBP had significant reductions in measured surface hydrophobicity as a result of oxidation. These data show for the first time that the choice of linker molecule significantly affects the efficiency of the linked phenolic antioxidant. PMID:20306526

Use of ChAd3-EBO-Z Ebola virus vaccine in Malian and US adults, and boosting of Malian adults with MVA-BN-Filo: a phase 1, single-blind, randomised trial, a phase 1b, open-label and double-blind, dose-escalation trial, and a nested, randomised, double-blind, placebo-controlled trial.

PubMed

Tapia, Milagritos D; Sow, Samba O; Lyke, Kirsten E; Haidara, Fadima Cheick; Diallo, Fatoumata; Doumbia, Moussa; Traore, Awa; Coulibaly, Flanon; Kodio, Mamoudou; Onwuchekwa, Uma; Sztein, Marcelo B; Wahid, Rezwanul; Campbell, James D; Kieny, Marie-Paule; Moorthy, Vasee; Imoukhuede, Egeruan B; Rampling, Tommy; Roman, Francois; De Ryck, Iris; Bellamy, Abbie R; Dally, Len; Mbaya, Olivier Tshiani; Ploquin, Aurélie; Zhou, Yan; Stanley, Daphne A; Bailer, Robert; Koup, Richard A; Roederer, Mario; Ledgerwood, Julie; Hill, Adrian V S; Ballou, W Ripley; Sullivan, Nancy; Graham, Barney; Levine, Myron M

2016-01-01

The 2014 west African Zaire Ebola virus epidemic prompted worldwide partners to accelerate clinical development of replication-defective chimpanzee adenovirus 3 vector vaccine expressing Zaire Ebola virus glycoprotein (ChAd3-EBO-Z). We aimed to investigate the safety, tolerability, and immunogenicity of ChAd3-EBO-Z in Malian and US adults, and assess the effect of boosting of Malians with modified vaccinia Ankara expressing Zaire Ebola virus glycoprotein and other filovirus antigens (MVA-BN-Filo). In the phase 1, single-blind, randomised trial of ChAd3-EBO-Z in the USA, we recruited adults aged 18-65 years from the University of Maryland medical community and the Baltimore community. In the phase 1b, open-label and double-blind, dose-escalation trial of ChAd3-EBO-Z in Mali, we recruited adults 18-50 years of age from six hospitals and health centres in Bamako (Mali), some of whom were also eligible for a nested, randomised, double-blind, placebo-controlled trial of MVA-BN-Filo. For randomised segments of the Malian trial and for the US trial, we randomly allocated participants (1:1; block size of six [Malian] or four [US]; ARB produced computer-generated randomisation lists; clinical staff did randomisation) to different single doses of intramuscular immunisation with ChAd3-EBO-Z: Malians received 1 × 10(10) viral particle units (pu), 2·5 × 10(10) pu, 5 × 10(10) pu, or 1 × 10(11) pu; US participants received 1 × 10(10) pu or 1 × 10(11) pu. We randomly allocated Malians in the nested trial (1:1) to receive a single dose of 2 × 10(8) plaque-forming units of MVA-BN-Filo or saline placebo. In the double-blind segments of the Malian trial, investigators, clinical staff, participants, and immunology laboratory staff were masked, but the study pharmacist (MK), vaccine administrator, and study statistician (ARB) were unmasked. In the US trial, investigators were not masked, but participants were. Analyses were per protocol. The primary outcome was safety, measured with occurrence of adverse events for 7 days after vaccination. Both trials are registered with ClinicalTrials.gov, numbers NCT02231866 (US) and NCT02267109 (Malian). Between Oct 8, 2014, and Feb 16, 2015, we randomly allocated 91 participants in Mali (ten [11%] to 1 × 10(10) pu, 35 [38%] to 2·5 × 10(10) pu, 35 [38%] to 5 × 10(10) pu, and 11 [12%] to 1 × 10(11) pu) and 20 in the USA (ten [50%] to 1 × 10(10) pu and ten [50%] to 1 × 10(11) pu), and boosted 52 Malians with MVA-BN-Filo (27 [52%]) or saline (25 [48%]). We identified no safety concerns with either vaccine: seven (8%) of 91 participants in Mali (five [5%] received 5 × 10(10) and two [2%] received 1 × 10(11) pu) and four (20%) of 20 in the USA (all received 1 × 10(11) pu) given ChAd3-EBO-Z had fever lasting for less than 24 h, and 15 (56%) of 27 Malians boosted with MVA-BN-Filo had injection-site pain or tenderness. 1 × 10(11) pu single-dose ChAd3-EBO-Z could suffice for phase 3 efficacy trials of ring-vaccination containment needing short-term, high-level protection to interrupt transmission. MVA-BN-Filo boosting, although a complex regimen, could confer long-lived protection if needed (eg, for health-care workers). Wellcome Trust, Medical Research Council UK, Department for International Development UK, National Cancer Institute, Frederick National Laboratory for Cancer Research, Federal Funds from National Institute of Allergy and Infectious Diseases. Copyright © 2016 Tapia et al. Open Access article distributed under the terms of CC BY. Published by Elsevier Ltd.. All rights reserved.

Accumulation, organ distribution, and excretion kinetics of ²⁴¹Am in Mayak Production Association workers.

PubMed

Suslova, Klara G; Sokolova, Alexandra B; Efimov, Alexander V; Miller, Scott C

2013-03-01

Americium-241 (²⁴¹Am) is the second most significant radiation hazard after ²³⁹Pu at some of the Mayak Production Association facilities. This study summarizes current data on the accumulation, distribution, and excretion of americium compared with plutonium in different organs from former Mayak PA workers. Americium and plutonium were measured in autopsy and bioassay samples and correlated with the presence or absence of chronic disease and with biological transportability of the aerosols encountered at different workplaces. The relative accumulation of ²⁴¹Am was found to be increasing in the workers over time. This is likely from ²⁴¹Pu that increases with time in reprocessed fuel and from the increased concentrations of ²⁴¹Am and ²⁴¹Pu in inhaled alpha-active aerosols. While differences were observed in lung retention with exposures to different industrial compounds with different transportabilities (i.e., dioxide and nitrates), there were no significant differences in lung retention between americium and plutonium within each transportability group. In the non-pulmonary organs, the highest ratios of ²⁴¹Am/²⁴¹Am + SPu were observed in the skeleton. The relative ratios of americium in the skeleton versus liver were significantly greater than for plutonium. The relative amounts of americium and plutonium found in the skeleton compared with the liver were even greater in workers with documented chronic liver diseases. Excretion rates of ²⁴¹Am in ‘‘healthy’’ workers were estimated using bioassay and autopsy data. The data suggest that impaired liver function leads to reduced hepatic ²⁴¹Am retention, leading to increased ²⁴¹Am excretion.

PuTTY | High-Performance Computing | NREL

Science.gov Websites

PuTTY PuTTY Learn how to use PuTTY to connect to NREL's high-performance computing (HPC) systems . Connecting When you start the PuTTY app, the program will display PuTTY's Configuration menu. When this comes . When prompted, type your password again followed by . Note: to increase

Fabrication of superhydrophobic coating for preventing microleakage in a dental composite restoration.

PubMed

Cao, Danfeng; Zhang, Yingchao; Li, Yao; Shi, Xiaoyu; Gong, Haihuan; Feng, Dan; Guo, Xiaowei; Shi, Zuosen; Zhu, Song; Cui, Zhanchen

2017-09-01

Superhydrophobic coatings were successfully fabricated by photo-crosslinked polyurethane (PU) and organic fluoro group-functionalized SiO 2 nanoparticles (F-SiO 2 NPs), and were introduced for preventing microleakage in a dental composite restoration. The F-SiO 2 NPs possessed low surface energy and the PU can not only improve the mechanical stability but also promote F-SiO 2 NPs to form multiscale structure, which could facilitate the properties of the as-prepared superhydrophobic coating by synergetic effect. The morphology and properties of the resulted superhydrophobic coatings with different PU/F-SiO 2 ratios were studied using 1 H NMR spectrum, fourier transform infrared spectra, scanning electron microscopy, atomic force microscopy and UV-vis spectrophotometry. The results showed that the superhydrophobic coatings with low PU/F-SiO 2 ratio (1:3) possessed excellent hierarchical papillae structure with trapped air pockets, high contact angle (160.1°), low sliding angle (<1°) and good transparency. Additionally, MTT experiments results certified the prominent cell viability and biocompatibility for clinical application. Based on its fantastically superhydrophobic property, the as-prepared superhydrophobic coatings effectively prevented water permeation in resin composite restoration evaluation. This research may provide an effective method to solve the problem of microleakage and will efficiently increase the success rate of dental composite restorations. Copyright © 2017 Elsevier B.V. All rights reserved.

Pu 236 ( n , f ) , Pu 237 ( n , f ) , and Pu 238 ( n , f ) cross sections deduced from ( p , t ) , ( p , d ) , and ( p , p ' ) surrogate reactions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hughes, R. O.; Beausang, C. W.; Ross, T. J.

2014-07-01

The Pu 236(n,f), Pu 237(n,f) and Pu 238(n,f) cross sections have been inferred by utilizing the surrogate ratio method. Targets of Pu 239 and U 235 were bombarded with 28.5-MeV protons, and the light ion recoils, as well as fission fragments, were detected using the STARS detector array at the K150 Cyclotron at the Texas A&M cyclotron facility. The (p, tf) reaction on Pu 239 and U 235 targets was used to deduce the σ (Pu 236(n,f))/σ(U 232(n,f)) ratio, and the Pu 236(n,f) cross section was subsequently determined for En=0.5–7.5 MeV. Similarly, the (p,df) reaction on the same two targetsmore » was used to deduce the σ(Pu 237(n,f))/σ(U 233(n,f)) ratio, and the Pu 237(n,f) cross section was extracted in the energy range En=0.5–7 MeV. The Pu 238(n,f) cross section was also deduced by utilizing the (p,p') reaction channel on the same targets. There is good agreement with the recent ENDF/B-VII.1 evaluated cross section data for Pu 238(n,f) in the range En=0.5–10.5 MeV and for Pu 237(n,f) in the range En=0.5–7 MeV; however, the Pu 236(n,f) cross section deduced in the present work is higher than the evaluation between 2 and 7 MeV.« less

Theoretical studies of UO(2)(OH)(H(2)O)(n) (+), UO(2)(OH)(2)(H(2)O)(n), NpO(2)(OH)(H(2)O)(n), and PuO(2)(OH)(H(2)O)(n) (+) (n

PubMed

Cao, Zhiji; Balasubramanian, K

2009-10-28

Extensive ab initio calculations have been carried out to study equilibrium structures, vibrational frequencies, and the nature of chemical bonds of hydrated UO(2)(OH)(+), UO(2)(OH)(2), NpO(2)(OH), and PuO(2)(OH)(+) complexes that contain up to 21 water molecules both in first and second hydration spheres in both aqueous solution and the gas phase. The structures have been further optimized by considering long-range solvent effects through a polarizable continuum dielectric model. The hydrolysis reaction Gibbs free energy of UO(2)(H(2)O)(5) (2+) is computed to be 8.11 kcal/mol at the MP2 level in good agreement with experiments. Our results reveal that it is necessary to include water molecules bound to the complex in the first hydration sphere for proper treatment of the hydrated complex and the dielectric cavity although water molecules in the second hydration sphere do not change the coordination complex. Structural reoptimization of the complex in a dielectric cavity seems inevitable to seek subtle structural variations in the solvent and to correlate with the observed spectra and thermodynamic properties in the aqueous environment. Our computations reveal dramatically different equilibrium structures in the gas phase and solution and also confirm the observed facile exchanges between the complex and bulk solvent. Complete active space multiconfiguration self-consistent field followed by multireference singles+doubles CI (MRSDCI) computations on smaller complexes confirm predominantly single-configurational nature of these species and the validity of B3LYP and MP2 techniques for these complexes in their ground states.

Neutron-induced fission cross section of 240Pu from 0.5 MeV to 3 MeV

NASA Astrophysics Data System (ADS)

Salvador-Castiñeira, P.; Bryś, T.; Eykens, R.; Hambsch, F.-J.; Göök, A.; Moens, A.; Oberstedt, S.; Sibbens, G.; Vanleeuw, D.; Vidali, M.; Pretel, C.

2015-07-01

240Pu has recently been pointed out by a sensitivity study of the Organization for Economic Cooperation and Development (OECD) Nuclear Energy Agency (NEA) to be one of the isotopes whose fission cross section lacks accuracy to meet the upcoming needs for the future generation of nuclear power plants (GEN-IV). In the High Priority Request List (HPRL) of the OECD, it is suggested that the knowledge of the 240Pu(n ,f ) cross section should be improved to an accuracy within 1-3 %, compared to the present 5%. A measurement of the 240Pu cross section has been performed at the Van de Graaff accelerator of the Joint Research Center (JRC) Institute for Reference Materials and Measurements (IRMM) using quasi-monoenergetic neutrons in the energy range from 0.5 MeV to 3 MeV. A twin Frisch-grid ionization chamber (TFGIC) has been used in a back-to-back configuration as fission fragment detector. The 240Pu(n ,f ) cross section has been normalized to three different isotopes: 237Np(n ,f ) , 235U (n ,f ) , and 238U (n ,f ) . Additionally, the secondary standard reactions were benchmarked through measurements against the primary standard reaction 235U (n ,f ) in the same geometry. A comprehensive study of the corrections applied to the data and the associated uncertainties is given. The results obtained are in agreement with previous experimental data at the threshold region. For neutron energies higher than 1 MeV, the results of this experiment are slightly lower than the ENDF/B-VII.1 evaluation, but in agreement with the experiments of Laptev et al. (2004) as well as Staples and Morley (1998).

A Comparison of ACQ, AIE and AEE-Based Polymers Loaded on Polyurethane Foams as Sensors for Explosives Detection.

PubMed

Chu, Zhiwei; Fan, Zhuxin; Zhang, Xiang; Tan, Xiaofeng; Li, Dongxu; Chen, Guohua; Zhao, Qinghua

2018-05-15

An aggregation-caused quenching (ACQ)-active polymer (PF), an aggregation-induced emission (AIE)-active polymer (PFTPE) and an aggregation-enhanced emission (AEE)-active polymer (PTTPE) were synthesized by tetraphenylethane (TPE), fluorene and thiophene moieties. Polyurethane (PU) foams modified by PF, PFTPE and PTTPE, namely PU-PF, PU-PFTPE and PU-PTTPE, using ultrasonication-assisted method have been prepared. A comparative study of PU-PF, PU-PFTPE and PU-PTTPE for detection explosives had been performed, and significant fluorescence quenching was observed with the introduction of PA solutions. The as-prepared PU-PF, PU-PFTPE and PU-PTTPE sensors exhibited a superior sensitivity for PA solutions with different concentrations. Remarkably, PU-PF gave a quenching efficiency of 96.2%, higher than 93.5% for PU-PFTPE and 86.7% for PU-PTTPE at a PA concentration of 180 µg·mL -1 in methanol, which was attributed to the effective energy transfer from the fluorophore (PF) to the nitro explosive (PA). This suggested that some ACQ polymers, applied to detect explosives, could afford better performances than AIE or AEE polymers through modification of structures and selection of adequate carriers. At the same time, these chemical sensors can be recycled many times.

A Comparison of ACQ, AIE and AEE-Based Polymers Loaded on Polyurethane Foams as Sensors for Explosives Detection

PubMed Central

Chu, Zhiwei; Fan, Zhuxin; Zhang, Xiang; Tan, Xiaofeng; Chen, Guohua; Zhao, Qinghua

2018-01-01

An aggregation-caused quenching (ACQ)-active polymer (PF), an aggregation-induced emission (AIE)-active polymer (PFTPE) and an aggregation-enhanced emission (AEE)-active polymer (PTTPE) were synthesized by tetraphenylethane (TPE), fluorene and thiophene moieties. Polyurethane (PU) foams modified by PF, PFTPE and PTTPE, namely PU-PF, PU-PFTPE and PU-PTTPE, using ultrasonication-assisted method have been prepared. A comparative study of PU-PF, PU-PFTPE and PU-PTTPE for detection explosives had been performed, and significant fluorescence quenching was observed with the introduction of PA solutions. The as-prepared PU-PF, PU-PFTPE and PU-PTTPE sensors exhibited a superior sensitivity for PA solutions with different concentrations. Remarkably, PU-PF gave a quenching efficiency of 96.2%, higher than 93.5% for PU-PFTPE and 86.7% for PU-PTTPE at a PA concentration of 180 µg·mL−1 in methanol, which was attributed to the effective energy transfer from the fluorophore (PF) to the nitro explosive (PA). This suggested that some ACQ polymers, applied to detect explosives, could afford better performances than AIE or AEE polymers through modification of structures and selection of adequate carriers. At the same time, these chemical sensors can be recycled many times. PMID:29762497

Electronic and thermodynamic properties of α-Pu2O3

NASA Astrophysics Data System (ADS)

Lu, Yong; Yang, Yu; Zheng, Fawei; Zhang, Ping

2014-08-01

Based on density functional theory+U calculations and the quasi-annealing simulation method, we obtain the ground electronic state for α-Pu2O3 and present its phonon dispersion curves as well as various thermodynamic properties, which have seldom been theoretically studied because of the huge unit cell. We find that the Pu-O chemical bonding is weaker in α-Pu2O3 than in fluorite PuO2, and subsequently a frequency gap appears between oxygen and plutonium vibration density of states. Based on the calculated Helmholtz free energies at different temperatures, we further study the reaction energies for Pu oxidation, PuO2 reduction, and transformation between PuO2 and α-Pu2O3. Our reaction energy results are in agreements with available experiment. And it is revealed that high temperature and insufficient oxygen environment are in favor of the formation of α-Pu2O3.

New Insights into Clinical Characteristics of Gilles de la Tourette Syndrome: Findings in 1032 Patients from a Single German Center

PubMed Central

Sambrani, Tanvi; Jakubovski, Ewgeni; Müller-Vahl, Kirsten R.

2016-01-01

Background: Gilles de la Tourette syndrome (TS) is a complex neuropsychiatric disorder defined by the presence of motor and phonic tics, but often associated with psychiatric comorbidities. The main objective of this study was to explore the clinical presentation and comorbidities of TS. Method: We analyzed clinical data obtained from a large sample (n = 1032; 529 children and 503 adults) of patients with tic disorders from one single German TS center assessed by one investigator. Data was collected with the help of an expert-reviewed semi-structured interview, designed to assess tic severity and certain comorbidities. Group comparisons were carried out via independent sample t-tests and chi-square tests. Results: The main findings of the study are: (1) tic severity is associated with the presence of premonitory urges (PU), copro-, echo-, and paliphenomena and the number of comorbidities, but not age at tic onset; it is higher in patients with comorbid obsessive-compulsive disorder (OCD) than in patients with comorbid attention deficit/hyperactivity disorder (ADHD). (2) PU were found to be highly associated with “not just right experiences” and to emerge much earlier than previously thought alongside with the ability to suppress tics (PU in >60% and suppressibility in >75% at age 8–10 years). (3) Self-injurious behavior (SIB) is highly associated with complex motor tics and coprophenomena, but not with OCD/obsessive-compulsive behavior (OCB). While comorbid ADHD is associated with a lower ability to suppress tics, comorbid depression is associated with sleeping problems. Discussion: Our results demonstrate that tic severity is not influenced by age at onset. From our data, it is suggested that PU represent a specific type of “not just right experience” that is not a prerequisite for tic suppression. Comorbid ADHD reduces patients' ability of successful tic suppression. Our data suggest that SIB belongs to the coprophenomena spectrum and hence should be conceptualized as a complex tic rather than a compulsion. Finally, this study strongly supports the hypothesis that TS+OCD is a more severe form of TS and that comorbid OCD/OCB, depression, and anxiety belong to the TS spectrum, while ADHD should be better conceptualized as a separate problem. PMID:27672357

Oxidation and reduction behaviors of a prototypic MgO-PuO2-x inert matrix fuel

NASA Astrophysics Data System (ADS)

Miwa, Shuhei; Osaka, Masahiko

2017-04-01

Oxidation and reduction behaviors of prototypic MgO-based inert matrix fuels (IMFs) containing PuO2-x were experimentally investigated by means of thermogravimetry. The oxidation and reduction kinetics of the MgO-PuO2-x specimen were determined. The oxidation and reduction rates of the MgO-PuO2-x were found to be low compared with those of PuO2-x. It is note that the changes in O/Pu ratios of MgO-PuO2-x from stoichiometry were smaller than those of PuO2-x at high oxygen partial pressure.

Age determination of single plutonium particles after chemical separation

NASA Astrophysics Data System (ADS)

Shinonaga, T.; Donohue, D.; Ciurapinski, A.; Klose, D.

2009-01-01

Age determination of single plutonium particles was demonstrated using five particles of the standard reference material, NBS 947 (Plutonium Isotopic Standard. National Bureau of Standards, Washington, D.C. 20234, August 19, 1982, currently distributed as NBL CRM-137) and the radioactive decay of 241Pu into 241Am. The elemental ratio of Am/Pu in Pu particles found on a carbon planchet was measured by wavelength dispersive X-ray spectrometry (WDX) coupled to a scanning electron microscope (SEM). After the WDX measurement, each plutonium particle, with an average size of a few μm, was picked up and relocated to a silicon wafer inside the SEM chamber using a micromanipulator. The silicon wafer was then transferred to a quartz tube for dissolution in an acid solution prior to chemical separation. After the Pu was chemically separated from Am and U, the isotopic ratios of Pu ( 240Pu/ 239Pu, 241Pu/ 239Pu and 242Pu/ 239Pu) were measured with a thermal ionization mass spectrometer (TIMS) for the calculation of Pu age. The age of particles determined in this study was in good agreement with the expected age (35.9 a) of NBS 947 within the measurement uncertainty.

Spatially resolved analysis of plutonium isotopic signatures in environmental particle samples by laser ablation-MC-ICP-MS.

PubMed

Konegger-Kappel, Stefanie; Prohaska, Thomas

2016-01-01

Laser ablation-multi-collector-inductively coupled plasma mass spectrometry (LA-MC-ICP-MS) was optimized and investigated with respect to its performance for determining spatially resolved Pu isotopic signatures within radioactive fuel particle clusters. Fuel particles had been emitted from the Chernobyl nuclear power plant (ChNPP) where the 1986 accident occurred and were deposited in the surrounding soil, where weathering processes caused their transformation into radioactive clusters, so-called micro-samples. The size of the investigated micro-samples, which showed surface alpha activities below 40 mBq, ranged from about 200 to 1000 μm. Direct single static point ablations allowed to identify variations of Pu isotopic signatures not only between distinct fuel particle clusters but also within individual clusters. The resolution was limited to 100 to 120 μm as a result of the applied laser ablation spot sizes and the resolving power of the nuclear track radiography methodology that was applied for particle pre-selection. The determined (242)Pu/(239)Pu and (240)Pu/(239)Pu isotope ratios showed a variation from low to high Pu isotope ratios, ranging from 0.007(2) to 0.047(8) for (242)Pu/(239)Pu and from 0.183(13) to 0.577(40) for (240)Pu/(239)Pu. In contrast to other studies, the applied methodology allowed for the first time to display the Pu isotopic distribution in the Chernobyl fallout, which reflects the differences in the spent fuel composition over the reactor core. The measured Pu isotopic signatures are in good agreement with the expected Pu isotopic composition distribution that is typical for a RBMK-1000 reactor, indicating that the analyzed samples are originating from the ill-fated Chernobyl reactor. The average Pu isotope ratios [(240)Pu/(239)Pu = 0.388(86), (242)Pu/(239)Pu = 0.028(11)] that were calculated from all investigated samples (n = 48) correspond well to previously published results of Pu analyses in contaminated samples from the vicinity of the Chernobyl NPP [e.g. (240)Pu/(239)Pu = 0.394(2) and (242)Pu/(239)Pu = 0.027(1); Nunnemann et al. (J Alloys Compd 271-273:45-48, 1998)].

SEMIANNUAL PROGRESS REPORT ON CHEMISTRY FOR THE PERIOD, JANUARY 1961-JULY 1961

DOE Office of Scientific and Technical Information (OSTI.GOV)

None

1962-03-01

A procedure is presented for the determination of both Mo and Sn in a wide variety of samples with 8-quinolinol (oxine). The Mo complex is extracted with chloroform from a sulfate solution of the sample at pH 0.85 and determined spectrophotometrically at 385 m mu . The Sn complex is then similarly extracted and determined after the addition of chloride to the sample solution. A procedure is also given in which B is separated quantitatively from various B minerals by pyrohydrolysis. The distillate is passed through a cation-exchange resin column to remove interfering Sr, Ru, and other cations, after whichmore » the effluent is neutralized to pH 9.3 tc 9.4 and evaporated to dryness. The residue is suitable for the mass spectrometric determination of the B/sup 11//B/sup 10/ ratio. In other work, a single-focusing mass spectrometer of 6-in. radius, 60 deg sector magnetic analyzer was designed to analyze a wide range of sample materials that require high precision and accuracy in the low-mass range but which offers considerable flexibility to evaluate highmass materials for comparison purposes. A gas, solid, or liquid type of analysis may be performed. A change-over can be raade from one type of analysis to another with minimum loss of instrument tirae and requiring minimum technical knowledge. Single peak measurement, or ratio measurement may be made from M/e 6/7 to M/e 238/235, with the use of vibrating reed electrometers or an electron multiplier for measuring the ion beams. The stability of plutonium sulfate tetrshydrate and anhydrous plutonium sulfate was evaluated. Recent tests disclose no signlficant change in the Pu content of the tetrahydrate or the anhydrous salt for periods of at least 18 and 6 months, respectively. Both thermogravimetry and chemical analysis showed the formula of anhydrous plutonium sulfate to be Pu(SO/sub 4/)/sub 2.000/ / sub plus or minus / /sub 0.002/. Preparation of dicesium plutoniu m hexachloride is reported along with evaluation of its suitability as a primary standard for Pu. The composition of the material was determined by analysis and fits the formula susceptible to changes in relative humidities greater than 17%, and showed a small but significant weight loss during a six-month testing period. A procedure is described for Si separation from Pu using a cation-exchange procedure prior to spectrographic determination. Plutonium(III) in 0.2N nitric acid is adsorbed on Dowex-50 cation resin while Si, as silicate anion or colloid, passes unadsorbed into the effluent. The effluent is evaporated to dryness and the residue is dissolved in dilute nitric acid containing hydrofluoric acid. Aliquots of the solution are dried on graphite electrodes and excited in a d-c arc. Typical results on synthetic solutions give an estimated over-all average deviation of plus or minus 25% and sensitivities from 1 to 5 ppm Si. This method offers an alternate procedure to the carrier distillation technique which employs large amounts of PuO/sub 2/ as matrix for the determination of Si in Pu. The development of a sensitive method for the spectrographic determination of trace impurities in Pu is continuing. The method was modified for use with plutonium sulfate samples, and enlarged to include the determination of B, Cd, and some alkali elements, and also for the estimation of Am. Pu breakthrough during the ion-exchange separation of Pu from its impurities was found to be < 0.001%. Methods were investigated for preparing high-purity reagents and reducing reference blank values in order to obtain greater sensitivity. At present seventeen elements may be determined in the 1st and 2nd optical orders using only 200 mg. of sample. (auth)« less

Neptunium and plutonium complexes with a sterically encumbered triamidoamine (TREN) scaffold

DOE PAGES

Brown, Jessie L.; Gaunt, Andrew J.; King, David M.; ...

2016-03-11

Here, the syntheses and characterization of isostructural neptunium(IV) and plutonium(IV) complexes [M IV(TREN TIPS)(Cl)] [An = Np, Pu; TREN TIPS = {N(CH 2CH 2NSiPr i 3) 3} 3] are reported, along with the demonstration that they are likely reduced to the corresponding neptunium(III) and plutonium(III) products [M III(TREN TIPS)]; this chemistry provides new platforms from which to target a plethora of unprecedented molecular functionalities in transuranic chemistry and the neptunium(IV) molecule is the first structurally characterized neptunium(IV)–amide complex.

Sources of the transuranic elements plutonium and neptunium in arctic marine sediments.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cooper, L. W.; Kelley, J. M.; Bond, L. A.

2000-01-01

We report here thermal ionization mass spectrometry measurements of {sup 239}Pu, {sup 240}Pu, {sup 241}Pu, {sup 242}Pu, and {sup 237}Np isolated from oceanic, estuarine, and riverine sediments from the Arctic Ocean Basin. {sup 238}Pu/{sup 239+240}Pu activity ratios are also reported for alpha spectrometric analyses undertaken on a subset of these samples. Our results indicate that the Pu in sediments on the Alaskan shelf and slope, as well as that in the deep basins (Amerasian and Eurasian) of the Arctic Ocean, has its origin in stratospheric and tropospheric fallout. Sediments from the Ob and Yenisei Rivers show isotopic Pu signatures thatmore » are distinctly different from those of northern-hemisphere stratospheric fallout and indicate the presence of weapons-grade Pu originating from nuclear fuel reprocessing wastes generated at Russian facilities within these river catchments. Consequently, sediments of the Eurasian Arctic Ocean, particularly those in the Barents and Kara Seas, probably contain a mixture of Pu from stratospheric fallout, tropospheric fallout, and fuel-reprocessing wastes of riverine origin. In particular, the {sup 241}Pu/{sup 239}Pu ratios observed in these sediments are inconsistent with significant contributions of Pu to the arctic sediments studied from western European reprocessing facilities, principally Sellafield in the UK. Several other potential sources of Pu to arctic sediments can also be excluded as significant based upon the transuranic isotope ratios presented.« less

Volcanology curricula development aided by online educational resource

USGS Publications Warehouse

Poland, Michael P.; van der Hoeven Kraft, Katrien J.; Teasdale, Rachel

2011-01-01

Volcanic activity is an excellent hook for engaging college and university students in geoscience classes. An increasing number of Internet-accessible real-time and near–real time volcano monitoring data are now available and constitute an important resource for geoscience education; however, relatively few data sets are comprehensive, and many lack background information to aid in interpretation. In response to the need for organized, accessible, and well-documented volcano education resources, the U.S. Geological Survey's Hawaiian Volcano Observatory (HVO), in collaboration with NASA and the University of Hawai`i at Manoa, established the Volcanoes Exploration Project: Pu`u `Ō`ō (VEPP). The VEPP Web site (http://vepp.wr.usgs.gov) is an educational resource that provides access, in near real time, to geodetic, seismic, and geologic data from the active Pu`u `Ō`ō eruptive vent on Kilauea volcano, Hawaii, along with background and context information. A strength of the VEPP site is the common theme of the Pu`u `Ō`ō eruption, which allows the site to be revisited multiple times to demonstrate different principles and integrate many aspects of volcanology.

X-ray excited Auger transitions of Pu compounds

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nelson, Art J., E-mail: nelson63@llnl.gov; Grant, William K.; Stanford, Jeff A.

2015-05-15

X-ray excited Pu core–valence–valence and core–core–valence Auger line-shapes were used in combination with the Pu 4f photoelectron peaks to characterize differences in the oxidation state and local electronic structure for Pu compounds. The evolution of the Pu 4f core-level chemical shift as a function of sputtering depth profiling and hydrogen exposure at ambient temperature was quantified. The combination of the core–valence–valence Auger peak energies with the associated chemical shift of the Pu 4f photoelectron line defines the Auger parameter and results in a reliable method for definitively determining oxidation states independent of binding energy calibration. Results show that PuO{sub 2},more » Pu{sub 2}O{sub 3}, PuH{sub 2.7}, and Pu have definitive Auger line-shapes. These data were used to produce a chemical state (Wagner) plot for select plutonium oxides. This Wagner plot allowed us to distinguish between the trivalent hydride and the trivalent oxide, which cannot be differentiated by the Pu 4f binding energy alone.« less

A DFT+U study of Pu immobilization in Gd2Zr2O7

NASA Astrophysics Data System (ADS)

Zhao, F. A.; Xiao, H. Y.; Jiang, M.; Liu, Z. J.; Zu, X. T.

2015-12-01

The solubility of Pu in Gd2Zr2O7 has been investigated by the density functional theory plus Hubbard U correction. It is found that the formation of PuGdZr2O7, Gd2PuZrO7 and Gd2Pu1.5Zr0.5O7 are exothermic, whereas Pu0.5Gd1.5Zr2O7, Pu1.5Gd0.5Zr2O7 and Gd2Pu0.5Zr1.5O7 are energetically less stable than their respective separated states. The calculations show that both the Gd and Zr lattice sites can be substituted by the Pu, which is consistent with the immobilization behavior of uranium in Gd2Zr2O7 observed experimentally. The site preference of Pu in Gd2Zr2O7 is found to be dependent on the chemical environment, i.e., Pu prefers to substitute for Gd-site under Gd-rich and O2-rich conditions and for Zr-site under Zr-rich and O2-rich conditions.

Synthesis, Crystal Chemistry, and Physical Properties of Ternary Intermetallic Compounds An2T2X( An=Pu, Am; X=ln, Sn; T=Co, Ir, Ni, Pd, Pt, Rh)

NASA Astrophysics Data System (ADS)

Pereira, L. C. J.; Wastin, F.; Winand, J. M.; Kanellakopoulos, B.; Rebizant, J.; Spirlet, J. C.; Almeida, M.

1997-11-01

The synthesis, structural, and physical characterization of nine new ternary intermetallic compounds belonging to the isostructural An2T2Xfamily with the transuranium Pu and Am elements, namely, Pu 2Ni 2In, Pu 2Pd 2In, Pu 2Pt 2In, Pu 2Rh 2In, Pu 2Ni 2Sn, Pu 2Pd 2Sn, Pu 2Pt 2Sn, Am 2Ni 2Sn, and Am 2Pd 2Sn, are reported. From these compounds only Pu 2Rh 2In, Am 2Ni 2Sn, and Am 2Pd 2Sn melt incongruently. All of these compounds crystallize in a tetragonal U 3Si 2-type structure, with the space group P4/ mbm, ( Z=2) as most of the U and Np 2-2-1 compounds already found. In this structure, Anatoms occupy the 4 h( x1, x1+0.5, 0.5), Tthe 4 g( x2, x2+0.5, 0), and Xthe 2 a(0, 0, 0) positions. The average values of x1and x2are, respectively, 0.17 and 0.37. Single-crystal X-ray data were refined to R/ RW=0.045/0.066, 0.043/0.072, 0.066/0.080, 0.070/0.098, 0.029/0.048, 0.055/0.080, 0.073/0.096, 0.048/0.086, 0.048/0.065 for Pu 2Ni 2In, Pu 2Pd 2In, Pu 2Pt 2In, Pu 2Rh 2In, Pu 2Ni 2Sn, Pu 2Pd 2Sn, Pu 2Pt 2Sn, Am 2Ni 2Sn, and Am 2Pd 2Sn, respectively, for seven variables. The variation of the lattice parameters and the range of stability of the 2-2-1 phase are discussed in terms of the substitution of different An(actinide), T(transition metal), and X( p-electron) elements in their crystal structure. The possible role of spin fluctuations in the low-temperature behavior of the Pu samples is indicated by magnetic and electrical resistivity measurements.

Determination of 240Pu/239Pu isotopic ratios in human tissues collected from areas around the Semipalatinsk Nuclear Test Site by sector-field high resolution ICP-MS.

PubMed

Yamamoto, M; Oikawa, S; Sakaguchi, A; Tomita, J; Hoshi, M; Apsalikov, K N

2008-09-01

Information on the 240Pu/239Pu isotope ratios in human tissues for people living around the Semipalatinsk Nuclear Test Site (SNTS) was deduced from 9 sets of soft tissues and bones, and 23 other bone samples obtained by autopsy. Plutonium was radiochemically separated and purified, and plutonium isotopes (239Pu and 240Pu) were determined by sector-field high resolution inductively coupled plasma-mass spectrometry. For most of the tissue samples from the former nine subjects, low 240Pu/239Pu isotope ratios were determined: bone, 0.125 +/- 0.018 (0.113-0.145, n = 4); lungs, 0.063 +/- 0.010 (0.051-0.078, n = 5); and liver, 0.148 +/- 0.026 (0.104-0.189, n = 9). Only 239Pu was detected in the kidney samples; the amount of 240Pu was too small to be measured, probably due to the small size of samples analyzed. The mean 240Pu/239Pu isotope ratio for bone samples from the latter 23 subjects was 0.152 +/- 0.034, ranging from 0.088 to 0.207. A significant difference (a two-tailed Student's t test; 95% significant level, alpha = 0.05) between mean 240Pu/239Pu isotope ratios for the tissue samples and for the global fallout value (0.178 +/- 0.014) indicated that weapons-grade plutonium from the atomic bombs has been incorporated into the human tissues, especially lungs, in the residents living around the SNTS. The present 239,240Pu concentrations in bone, lung, and liver samples were, however, not much different from ranges found for human tissues from other countries that were due solely to global fallout during the 1970's-1980's.

Ultra-trace determination of plutonium in marine samples using multi-collector inductively coupled plasma mass spectrometry.

PubMed

Lindahl, Patric; Keith-Roach, Miranda; Worsfold, Paul; Choi, Min-Seok; Shin, Hyung-Seon; Lee, Sang-Hoon

2010-06-25

Sources of plutonium isotopes to the marine environment are well defined, both spatially and temporally, which makes Pu a potential tracer for oceanic processes. This paper presents the selection, optimisation and validation of a sample preparation method for the ultra-trace determination of Pu isotopes ((240)Pu and (239)Pu) in marine samples by multi-collector (MC) ICP-MS. The method was optimised for the removal of the interference from (238)U and the chemical recovery of Pu. Comparison of various separation strategies using AG1-X8, TEVA, TRU, and UTEVA resins to determine Pu in marine calcium carbonate samples is reported. A combination of anion-exchange (AG1-X8) and extraction chromatography (UTEVA/TRU) was the most suitable, with a radiochemical Pu yield of 87+/-5% and a U decontamination factor of 1.2 x 10(4). Validation of the method was accomplished by determining Pu in various IAEA certified marine reference materials. The estimated MC-ICP-MS instrumental limit of detection for (239)Pu and (240)Pu was 0.02 fg mL(-1), with an absolute limit of quantification of 0.11 fg. The proposed method allows the determination of ultra-trace Pu, at femtogram levels, in small size marine samples (e.g., 0.6-2.0 g coral or 15-20 L seawater). Finally, the analytical method was applied to determining historical records of the Pu signature in coral samples from the tropical Northwest Pacific and (239+240)Pu concentrations and (240)Pu/(239)Pu atom ratios in seawater samples as part of the 2008 GEOTRACES intercalibration exercise. Copyright 2010 Elsevier B.V. All rights reserved.

Real-time monitoring of plutonium content in uranium-plutonium alloys

DOEpatents

Li, Shelly Xiaowei; Westphal, Brian Robert; Herrmann, Steven Douglas

2015-09-01

A method and device for the real-time, in-situ monitoring of Plutonium content in U--Pu Alloys comprising providing a crucible. The crucible has an interior non-reactive to a metallic U--Pu alloy within said interior of said crucible. The U--Pu alloy comprises metallic uranium and plutonium. The U--Pu alloy is heated to a liquid in an inert or reducing atmosphere. The heated U--Pu alloy is then cooled to a solid in an inert or reducing atmosphere. As the U--Pu alloy is cooled, the temperature of the U--Pu alloy is monitored. A solidification temperature signature is determined from the monitored temperature of the U--Pu alloy during the step of cooling. The amount of Uranium and the amount of Plutonium in the U--Pu alloy is then determined from the determined solidification temperature signature.

Virgin olive oil blended polyurethane micro/nanofibers ornamented with copper oxide nanocrystals for biomedical applications

PubMed Central

Amna, Touseef; Hassan, M Shamshi; Yang, Jieun; Khil, Myung-Seob; Song, Ki-Duk; Oh, Jae-Don; Hwang, Inho

2014-01-01

Recently, substantial interest has been generated in using electrospun biomimetic nanofibers of hybrids, particularly organic/inorganic, to engineer different tissues. The present work, for the first time, introduced a unique natural and synthetic hybrid micronanofiber wound dressing, composed of virgin olive oil/copper oxide nanocrystals and polyurethane (PU), developed via facile electrospinning. The as-spun organic/inorganic hybrid micronanofibers were characterized by scanning electron microscopy (SEM), energy dispersive X-ray analysis, X-ray diffraction, electron probe microanalysis, and transmission electron microscopy. The interaction of cells with scaffold was studied by culturing NIH 3T3 fibroblasts on an as-spun hybrid micronanofibrous mat, and viability, proliferation, and growth were assessed. The 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide assay results and SEM observation showed that the hybrid micronanofibrous scaffold was noncytotoxic to fibroblast cell culture and was found to benefit cell attachment and proliferation. Hence our results suggest the potential utilization of as-spun micronanoscaffolds for tissue engineering. Copper oxide–olive oil/PU wound dressing may exert its positive beneficial effects at every stage during wound-healing progression, and these micronanofibers may serve diverse biomedical applications, such as tissue regeneration, damaged skin treatment, wound healing applications, etc. Conclusively, the fabricated olive oil–copper oxide/PU micronanofibers combine the benefits of virgin olive oil and copper oxide, and therefore hold great promise for biomedical applications in the near future. PMID:24611006

Evaluation of different methods for immobilization of Candida antarctica lipase B (CalB lipase) in polyurethane foam and its application in the production of geranyl propionate.

PubMed

Nicoletti, Gabrieli; Cipolatti, Eliane P; Valério, Alexsandra; Carbonera, NatáliaThaisa Gamba; Soares, Nicole Spillere; Theilacker, Eron; Ninow, Jorge L; de Oliveira, Débora

2015-09-01

With the aim of studying the best method for the interaction of polyurethane (PU) foam and Candida antarctica lipase B, different methods of CalB immobilization were studied: adsorption (PU-ADS), bond (using polyethyleneimine) (PU-PEI), ionic adsorption by PEI with cross-linking with glutaraldehyde (PU-PEI-GA) and entrapment (PU). The characterization of immobilized enzyme derivatives was performed by apparent density and Fourier transform infrared spectroscopy. The free enzyme and enzyme preparations were evaluated at different pH values and temperatures. The highest enzyme activity was obtained using the PU method (5.52 U/g). The methods that stood out to compare the stabilities and kinetic parameters were the PU and PU-ADS. Conversions of 83.5 and 95.9 % for PU and PU-ADS derivatives were obtained, in 24 h reaction, using citronella oil and propionic acid as substrates.

On the presence of plutonium in Madagascar following the SNAP-9A satellite failure.

PubMed

Rääf, C; Holm, E; Rabesiranana, N; Garcia-Tenorio, R; Chamizo, E

2017-10-01

This study examined the 238 Pu and 239+240 Pu activity concentration and the 240 Pu/ 239 Pu atomic ratio in peat bogs sampled in 2012 from marshlands in central Madagascar. The purpose was to investigate the presence of plutonium isotopes, 238, 239, 240 Pu, from the 1964 satellite failure carrying a SNAP-9A radiothermal generator. With an average 238 Pu/ 239+240 Pu activity ratio of 0.165 ± 0.02 (decay corrected to 1964), the peat bogs in Madagascar exhibit similar values as the ones found in the southeastern African continent, except they are one order of magnitude higher than expected (0.025) from global fallout in the Southern Hemisphere. The 240 Pu/ 239 Pu atomic ratio showed a distinct decrease for layers dating back to the mid-1960s (down to 0.069 compared with an anticipated ratio of 0.17 for global fallout), indicating that the SNAP-9A failure also resulted in an elevated deposition of 239 Pu. The obtained results demonstrate that further Pu analysis in Madagascar and in southeastern continental Africa is necessary to fully account for the regional Pu deposition from the SNAP-9A event. Copyright © 2017 Elsevier Ltd. All rights reserved.

Preparation of High Density Polyethylene/Waste Polyurethane Blends Compatibilized with Polyethylene-Graft-Maleic Anhydride by Radiation

PubMed Central

Park, Jong-Seok; Lim, Youn-Mook; Nho, Young-Chang

2015-01-01

Polyurethane (PU) is a very popular polymer that is used in a variety of applications due to its good mechanical, thermal, and chemical properties. However, PU recycling has received significant attention due to environmental issues. In this study, we developed a recycling method for waste PU that utilizes the radiation grafting technique. Grafting of waste PU was carried out using a radiation technique with polyethylene-graft-maleic anhydride (PE-g-MA). The PE-g-MA-grafted PU/high density polyethylene (HDPE) composite was prepared by melt-blending at various concentrations (0–10 phr) of PE-g-MA-grafted PU. The composites were characterized using fourier transform infrared spectroscopy (FT-IR), and their surface morphology and thermal/mechanical properties are reported. For 1 phr PU, the PU could be easily introduced to the HDPE during the melt processing in the blender after the radiation-induced grafting of PU with PE-g-MA. PE-g-MA was easily reacted with PU according to the increasing radiation dose and was located at the interface between the PU and the HDPE during the melt processing in the blender, which improved the interfacial interactions and the mechanical properties of the resultant composites. However, the elongation at break for a PU content >2 phr was drastically decreased. PMID:28788022

AMS of the Minor Plutonium Isotopes

NASA Astrophysics Data System (ADS)

Steier, P.; Hrnecek, E.; Priller, A.; Quinto, F.; Srncik, M.; Wallner, A.; Wallner, G.; Winkler, S.

2013-01-01

VERA, the Vienna Environmental Research Accelerator, is especially equipped for the measurement of actinides, and performs a growing number of measurements on environmental samples. While AMS is not the optimum method for each particular plutonium isotope, the possibility to measure 239Pu, 240Pu, 241Pu, 242Pu and 244Pu on the same AMS sputter target is a great simplification. We have obtained a first result on the global fallout value of 244Pu/239Pu = (5.7 ± 1.0) × 10-5 based on soil samples from Salzburg prefecture, Austria. Furthermore, we suggest using the 242Pu/240Pu ratio as an estimate of the initial 241Pu/239Pu ratio, which allows dating of the time of irradiation based solely on Pu isotopes. We have checked the validity of this estimate using literature data, simulations, and environmental samples from soil from the Salzburg prefecture (Austria), from the shut down Garigliano Nuclear Power Plant (Sessa Aurunca, Italy) and from the Irish Sea near the Sellafield nuclear facility. The maximum deviation of the estimated dates from the expected ages is 6 years, while relative dating of material from the same source seems to be possible with a precision of less than 2 years. Additional information carried by the minor plutonium isotopes may allow further improvements of the precision of the method.

Treatment seeking for problematic pornography use among women.

PubMed

Lewczuk, Karol; Szmyd, Joanna; Skorko, Maciej; Gola, Mateusz

2017-12-01

Background and aims Previous studies examined psychological factors related to treatment seeking for problematic pornography use (PU) among males. In this study, we focused on females who seek treatment for problematic PU and compared them with non-problematic pornography users with regard to variables related to problematic PU. Second, we investigated the relationships between critical constructs related to problematic PU with the path analysis method, emphasizing the predictors for treatment seeking among women. We also compared our results with previous studies on males. Methods A survey study was conducted on 719 Polish-speaking Caucasian females, 14-63 years old, including 39 treatment seekers for problematic PU. Results The positive relationship between the mere amount of PU and treatment seeking loses its significance after introducing two other predictors of treatment-seeking: religiosity and negative symptoms associated with PU. This pattern is different from the results obtained in previous studies on males. Discussion Different from previous studies on male samples, our analysis showed that in the case of women, mere amount of PU may be related to treatment-seeking behavior even after accounting for negative symptoms associated with PU. Moreover, religiousness is a significant predictor of treatment seeking among women, which may indicate that in the case of women, treatment seeking for problematic PU is motivated not only by experienced negative symptoms of PU but also by personal beliefs about PU and social norms. Conclusion For females, negative symptoms associated with PU, the amount of PU and religiosity is associated with treatment seeking. Those factors should be considered in treatment.

Silver-nanoparticle-coated biliary stent inhibits bacterial adhesion in bacterial cholangitis in swine.

PubMed

Wen, Wei; Ma, Li-Mei; He, Wei; Tang, Xiao-Wei; Zhang, Yin; Wang, Xiang; Liu, Li; Fan, Zhi-Ning

2016-02-01

One of the major limitations of biliary stents is the stent occlusion, which is closely related to the over-growth of bacteria. This study aimed to evaluate the feasibility of a novel silver-nanoparticle-coated polyurethane (Ag/PU) stent in bacterial cholangitis model in swine. Ag/PU was designed by coating silver nanoparticles on polyurethane (PU) stent. Twenty-four healthy pigs with bacterial cholangitis using Ag/PU and PU stents were randomly divided into an Ag/PU stent group (n=12) and a PU stent group (n=12), respectively. The stents were inserted by standard endoscopic retrograde cholangiopancreatography. Laboratory assay was performed for white blood cell (WBC) count, alanine aminotransferase (ALT), interleukin-1beta (IL-1beta), tumor necrosis factor-alpha (TNF-alpha) at baseline time, 8 hours, 1, 2, 3, and 7 days after stent placements. The segment of bile duct containing the stent was examined histologically ex vivo. Implanted biliary stents were examined by a scan electron microscope. The amount of silver release was also measured in vitro. The number of inflammatory cells and level of ALT, IL-1beta and TNF-alpha were significantly lower in the Ag/PU stent group than in the PU stent group. Hyperplasia of the mucosa was more severe in the PU stent group than in the Ag/PU stent group. In contrast to the biofilm of bacteria on the PU stent, fewer bacteria adhered to the Ag/PU stent. PU biliary stents modified with silver nanoparticles are able to alleviate the inflammation of pigs with bacterial cholangitis. Silver-nanoparticle-coated stents are resistant to bacterial adhesion.

Siderophore production and facilitated uptake of iron plutonium in p. putida.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Boukhalfa, H.; Lack, J. G.; Reilly, S. D.

2003-01-01

Bioremediation is a very attractive alternative for restoration of contaminated soil and ground water . This is particularly true for radionuclide contamination, which tends to be low in concentration and distributed over large surface areas . Microorganisms, through their natural metabolism, produce a large variety of organic molecules of different size and functionality . These molecules interact with contaminants present in the microbe's environment . Through these interactions bio-molecules can solubilize, oxidize, reduce or precipitate major metal contaminant in soils and ground water . We are studying these interaction for actinides and common soil subsurface bacteria . One focus hasmore » been on siderophores, small molecules that have great affinity for hard metal ions, and their potential to affect the distribution and mobility of actinide contaminants . The metal siderophores assembly can be recognized and taken up by micro-organisms through their interference with their iron uptake system . The first step in the active iron transport consists of Fe(III)-siderophore recognition by membrane receptors, which requires specific stereo orientation of the Fe(III)-siderophore complex . Recent investigations have shown that siderophores can form strong complexes with a large variety of toxic metals and may mediate their introduction inside the cell . We have previously shown that a Puhydroxamate siderophore assembly is recognized and taken up by the Microbacterium flavescens (JG-9). However, it is not clear if Pu-siderophore assemblies of other siderophores are also recognized.« less

Analytical Capability of Plasma Spectrometry Team

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gallimore, David L.

2012-07-19

Samples analyzed were: (1) Pu and U metal; (2) Pu oxide for nuclear fuel; (3) {sup 238}Pu oxide for heat source; and (4) Nuclear forensic samples - filters, swipes. Sample preparations that we did were: metal dissolution, marple filter dissolution, Pu oxide closed vessel acid digestion, and column separation to remove Pu.

Uranium (III)-Plutonium (III) co-precipitation in molten chloride

NASA Astrophysics Data System (ADS)

Vigier, Jean-François; Laplace, Annabelle; Renard, Catherine; Miguirditchian, Manuel; Abraham, Francis

2018-02-01

Co-management of the actinides in an integrated closed fuel cycle by a pyrochemical process is studied at the laboratory scale in France in the CEA-ATALANTE facility. In this context the co-precipitation of U(III) and Pu(III) by wet argon sparging in LiCl-CaCl2 (30-70 mol%) molten salt at 705 °C is studied. Pu(III) is prepared in situ in the molten salt by carbochlorination of PuO2 and U(III) is then introduced as UCl3 after chlorine purge by argon to avoid any oxidation of uranium up to U(VI) by Cl2. The oxide conversion yield through wet argon sparging is quantitative. However, the preferential oxidation of U(III) in comparison to Pu(III) is responsible for a successive conversion of the two actinides, giving a mixture of UO2 and PuO2 oxides. Surprisingly, the conversion of sole Pu(III) in the same conditions leads to a mixture of PuO2 and PuOCl, characteristic of a partial oxidation of Pu(III) to Pu(IV). This is in contrast with coconversion of U(III)-Pu(III) mixtures but in agreement with the conversion of Ce(III).

Ski can negatively regulates macrophage differentiation through its interaction with PU.1

PubMed Central

Ueki, N; Zhang, L; Haymann, MJ

2010-01-01

In the hematopoietic cell system, the oncoprotein Ski dramatically affects growth and differentiation programs, in some cases leading to malignant leukemia. However, little is known about the interaction partners or signaling pathways involved in the Ski-mediated block of differentiation in hematopoietic cells. Here we show that Ski interacts with PU.1, a lineage-specific transcription factor essential for terminal myeloid differentiation, and thereby represses PU.1-dependent transcriptional activation. Consistent with this, Ski inhibits the biological function of PU.1 to promote myeloid cells to differentiate into macrophage colony-stimulating factor receptor (M-CSFR)-positive macrophages. Using a Ski mutant deficient in PU.1 binding, we demonstrate that Ski–PU.1 interaction is critical for Ski's ability to repress PU.1-dependent transcription and block macrophage differentiation. Furthermore, we provide evidence that Ski-mediated repression of PU.1 is due to Ski's ability to recruit histone deacetylase 3 to PU.1 bound to DNA. Since inactivation of PU.1 is closely related to the development of myeloid leukemia and Ski strongly inhibits PU.1 function, we propose that aberrant Ski expression in certain types of myeloid cell lineages might contribute to leukemogenesis. PMID:17621263

Isotopic composition and distribution of plutonium in northern South China Sea sediments revealed continuous release and transport of Pu from the Marshall Islands.

PubMed

Wu, Junwen; Zheng, Jian; Dai, Minhan; Huh, Chih-An; Chen, Weifang; Tagami, Keiko; Uchida, Shigeo

2014-03-18

The (239+240)Pu activities and (240)Pu/(239)Pu atom ratios in sediments of the northern South China Sea and its adjacent Pearl River Estuary were determined to examine the spatial and temporal variations of Pu inputs. We clarified that Pu in the study area is sourced from a combination of global fallout and close-in fallout from the Pacific Proving Grounds in the Marshall Islands where above-ground nuclear weapons testing was carried out during the period of 1952-1958. The latter source dominated the Pu input in the 1950s, as evidenced by elevated (240)Pu/(239)Pu atom ratios (>0.30) in a dated sediment core. Even after the 1950s, the Pacific Proving Grounds was still a dominant Pu source due to continuous transport of remobilized Pu from the Marshall Islands, about 4500 km away, along the North Equatorial Current followed by the transport of the Kuroshio current and its extension into the South China Sea through the Luzon Strait. Using a simple two end-member mixing model, we have quantified the contributions of Pu from the Pacific Proving Grounds to the northern South China Sea shelf and the Pearl River Estuary are 68% ± 1% and 30% ± 5%, respectively. This study also confirmed that there were no clear signals of Pu from the Fukushima Daiichi Nuclear Power Plant accident impacting the South China Sea.

ICE1 of Pyrus ussuriensis functions in cold tolerance by enhancing PuDREBa transcriptional levels through interacting with PuHHP1

NASA Astrophysics Data System (ADS)

Huang, Xiaosan; Li, Kongqing; Jin, Cong; Zhang, Shaoling

2015-12-01

ICE1 transcription factor plays an important role in plant cold stress via regulating the expression of stress-responsive genes. In this study, a PuICE1 gene isolated from Pyrus ussuriensis was characterized for its function in cold tolerance. The expression levels of the PuICE1 were induced by cold, dehydration and salt, with the greatest induction under cold conditions. PuICE1 was localized in the nucleus and could bind specifically to the MYC element in the PuDREBa promoter. The PuICE1 fused to the GAL4 DNA-binding domain to have transcriptional activation activity. Ectopic expression of the PuICE1 in tomato conferred enhanced tolerance to cold stress at cold temperatures, less electrolyte leakage, less MDA content, higher chlorophyll content, higher survival rate, higher proline content, higher activities of enzymes. In additon, steady-state mRNA levels of six stress-responsive genes coding for either functional or regulatory genes were induced to higher levels in the transgenic lines by cold stress. Yeast two-hybrid, transient assay, split luciferase complementation and BiFC assays all revealed that PuHHP1 protein can physically interact with PuICE1. Taken together, these results demonstrated that PuICE1 plays a positive role in cold tolerance, which may be due to enhancement of PuDREBa transcriptional levels through interacting with the PuHHP1.

Photoluminescence studies on the complexation of Eu(III) and Tb(III) with acetohydroxamic acid (AHA) in nitrate medium

NASA Astrophysics Data System (ADS)

Pathak, P. N.; Mohapatra, M.; Godbole, S. V.

2013-11-01

UREX process has been proposed for selective extraction of U(VI) and Tc(VII) from nitric acid medium (∼1 M HNO3) using tri-n-butyl phosphate (TBP) as extractant and retaining Pu, Np and fission products in the aqueous phase. The feasibility of the use of luminescence spectroscopy as a technique to understand the complexation of trivalent f-elements cations viz. Eu(III) and Tb(III) with acetohydroxamic acid (AHA) in nitric acid medium has been examined. The luminescence lifetimes for the 1 × 10-3 M Eu(III) and AHA complex system decreased with increased AHA concentration from 116 ± 0.2 μs (no AHA) to 1.6 ± 0.1 μs (0.1 M AHA) which was attributed to dynamic quenching. The corrected fluorescence intensities were used to calculate the stability constant (log K) for the formation of 1:1 Eu3+-AHA complex as 1.42 ± 0.64 under the conditions of this study. By contrast, the Tb(III)-AHA system at pH 3 (HNO3) did not show any significant variation in the life times of the excited state (364 ± 9 μs) suggesting the absence of dynamic quenching. The spectral changes in Tb(III)-AHA system showed the formation of 1:1 complex (log K: 1.72 ± 0.21). These studies suggest that the extent of AHA complexation with the rare earth elements will be insignificant as compared to tetravalent metal ions Pu(IV) and Np(IV) under UREX process conditions.

Sources and transport of anthropogenic radionuclides in the Ob River system, Siberia

NASA Astrophysics Data System (ADS)

Cochran, J. Kirk; Moran, S. Bradley; Fisher, Nicholas S.; Beasley, Thomas M.; Kelley, James M.

2000-06-01

The potential sources of anthropogenic radionuclides to the Ob River system of western Siberia include global stratospheric fallout, tropospheric fallout from atomic weapons tests and releases from production and reprocessing facilities. Samples of water, suspended and bottom sediments collected in 1994 and 1995 have been used to characterize the sources and transport of 137Cs, Pu isotopes, 237Np and 129I through the system. For the radionuclides that associate with particles, isotope ratios provide clues to their sources, providing any geochemical fractionation can be taken into account. Activity ratios of 239,240Pu/ 137Cs in suspended sediments are lower than the global fallout ratio in the Irtysh River before its confluence with the Ob, comparable to fallout in the central reach of the Ob, and greater than the fallout values in the lower Ob and in the Taz River. This pattern mirrors the downriver decrease in dissolved organic carbon (DOC) concentrations. Laboratory adsorption experiments with Ob River sediment and water show that Kd values for Am (and presumably other actinides) are depressed by two orders of magnitude in the presence of Ob DOC concentrations, relative to values measured in DOC-free Ob water. Iodine and cesium Kd values show little or no (less than a factor of 2) dependence on DOC. Mixing plots using plutonium isotope ratios (atom ratios) show that Pu in suspended sediments of the Ob is a mixture of stratospheric global fallout at northern latitudes, tropospheric fallout from the former Soviet Union test site at Semipalatinsk and reprocessing of spent fuel at Tomsk-7. Plutonium from Semipalatinsk is evident in the Irtysh River above its confluence with the Tobal. Suspended sediment samples taken in the Ob above its confluence with the Irtysh indicate the presence of Pu derived from the Tomsk-7 reprocessing facilities. A mixing plot constructed using 237Np/ 239Pu vs. 240Pu/ 239Pu shows similar mixtures of stratospheric and tropospheric fallout, with the likely addition of inputs from reprocessing facilities and reactor operations. As with Pu/Cs ratios, Np/Pu ratios could be modified by differential geochemical behaviors of Np and Pu. Dissolved 129I only weakly interacts with particles in the Ob; size-fractionated sampling shows that the colloidal 129I fraction (defined as 1 kDa-0.2 μm) contains generally <5% relative to that passing a 0.2 μm filter. Iodine-129 concentrations decrease from 8.3×10 9 to 0.65×10 9 atoms l -1 through the Ob system toward the Kara Sea, with highest values in the Tobal River and lowest in the Taz River. The likely source of the elevated 129I in the Tobal is release from the production-reprocessing facilities at Mayak, and decreases downriver are predominantly due to dilution as the various tributaries with low 129I join the system. Fluxes of 129I to the lower Ob at Salekhard are <1% of the releases of this radionuclide from the nuclear fuel reprocessing facilities at Sellafield, UK and La Hague, France.

Dynamics and transformations of radionuclides in soils and ecosystem health

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fellows, Robert J.; Ainsworth, Calvin C.; Driver, Crystal J.

1998-12-01

The chemical behavior of radionuclides can vary widely in soil and sediment environments. Equally important, for a given radionuclide the physico-chemical properties of the solids and aqueous phase can greatly influence a radionuclides behavior. Radionuclides can conceivably occur in soils as soluble-free, inorganic-soluble-complexed, organic-soluble, complexed, adsorbed, precipitated, coprecipitated, or solid structural species. While it is clear that an assessment of a radionuclide?s soil chemistry and potential shifts in speciation will yield a considerable understanding of its behavior in the natural environment, it does not directly translate to bioavailability or its impact on ecosystems health. The soil chemical factors have tomore » be linked to food chain considerations and other ecological parameters that directly tie to an analysis of ecosystem health. In general, the movement of radionuclides from lower to higher trophic levels diminishes with each trophic level in both aqua tic and terrestrial systems. In some cases, transfer is limited because of low absorption/assimilation by successive trophic organisms (Pu, U); for other radionuclides (Tc, H) assimilation may be high but rapid metabolic turnover and low retention greatly reduce tissue concentrations available to predator species. Still others are chemical analogs of essential elements whose concentrations are maintained under strict metabolic control in tissues (Cs) or are stored in tissues seldom consumed by other organisms (Sr storage in exoskeleton, shells, and bone). Therefore, the organisms that receive the greatest ingestion exposures are those in lower trophic positions or are in higher trophic levels but within simple, short food chains. Food source, behavior, and habitat influence the accumulation of radionuclides in animals.« less

Effect of biostimulation and bioaugmentation on degradation of polyurethane buried in soil.

PubMed

Cosgrove, L; McGeechan, P L; Handley, P S; Robson, G D

2010-02-01

This work investigated biostimulation and bioaugmentation as strategies for removing polyurethane (PU) waste in soil. Soil microcosms were biostimulated with the PU dispersion agent "Impranil" and/or yeast extract or were bioaugmented with PU-degrading fungi, and the degradation of subsequently buried PU was determined. Fungal communities in the soil and colonizing buried PU were enumerated on solid media and were analyzed using denaturing gradient gel electrophoresis (DGGE). Biostimulation with yeast extract alone or in conjunction with Impranil increased PU degradation 62% compared to the degradation in untreated control soil and was associated with a 45% increase in putative PU degraders colonizing PU. Specific fungi were enriched in soil following biostimulation; however, few of these fungi colonized the surface of buried PU. Fungi used for soil bioaugmentation were cultivated on the surface of sterile wheat to form a mycelium-rich inoculum. Wheat, when added alone to soil, increased PU degradation by 28%, suggesting that wheat biomass had a biostimulating effect. Addition of wheat colonized with Nectria haematococca, Penicillium viridicatum, Penicillium ochrochloron, or an unidentified Mucormycotina sp. increased PU degradation a further 30 to 70%, suggesting that biostimulation and bioaugmentation were operating in concert to enhance PU degradation. Interestingly, few of the inoculated fungi could be detected by DGGE in the soil or on the surface of the PU 4 weeks after inoculation. Bioaugmentation did, however, increase the numbers of indigenous PU-degrading fungi and caused an inoculum-dependent change in the composition of the native fungal populations, which may explain the increased degradation observed. These results demonstrate that both biostimulation and bioaugmentation may be viable tools for the remediation of environments contaminated with polyurethane waste.

Carbazole ligands as c-myc G-quadruplex binders.

PubMed

Głuszyńska, Agata; Juskowiak, Bernard; Kuta-Siejkowska, Martyna; Hoffmann, Marcin; Haider, Shozeb

2018-07-15

The interactions of c-myc G-quadruplex with three carbazole derivatives were investigated by UV-Vis spectrophotometry, fluorescence, CD spectroscopy, and molecular modeling. The results showed that a combination of carbazole scaffold functionalized with ethyl, triazole and imidazole groups resulted in stabilization of the intramolecular G-quadruplex formed by the DNA sequence derived from the NHE III 1 region of c-myc oncogene (Pu22). Binding to the G-quadruplex Pu22 resulted in the significant increase in fluorescence intensity of complexed ligands 1-3. All ligands were capable of interacting with G4 DNA with binding stoichiometry indicating that two ligand molecules bind to G-quadruplex with comparable affinity, which agrees with binding model of end-stacking on terminal G-tetrads. Copyright © 2018 Elsevier B.V. All rights reserved.

Infrasonic tremor observed at Kilauea Volcano, Hawaii'i

USGS Publications Warehouse

Garces, M.; Harris, A.; Hetzer, C.; Johnson, J.; Rowland, S.; Marchetti, E.; Okubo, P.

2003-01-01

Infrasonic array data collected at Ki??lauea Volcano, Hawai'i, during November 12-21, 2002 indicate that the active vents and lava tube system near the P'u 'O??'o?? vent complex emit almost continuous infrasound in the 0.310 Hz frequency band. The spectral content of these infrasonic signals matches well that of synchronous seismic tremor. In sites protected from wind noise, significant signal to noise ratios were recorded as far as ???13 km from the crater of Pu'u 'O??'o??. The infrasonic recordings suggest that one or more tremor sources may be close to the surface. In addition, these results demonstrate that adequate site and instrument selections for infrasonic arrays are essential in order to obtain consistent and reliable infrasonic detections. ?? 2003 by the American Geophysical Union.

Phase Diagram and Electronic Structure of Praseodymium and Plutonium

DOE PAGES

Lanatà, Nicola; Yao, Yongxin; Wang, Cai-Zhuang; ...

2015-01-29

We develop a new implementation of the Gutzwiller approximation in combination with the local density approximation, which enables us to study complex 4f and 5f systems beyond the reach of previous approaches. We calculate from first principles the zero-temperature phase diagram and electronic structure of Pr and Pu, finding good agreement with the experiments. Our study of Pr indicates that its pressure-induced volume-collapse transition would not occur without change of lattice structure—contrarily to Ce. Our study of Pu shows that the most important effect originating the differentiation between the equilibrium densities of its allotropes is the competition between the Peierlsmore » effect and the Madelung interaction and not the dependence of the electron correlations on the lattice structure.« less

A thermodynamic approach for advanced fuels of gas-cooled reactors

NASA Astrophysics Data System (ADS)

Guéneau, C.; Chatain, S.; Gossé, S.; Rado, C.; Rapaud, O.; Lechelle, J.; Dumas, J. C.; Chatillon, C.

2005-09-01

For both high temperature reactor (HTR) and gas cooled fast reactor (GFR) systems, the high operating temperature in normal and accidental conditions necessitates the assessment of the thermodynamic data and associated phase diagrams for the complex system constituted of the fuel kernel, the inert materials and the fission products. A classical CALPHAD approach, coupling experiments and thermodynamic calculations, is proposed. Some examples of studies are presented leading with the CO and CO 2 gas formation during the chemical interaction of [UO 2± x/C] in the HTR particle, and the chemical compatibility of the couples [UN/SiC], [(U, Pu)N/SiC], [(U, Pu)N/TiN] for the GFR system. A project of constitution of a thermodynamic database for advanced fuels of gas-cooled reactors is proposed.

Induced fission of Pu 240 within a real-time microscopic framework

DOE PAGES

Bulgac, Aurel; Magierski, Piotr; Roche, Kenneth J.; ...

2016-03-25

Here, we describe the fissioning dynamics of 240Pu from a configuration in the proximity of the outer fission barrier to full scission and the formation of the fragments within an implementation of density functional theory extended to superfluid systems and real-time dynamics. The fission fragments emerge with properties similar to those determined experimentally, while the fission dynamics appears to be quite complex, with many excited shape and pairing modes. The evolution is found to be much slower than previously expected, and the ultimate role of the collective inertia is found to be negligible in this fully nonadiabatic treatment of nuclearmore » dynamics, where all collective degrees of freedom (CDOF) are included (unlike adiabatic treatments with a small number of CDOF).« less

Pu isotopes in the western North Pacific Ocean before the accident at Fukushima Dai-ichi Nuclear Power Station

NASA Astrophysics Data System (ADS)

Yamada, M.; Zheng, J.; Aono, T.

2011-12-01

Anthropogenic radionuclides such as Pu-239 (half-life: 24100 yr), Pu-240 (half-life: 6560 yr) and Pu-241 (half-life: 14.325 yr) mainly have been released into the environment as the result of atmospheric nuclear weapons testing. In the North Pacific Ocean, two distinct sources of Pu isotopes can be identified; i.e., the global stratospheric fallout and close-in tropospheric fallout from nuclear weapons testing at the Pacific Proving Grounds in the Marshall Islands. The atom ratio of Pu-240/Pu-239 is a powerful fingerprint to identify the sources of Pu in the ocean. The Pu-240/Pu-239 atom ratios in seawater and marine sediment samples collected in the western North Pacific before the accident at Fukushima Dai-ichi Nuclear Power Station will provide useful background data for understanding the process controlling Pu transport and for distinguishing future Pu sources. The atom ratios of Pu-240/Pu-239 in water columns from the Yamato and Tsushima Basins in the Japan Sea were significantly higher than the mean global fallout ratio of 0.18; however, there were no temporal variation of atom ratios during the period from 1984 to 1993 in the Japan Sea. The total Pu-239+240 inventories in the whole water columns were approximately doubled during the period from 1984 to 1993 in the two basins. The atom ratio of Pu-240/Pu-239 in surface water from Sagami Bay, western North Pacific Ocean, was 0.224 and showed no notable variation from the surface to the bottom with the mean atom ratio being 0.234. The atom ratios for the Pacific coast, near the Rokkasho nuclear fuel reprocessing plant, were approximately the same as the 0.224 ratio obtained from Sagami Bay, western North Pacific margin. The atom ratios in the surficial sediments from Sagami Bay ranged from 0.229 to 0.247. The mean atom ratio in the sediment columns in the East China Sea ranged from 0.248 for the Changjiang estuary to 0.268 for the shelf edge. The observed atom ratios were significantly higher than the mean global fallout ratio of 0.180, proving the existence of close-in fallout Pu originating from the Pacific Proving Grounds. The North Equatorial Current and Kuroshio Current were proposed as pathways for transporting Pacific Proving Grounds-origin Pu to the western North Pacific Ocean.

Determination of ultra-low level plutonium isotopes (239Pu, 240Pu) in environmental samples with high uranium.

PubMed

Xing, Shan; Zhang, Weichao; Qiao, Jixin; Hou, Xiaolin

2018-09-01

In order to measure trace plutonium and its isotopes ratio ( 240 Pu/ 239 Pu) in environmental samples with a high uranium, an analytical method was developed using radiochemical separation for separation of plutonium from matrix and interfering elements including most of uranium and ICP-MS for measurement of plutonium isotopes. A novel measurement method was established for extensively removing the isobaric interference from uranium ( 238 U 1 H and 238 UH 2 + ) and tailing of 238 U, but significantly improving the measurement sensitivity of plutonium isotopes by employing NH 3 /He as collision/reaction cell gases and MS/MS system in the triple quadrupole ICP-MS instrument. The results show that removal efficiency of uranium interference was improved by more than 15 times, and the sensitivity of plutonium isotopes was increased by a factor of more than 3 compared to the conventional ICP-MS. The mechanism on the effective suppress of 238 U interference for 239 Pu measurement using NH 3 -He reaction gases was explored to be the formation of UNH + and UNH 2 + in the reactions of UH + and U + with NH 3 , while no reaction between NH 3 and Pu + . The detection limits of this method were estimated to be 0.55 fg mL -1 for 239 Pu, 0.09 fg mL -1 for 240 Pu. The analytical precision and accuracy of the method for Pu isotopes concentration and 240 Pu/ 239 Pu atomic ratio were evaluated by analysis of sediment reference materials (IAEA-385 and IAEA-412) with different levels of plutonium and uranium. The developed method were successfully applied to determine 239 Pu and 240 Pu concentrations and 240 Pu/ 239 Pu atomic ratios in soil samples collected in coastal areas of eastern China. Copyright © 2018 Elsevier B.V. All rights reserved.

Hydrothermal Alteration of Glass from Underground Nuclear Tests: Formation and Transport of Pu-clay Colloids at the Nevada National Security Site

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zavarin, M.; Zhao, P.; Joseph, C.

2015-05-27

The testing of nuclear weapons at the Nevada National Security Site (NNSS), formerly the Nevada Test Site (NTS), has led to the deposition of substantial quantities of plutonium into the environment. Approximately 2.8 metric tons (3.1×10 4 TBq) of Pu were deposited in the NNSS subsurface as a result of underground nuclear testing. While 3H is the most abundant anthropogenic radionuclide deposited in the NNSS subsurface (4.7×10 6 TBq), plutonium is the most abundant from a molar standpoint. The only radioactive elements in greater molar abundance are the naturally occurring K, Th, and U isotopes. 239Pu and 240Pu represent themore » majority of alpha-emitting Pu isotopes. The extreme temperatures associated with underground nuclear tests and the refractory nature of Pu results in most of the Pu (98%) being sequestered in melted rock, referred to as nuclear melt glass (Iaea, 1998). As a result, Pu release to groundwater is controlled, in large part, by the leaching (or dissolution) of nuclear melt glass over time. The factors affecting glass dissolution rates have been studied extensively. The dissolution of Pu-containing borosilicate nuclear waste glasses at 90ºC has been shown to lead to the formation of dioctahedral smectite colloids. Colloid-facilitated transport of Pu at the NNSS has been observed. Recent groundwater samples collected from a number of contaminated wells have yielded a wide range of Pu concentrations from 0.00022 to 2.0 Bq/L. While Pu concentrations tend to fall below the Maximum Contaminant Level (MCL) established by the Environmental Protection Agency (EPA) for drinking water (0.56 Bq/L), we do not yet understand what factors limit the Pu concentration or its transport behavior. To quantify the upper limit of Pu concentrations produced as a result of melt glass dissolution and determine the nature of colloids and Pu associations, we performed a 3 year nuclear melt glass dissolution experiment across a range of temperatures (25-200 °C) that represent hydrothermal conditions representative of the underground nuclear test cavities (when groundwater has re-saturated the nuclear melt glass and glass dissolution occurs). Colloid loads and Pu concentrations were monitored along with the mineralogy of both the colloids and the secondary mineral phases. The intent was to establish an upper limit for Pu concentrations at the NNSS, provide context regarding the Pu concentrations observed at the NNSS to date and the Pu concentrations that may be observed in the future. The results provide a conceptual model for the risks posed by Pu migration at the NNSS.« less

Airborne Plutonium and non-natural Uranium from the Fukushima DNPP found at 120 km distance a few days after reactor hydrogen explosions.

PubMed

Shinonaga, Taeko; Steier, Peter; Lagos, Markus; Ohkura, Takehisa

2014-04-01

Plutonium (Pu) and non-natural uranium (U) originating from the Fukushima Daiichi Nuclear Power Plant (FDNPP) were identified in the atmosphere at 120 km distance from the FDNPP analyzing the ratio of number of atoms, following written as n(isotope)/n(isotope), of Pu and U. The n((240)Pu)/n((239)Pu), n((241)Pu)/n((239)Pu), n((234)U)/n((238)U), n((235)U)/n((238)U) and n((236)U)/n((238)U) in aerosol samples collected before and after the FDNPP incident were analyzed by accelerator mass spectrometry (AMS) and inductively coupled plasma mass spectrometry (ICPMS). The activity concentrations of (137)Cs and (134)Cs in the same samples were also analyzed by gamma spectrometry before the destructive analysis. Comparing the time series of analytical data on Pu and U obtained in this study with previously reported data on Pu, U, and radioactive Cs, we concluded that Pu and non-natural U from the FDNPP were transported in the atmosphere directly over a 120 km distance by aerosol and wind within a few days after the reactor hydrogen explosions. Effective dose of Pu were calculated using the data of Pu: (130 ± 21) nBq/m(3), obtained in this study. We found that the airborne Pu contributes only negligibly to the total dose at the time of the incident. However the analytical results show that the amount of Pu and non-natural U certainly increased in the environment after the incident.

Data Evaluation of Actinide Cross Sections: 238Pu, 237Pu, and 236Pu

DOE Office of Scientific and Technical Information (OSTI.GOV)

Guaglioni, S.; Jurgenson, E.; Descalle, M. A.

This report documents the recent evaluation of the 236Pu, 237Pu, and 238Pu cross section sets. Nuclear data evaluation is the fundamental interface that takes measured nuclear cross section data and turns them into a continuous curve that 1) is consistent with other measurements and nuclear reaction theory/models, and 2) is required by down-stream users. All experiments that generate nuclear data need to include an evaluation step for their data to be broadly useful to the end users.

Antibiofilm properties of silver and gold incorporated PU, PCLm, PC and PMMA nanocomposites under two shear conditions.

PubMed

Sawant, Shilpa N; Selvaraj, Veerapandian; Prabhawathi, Veluchamy; Doble, Mukesh

2013-01-01

Silver and gold nanoparticles (of average size ∼20-27 nm) were incorporated in PU (Polyurethane), PCLm (Polycaprolactam), PC (polycarbonate) and PMMA (Polymethylmethaacrylate) by swelling and casting methods under ambient conditions. In the latter method the nanoparticle would be present not only on the surface, but also inside the polymer. These nanoparticles were prepared initially by using a cosolvent, THF. PU and PCLm were dissolved and swollen with THF. PC and PMMA were dissolved in CHCl₃ and here the cosolvent, THF, acted as an intermediate between water and CHCl₃. FTIR indicated that the interaction between the polymer and the nanoparticle was through the functional group in the polymer. The formation of E.coli biofilm on these nanocomposites under low (in a Drip flow biofilm reactor) and high shear (in a Shaker) conditions indicated that the biofilm growth was higher (twice) in the former than in the latter (ratio of shear force = 15). A positive correlation between the contact angle (of the virgin surface) and the number of colonies, carbohydrate and protein attached on it were observed. Ag nanocomposites exhibited better antibiofilm properties than Au. Bacterial attachment was highest on PC and least on PU nanocomposite. Casting method appeared to be better than swelling method in reducing the attachment (by a factor of 2). Composites reduced growth of organisms by six orders of magnitude, and protein and carbohydrate by 2-5 times. This study indicates that these nanocomposites may be suitable for implant applications.

Pu isotopes in soils collected downwind from Lop Nor: regional fallout vs. global fallout.

PubMed

Bu, Wenting; Ni, Youyi; Guo, Qiuju; Zheng, Jian; Uchida, Shigeo

2015-07-17

For the first time, soil core samples from the Jiuquan region have been analyzed for Pu isotopes for radioactive source identification and radiological assessment. The Jiuquan region is in downwind from the Lop Nor Chinese nuclear test (CNT) site. The high Pu inventories (13 to 546 Bq/m(2)) in most of the sampling locations revealed that this region was heterogeneously contaminated by the regional fallout Pu from the CNTs. The contributions of the CNTs to the total Pu in soils were estimated to be more than 40% in most cases. The (240)Pu/(239)Pu atom ratios in the soils ranged from 0.059 to 0.186 with an inventory-weighted average of 0.158, slightly lower than that of global fallout. This atom ratio could be considered as a mixed fingerprint of Pu from the CNTs. In addition, Pu in soils of Jiuquan region had a faster downward migration rate compared with other investigated places in China.

Pu isotopes in soils collected downwind from Lop Nor: regional fallout vs. global fallout

PubMed Central

Bu, Wenting; Ni, Youyi; Guo, Qiuju; Zheng, Jian; Uchida, Shigeo

2015-01-01

For the first time, soil core samples from the Jiuquan region have been analyzed for Pu isotopes for radioactive source identification and radiological assessment. The Jiuquan region is in downwind from the Lop Nor Chinese nuclear test (CNT) site. The high Pu inventories (13 to 546 Bq/m2) in most of the sampling locations revealed that this region was heterogeneously contaminated by the regional fallout Pu from the CNTs. The contributions of the CNTs to the total Pu in soils were estimated to be more than 40% in most cases. The 240Pu/239Pu atom ratios in the soils ranged from 0.059 to 0.186 with an inventory-weighted average of 0.158, slightly lower than that of global fallout. This atom ratio could be considered as a mixed fingerprint of Pu from the CNTs. In addition, Pu in soils of Jiuquan region had a faster downward migration rate compared with other investigated places in China. PMID:26184740

Sources and accumulation of plutonium in a large Western Pacific marginal sea: The South China Sea.

PubMed

Wu, Junwen; Dai, Minhan; Xu, Yi; Zheng, Jian

2018-01-01

In order to examine the sources of plutonium (Pu) and elaborate its scavenging and accumulation processes, 240 Pu/ 239 Pu atom ratios and 239+240 Pu activities in the water column of the South China Sea (SCS) were determined and compared with our previously reported data for the sediments. Consistently high 240 Pu/ 239 Pu atom ratios that ranged from 0.184-0.250 (average=0.228±0.015), indicative of non-global fallout Pu sources were observed both in the surface water and at depth during 2012-2014. The spatial distribution of the 240 Pu/ 239 Pu atom ratio in the SCS showed a decreasing trend away from the Luzon Strait, which was very consistent with the introduction pathway of the Kuroshio Current. The Kuroshio had an even heavier Pu isotopic ratio ranging from 0.250-0.263 (average=0.255±0.006), traceable to the non-global fallout Pu signature from the Pacific Proving Grounds (PPG). Using a simple two end-member mixing model, we further revealed that this PPG source contributed 41±17% of the Pu in the SCS water column. The 239+240 Pu activities in the SCS surface seawater varied from 1.59 to 2.94mBqm -3 , with an average of 2.34±0.38mBqm -3 . Such an activity level was ~40% higher than that in the Kuroshio. The distribution of 239+240 Pu in the surface seawater further showed a general trend of increase from the Kuroshio to the SCS basin, suggesting significant accumulation of Pu within the SCS. The 239+240 Pu inventory of the water column in the SCS basin at the SEATS station with a total depth of ~3840m was estimated to be ~29Bqm -2 , which was substantially higher than the sediment core estimates made for the SCS basin (3.75Bqm -2 ) but much lower than the sediment core estimates made for the shelf of the northern SCS (365.6Bqm -2 ). Such differences were determined by the lower scavenging efficiency of Pu in the SCS basin compared to the northern SCS shelf. Copyright © 2017 Elsevier B.V. All rights reserved.

Plutonium activities and 240Pu/ 239Pu atom ratios in sediment cores from the east China sea and Okinawa Trough: Sources and inventories

NASA Astrophysics Data System (ADS)

Wang, Zhong-liang; Yamada, Masatoshi

2005-05-01

Plutonium concentrations and 240Pu/ 239Pu atom ratios in the East China Sea and Okinawa Trough sediment cores were determined by isotope dilution inductively coupled plasma mass spectrometry after separation using ion-exchange chromatography. The results showed that 240Pu/ 239Pu atom ratios in the East China Sea and Okinawa Trough sediments, ranging from 0.21 to 0.33, were much higher than the reported value of global fallout (0.18). The highest 240Pu/ 239Pu ratios (0.32-0.33) were observed in the deepest Okinawa Trough sediment samples. These ratios suggested the US nuclear weapons tests in the early 1950s at the Pacific Proving Grounds in the Marshall Islands were a major source of plutonium in the East China Sea and Okinawa Trough sediments, in addition to the global fallout source. It was proposed that close-in fallout plutonium was delivered from the Pacific Proving Grounds test sites via early direct tropospheric fallout and transportation by the North Pacific Equatorial Circulation system and Kuroshio Current into the Okinawa Trough and East China Sea. The total 239 + 240 Pu inventories in the cores were about 150-200% of that expected from direct global fallout; about 46-67% of the total inventories were delivered from the Pacific Proving Grounds. Much higher 239 + 240 Pu inventories were observed in the East China Sea sediments than in sediments of the Okinawa Trough, because in the open oceans, part of the 239 + 240 Pu was still retained in the water column, and continued Pu scavenging was higher over the margin than the trough. According to the vertical distributions of 239 + 240 Pu activities and 240Pu/ 239Pu atom ratios in these cores, it was concluded that sediment mixing was the dominant process in controlling profiles of plutonium in this area. Faster mixing in the coastal samples has homogenized the entire 240Pu/ 239Pu ratio record today; slightly slower mixing and less scavenging in the Okinawa Trough have left the surface sediment ratios closer to the modern North Pacific water end member and higher ratios (0.30-0.34) at the bottom of the cores.

FCRD Transmutation Fuels Handbook 2015

DOE Office of Scientific and Technical Information (OSTI.GOV)

Janney, Dawn Elizabeth; Papesch, Cynthia Ann

2015-09-01

Transmutation of minor actinides such as Np, Am, and Cm in spent nuclear fuel is of international interest because of its potential for reducing the long-term health and safety hazards caused by the radioactivity of the spent fuel. One important approach to transmutation (currently being pursued by the DOE Fuel Cycle Research & Development Advanced Fuels Campaign) involves incorporating the minor actinides into U-Pu-Zr alloys, which can be used as fuel in fast reactors. It is, therefore, important to understand the properties of U-Pu-Zr alloys, both with and without minor actinide additions. In addition to requiring extensive safety precautions, alloysmore » containing U and Pu are difficult to study for numerous reasons, including their complex phase transformations, characteristically sluggish phase-transformation kinetics, tendency to produce experimental results that vary depending on the histories of individual samples, and sensitivity to contaminants such as oxygen in concentrations below a hundred parts per million. Many of the experimental measurements were made before 1980, and the level of documentation for experimental methods and results varies widely. It is, therefore, not surprising that little is known with certainty about U-Pu-Zr alloys, and that general acceptance of results sometimes indicates that there is only a single measurement for a particular property. This handbook summarizes currently available information about U, Pu, Zr, and alloys of two or three of these elements. It contains information about phase diagrams and related information (including phases and phase transformations); heat capacity, entropy, and enthalpy; thermal expansion; and thermal conductivity and diffusivity. In addition to presenting information about materials properties, it attempts to provide information about how well the property is known and how much variation exists between measurements. Although the handbook includes some references to publications about modeling, its primary focus is experimental data. Most of the data has been published elsewhere (although scattered throughout numerous references, some quite obscure); however, some data is presented here for the first time.« less

Direct Determination of the Intracellular Oxidation State of Plutonium

PubMed Central

Gorman-Lewis, Drew; Aryal, Baikuntha P.; Paunesku, Tatjana; Vogt, Stefan; Lai, Barry; Woloschak, Gayle E.; Jensen, Mark P.

2013-01-01

Microprobe X-ray absorption near edge structure (μ-XANES) measurements were used to determine directly, for the first time, the oxidation state of intracellular plutonium in individual 0.1 μm2 areas within single rat pheochromocytoma cells (PC12). The living cells were incubated in vitro for 3 hours in the presence of Pu added to the media in different oxidation states (Pu(III), Pu(IV), and Pu(VI)) and in different chemical forms. Regardless of the initial oxidation state or chemical form of Pu presented to the cells, the XANES spectra of the intracellular Pu deposits was always consistent with tetravalent Pu even though the intracellular milieu is generally reducing. PMID:21755934

Plutonium Metallurgy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Freibert, Franz J.

2012-08-09

Due to its nuclear properties, Pu will remain a material of global interest well into the future. Processing, Structure, Properties and Performance remains a good framework for discussion of Pu materials science Self-irradiation and aging effects continue to be central in discussions of Pu metallurgy Pu in its elemental form is extremely unstable, but alloying helps to stabilize Pu; but, questions remain as to how and why this stabilization occurs. Which is true Pu-Ga binary phase diagram: US or Russian? Metallurgical issues such as solute coring, phase instability, crystallographic texture, etc. result in challenges to casting, processing, and properties modelingmore » and experiments. For Ga alloyed FCC stabilized Pu, temperature and pressure remain as variables impacting phase stability.« less

Topological analysis of void space in phosphate frameworks: Assessing storage properties for the environmentally important guest molecules and ions: CO 2, H 2O, UO 2, PuO 2, U, Pu, Sr 2+, Cs +, CH 4, and H 2

DOE PAGES

Cramer, Alisha J.; Cole, Jacqueline M.

2016-06-27

The entrapment of environmentally important materials to enable containment of polluting wastes from industry or energy production, storage of alternative fuels, or water sanitation, is of vital and immediate importance. Many of these materials are small molecules or ions that can be encapsulated via their adsorption into framework structures to create a host-guest complex. This is an ever-growing field of study and, as such, the search for more suitable porous materials for environmental applications is fundamental to progress. However, many industrial areas that require the use of adsorbents are fraught with practical challenges such as high temperatures, rapid gas expansion,more » radioactivity, or repetitive gas cycling, that the host material must withstand. Inorganic phosphates have a proven history of rigid structures, thermal stability, and are suspected to possess good resistance to radiation over geologic time scales. Furthermore, various experimental studies have established their ability to adsorb small molecules, such as water. In light of this, all known crystal structures of phosphate frameworks with meta- (P 3O 9) or ultra- (P 5O 14) stoichiometries are combined in a data-mining survey together with all theoretically possible structures of Ln aP bO c (where a, b, c are any integer, and Ln = La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, or Tm) that are statistically likely to form. Topological patterns within these framework structures are used to assess their suitability for hosting a variety of small guest molecules or ions that are important for environmental applications: CO 2, H 2O, UO 2, PuO 2, U, Pu, Sr 2+, Cs +, CH 4 and H 2. A range of viable phosphate-based host-guest complexes are identified from this data-mining and pattern-based structural analysis. Moreover, distinct topological preferences for hosting such guests are found, and metaphosphate stoichiometries are generally preferred over ultraphosphate configurations.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Burke, J. T.; Alan, B. S.; Akindele, O. A.

The goal of this project was to develop a new approach to measuring (n,2n) reactions for isotopes of interest. We set out to measure the 239Pu(n,2n) and 241Pu(n,2n) cross sections by directly detecting the 2n neutrons that are emitted. With the goal of improving the 239Pu(n,2n) cross section and to measure the 241Pu(n,2n) cross section for the first time. To that end, we have constructed a new neutron-charged-particle detector array called NeutronSTARS. It has been described extensively in Casperson et al. [1] and in Akindele et al. [2]. We have used this new neutron-charged-particle array to measure the 241Pu andmore » 239Pu fission neutron multiplicity as a function of equivalent incident-neutron energy from 100 keV to 20 MeV. We have made a preliminary determination of the 239Pu(n,2n) and 241Pu(n,2n) cross sections from the surrogate 240Pu(α,α’2n) and 242Pu(α,α’2n) reactions respectively. The experimental approach, detector array, data analysis, and results to date are summarized in the following sections.« less

Am phases in the matrix of a U–Pu–Zr alloy with Np, Am, and rare-earth elements

DOE Office of Scientific and Technical Information (OSTI.GOV)

Janney, Dawn E.; Kennedy, J. Rory; Madden, James W.

2015-01-01

Phases and microstructures in the matrix of an as-cast U-Pu-Zr alloy with 3 wt% Am, 2% Np, and 8% rare-earth elements were characterized by scanning and transmission electron microscopy. The matrix consists primarily of two phases, both of which contain Am: ζ-(U, Np, Pu, Am) (~70 at% U, 5% Np, 14% Pu, 1% Am, and 10% Zr) and δ-(U, Np, Pu, Am)Zr 2 (~25% U, 2% Np, 10-15% Pu, 1-2% Am, and 55-60 at% Zr). These phases are similar to those in U-Pu-Zr alloys, although the Zr content in ζ-(U, Np, Pu, Am) is higher than that in ζ-(U, Pu)more » and the Zr content in δ-(U, Np, Pu, Am)Zr 2 is lower than that in δ-UZr 2. Nanocrystalline actinide oxides with structures similar to UO2 occurred in some areas, but may have formed by reactions with the atmosphere during sample handling. Planar features consisting of a central zone of ζ-(U, Np, Pu, Am) bracketed by zones of δ-(U, Np, Pu, Am)Zr 2 bound irregular polygons ranging in size from a few micrometers to a few tens of micrometers across. The rest of the matrix consists of elongated domains of ζ-(U, Np, Pu, Am) and δ-(U, Np, Pu, Am)Zr 2. Each of these domains is a few tens of nanometers across and a few hundred nanometers long. The domains display strong preferred orientations involving areas a few hundred nanometers to a few micrometers across.« less

Use of anthropogenic radioisotopes to estimate rates of soil redistribution by wind II: The potential for future use of 239+240Pu

NASA Astrophysics Data System (ADS)

Van Pelt, R. Scott; Ketterer, Michael E.

2013-06-01

In the previous paper, the use of soilborne 137Cs from atmospheric fallout to estimate rates of soil redistribution, particularly by wind, was reviewed. This method relies on the assumption that the source of 137Cs in the soil profile is from atmospheric fallout following the period of atmospheric weapons testing so that the temporal and, to a certain extent, the spatial patterns of 137Cs deposition are known. One of the major limitations occurs when local or regional sources of 137Cs contamination mask the pulse from global fallout, making temporal estimates of redistribution difficult or impossible. Like 137Cs, Pu exhibits strong affinity for binding to soil particle surfaces, and therefore, re-distribution of Pu inventory indicates inferred soil re-distribution. Compared to 137Cs, 239Pu and 240Pu offer several important advantages: (a) the two major Pu isotopes have much longer half-lives than 137Cs and (b) the ratio 240Pu/239Pu is used to examine whether the Pu is from stratospheric fallout. In this paper, we review the literature concerning Pu in soil and of current attempts to use this tracer to estimate rates of soil redistribution. We also present preliminary, unpublished data from a pilot study designed to test whether or not 239+240Pu can be used to estimate rates of soil redistribution by wind. Based on similarities of profile distribution and relative inventories between 137Cs measurements and 239+240Pu measurements of split samples from a series of fields with documented wind erosion histories, we conclude that 239+240Pu may well be the anthropogenic radioisotope of choice for future soil redistribution investigations.

Analysis of gene expression and Ig transcription in PU.1/Spi-B-deficient progenitor B cell lines.

PubMed

Schweitzer, Brock L; DeKoter, Rodney P

2004-01-01

A number of presumptive target genes for the Ets-family transcription factor PU.1 have been identified in the B cell lineage. However, the precise function of PU.1 in B cells has not been studied because targeted null mutation of the PU.1 gene results in a block to lymphomyeloid development at an early developmental stage. In this study, we take advantage of recently developed PU.1(-/-)Spi-B(-/-) IL-7 and stromal cell-dependent progenitor B (pro-B) cell lines to analyze the function of PU.1 and Spi-B in B cell development. We show that contrary to previously published expectations, PU.1 and/or Spi-B are not required for Ig H chain (IgH) gene transcription in pro-B cells. In fact, PU.1(-/-)Spi-B(-/-) pro-B cells have increased levels of IgH transcription compared with wild-type pro-B cells. In addition, high levels of Igkappa transcription are induced after IL-7 withdrawal of wild-type or PU.1(-/-)Spi-B(-/-) pro-B cells. In contrast, we found that Iglambda transcription is reduced in PU.1(-/-)Spi-B(-/-) pro-B cells relative to wild-type pro-B cells after IL-7 withdrawal. These results suggest that Iglambda, but not IgH or Igkappa, transcription, is dependent on PU.1 and/or Spi-B. The PU.1(-/-)Spi-B(-/-) pro-B cells have other phenotypic changes relative to wild-type pro-B cells including increased proliferation, increased CD25 expression, decreased c-Kit expression, and decreased RAG-1 expression. Taken together, our observations suggest that reduction of PU.1 and/or Spi-B activity in pro-B cells promotes their differentiation to a stage intermediate between late pro-B cells and large pre-B cells.

Reductive Dissolution of PuO2(am): The Effect of Fe(II) and Hydroquinone

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rai, Dhanpat; Gorby, Yuri A.; Fredrickson, Jim K.

2002-06-01

SYNOPIS-Reducing agents commonly present in geologic environments can increase solubility of PuO2(am), which is otherwise very insoluble, by many orders of magnitude through reduction of Pu(IV) to Pu(III). The reduction reactions involving Fe(II) and hydroquinone, hitherto unquantified under environmental pH values, were found to be relatively fast and controlled the extent of PuO2(am) dissolution: a decrease in redox potential (pe + pH) resulted in concomitant increase in PuO2(am) solubility.

DEVELOPMENT OF PLUTONIUM-BEARING FUEL MATERIALS. Progress Report, October 1-December 31, 1961

DOE Office of Scientific and Technical Information (OSTI.GOV)

None

1962-10-31

Continued effort is reported on preparation and characterization of PuO/ sub 2/ and UO/sub 2/-- PuO/sub 2/ mixtures. Sintering and characterization of pellets for irradiation tests was emphasized, and efforts were also devoted to plasma torch production of spherical PuO /sub 2/ and coating of oxide materials. PuO/sub 2/ produced by the oxalate process from low concentration feed contains agglomerates which are not readily broken down, while that produced from normal feed contains larger agglomerates which are easily dispersed ultrasonically, and are more easily calcined. The water filtration method for determining total porosity of powders was adapted for use withmore » PuO/sub 2/. Moisture pickup studies show that the problems encountered with PuO/sub 2/ are similar to those found in handling ceramic-grade UO/. Reproducibility tests carried out on UO/sub 2/--PuO/ sub 2/ mixtures indicate that production methods are satisfactory. Lab-scale experiments on production of PuO/sub 2/-- UO/sub 2/feed for the plasma torch indicate that further work is worthwhile. Adaptation of a potentiometric filtration for Pu is reported. A twophase microstructure found in PuO/ after sintering in N6% H atmosphere was identified as PuO/sub 2/ and cubic Pu/sub 2/O/ sub 3/. Spherical particles were produced in the plasma torch using crushed or preformed high-fired particles. Spherical particles of PuO/sub 2/ were also produced by a multi-step process of drying, pressing, granulation, sizing, shaping, and sintering. Reactor physics studies were continued to determine the effect of cross section assumptions on the calculated behavior of Pu-fueled near- thermal reactor systems. It was concluded that relatively long core life (reactivity limiting) is attainable with these systems. (J.R.D.)« less

Pu-erh Tea Inhibits Tumor Cell Growth by Down-Regulating Mutant p53

PubMed Central

Zhao, Lanjun; Jia, Shuting; Tang, Wenru; Sheng, Jun; Luo, Ying

2011-01-01

Pu-erh tea is a kind of fermented tea with the incorporation of microorganisms’ metabolites. Unlike green tea, the chemical characteristics and bioactivities of Pu-erh tea are still not well understood. Using water extracts of Pu-erh tea, we analyzed the tumor cell growth inhibition activities on several genetically engineered mouse tumor cell lines. We found that at the concentration that did not affect wild type mouse embryo fibroblasts (MEFs) growth, Pu-erh tea extracts could inhibit tumor cell growth by down-regulated S phase and cause G1 or G2 arrest. Further study showed that Pu-erh tea extracts down-regulated the expression of mutant p53 in tumor cells at the protein level as well as mRNA level. The same concentration of Pu-erh tea solution did not cause p53 stabilization or activation of its downstream pathways in wild type cells. We also found that Pu-erh tea treatment could slightly down-regulate both HSP70 and HSP90 protein levels in tumor cells. These data revealed the action of Pu-erh tea on tumor cells and provided the possible mechanism for Pu-erh tea action, which explained its selectivity in inhibiting tumor cells without affecting wild type cells. Our data sheds light on the application of Pu-erh tea as an anti-tumor agent with low side effects. PMID:22174618

242Pu absolute neutron-capture cross section measurement

NASA Astrophysics Data System (ADS)

Buckner, M. Q.; Wu, C. Y.; Henderson, R. A.; Bucher, B.; Chyzh, A.; Bredeweg, T. A.; Baramsai, B.; Couture, A.; Jandel, M.; Mosby, S.; O'Donnell, J. M.; Ullmann, J. L.

2017-09-01

The absolute neutron-capture cross section of 242Pu was measured at the Los Alamos Neutron Science Center using the Detector for Advanced Neutron-Capture Experiments array along with a compact parallel-plate avalanche counter for fission-fragment detection. During target fabrication, a small amount of 239Pu was added to the active target so that the absolute scale of the 242Pu(n,γ) cross section could be set according to the known 239Pu(n,f) resonance at En,R = 7.83 eV. The relative scale of the 242Pu(n,γ) cross section covers four orders of magnitude for incident neutron energies from thermal to ≈ 40 keV. The cross section reported in ENDF/B-VII.1 for the 242Pu(n,γ) En,R = 2.68 eV resonance was found to be 2.4% lower than the new absolute 242Pu(n,γ) cross section.

Precise U and Pu isotope ratio measurements in nuclear samples by hyphenating capillary electrophoresis and MC-ICPMS.

PubMed

Martelat, Benoit; Isnard, Helene; Vio, Laurent; Dupuis, Erwan; Cornet, Terence; Nonell, Anthony; Chartier, Frederic

2018-06-22

Precise isotopic and elemental characterization of spent nuclear fuel is a major concern for the validation of the neutronic calculation codes and waste management strategy in the nuclear industry. Generally, the elements of interest, particularly U and Pu which are the two major elements present in spent fuel, are purified by ion exchange or extractant resins before off-line measurements by thermal ionization mass spectrometry. The aim of the present work was to develop a new analytical approach based on capillary electrophoresis (CE) hyphenated to a multicollector inductively coupled plasma mass spectrometer (MC-ICPMS) for online isotope ratio measurements. An electrophoretic separation protocol of U, Pu and the fraction containing fission products and minor actinides (Am and Cm) was developed using acetic acid as the electrolyte and complexing agent. The instrumentation for CE was designed to be used in a glove box and a laboratory-built interface was developed for hyphenation with MC-ICPMS. The separation was realized with only a few nL of a solution of spent nuclear fuel and the reproducibilities obtained on the U and Pu isotope ratios were on the order of a few ‰ which is comparable to those obtained by thermal ionization mass spectrometer (TIMS). This innovative protocol allowed a tremendous reduction of the analyte masses from μg to ng and also a drastic reduction of the liquid waste production from mL to μL. In addition, the time of analysis was shorted by at least a factor three. All of these improved parameters are of major interest for nuclear applications.

Plutonium as a tracer for soil erosion assessment in northeast China.

PubMed

Xu, Yihong; Qiao, Jixin; Pan, Shaoming; Hou, Xiaolin; Roos, Per; Cao, Liguo

2015-04-01

Soil erosion is one of the most serious environmental and agricultural problems faced by human society. Assessing intensity is an important issue for controlling soil erosion and improving eco-environmental quality. The suitability of the application of plutonium (Pu) as a tracer for soil erosion assessment in northeast China was investigated by comparing with that of 137Cs. Here we build on preliminary work, in which we investigated the potential of Pu as a soil erosion tracer by sampling additional reference sites and potential erosive sites, along the Liaodong Bay region in northeast China, for Pu isotopes and 137Cs. 240Pu/239Pu atomic ratios in all samples were approximately 0.18, which indicated that the dominant source of Pu was the global fallout. Pu showed very similar distribution patterns to those of 137Cs at both uncultivated and cultivated sites. 239+240Pu concentrations in all uncultivated soil cores followed an exponential decline with soil depth, whereas at cultivated sites, Pu was homogenously distributed in plow horizons. Factors such as planted crop types, as well as methods and frequencies of irrigation and tillage were suggested to influence the distribution of radionuclides in cultivated land. The baseline inventories of 239+240Pu and 137Cs were 88.4 and 1688 Bq m(-2) respectively. Soil erosion rates estimated by 239+240Pu tracing method were consistent with those obtained by the 137Cs method, confirming that Pu is an effective tracer with a similar tracing behavior to that of 137Cs for soil erosion assessment. Copyright © 2014 Elsevier B.V. All rights reserved.

Developing the Pulsed Fission-Fusion (PuFF) Engine

NASA Technical Reports Server (NTRS)

Adams, Robert B.; Cassibry, Jason; Bradley, David; Fabisinski, Leo; Statham, Geoffrey

2014-01-01

In September 2013 the NASA Innovative Advanced Concept (NIAC) organization awarded a phase I contract to the PuFF team. Our phase 1 proposal researched a pulsed fission-fusion propulsion system that compressed a target of deuterium (D) and tritium (T) as a mixture in a column, surrounded concentrically by Uranium. The target is surrounded by liquid lithium. A high power current would flow down the liquid lithium and the resulting Lorentz force would compress the column by roughly a factor of 10. The compressed column would reach criticality and a combination of fission and fusion reactions would occur. Our Phase I results, summarized herein, review our estimates of engine and vehicle performance, our work to date to model the fission-fusion reaction, and our initial efforts in experimental analysis.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Peng, Ying; Xu, Feng, E-mail: xuf@xtal.tsinghua.edu.cn; Bell, Stephen G.

Palustrisredoxin reductase (RPA3782, PuR), a flavin-dependent ferredoxin reductase, is an essential component of the Class I cytochrome P450 systems in Rhodopseudomonas palustris CGA009. Crystals of PuR that diffract to 2.2 Å resolution have been obtained. Palustrisredoxin reductase from Rhodopseudomonas palustris CGA009, a member of the oxygenase-coupled NADH-dependent ferredoxin reductase (ONFR) family, catalyzes electron transfer from NADH to ferredoxins. It is an essential component of the cytochrome P450 systems in R. palustris CGA009, a model organism with diverse metabolic pathways. Here, the crystallization of palustrisredoxin reductase is reported. The crystals belong to the trigonal space group P3{sub 2}21, with unit-cell parametersmore » a = 107.5, b = 107.5, c = 69.9 Å, and diffract to 2.2 Å resolution on a synchrotron source.« less

Synthesis of plutonium trifluoride by hydro-fluorination and novel thermodynamic data for the PuF3-LiF system

NASA Astrophysics Data System (ADS)

Tosolin, A.; Souček, P.; Beneš, O.; Vigier, J.-F.; Luzzi, L.; Konings, R. J. M.

2018-05-01

PuF3 was synthetized by hydro-fluorination of PuO2 and subsequent reduction of the product by hydrogenation. The obtained PuF3 was analysed by X-Ray Diffraction (XRD) and found phase-pure. High purity was also confirmed by the melting point analysis using Differential Scanning Calorimetry (DSC). PuF3 was then used for thermodynamic assessment of the PuF3-LiF system. Phase equilibrium points and enthalpy of fusion of the eutectic composition were measured by DSC. XRD analyses of selected samples after DSC measurement confirm that after solidification from the liquid, the system returns to a mixture of LiF and PuF3.

High-Precision Plutonium Isotopic Compositions Measured on Los Alamos National Laboratory’s General’s Tanks Samples: Bearing on Model Ages, Reactor Modelling, and Sources of Material. Further Discussion of Chronometry

DOE Office of Scientific and Technical Information (OSTI.GOV)

Spencer, Khalil J.; Rim, Jung Ho; Porterfield, Donivan R.

2015-06-29

In this study, we re-analyzed late-1940’s, Manhattan Project era Plutonium-rich sludge samples recovered from the ''General’s Tanks'' located within the nation’s oldest Plutonium processing facility, Technical Area 21. These samples were initially characterized by lower accuracy, and lower precision mass spectrometric techniques. We report here information that was previously not discernable: the two tanks contain isotopically distinct Pu not only for the major (i.e., 240Pu, 239Pu) but trace ( 238Pu , 241Pu, 242Pu) isotopes. Revised isotopics slightly changed the calculated 241Am- 241Pu model ages and interpretations.

Prompt fission neutron spectra from fission induced by 1 to 8 MeV neutrons on U235 and Pu239 using the double time-of-flight technique

NASA Astrophysics Data System (ADS)

Noda, S.; Haight, R. C.; Nelson, R. O.; Devlin, M.; O'Donnell, J. M.; Chatillon, A.; Granier, T.; Bélier, G.; Taieb, J.; Kawano, T.; Talou, P.

2011-03-01

Prompt fission neutron spectra from U235 and Pu239 were measured for incident neutron energies from 1 to 200 MeV at the Weapons Neutron Research facility (WNR) of the Los Alamos Neutron Science Center, and the experimental data were analyzed with the Los Alamos model for the incident neutron energies of 1-8 MeV. A CEA multiple-foil fission chamber containing deposits of 100 mg U235 and 90 mg Pu239 detected fission events. Outgoing neutrons were detected by the Fast Neutron-Induced γ-Ray Observer array of 20 liquid organic scintillators. A double time-of-flight technique was used to deduce the neutron incident energies from the spallation target and the outgoing energies from the fission chamber. These data were used for testing the Los Alamos model, and the total kinetic energy parameters were optimized to obtain a best fit to the data. The prompt fission neutron spectra were also compared with the Evaluated Nuclear Data File (ENDF/B-VII.0). We calculate average energies from both experimental and calculated fission neutron spectra.

The heat of formation of gaseous PuO(2)2+ from relativistic density functional calculations.

PubMed

Moskaleva, Lyudmila V; Matveev, Alexei V; Dengler, Joachim; Rösch, Notker

2006-08-28

Using a set of model reactions, we estimated the heat of formation of gaseous PuO2(2+) from quantum-chemical reaction enthalpies and experimental heats of formation of reference species. To this end, we carried out relativistic density functional calculations on the molecules PuO(2)2+, PuO2, PuF6, and PuF4. We used a revised variant (PBEN) of the Perdew-Burke-Ernzerhof gradient-corrected exchange-correlation functional, and we accounted for spin-orbit interaction in a self-consistent fashion. As open-shell Pu species with two or more unpaired 5f electrons are involved, spin-orbit interaction significantly affects the energies of the model reactions. Our theoretical estimate for the heat of formation DeltafH degree 0(PuO2(2+),g), 418+/-15 kcal mol-1, evaluated using plutonium fluorides as references, is in good agreement with a recent experimental result, 413+/-16 kcal mol-1. The theoretical value connected to the experimental heat of formation of PuO2(g) has a notably higher uncertainty and therefore was not included in the final result.

Self-irradiation damage to the local structure of plutonium and plutonium intermetallics

NASA Astrophysics Data System (ADS)

Booth, C. H.; Jiang, Yu; Medling, S. A.; Wang, D. L.; Costello, A. L.; Schwartz, D. S.; Mitchell, J. N.; Tobash, P. H.; Bauer, E. D.; McCall, S. K.; Wall, M. A.; Allen, P. G.

2013-03-01

The effect of self-irradiation damage on the local structure of δ-Pu, PuAl2, PuGa3, and other Pu intermetallics has been determined for samples stored at room temperature using the extended x-ray absorption fine-structure (EXAFS) technique. These measurements indicate that the intermetallic samples damage at a similar rate as indicated in previous studies of PuCoGa5. In contrast, δ-Pu data indicate a much slower damage accumulation rate. To explore the effect of storage temperature and possible room temperature annealing effects, we also collected EXAFS data on a δ-Pu sample that was held at less than 32 K for a two month period. This sample damaged much more quickly. In addition, the measurable damage was annealed out at above only 135 K. Data from samples of δ-Pu with different Ga concentrations and results on all samples collected from different absorption edges are also reported. These results are discussed in terms of the vibrational properties of the materials and the role of Ga in δ-Pu as a network former.

Galactosylated pullulan-curcumin conjugate micelles for site specific anticancer activity to hepatocarcinoma cells.

PubMed

Sarika, P R; James, Nirmala Rachel; Nishna, N; Anil Kumar, P R; Raj, Deepa K

2015-09-01

Galactosylated pullulan-curcumin conjugate (LANH2-Pu Ald-Cur SA) is developed for target specific delivery of curcumin to hepatocarcinoma cells by five step synthetic strategy, which includes oxidation of pullulan (Pu Ald), introduction of amino group to the targeting ligand (LANH2), grafting of the LANH2 to Pu Ald, modification of curcumin (Cur SA) and conjugation of Cur SA to pullulan. Nongalactosylated pullulan-curcumin conjugate (Pu-Cur SA) is also prepared to compare the enhancement in cytotoxicity offered by the targeting group. Both LANH2-Pu Ald-Cur SA and Pu-Cur SA conjugates could self assemble to micelle in water with hydrodynamic diameters of 355±9nm and 363±10nm, respectively. Both conjugates show spherical morphology and enhance stability of curcumin in physiological pH. Compared to Pu-Cur SA, LANH2-Pu Ald-Cur SA exhibits higher toxicity and internalization towards HepG2 cells. This indicates the enhanced uptake of LANH2-Pu Ald-Cur SA conjugate via ASGPR (asialoglycoprotein receptor) mediated endocytosis into HepG2 cells. Copyright © 2015 Elsevier B.V. All rights reserved.

Electronic structures of of PuX (X=S, Se, Te)

NASA Astrophysics Data System (ADS)

Maehira, Takahiro; Sakai, Eijiro; Tatetsu, Yasutomi

2013-08-01

We have calculated the energy band structures and the Fermi surfaces of PuS, PuSe, and PuTe by using a self-consistent relativistic linear augmented-plane-wave method with the exchange and correlation potential in the local density approximation. In general, the energy bands near the Fermi level are mainly caused by the hybridization between the Pu 5 f and the monochalcogenide p electrons. The obtained main Fermi surfaces consisted of two hole sheets and one electron sheet, which were constructed from the band having both the Pu 5 f state and the monochalcogenide p state.

Synthesis and properties of shape memory polyurethanes generated from schiff-base chain extender containing benzoyl and pyridyl rings

PubMed Central

Weng, Neng-Chiao; Wu, Chih-Fu; Tsen, Wen-Chin; Wu, Cheng-Lung; Suen, Maw-Cherng

2018-01-01

Abstract In this study, 4,4′-diphenylmethane diisocyanate and polytetramethylene glycol were used to prepare a prepolymer; N,N′-bis(4-hydroxybenzylidene)-2,6-diaminopyridine (BHBP) was used as a chain extender; and these elements were combined to prepare a novel polyurethane, BHBP/PU. Gel permeation chromatography revealed that the molecular weight of the BHBP/PU samples increased as the BHBP content was increased. Fourier transform infrared spectroscopy demonstrated that high BHBP content facilitated strong hydrogen bonding in the samples. Differential thermogravimetry indicated that the initial decomposition temperature of BHBP/PU-3 was approximately 10 °C higher than that of BHBP/PU-1. Differential scanning calorimetry and dynamic mechanical analysis revealed that increasing the BHBP content substantially increased both the glass transition and dynamic glass transition temperatures of the BHBP/PU samples. The tensile strengths of BHBP/PU-1, BHBP/PU-2, and BHBP/PU-3 were 7.7, 10.9, and 21.6 MPa, respectively, with corresponding Young’s moduli of 0.7, 1.9, and 3.3 MPa. These results demonstrated that both the tensile strength and Young’s modulus of the BHBP/PU samples increased as the BHBP content was increased. Moreover, the BHBP/PU samples exhibited excellent shape recovery of >90%. PMID:29706848

Release of plutonium isotopes into the environment from the Fukushima Daiichi Nuclear Power Plant accident: what is known and what needs to be known.

PubMed

Zheng, Jian; Tagami, Keiko; Uchida, Shigeo

2013-09-03

The Fukushima Daiichi Nuclear Power Plant (FDNPP) accident has caused serious contamination in the environment. The release of Pu isotopes renewed considerable public concern because they present a large risk for internal radiation exposure. In this Critical Review, we summarize and analyze published studies related to the release of Pu from the FDNPP accident based on environmental sample analyses and the ORIGEN model simulations. Our analysis emphasizes the environmental distribution of released Pu isotopes, information on Pu isotopic composition for source identification of Pu releases in the FDNPP-damaged reactors or spent fuel pools, and estimation of the amounts of Pu isotopes released from the FDNPP accident. Our analysis indicates that a trace amount of Pu isotopes (∼2 × 10(-5)% of core inventory) was released into the environment from the damaged reactors but not from the spent fuel pools located in the reactor buildings. Regarding the possible Pu contamination in the marine environment, limited studies suggest that no extra Pu input from the FDNPP accident could be detected in the western North Pacific 30 km off the Fukushima coast. Finally, we identified knowledge gaps remained on the release of Pu into the environment and recommended issues for future studies.

A Method for Continuous (239)Pu Determinations in Arctic and Antarctic Ice Cores.

PubMed

Arienzo, M M; McConnell, J R; Chellman, N; Criscitiello, A S; Curran, M; Fritzsche, D; Kipfstuhl, S; Mulvaney, R; Nolan, M; Opel, T; Sigl, M; Steffensen, J P

2016-07-05

Atmospheric nuclear weapons testing (NWT) resulted in the injection of plutonium (Pu) into the atmosphere and subsequent global deposition. We present a new method for continuous semiquantitative measurement of (239)Pu in ice cores, which was used to develop annual records of fallout from NWT in ten ice cores from Greenland and Antarctica. The (239)Pu was measured directly using an inductively coupled plasma-sector field mass spectrometer, thereby reducing analysis time and increasing depth-resolution with respect to previous methods. To validate this method, we compared our one year averaged results to published (239)Pu records and other records of NWT. The (239)Pu profiles from the Arctic ice cores reflected global trends in NWT and were in agreement with discrete Pu profiles from lower latitude ice cores. The (239)Pu measurements in the Antarctic ice cores tracked low latitude NWT, consistent with previously published discrete records from Antarctica. Advantages of the continuous (239)Pu measurement method are (1) reduced sample preparation and analysis time; (2) no requirement for additional ice samples for NWT fallout determinations; (3) measurements are exactly coregistered with all other chemical, elemental, isotopic, and gas measurements from the continuous analytical system; and (4) the long half-life means the (239)Pu record is stable through time.

Photoluminescence studies on the complexation of Eu(III) and Tb(III) with acetohydroxamic acid (AHA) in nitrate medium.

PubMed

Pathak, P N; Mohapatra, M; Godbole, S V

2013-11-01

UREX process has been proposed for selective extraction of U(VI) and Tc(VII) from nitric acid medium (∼1M HNO3) using tri-n-butyl phosphate (TBP) as extractant and retaining Pu, Np and fission products in the aqueous phase. The feasibility of the use of luminescence spectroscopy as a technique to understand the complexation of trivalent f-elements cations viz. Eu(III) and Tb(III) with acetohydroxamic acid (AHA) in nitric acid medium has been examined. The luminescence lifetimes for the 1×10(-3)M Eu(III) and AHA complex system decreased with increased AHA concentration from 116±0.2μs (no AHA) to 1.6±0.1μs (0.1M AHA) which was attributed to dynamic quenching. The corrected fluorescence intensities were used to calculate the stability constant (log K) for the formation of 1:1 Eu(3+)-AHA complex as 1.42±0.64 under the conditions of this study. By contrast, the Tb(III)-AHA system at pH 3 (HNO3) did not show any significant variation in the life times of the excited state (364±9μs) suggesting the absence of dynamic quenching. The spectral changes in Tb(III)-AHA system showed the formation of 1:1 complex (log K: 1.72±0.21). These studies suggest that the extent of AHA complexation with the rare earth elements will be insignificant as compared to tetravalent metal ions Pu(IV) and Np(IV) under UREX process conditions. Copyright © 2013 Elsevier B.V. All rights reserved.

The association between the parenchymal neurological involvement and posterior uveitis in Behçet's syndrome.

PubMed

Bitik, Berivan; Tufan, Abdurrahman; Sahin, Kubilay; Sucullu Karadag, Yesim; Can Sandikci, Sevinc; Mercan, Ridvan; Ak, Fikri; Karaaslan, Yasar; Ozturk, Mehmet Akif; Goker, Berna; Haznedaroglu, Seminur

2016-01-01

Behçet's syndrome (BS) is a systemic vasculitis, which may involve multiple organ systems simultaneously. Clinical findings in BS often fit into well-recognized patterns, such as the association between papulo-pustular skin lesions and arthritis. We have recently observed a distinct pattern, in which a subtype of neuro-Behçet's syndrome (NBS) is often preceded by specific ophthalmic manifestations of the disease process. The purpose of this study is to evaluate the association between the parenchymal subtype of NBS and posterior uveitis (PU). We have retrospectively reviewed the clinical records of 295 patients with BS, who met the international classification criteria for BS, diagnosed at two major rheumatology clinics from 2010 to 2014. Patient demographics, ophthalmic examinations, clinical and radiologic patterns of neurological involvement were recorded. Manifestations of BS were classified as PU, NBS, vascular involvement, and arthritis. The association between clinical findings was analysed for statistical significance. Of the 295 patients, 100 had PU and 44 had NBS. 30 patients had parenchymal NBS and 14 had vascular NBS. Patients with PU were significantly more likely to have neurological involvement compared to those without PU (p<0.001; Odds Ratio: 3.924; 95% CI: 1.786-8.621). Rate of posterior uveitis was higher in patients with parenchymal NBS when compared to patients with vascular NBS, vascular BS or arthritis (63.3%, 21.4%, 22% and 4.2% respectively, p<0.001). Our findings suggest a clinically and statistically significant association between posterior uveitis and parenchymal type of neurologic involvement in BS. The development of posterior uveitis in a patient with previously diagnosed BS should be recognized as a "warning sign" for predisposition to neurologic involvement. These patients should be informed about the possible signs and symptoms of neurological involvement, which can cause very rapid and irreversible damage unless recognized and treated immediately.

Uranium and plutonium in anoxic marine sediments of the Santiago River mouth (Eastern Pacific, Mexico).

PubMed

Almazán-Torres, María Guadalupe; Ordóñez-Regil, Eduardo; Ruiz-Fernández, Ana Carolina

2016-11-01

The uranium (U) and plutonium (Pu) content with depth in a sediment core collected in the continental shelf off the mouth of the Santiago River in the Mexican Pacific was studied to evaluate the contamination effects of the effluent of the Santiago-Lerma River as it moves into the sea. The large mass of terrestrial detritus delivered by the river influences the physicochemical and geochemical processes in the seafloor. Abnormal concentrations of U and Pu in sediments were examined as indicative of the effects of anoxic conditions. One of the indicators of pollution of seawater is the bacterial activity of the shallow seabed layer; and among the prevailing bacteria, the magnetotactic ones induce the formation of euhedral and framboidal shapes (pyrite). These pyrite entities are by-products of anoxic environments loaded with decomposing detrital material and are very abundant in the surface layers of the sediment core analyzed. The pyrite formation is the result of a biochemical reaction between iron and organic sulphur reduced by bacteria, and the pyrite entities precipitate to the seafloor. In the same upper zone of the profile, 238 U is readily immobilized, while 234 U is oxidized and dissolved in seawater by the effect of hot atom chemistry. This may cause the activity ratio (AR) 234 U/ 238 U disequilibrium (near 0.41). Furthermore, in the shallow layer of the sediment core, an abnormally high concentration of 239+240 Pu was detected. In this upper layer, the activity concentrations found were 3.19 Bq kg -1 for 238 U, 1.32 kg -1 for 234 U and 2.78 Bq kg -1 for 239+240 Pu. In the lower fractions of the sediment core, normal values of AR 234 U/ 238 U (≈1) were found, with traces of 239+240 Pu. Copyright © 2016 Elsevier Ltd. All rights reserved.

Zwitterionic modification of polyurethane membranes for enhancing the anti-fouling property.

PubMed

Liu, Peiming; Huang, Tao; Liu, Pingsheng; Shi, Shufeng; Chen, Qiang; Li, Li; Shen, Jian

2016-10-15

Polyurethane (PU) is a biopolymer that has been commonly used for biomedical applications. However, the biofouling phenomenon on the hydrophobic PU surface is one of the crucial issues that embarrassing its applications. Here, we report a facile & efficient approach to improve the anti-biofouling ability of the PU substrates. Active residues were firstly generated on the PU surface by using the low temperature air-plasma treatment, promoting the immobilization of the atom transfer radical polymerization (ATRP) initiators on the surface. Then, three types of zwitterionic polymer brushes, as well as PEG brushes, have been fabricated on the PU substrates through surface-initiated ATRP (SI-ATRP). Robust surface characterizations that capable of revealing the surface chemistry (including X-ray photoelectron spectroscopy (XPS) and wettability tests), and antifouling evaluations of the PU substrates (protein adsorption, platelet adhesion, and cell adhesion measurements) were performed. Results showed that three types of zwitterionic brushes have been successful grafted on the PU surface, respectively. And the three types of zwitterionic brushes, in general, significantly inhibited the protein adsorption, the platelet adhesion, and the cell adhesion on the PU surface, endowing a significantly improved anti-fouling ability to the PU substrates. Furthermore, we found that this facial zwitterionic surface modification did not compromise the mechanical property of the PU substrates. This strategy could be easily exploited to PU-based biomaterials to improve their performance in many applications. Copyright © 2016 Elsevier Inc. All rights reserved.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Simpson, H.J.; Trier, R.M.

We have obtained a large set of sediment cores from the Hudson estuary through much of the ambient salinity range. A number of core sections and samples of suspended particles have been analyzed for /sup 137/Cs, /sup 134/Cs and /sup 60/Co by direct gamma counting, and /sup 239/Pu, /sup 240/Pu, and /sup 238/Pu by alpha spectrometry. The distribution of both /sup 137/Cs and /sup 239/Pu, /sup 240/Pu indicates rapid accumulation in marginal cover areas, and especially in the harbor region adjacent to New York City. The distributions of both /sup 137/Cs and /sup 239/Pu, /sup 240/Pu are similar in surfacemore » sediments and with depth in cores, but there are deviations from the fallout ratio due to addition of reactor /sup 137/Cs and loss of /sup 137/Cs from the particle phases at higher salinities. Measureable amounts of reactor-derived /sup 134/Cs and /sup 60/Co are found in nearly all sediment samples containing appreciable /sup 137/Cs, between 15 km upstream of Indian Point and the downstream extent of our sampling, 70 km south of the reactor. Accumulations of /sup 239/Pu, /sup 240/Pu in New York harbor sediments are more than an order of magnitude greater than the fallout delivery rate. The most likely explanation is accumulation of fine particles in the harbor which have been transported from upstream areas of the Hudson. Our evidence so far indicates that Indian Point is probably not a significant source of /sup 239/Pu, /sup 240/Pu or /sup 238/Pu compared with the fallout burden of these nuclides already in the sediments.« less

Plutonium age dating reloaded

NASA Astrophysics Data System (ADS)

Sturm, Monika; Richter, Stephan; Aregbe, Yetunde; Wellum, Roger; Mayer, Klaus; Prohaska, Thomas

2014-05-01

Although the age determination of plutonium is and has been a pillar of nuclear forensic investigations for many years, additional research in the field of plutonium age dating is still needed and leads to new insights as the present work shows: Plutonium is commonly dated with the help of the 241Pu/241Am chronometer using gamma spectrometry; in fewer cases the 240Pu/236U chronometer has been used. The age dating results of the 239Pu/235U chronometer and the 238Pu/234U chronometer are scarcely applied in addition to the 240Pu/236U chronometer, although their results can be obtained simultaneously from the same mass spectrometric experiments as the age dating result of latter. The reliability of the result can be tested when the results of different chronometers are compared. The 242Pu/238U chronometer is normally not evaluated at all due to its sensitivity to contamination with natural uranium. This apparent 'weakness' that renders the age dating results of the 242Pu/238U chronometer almost useless for nuclear forensic investigations, however turns out to be an advantage looked at from another perspective: the 242Pu/238U chronometer can be utilized as an indicator for uranium contamination of plutonium samples and even help to identify the nature of this contamination. To illustrate this the age dating results of all four Pu/U clocks mentioned above are discussed for one plutonium sample (NBS 946) that shows no signs of uranium contamination and for three additional plutonium samples. In case the 242Pu/238U chronometer results in an older 'age' than the other Pu/U chronometers, contamination with either a small amount of enriched or with natural or depleted uranium is for example possible. If the age dating result of the 239Pu/235U chronometer is also influenced the nature of the contamination can be identified; enriched uranium is in this latter case a likely cause for the missmatch of the age dating results of the Pu/U chronometers.

Thermodynamic assessment of the LiF-ThF4-PuF3-UF4 system

NASA Astrophysics Data System (ADS)

Capelli, E.; Beneš, O.; Konings, R. J. M.

2015-07-01

The LiF-ThF4-PuF3-UF4 system is the reference salt mixture considered for the Molten Salt Fast Reactor (MSFR) concept started with PuF3. In order to obtain the complete thermodynamic description of this quaternary system, two binary systems (ThF4-PuF3 and UF4-PuF3) and two ternary systems (LiF-ThF4-PuF3 and LiF-UF4-PuF3) have been assessed for the first time. The similarities between CeF3/PuF3 and ThF4/UF4 compounds have been taken into account for the presented optimization as well as in the experimental measurements performed, which have confirmed the temperatures predicted by the model. Moreover, the experimental results and the thermodynamic database developed have been used to identify potential compositions for the MSFR fuel and to evaluate the influence of partial substitution of ThF4 by UF4 in the salt.

Thermodynamic assessments and inter-relationships between systems involving Al, Am, Ga, Pu, and U

NASA Astrophysics Data System (ADS)

Perron, A.; Turchi, P. E. A.; Landa, A.; Oudot, B.; Ravat, B.; Delaunay, F.

2016-12-01

A newly developed self-consistent CALPHAD thermodynamic database involving Al, Am, Ga, Pu, and U is presented. A first optimization of the slightly characterized Am-Al and completely unknown Am-Ga phase diagrams is proposed. To this end, phase diagram features as crystal structures, stoichiometric compounds, solubility limits, and melting temperatures have been studied along the U-Al → Pu-Al → Am-Al, and U-Ga → Pu-Ga → Am-Ga series, and the thermodynamic assessments involving Al and Ga alloying are compared. In addition, two distinct optimizations of the Pu-Al phase diagram are proposed to account for the low temperature and Pu-rich region controversy. The previously assessed thermodynamics of the other binary systems (Am-Pu, Am-U, Pu-U, and Al-Ga) is also included in the database and is briefly described in the present work. Finally, predictions on phase stability of ternary and quaternary systems of interest are reported to check the consistency of the database.

Nondestructive assay of EBR-II blanket elements using resonance transmission analysis

NASA Astrophysics Data System (ADS)

Klann, Raymond Todd

1998-10-01

Resonance transmission analysis utilizing a filtered reactor beam was examined as a means of determining the 239Pu content in Experimental Breeder Reactor - II depleted uranium blanket elements. The technique uses cadmium and gadolinium filters along with a 239Pu fission chamber to isolate the 0.3 eV resonance in 239Pu. In the energy range of this resonance (0.1 eV to 0.5 eV), the total microscopic cross-section of 239Pu is significantly greater than the cross- sections of 238U and 235U. This large difference allows small changes in the 239Pu content of a sample to result in large changes in the mass signal response. Tests with small stacks of depleted uranium and 239Pu foils indicate a significant change in response based on the 239Pu content of the foil stack. In addition, the tests indicate good agreement between the measured and predicted values of 239Pu up to approximately two weight percent.

Thermodynamic assessments and inter-relationships between systems involving Al, Am, Ga, Pu, and U

DOE PAGES

Perron, A.; Turchi, P. E. A.; Landa, A.; ...

2016-12-01

We present a newly developed self-consistent CALPHAD thermodynamic database involving Al, Am, Ga, Pu, and U. A first optimization of the slightly characterized Am-Al and completely unknown Am-Ga phase diagrams is proposed. To this end, phase diagram features as crystal structures, stoichiometric compounds, solubility limits, and melting temperatures have been studied along the U-Al → Pu-Al → Am-Al, and U-Ga → Pu-Ga → Am-Ga series, and the thermodynamic assessments involving Al and Ga alloying are compared. In addition, two distinct optimizations of the Pu-Al phase diagram are proposed to account for the low temperature and Pu-rich region controversy. We includedmore » the previously assessed thermodynamics of the other binary systems (Am-Pu, Am-U, Pu-U, and Al-Ga) in the database and is briefly described in the present work. In conclusion, predictions on phase stability of ternary and quaternary systems of interest are reported to check the consistency of the database.« less

Determining Pu-239 content by resonance transmission analysis using a filtered reactor beam.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Klann, R. T.

A novel technique has been developed at Argonne National Laboratory to determine the {sup 239}Pu content in EBR-II blanket elements using resonance transmission analysis (RTA) with a filtered reactor beam. The technique uses cadmium and gadolinium filters along with a {sup 239}Pu fission chamber to isolate the 0.3 eV resonance in {sup 239}Pu. In the energy range from 0.1 to 0.5 eV, the total microscopic cross-section of {sup 239}Pu is significantly larger than the cross-sections of {sup 238}U and {sup 235}U. This large difference in cross-section allows small amounts of {sup 239}Pu to be detected in uranium samples. Tests usingmore » a direct beam from a 250 kW TRIGA reactor have been performed with stacks of depleted uranium and {sup 239}Pu foils. Preliminary measurement results are in good agreement with the predicted results up to about two weight percent of {sup 239}Pu in the sample. In addition, measured {sup 239}Pu masses were in agreement with actual sample masses with uncertainties less than 3.8 percent.« less

Highly Stable and Flexible Pressure Sensors with Modified Multi-Walled Carbon Nanotube/Polymer Composites for Human Monitoring

PubMed Central

He, Yin; Ming, Yue; Li, Wei; Li, Yafang; Wu, Maoqi; Song, Jinzhong; Li, Xiaojiu; Liu, Hao

2018-01-01

A facile method for preparing an easy processing, repeatable and flexible pressure sensor was presented via the synthesis of modified multi-walled carbon nanotubes (m-MWNTs) and polyurethane (PU) films. The surface modification of multi-walled carbon nanotubes (MWNTs) simultaneously used a silane coupling agent (KH550) and sodium dodecyl benzene sulfonate (SDBS) to improve the dispersibility and compatibility of the MWNTs in a polymer matrix. The electrical property and piezoresistive behavior of the m-MWNT/PU composites were compared with raw multi-walled carbon nanotube (raw MWNT)/PU composites. Under linear uniaxial pressure, the m-MWNT/PU composite exhibited 4.282%kPa−1 sensitivity within the pressure of 1 kPa. The nonlinear error, hysteresis error and repeatability error of the piezoresistivity of m-MWNT/PU decreased 9%, 16.72% and 54.95% relative to raw MWNT/PU respectively. Therefore, the piezoresistive response of m-MWNT/PU had better stability than that of raw MWNT/PU composites. The m-MWNT/PU sensors could be utilized in wearable devices for body movement detection, monitoring of respiration and pressure detection in garments. PMID:29701643

Air concentrations of /sup 239/Pu and /sup 240/Pu and potential radiation doses to persons living near Pu-contaminated areas in Palomares, Spain

DOE Office of Scientific and Technical Information (OSTI.GOV)

Iranzo, E.; Salvador, S.; Iranzo, C.E.

1987-04-01

On 17 January 1966, an accident during a refueling operation resulted in the destruction of an air force KC-135 tanker and a B-52 bomber carrying four thermonuclear weapons. Two weapons, whose parachutes opened, were found intact. The others experienced non-nuclear explosion with some burning and release of the fissile fuel at impact. Joint efforts by the United States and Spain resulted in remedial action and a long-term program to monitor the effectiveness of the cleanup. Air concentrations of /sup 239/Pu and /sup 240/Pu have been continuously monitored since the accident. The average annual air concentration for each location was usedmore » to estimate committed dose equivalents for individuals living and working around the air sampling stations. The average annual /sup 239/Pu and /sup 240/Pu air concentrations during the 15-y period corresponding to 1966-1980 and the potential committed dose equivalents for various tissues due to the inhalation of the /sup 239/Pu and /sup 240/Pu average annual air concentration during this period are shown and discussed in the report.« less

Highly Stable and Flexible Pressure Sensors with Modified Multi-Walled Carbon Nanotube/Polymer Composites for Human Monitoring.

PubMed

He, Yin; Ming, Yue; Li, Wei; Li, Yafang; Wu, Maoqi; Song, Jinzhong; Li, Xiaojiu; Liu, Hao

2018-04-26

A facile method for preparing an easy processing, repeatable and flexible pressure sensor was presented via the synthesis of modified multi-walled carbon nanotubes (m-MWNTs) and polyurethane (PU) films. The surface modification of multi-walled carbon nanotubes (MWNTs) simultaneously used a silane coupling agent (KH550) and sodium dodecyl benzene sulfonate (SDBS) to improve the dispersibility and compatibility of the MWNTs in a polymer matrix. The electrical property and piezoresistive behavior of the m-MWNT/PU composites were compared with raw multi-walled carbon nanotube (raw MWNT)/PU composites. Under linear uniaxial pressure, the m-MWNT/PU composite exhibited 4.282%kPa −1 sensitivity within the pressure of 1 kPa. The nonlinear error, hysteresis error and repeatability error of the piezoresistivity of m-MWNT/PU decreased 9%, 16.72% and 54.95% relative to raw MWNT/PU respectively. Therefore, the piezoresistive response of m-MWNT/PU had better stability than that of raw MWNT/PU composites. The m-MWNT/PU sensors could be utilized in wearable devices for body movement detection, monitoring of respiration and pressure detection in garments.

PLUTONIUM UPTAKE AND BEHAVIOR IN PLANTS OF THE DESERT SOUTHWEST: A PRELIMINARY ASSESSMENT

DOE Office of Scientific and Technical Information (OSTI.GOV)

Caldwell, E.; Duff, M.; Ferguson, C.

2011-03-01

Eight species of desert vegetation and associated soils were collected from the Nevada National Security Site (N2S2) and analyzed for 238Pu and 239+240Pu concentrations. Amongst the plant species sampled were: atmospheric elemental accumulators (moss and lichen), the very slow growing, long-lived creosote bush and the rapidly growing, short-lived cheatgrass brome. The diversity of growth strategies provided insight into the geochemical behavior and bio-availability of Pu at the N2S2. The highest concentrations of Pu were measured in the onion moss (24.27 Bq kg-1 238Pu and 52.78 Bq kg-1 239+240Pu) followed by the rimmed navel lichen (8.18 Bq kg-1 and 18.4 Bqmore » kg-1 respectively), pointing to the importance of eolian transport of Pu. Brome and desert globemallow accumulated between 3 and 9 times higher concentrations of Pu than creosote and sage brush species. These results support the importance of species specific elemental accumulation strategies rather than exposure duration as the dominant variable influencing Pu concentrations in these plants. Total vegetation elemental concentrations of Ce, Fe, Al, Sm and others were also analyzed. Strong correlations were observed between Fe and Pu. This supports the conclusion that Pu was accumulated as a consequence of the active accumulation of Fe and other plant required nutrients. Cerium and Pu are considered to be chemical analogs. Strong correlations observed in plants support the conclusion that these elements displayed similar geochemical behavior in the environment as it related to the biochemical uptake process of vegetation. Soils were also sampled in association with vegetation samples. This allowed for the calculation of a concentration ratio (CR). The CR values for Pu in plants were highly influenced by the heterogeneity of Pu distribution among sites. Results from the naturally occurring elements of concern were more evenly distributed between sample sites. This allowed for the development of a pattern of plant species that accumulated Ce, Sm, Fe and Al. The highest accumulators of these elements were onion moss, lichen flowed by brome. The lowest accumulators were creosote bush and fourwing saltbush. This ranked order corresponds to plant accumulations of Pu.« less

Examining (239+240)Pu, (210)Pb and historical events to determine carbon, nitrogen and phosphorus burial in mangrove sediments of Moreton Bay, Australia.

PubMed

Sanders, Christian J; Santos, Isaac R; Maher, Damien T; Breithaupt, Joshua L; Smoak, Joseph M; Ketterer, Michael; Call, Mitchell; Sanders, Luciana; Eyre, Bradley D

2016-01-01

Two sediment cores were collected in a mangrove forest to construct geochronologies for the previous century using natural and anthropogenic radionuclide tracers. Both sediment cores were dated using (239+240)Pu global fallout signatures as well as (210)Pb, applying both the Constant Initial Concentration (CIC) and the Constant Rate of Supply (CRS) models. The (239+240)Pu and CIC model are interpreted as having comparable sediment accretion rates (SAR) below an apparent mixed region in the upper ∼5 to 10 cm. In contrast, the CRS dating method shows high sediment accretion rates in the uppermost intervals, which is substantially reduced over the lower intervals of the 100-year record. A local anthropogenic nutrient signal is reflected in the high total phosphorus (TP) concentration in younger sediments. The carbon/nitrogen molar ratios and δ(15)N values further support a local anthropogenic nutrient enrichment signal. The origin of these signals is likely the treated sewage discharge to Moreton Bay which began in the early 1970s. While the (239+240)Pu and CIC models can only produce rates averaged over the intervals of interest within the profile, the (210)Pb CRS model identifies elevated rates of sediment accretion, organic carbon (OC), nitrogen (N), and TP burial from 2000 to 2013. From 1920 to 2000, the three dating methods provide similar OC, N and TP burial rates, ∼150, 10 and 2 g m(-2) year(-1), respectively, which are comparable to global averages. Copyright © 2015 Elsevier Ltd. All rights reserved.

Actinide Sorption in Rainier Mesa Tunnel Waters from the Nevada Test Site

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhao, P; Zavarin, M; Leif, R

2007-12-17

The sorption behavior of americium (Am), plutonium (Pu), neptunium (Np), and uranium (U) in perched Rainier Mesa tunnel water was investigated. Both volcanic zeolitized tuff samples and groundwater samples were collected from Rainier Mesa, Nevada Test Site, NV for a series of batch sorption experiments. Sorption in groundwater with and without the presence of dissolved organic matter (DOM) was investigated. Am(III) and Pu(IV) are more soluble in groundwater that has high concentrations of DOM. The sorption K{sub d} for Am(III) and Pu(IV) on volcanic zeolitized tuff was up to two orders of magnitude lower in samples with high DOM (15more » to 19 mg C/L) compared to samples with DOM removed (< 0.4 mg C/L) or samples with naturally low DOM (0.2 mg C/L). In contrast, Np(V) and U(VI) sorption to zeolitized tuff was much less affected by the presence of DOM. The Np(V) and U(VI) sorption Kds were low under all conditions. Importantly, the DOM was not found to significantly sorb to the zeolitized tuff during these experiment. The concentration of DOM in groundwater affects the transport behavior of actinides in the subsurface. The mobility of Am(III) and Pu(IV) is significantly higher in groundwater with elevated levels of DOM resulting in potentially enhanced transport. To accurately model the transport behavior of actinides in groundwater at Rainier Mesa, the low actinide Kd values measured in groundwater with high DOM concentrations must be incorporated in predictive transport models.« less

Plutonium partitioning in water-granite and water-α-FeOOH systems: from a viewpoint of a three-phase system.

PubMed

Lin, Jianfeng; Dang, Haijun; Xie, Jinchuan; Zhou, Guoqing; Li, Mei; Zhang, Jihong

2015-09-01

Traditional sorption experiments commonly treat the colloidal species of low-solubility contaminants as immobile species when separated by centrifugation or ultrafiltration. This study shows that, from a viewpoint of a three-phase system, the mobile Pu species, especially the colloidal species, play an important role in Pu partitioning in water-granite and water-α-FeOOH systems. A new distribution coefficient term Ks/(d+c) was defined to take the mobile colloidal species into consideration, and it differs to the traditional distribution coefficient Ks/d by orders of magnitude in the water-granite and water-α-FeOOH systems. This term, Ks/(d+c), can quantitatively describe Pu partitioning in the suspension, in particular the fraction of mobile species that dominate Pu migration in the environment. The effects of ionic strength (I) and pH on the Pu partitioning in water-granite and water-α-FeOOH systems are well interpreted with respect to the zeta potential change of granite grains, α-FeOOH colloid particles and polymeric Pu. It is concluded that the presence of the α-FeOOH colloid with a low concentration (<10 mg L(-1)) is favorable for the stability of colloidal Pu and leads to large proportion of mobile Pu, especially colloid-associated Pu, which will migrate much faster than dissolved Pu in groundwater.

A fast semi-quantitative method for Plutonium determination in an alpine firn/ice core

NASA Astrophysics Data System (ADS)

Gabrieli, J.; Cozzi, G.; Vallelonga, P.; Schwikowski, M.; Sigl, M.; Boutron, C.; Barbante, C.

2009-04-01

Plutonium is present in the environment as a consequence of atmospheric nuclear tests carried out in the 1960s, nuclear weapons production and releases by the nuclear industry over the past 50 years. Plutonium, unlike uranium, is essentially anthropogenic and it was first produced and isolated in 1940 by deuteron bombardment of uranium in the cyclotron of Berkeley University. It exists in five main isotopes, 238Pu, 239Pu, 240Pu, 241Pu, 242Pu, derived from civilian and military sources (weapons production and detonation, nuclear reactors, nuclear accidents). In the environment, 239Pu is the most abundant isotope. Approximately 6 tons of 239Pu have been released into the environment as a result of 541 atmospheric weapon tests Nuclear Pu fallout has been studied in various environmental archives, such as sediments, soil and herbarium grass. Mid-latitude ice cores have been studied as well, on Mont Blanc, the Western Alps and on Belukha Glacier, Siberian Altai. We present a Pu record obtained by analyzing 52 discrete samples of an alpine firn/ice core from Colle Gnifetti (M. Rosa, 4450 m a.s.l.), dating from 1945 to 1991. The239Pu signal was recorded directly, without preliminary cleaning or preconcentration steps, using an ICP-SFMS (Thermo Element2) equipped with a desolvation system (APEX). 238UH+ interferences were negligible for U concentrations lower than 50 ppt as verified both in spiked fresh snow and pre-1940 ice samples. The shape of 239Pu profile reflects the three main periods of atmospheric nuclear weapons testing: the earliest peak starts in 1954/55 to 1958 and includes the first testing period which reached a maximum in 1958. Despite a temporary halt in testing in 1959/60, the Pu concentration decreased only by half with respect to the 1958 peak. In 1961/62 Pu concentrations rapidly increased reaching a maximum in 1963, which was about 40% more intense than the 1958 peak. After the sign of the "Limited Test Ban Treaty" between USA and URSS in 1964, Pu deposition decreased very sharply reaching a minimum in 1967. The third period (1967-1975) is characterized by irregular Pu profiles with smaller peaks (about 20-30% compared to the 1964 peak) which could be due to French and Chinese tests. Comparison with the Pu profiles obtained from the Col du Dome and Belukha ice cores by AMS (Accelerator Mass Spectrometry) shows very good agreement. Considering the semi-quantitative method and the analytical uncertainty, the results are also quantitatively comparable. However, the Pu concentrations at Colle Gnifetti are normally 2-3 times greater than in Col du Dome. This could be explained by different air mass transport or, more likely, different accumulation rates at each site.

Actuators based on polyurethanes with different types of polyol

NASA Astrophysics Data System (ADS)

Lim, Hyun-Ok; Bark, Geong-Mi; Jo, Nam-Ju

2007-07-01

This study dealt with the electrostrictive responses of polyurethane (PU) actuators with different microphase separation structure, which was a promising candidate for a material used in polymer actuators. In order to construct PUs with different higher-order structure, we synthesized PUs with different diols; poly(neopentyl glycol adipate) (PNAD), poly(tetramethylene glycol) (PTMG), and poly(dimethyl siloxnae) (PDMS). Synthesized PU was characterized by FT-IR spectroscopy and GPC. Thermal analysis and mechanical properties of PU films were carried out with DSC and UTM, respectively. And PU actuator was formed in a monomorph type which made by carbon black electrodes on the both surfaces of PU film by spin coating method. Actuation behavior was mainly influenced on microphase separation structure and mechanical property of PU. In result, PU actuator with PNAD, polyester urethane, had the largest field-induced displacement.

Chemical thermodynamic representation of (U, Pu, Am)O 2- x

NASA Astrophysics Data System (ADS)

Osaka, Masahiko; Namekawa, Takashi; Kurosaki, Ken; Yamanaka, Shinsuke

2005-09-01

The oxygen potential isotherms of (U, Pu, Am)O 2- x were represented by a chemical thermodynamic model proposed by Lindemer et al. It was assumed in the present model that (U, Pu, Am)O 2- x consisted of the chemical species [UO 2], [PuO 2], [Pu 4/3O 2], [AmO 2] and [Am 5/4O 2] in a pseudo-quaternary system by treating the reduction rates of Pu and Am as identical; furthermore an interaction between [Am 5/4O 2] and [UO 2] was introduced. The agreement between analytical and experimental isotherms was good, but the analytical values slightly overestimated the experimental values especially in the case of lower Am content. Adding an interaction between [Am 5/4O 2] and [PuO 2] to the model resulted in a better representation.

239Pu fallout across continental Australia: Implications on 239Pu use as a soil tracer.

PubMed

Lal, R; Fifield, L K; Tims, S G; Wasson, R J

2017-11-01

At present there is a need for the development of new radioisotopes for soil erosion and sediment tracing especially as fallout 137 Cs levels become depleted. Recent studies have shown that 239 Pu can be a useful new soil erosion and sediment radioisotope tracer. 239 Pu was released in the major atmospheric nuclear weapons tests of 1950's and 1960's. However 239 Pu has a half-life of 24110 years and more than 99% of this isotope is still present in the environment today. In contrast 137 Cs with a half-life of 30.07 year has decayed to <35% of initially deposited activities and this isotope will become increasingly difficult to measure in the coming decades especially in the southern hemisphere, which received only about a third of the total global fallout from the atmospheric tests (UNSCEAR, 2000). In this study an assessment of the 239 Pu fallout in Australia was carried out from comparison of measured 239 Pu inventories with expected 239 Pu inventories from fallout models. 239 Pu inventories were also compared with rainfall and measured 240 Pu/ 239 Pu ratios across Australia. 239 Pu fallout inventories ranged from 430 to 1461 μB/cm 2 . Central Australia, with fallout 107% in excess of expected values, seems to be strongly impacted by local fallout deposition. In comparison other sites typically show 5-40% variation between expected and measured fallout values. The fallout inventories were found to weakly correlate (using power functions, y = ax b ) with rainfall with r 2  = 0.50 across the southern catchments (25-40°S latitude band). Across the northern catchments (10-25°S latitude band) fallout showed greater variability with rainfall with r 2  = 0.24. Central Australia and Alice Springs which seem to be strongly impacted by local fallout are excluded from the rainfall correlation data (with these sites included r 2  = 0.08 and r 2  < 0.01 respectively). 240 Pu/ 239 Pu atom ratios range from 0.045 to 0.197, with averages of 0.139(0.017), 0.111(0.052) and 0.160(0.027) in the 10-20°S, 20-30°S and 30-40°S latitude bands respectively. The 240 Pu/ 239 Pu atom ratios in Central Australia (0.069) likely represent fallout from the Australian tests which also have low 240 Pu/ 239 Pu atom ratios i.e., Maralinga (0.113) and Montebello (0.045). The average ratios in the 20-30°S and 30-40° bands are closer to the global average (0.139 and 0.177 respectively when not including the close-in fallout data from the nuclear test sites) if the Australian test sites and Central Australian sites are neglected as they clearly represent the effects of close in fallout. Copyright © 2017 Elsevier Ltd. All rights reserved.

Chemical resolution of Pu+ from U+ and Am+ using a band-pass reaction cell inductively coupled plasma mass spectrometer.

PubMed

Tanner, Scott D; Li, Chunsheng; Vais, Vladimir; Baranov, Vladimir I; Bandura, Dmitry R

2004-06-01

Determination of the concentration and distribution of the Pu and Am isotopes is hindered by the isobaric overlaps between the elements themselves and U, generally requiring time-consuming chemical separation of the elements. A method is described in which chemical resolution of the elemental ions is obtained through ion-molecule reactions in a reaction cell of an ICPMS instrument. The reactions of "natural" U(+), (242)Pu(+), and (243)Am(+) with ethylene, carbon dioxide, and nitric oxide are reported. Since the net sensitivities to the isotopes of an element are similar, chemical resolution is inferred when one isobaric element reacts rapidly with a given gas and the isobar (or in this instance surrogate isotope) is unreactive or slowly reactive. Chemical resolution of the m/z 238 isotopes of U and Pu can be obtained using ethylene as a reaction gas, but little improvement in the resolution of the m/z 239 isobars is obtained. However, high efficiency of reaction of U(+) and UH(+) with CO(2), and nonreaction of Pu(+), allows the sub-ppt determination of (239)Pu, (240)Pu, and (242)Pu (single ppt for (238)Pu) in the presence of 7 orders of magnitude excess U matrix without prior chemical separation. Similarly, oxidation of Pu(+) by NO, and nonreaction of Am(+), permit chemical resolution of the isobars of Pu and Am over 2-3 orders of magnitude relative concentration. The method provides the potential for analysis of the actinides with reduced sample matrix separation.

Prompt fission γ-ray data from spontaneous fission and the mechanism of fission-fragment de-excitation

NASA Astrophysics Data System (ADS)

Oberstedt, Stephan; Dragic, Aleksandar; Gatera, Angelique; Göök, Alf; Hambsch, Franz-Josef; Oberstedt, Andreas

2017-09-01

The investigation of prompt γ-ray emission in nuclear fission has a great relevance for the assessment of prompt heat generation in a reactor core and for the better understanding of the de-excitation mechanism of fission fragments. Some years ago experimental data was scarce and available only from a few fission reactions, 233,235U(nth, f), 239Pu(nth, f), and 252Cf(sf). Initiated by a high priority data request published by the OECD/NEA a dedicated prompt fission γ-ray measurement program is being conducted at the Joint Research Centre Geel. In recent years we obtained new and accurate prompt fission γ-ray spectrum (PFGS) characteristics (average number of photons per fission, average total energy per fission and mean photon energy) from 252Cf(sf), 235U(nth, f) and 239,241Pu(nth, f) within 2% of uncertainty. In order to understand the dependence of prompt fission γ-ray emission on the compound nuclear mass and excitation energy, we started a first measurement campaign on spontaneously fissioning plutonium and curium isotopes. Results on PFGS characteristics from 240,242Pu(sf) show a dependence on the fragment mass distribution rather than on the average prompt neutron multiplicity, pointing to a more complex competition between prompt fission γ-ray and neutron emission.

Highly Efficient and Reliable Transparent Electromagnetic Interference Shielding Film.

PubMed

Jia, Li-Chuan; Yan, Ding-Xiang; Liu, Xiaofeng; Ma, Rujun; Wu, Hong-Yuan; Li, Zhong-Ming

2018-04-11

Electromagnetic protection in optoelectronic instruments such as optical windows and electronic displays is challenging because of the essential requirements of a high optical transmittance and an electromagnetic interference (EMI) shielding effectiveness (SE). Herein, we demonstrate the creation of an efficient transparent EMI shielding film that is composed of calcium alginate (CA), silver nanowires (AgNWs), and polyurethane (PU), via a facile and low-cost Mayer-rod coating method. The CA/AgNW/PU film with a high optical transmittance of 92% achieves an EMI SE of 20.7 dB, which meets the requirements for commercial shielding applications. A superior EMI SE of 31.3 dB could be achieved, whereas the transparent film still maintains a transmittance of 81%. The integrated efficient EMI SE and high transmittance are superior to those of most previously reported transparent EMI shielding materials. Moreover, our transparent films exhibit a highly reliable shielding ability in a complex service environment, with 98 and 96% EMI SE retentions even after 30 min of ultrasound treatment and 5000 bending cycles (1.5 mm radius), respectively. The comprehensive performance that is associated with the facile fabrication strategy imparts the CA/AgNW/PU film with great potential as an optimized EMI shielding material in emerging optoelectronic devices, such as flexible solar cells, displays, and touch panels.

Wall stress reduction in abdominal aortic aneurysms as a result of polymeric endoaortic paving.

PubMed

Ashton, John H; Ayyalasomayajula, Avinash; Simon, Bruce R; Vande Geest, Jonathan P

2011-06-01

Polymeric endoaortic paving (PEAP) may improve endovascular repair of abdominal aortic aneurysms (AAA) since it has the potential to treat patients with complex AAA geometries while reducing the incidence of migration and endoleak. Polycaprolactone (PCL)/polyurethane (PU) blends are proposed as PEAP materials due to their range of mechanical properties, thermoformability, and resistance to biodegradation. In this study, the reduction in AAA wall stress that can be achieved using PEAP was estimated and compared to that resulting from stent-grafts. This was accomplished by mechanically modeling the anisotropic response of PCL/PU blends and implementing these results into finite element model (FEM) simulations. We found that at the maximum diameter of the AAA, the 50/50 and 10/90 PCL/PU blends reduced wall stress by 99 and 98%, respectively, while a stent-graft reduced wall stress by 99%. Our results also show that wall stress reduction increases with increasing PEAP thickness and PCL content in the blend ratio. These results indicate that PEAP can reduce AAA wall stress as effectively as a stent-graft. As such, we propose that PEAP may provide an improved treatment alternative for AAA, since many of the limitations of stent-grafts have the potential to be solved using this approach.

Biological inventory of anchialine pools in the Pu'uhonua o Hōnaunau National Historical Park and Pu'ukoholā Heiau National Historical Site, Hawaii Island

USGS Publications Warehouse

Tango, Lori K.; Foote, David; Magnacca, Karl N.; Foltz, Sarah J.; Cutler, Kerry

2012-01-01

Inventories for major groups of invertebrates were completed at anchialine pool complexes in Pu‘uhonua o Hōnaunau National Historical Park (PUHO) and Pu‘ukoholā Heiau National Historic Site (PUHE) on the island of Hawai‘i. Nine pools within two pool complexes were surveyed at PUHO, along with one extensive pool at the terminus of Makeāhua Gulch at PUHE. At both parks, inventories documented previously unreported diversity, with pool complexes at PUHO exhibiting greater species richness for most taxa than the pool at PUHE. Inventories at PUHO recorded five species of molluscs, four species of crustaceans (including the candidate endangered shrimp Metabetaeus lohena), two species of Orthoptera, four species of Odonata (including the candidate endangered damselfly Megalagrion xanthomelas), fourteen species of Diptera, nine taxa of plankton, and thirteen species of ants; inventories at the PUHE pool produced only one species of mollusc, two species of crustacean, at least one species of Orthoptera, four species of Odonata, thirty species of Diptera, five taxa of plankton, and four species of ants. Further survey work may be necessary to document the full diversity of pool fauna, especially in species-rich groups like the Diptera. Inventory data will be used to generate a network wide database of species presence and distribution, and will aid in developing management plans for anchialine pool resources.

Uranium daughter growth must not be neglected when adjusting plutonium materials for assay and isotopic contents

DOE Office of Scientific and Technical Information (OSTI.GOV)

Marsh, S.F.; Spall, W.D.; Abernathey, R.M.

1976-11-01

Relationships are provided to compute the decreasing plutonium content and changing isotopic distribution of plutonium materials for the radioactive decay of /sup 238/Pu, /sup 239/Pu, /sup 240/Pu and /sup 242/Pu to long-lived uranium daughters and of /sup 241/Pu to /sup 241/Am. This computation is important to the use of plutonium reference materials to calibrate destructive and nondestructive methods for assay and isotopic measurements, as well as to accountability inventory calculations.

[Progress in research for pharmacological effects of Pu-erh tea].

PubMed

Gu, Xiao-Pan; Pan, Bo; Wu, Zhen; Zhao, Yun-Fang; Tu, Peng-Fei; Zheng, Jiao

2017-06-01

Pu-erh tea has gradually aroused general concern with social development and people's enhanced awareness of health. Pu-erh tea is rich in multiple active constitute such as flavonoids, catechins, phenolic acids, flavanols polymer, purine alkaloids, and hydrolysable tannin as a microbial-fermented tea.It is reported that Pu-erh tea have a variety of pharmacologically activities, such as anti-hyperlipidemic, anti-diabetic, anti-oxidative, anti-tumor, anti-bacterial, anti-inflammatory, and anti-viral effects. In this paper, the main pharmacological effects of Pu-erh tea are reviewed. We wish this work will provide some references and clues for further research of Pu-erh tea. Copyright© by the Chinese Pharmaceutical Association.

Evaluation of N,N-dialkylamides as promising process extractants

NASA Astrophysics Data System (ADS)

Pathak, P. N.; Prabhu, D. R.; Kanekar, A. S.; Manchanda, V. K.

2010-03-01

Studies carried out at BARC, India on the development of new extractants for reprocessing of spent fuel suggested that while straight chain N,N-dihexyloctanamide (DHOA) is promising alternative to TBP for the reprocessing of irradiated uranium based fuels, branched chain N,N-di(2-ethylhexyl)isobutyramide (D2EHIBA) is suitable for the selective recovery of 233U from irradiated Th. In advanced fuel cycle scenarios, the coprocessing of U/Pu stream appears attractive particularly with respect to development of proliferation resistant technologies. DHOA extracted Pu(IV) more efficiently than TBP, both at trace-level concentration as well as under uranium/plutonium loading conditions. Uranium extraction behavior of DHOA was however, similar to that of TBP during the extraction cycle. Stripping behavior of U and Pu (without any reductant) was better for DHOA than that of TBP. It was observed during batch studies that whereas 99% Pu is stripped in four stages in case of DHOA, only 89% Pu is stripped in case of TBP under identical experimental conditions. DHOA offered better fission product decontamination than that of TBP. GANEX (Group ActiNide EXtraction) and ARTIST (Amide-based Radio-resources Treatment with Interim Storage of Transuranics) processes proposed for actinide partitioning use branched chain amides for the selective extraction of uranium from spent fuel feed solutions. The branched-alkyl monoamide (BAMA) proposed to be used in ARTIST process is N,N-di-(2-ethylhexyl)butyramide (D2EHBA). In this context, the extraction behavior of U(VI) and Pu(IV) were compared using D2EHIBA, TBP, and D2EHBA under similar concentration of nitric acid (0.5 — 6M) and of uranium (0-50g/L). These studies suggested that D2EHIBA is a promising extractant for selective extraction of uranium over plutonium in process streams. Similarly, D2EHIBA offered distinctly better decontamination of 233U over Th and fission products under THOREX feed conditions. The possibility of simultaneous stripping and precipitation of thorium (as oxalate) from loaded organic phase was explored using 0.05M oxalic acid. Ammonium diuranate (ADU) precipitation was performed on the oxalate supernatant for the recovery of uranium. Quantitative recovery (>99.9%) of Th as well as of U was achieved. Radiolytic studies suggested that irradiated DHOA and D2EHIBA behaved better with respect to fission product decontamination as compared to that of TBP.

Determination of Low Level Alpha and Beta Emitters Using Liquid-Liquid Extraction and a Liquid Scintillation Spectrometer

NASA Astrophysics Data System (ADS)

Yu, Yu-Fu; BjØRnstad, H. E.; Salbu, B.

Two radiochemical procedures for determination of low level strontium-90 and plutonium-239+240 in environmental and biological materials using combined selective solvent extraction with low level liquid scintillation counting have been presented. Y-90, the daughter nuclide of Sr-90, and Pu-239+240 are selectively extracted from nitric acid solution into 5% di(-2ethylhexyl)phosphoric acid (HDEHP) in toluene and the radionuclides of interest in organic phase are counted with an ultra low level scintillation counter "Quantulus". The lower detection limits for Sr-90 and Pu-239+240 are estimated to be 20 mBq and 0.3 mBq respectively. The developed procedures have been tested for soma environmental and biological samples and the preminarly results show that they are more simple and time-saving than traditional methods.

Super-hydrophobic graphene coated polyurethane (GN@PU) sponge with great oil-water separation performance

NASA Astrophysics Data System (ADS)

Zhang, Xiaotan; Liu, Dongyan; Ma, Yuling; Nie, Jing; Sui, Guoxin

2017-11-01

The graphene/polyurethane (GN@PU) sponge was prepared via simple dip-coating PU sponges in graphene aqueous suspension containing cellulose nanowhiskers (CNWs), where CNWs played a vital role to facilitate the uniform graphene sheets coated on the skeletons of polyurethane sponge (PU). The super-hydrophobic GN@PU sponge was obtained by optimizing the ratio of GN and CNWs to choose the final coating suspensions of GN/CNWs mixture or pure graphene. The GN@PU sponge showed densely packed graphene sheets, contributing super-hydrophobicity to the sponge with water contact angle of 152° and a large lubricating oil absorption value of 31 g g-1. The elasticity, mechanical durability, thermal and chemical stability were all found to be improved after coating with the thin GN layers. Moreover, the GN@PU sponges possess outstanding recyclability and stability since no decline in absorption efficiency was observed after more than 100 cycles.

Effects of Pu-erh ripened tea on hyperuricemic mice studied by serum metabolomics.

PubMed

Zhao, Ran; Chen, Dong; Wu, Hualing

2017-11-15

To evaluate effects of Pu-erh ripened tea in hyperuricemic mice, a mouse hyperuricemia model was developed by oral administration of potassium oxonate for 7 d. Serum metabolomics, based on gas chromatography-mass spectrometry, was used to generate metabolic profiles from normal control, hyperuricemic and allopurinol-treated hyperuricemic mice, as well as hyperuricemic mice given Pu-erh ripened tea at three doses. Pu-erh ripened tea significantly lowered serum uric acid levels. Twelve potential biomarkers associated with hyperuricemia were identified. Pu-erh ripened tea and allopurinol differed in their metabolic effects in the hyperuricemic mice. Levels of glutamic acid, indolelactate, L-allothreonine, nicotinoylglycine, isoleucine, l-cysteine and glycocyamine, all involved in amino acid metabolism, were significantly changed in hyperuricemic mice treated Pu-erh ripened tea. Thus, modulating amino acid metabolism might be the primary mechanism of anti-hyperuricemia by Pu-erh ripened tea. Copyright © 2017 Elsevier B.V. All rights reserved.

Radiation-Induced Grafting with One-Step Process of Waste Polyurethane onto High-Density Polyethylene

PubMed Central

Park, Jong-Seok; Lim, Youn-Mook; Nho, Young-Chang

2015-01-01

The recycling of waste polyurethane (PU) using radiation-induced grafting was investigated. The grafting of waste PU onto a high-density polyethylene (HDPE) matrix was carried out using a radiation technique with maleic anhydride (MAH). HDPE pellets and PU powders were immersed in a MAH-acetone solution. Finally, the prepared mixtures were irradiated with an electron beam accelerator. The grafted composites were characterized by Fourier transformed infrared spectroscopy (FT-IR), surface morphology, and mechanical properties. To make a good composite, the improvement in compatibility between HDPE and PU is an important factor. Radiation-induced grafting increased interfacial adhesion between the PU domain and the HDPE matrix. When the absorbed dose was 75 kGy, the surface morphology of the irradiated PU/HDPE composite was nearly a smooth and single phase, and the elongation at break increased by approximately three times compared with that of non-irradiated PU/HDPE composite. PMID:28787813

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wong, Joe; Krisch, M.; Farber, D.

Plutonium (Pu) is well known to have complex and unique physico-chemical properties. Notably, the pure metal exhibits six solid-state phase transformations with large volume expansions and contractions along the way to the liquid state: {alpha} {yields} {beta} {yields} {gamma} {yields} {delta} {yields} {delta}{prime} {yields} {var_epsilon} {yields} liquid. Unalloyed Pu melts at a relatively low temperature {approx}640 C to yield a higher density liquid than that of the solid from which it melts, (Figure 1). Detailed understanding of the properties of plutonium and plutonium-based alloys is critical for the safe handling, utilization, and long-term storage of these important, but highly toxicmore » materials. However, both technical and and safety issues have made experimental observations extremely difficult. Phonon dispersion curves (PDCs) are key experimenta l data to the understanding of the basic properties of Pu materials such as: force constants, sound velocities, elastic constants, thermodynamics, phase stability, electron-phonon coupling, structural relaxation, etc. However, phonon dispersion curves (PDCs) in plutonium (Pu) and its alloys have defied measurement for the past few decades since the discovery of this element in 1941. This is due to a combination of the high thermal-neutron absorption cross section of plutonium and the inability to grow the large single crystals (with dimensions of a few millimeters) necessary for inelastic neutron scattering. Theoretical simulations of the Pu PDC continue to be hampered by the lack of suitable inter -atomic potentials. Thus, until recently the PDCs for Pu and its alloys have remained unknown experimentally and theoretically. The experimental limitations have recently been overcome by using a tightly focused undulator x-ray micro-beam scattered from single -grain domains in polycrystalline specimens. This experimental approach has been applied successfully to map the complete PDCs of an fcc d-Pu-Ga alloy using the high resolution inelastic x-ray scattering (HRIXS) capability on ID28. The complete PDCs for an fcc Pu-0.6 wt% Ga alloy are plotted in Figure 2, and represent the first full set of phonon dispersions ever determined for any Pu-bearing materials. The solid curves (red) are calculated using a standard Born-von Karman (B-vK) force constant model. An adequate fit to the experimental data is obtained if interactions up to the fourth-nearest neighbours are included. The dashed curves (blue) are recent dynamical mean field theory (DMFT) results by Dai et al. The elastic moduli calculated from the slopes of the experimental phonon dispersion curves near the {Lambda} point are: C{sub 11} = 35.3 {+-} 1.4 GPa, C{sub 12} = 25.5 {+-} 1.5 GPa and C{sub 44} = 30.53 {+-} 1.1 GPa. These values are in excellent agreement with those of the only other measurement on a similar alloy (1 wt % Ga) using ultrasonic techniques as well as with those recently calculated from a combined DMFT and linear response theory for pure {delta}-Pu. Several unusual features, including a large elastic anisotropy, a small shear elastic modulus C{prime}, a Kohn-like anomaly in the T{sub 1}[011] branch, and a pronounced softening of the [111] transverse modes are found. These features can be related to the phase transitions of plutonium and to strong coupling between the lattice structure and the 5f valence instabilities. The HRIXS results also provide a critical test for theoretical treatments of highly correlated 5f electron systems as exemplified by recent dynamical mean field theory (DMFT) calculations for {delta}-plutonium. The experimental-theoretical agreements shown in Figure 2 in terms of a low shear elastic modulus C{prime}, a Kohn-like anomaly in the T{sub 1}[011] branch, and a large softening of the T[111] modes give credence to the DMFT approach for the theoretical treatment of 5f electron systems of which {delta}-Pu is a classic example. However, quantitative differences remain. These are the position of the Kohn anomaly along the T{sub 1}[011] branch, the energy maximum of the T[111] mode s and the softening of the calculated T[100] branch near the X point, which is not observed experimentally. These differences are significant and thus provide a framework for refined theoretical treatments. Systematic HRIXS experiments as a function of temperature and concentration in the fcc Pu-Ga alloys are underway.« less

Transcription factor PU.1 is expressed in white adipose and inhibits adipocyte differentiation

USDA-ARS?s Scientific Manuscript database

PU.1 transcription factor is a critical regulator of hematopoiesis and leukemogenesis. Because PU.1 interacts with transcription factors GATA-2 and C/EBPa, both of which are involved in the regulation of adipogenesis, we investigated whether PU.1 also plays a role in the regulation of adipocyte diff...

A Novel Method for Fabricating Wearable, Piezoresistive, and Pressure Sensors Based on Modified-Graphite/Polyurethane Composite Films

PubMed Central

He, Yin; Li, Wei; Yang, Guilin; Liu, Hao; Lu, Junyu; Zheng, Tongtong; Li, Xiaojiu

2017-01-01

A wearable, low-cost, highly repeatable piezoresistive sensor was fabricated by the synthesis of modified-graphite and polyurethane (PU) composites and polydimethylsiloxane (PDMS). Graphite sheets functionalized by using a silane coupling agent (KH550) were distributed in PU/N,N-dimethylformamide (DMF) solution, which were then molded to modified-graphite/PU (MG/PU) composite films. Experimental results show that with increasing modified-graphite content, the tensile strength of the MG/PU films first increased and then decreased, and the elongation at break of the composite films showed a decreasing trend. The electrical conductivity of the composite films can be influenced by filler modification and concentration, and the percolation threshold of MG/PU was 28.03 wt %. Under liner uniaxial compression, the 30 wt % MG/PU composite films exhibited 0.274 kPa−1 piezoresistive sensitivity within the range of low pressure, and possessed better stability and hysteresis. The flexible MG/PU composite piezoresistive sensors have great potential for body motion, wearable devices for human healthcare, and garment pressure testing. PMID:28773047

Electrical, thermal and structural properties of plasticized waste cooking oil-based polyurethane solid polymer electrolyte

NASA Astrophysics Data System (ADS)

Huzaizi, Rahmatina Mohd; Tahir, Syuhada Mohd; Mahbor, Kamisah Mohamad

2017-12-01

Waste cooking oil-based polyol was synthesized using epoxidation and hydroxylation methods. The polyol was combined with 4,4-diphenylmethane diisocyanate to produce polyurethane (PU) to be used as polymer host in solid polymer electrolyte. 30 wt% LiClO4 was added as doping salt and two types of plasticizers were used; ethylene carbonate (PU-EC) and polyethylene glycol (PU-PEG). The SPE films were characterized using Fourier transform infrared spectroscopy, electrochemical impedance spectroscopy, differential scanning calorimetry (DSC) and X-ray diffraction (XRD). The highest conductivity achieved was 8.4 x 10-8 S cm-1 upon addition of 10 wt% EC. The XRD results showed a decrease of crystalline peaks in PU-EC and the increase in PU-PEG. DSC results revealed that the films; PU, PU-EC and PU-PEG had glass transition temperatures of 159.7, 106.0 and 179.7 °C, respectively. The results showed that the addition of EC increased the amorphous region and the free volume in the SPE structure, thus resulted in higher ionic conductivity.

Plutonium isotopes and 241Am in the atmosphere of Lithuania: A comparison of different source terms

NASA Astrophysics Data System (ADS)

Lujanienė, G.; Valiulis, D.; Byčenkienė, S.; Šakalys, J.; Povinec, P. P.

2012-12-01

137Cs, 241Am and Pu isotopes collected in aerosol samples during 1994-2011 were analyzed with special emphasis on better understanding of Pu and Am behavior in the atmosphere. The results from long-term measurements of 240Pu/239Pu atom ratios showed a bimodal frequency distribution with median values of 0.195 and 0.253, indicating two main sources contributing to the Pu activities at the Vilnius sampling station. The low Pu atom ratio of 0.141 could be attributed to the weapon-grade plutonium derived from the nuclear weapon test sites. The frequency of air masses arriving from the North-West and North-East correlated with the Pu atom ratio indicating the input from the sources located in these regions (the Novaya Zemlya test site, Siberian nuclear plants), while no correlation with the Chernobyl region was observed. Measurements carried out during the Fukushima accident showed a negligible impact of this source with Pu activities by four orders of magnitude lower as compared to the Chernobyl accident. The activity concentration of actinides measured in the integrated sample collected in March-April, 2011 showed a small contribution of Pu with unusual activity and atom ratios indicating the presence of the spent fuel of different origin than that of the Chernobyl accident.

Determination of 90Sr and Pu isotopes in contaminated groundwater samples by inductively coupled plasma mass spectrometry

NASA Astrophysics Data System (ADS)

Zoriy, Miroslav V.; Ostapczuk, Peter; Halicz, Ludwik; Hille, Ralf; Becker, J. Sabine

2005-04-01

A sensitive analytical method for determining the artificial radionuclides 90Sr, 239Pu and 240Pu at the ultratrace level in groundwater samples from the Semipalatinsk Test Site area in Kazakhstan by double-focusing sector field inductively coupled plasma mass spectrometry (ICP-SFMS) was developed. In order to avoid possible isobaric interferences at m/z 90 for 90Sr determination (e.g. 90Zr+, 40Ar50Cr+, 36Ar54Fe+, 58Ni16O2+, 180Hf2+, etc.), the measurements were performed at medium mass resolution under cold plasma conditions. Pu was separated from uranium by means of extraction chromatography using Eichrom TEVA resin with a recovery of 83%. The limits of detection for 90Sr, 239Pu and 240Pu in water samples were determined as 11, 0.12 and 0.1 fg ml-1, respectively. Concentrations of 90Sr and 239Pu in contaminated groundwater samples ranged from 18 to 32 and from 28 to 856 fg ml-1, respectively. The 240Pu/239Pu isotopic ratio in groundwater samples was measured as 0.17. This isotope ratio indicates that the most probable source of contamination of the investigated groundwater samples was the nuclear weapons tests at the Semipalatinsk Test Site conducted by the USSR in the 1960s.

Preparation, process optimization and characterization of core-shell polyurethane/chitosan nanofibers as a potential platform for bioactive scaffolds.

PubMed

Maleknia, Laleh; Dilamian, Mandana; Pilehrood, Mohammad Kazemi; Sadeghi-Aliabadi, Hojjat; Hekmati, Amir Houshang

2018-06-01

In this paper, polyurethane (PU), chitosan (Cs)/polyethylene oxide (PEO), and core-shell PU/Cs nanofibers were produced at the optimal processing conditions using electrospinning technique. Several methods including SEM, TEM, FTIR, XRD, DSC, TGA and image analysis were utilized to characterize these nanofibrous structures. SEM images exhibited that the core-shell PU/Cs nanofibers were spun without any structural imperfections at the optimized processing conditions. TEM image confirmed the PU/Cs core-shell nanofibers were formed apparently. It that seems the inclusion of Cs/PEO to the shell, did not induce the significant variations in the crystallinity in the core-shell nanofibers. DSC analysis showed that the inclusion of Cs/PEO led to the glass temperature of the composition increased significantly compared to those of neat PU nanofibers. The thermal degradation of core-shell PU/Cs was similar to PU nanofibers degradation due to the higher PU concentration compared to other components. It was hypothesized that the core-shell PU/Cs nanofibers can be used as a potential platform for the bioactive scaffolds in tissue engineering. Further biological tests should be conducted to evaluate this platform as a three dimensional scaffold with the capabilities of releasing the bioactive molecules in a sustained manner.

Modulation of Macrophage Phenotype by Biodegradable Polyurethane Nanoparticles: Possible Relation between Macrophage Polarization and Immune Response of Nanoparticles.

PubMed

Huang, Yen-Jang; Hung, Kun-Che; Hung, Huey-Shan; Hsu, Shan-Hui

2018-06-13

Nanomaterials with surface functionalized by different chemical groups can either provoke or attenuate the immune responses of the nanomaterials, which is critical to their biomedical efficacies. In this study, we demonstrate that synthetic waterborne polyurethane nanoparticles (PU NPs) can inhibit the macrophage polarization toward the M1 phenotype but not M2 phenotype. The surface-functionalized PU NPs decrease the secretion levels of proinflammatory cytokines (TNF-α and IL-1β) for M1 macrophages. Specifically, PU NPs with carboxyl groups on the surface exhibit a greater extent of inhibition on M1 polarization than those with amine groups. These water-suspended PU NPs reduce the nuclear factor-κB (NF-κB) activation and suppress the subsequent NLR family pyrin domain containing 3 (NLRP3) inflammasome signals. Furthermore, the dried PU films assembled from PU NPs have a similar effect on macrophage polarization and present a smaller shifting foreign body reaction (FBR) in vivo than the conventional poly(l-lactic acid). Taken together, the biodegradable waterborne PU NPs demonstrate surface-dependent immunosuppressive properties and macrophage polarization effects. The findings suggest potential therapeutic applications of PU NPs in anti-inflammation and macrophage-related disorders and propose a mechanism for the low FBR observed for biodegradable PU materials.

The Microbiome and Metabolites in Fermented Pu-erh Tea as Revealed by High-Throughput Sequencing and Quantitative Multiplex Metabolite Analysis

PubMed Central

Sulyok, Michael; Liu, Xingzhong; Rao, Mingyong

2016-01-01

Pu-erh is a tea produced in Yunnan, China by microbial fermentation of fresh Camellia sinensis leaves by two processes, the traditional raw fermentation and the faster, ripened fermentation. We characterized fungal and bacterial communities in leaves and both Pu-erhs by high-throughput, rDNA-amplicon sequencing and we characterized the profile of bioactive extrolite mycotoxins in Pu-erh teas by quantitative liquid chromatography-tandem mass spectrometry. We identified 390 fungal and 629 bacterial OTUs from leaves and both Pu-erhs. Major findings are: 1) fungal diversity drops and bacterial diversity rises due to raw or ripened fermentation, 2) fungal and bacterial community composition changes significantly between fresh leaves and both raw and ripened Pu-erh, 3) aging causes significant changes in the microbial community of raw, but not ripened, Pu-erh, and, 4) ripened and well-aged raw Pu-erh have similar microbial communities that are distinct from those of young, raw Ph-erh tea. Twenty-five toxic metabolites, mainly of fungal origin, were detected, with patulin and asperglaucide dominating and at levels supporting the Chinese custom of discarding the first preparation of Pu-erh and using the wet tea to then brew a pot for consumption. PMID:27337135

Examining the role of common genetic variants on alcohol, tobacco, cannabis, and illicit drug dependence

PubMed Central

Palmer, RHC; Brick, L; Nugent, NR; Bidwell, LC; McGeary, JE; Knopik, VS; Keller, MC

2014-01-01

Background and Aims Twin and family studies suggest that genetic influences are shared across substances of abuse. However, despite evidence of heritability, genome-wide association and candidate gene studies have indicated numerous markers of limited effects, suggesting that much of the heritability remains missing. We estimated (1) the aggregate effect of common single nucleotide polymorphisms (SNPs) on multiple indicators of comorbid drug problems that are typically employed across community and population-based samples, and (2) the genetic covariance across these measures. Participants 2596 unrelated subjects from the “Study of Addiction: Genetics and Environment” provided information on alcohol, tobacco, cocaine, cannabis, and other illicit substance dependence. Phenotypic measures included: (1) a factor score based on DSM-IV drug dependence diagnoses (DD), (2) a factor score based on problem use (PU; i.e., 1+ DSM-IV symptoms), and (3) dependence vulnerability (DV; a ratio of DSM-IV symptoms to the number of substances used). Findings Univariate and bivariate Genome-wide complex trait analyses of this selected sample indicated that common SNPs explained 25-36% of the variance across measures, with DD and DV having the largest effects [h2SNP (CI)=0.36 (0.11-0.62) and 0.33(0.07-0.58), respectively; PU = 0.25 (-0.01-0.51)]. Genetic effects were shared across the three phenotypic measures of comorbid drug problems (rSNP; rDD-PU = 0.92 (0.76-1.00), rDD-DV = 0.97 (0.87-1.00), and rPU-DV = 0.96 (0.82-1.00)). Conclusion At least 20% of the variance in the generalized vulnerability to substance dependence is attributable to common single nucleotide polymorphisms. The additive effect of common single nucleotide polymorphisms is shared across important indicators of comorbid drug problems. PMID:25424661

Improving the elasticity and cytophilicity of biodegradable polyurethane by changing chain extender.

PubMed

Zhang, Changhong; Zhang, Ning; Wen, Xuejun

2006-11-01

Two types of biodegradable polyurethanes (PUs) were synthesized from methylene di-p-phenyl-diisocyanate (MDI), polycaprolactone diol (PCL-diol), and chain extenders of either butanediol (BD) or 2,2'-(methylimino)diethanol (MIDE). The effects of two types of chain extenders on the degradation, mechanical properties, hydrophilicity, and cytophilicity of PUs were evaluated. In vitro degradation studies showed that PU containing MIDE has a higher degradation rate than PU synthesized using BD as a chain extender. Mechanical testing on dry and wet samples demonstrated that PU containing MIDE has a much higher elongation in the elastic region than PU containing BD. PU containing MIDE is more hydrophilic and retains more liquid during in vitro culture. Furthermore, preliminary cytocompatibility studies showed that both types of degradable PU are nontoxic, and fibroblasts adhere better and proliferate faster on MIDE containing PU than BD containing PU. To compare the cytocompatibility and degradation behaviors of the synthesized PU with existing FDA approved biocompatible material, polylactide (PLA), with a similar degradation rate, was used as negative control. Two types of PU were shown to have similar cytocompatibility and degradation behaviors as those of the PLA material. To verify the effectiveness of the cytotoxicity assay, latex was used as a positive control. Latex samples showed toxicity to cultured cells as expected. In conclusion, by changing the type of chain extender used during the synthesis of degradable PUs, the degradation rate, mechanical properties, hydrophilicity, and cytophilicity can be adjusted for different tissue engineering applications. (c) 2006 Wiley Periodicals, Inc.

Depth profile of 236U/238U in soil samples in La Palma, Canary Islands

PubMed Central

Srncik, M.; Steier, P.; Wallner, G.

2011-01-01

The vertical distribution of the 236U/238U isotopic ratio was investigated in soil samples from three different locations on La Palma (one of the seven Canary Islands, Spain). Additionally the 240Pu/239Pu atomic ratio, as it is a well establish tool for the source identification, was determined. The radiochemical procedure consisted of a U separation step by extraction chromatography using UTEVA® Resin (Eichrom Technologies, Inc.). Afterwards Pu was separated from Th and Np by anion exchange using Dowex 1x2 (Dow Chemical Co.). Furthermore a new chemical procedure with tandem columns to separate Pu and U from the matrix was tested. For the determination of the uranium and plutonium isotopes by alpha spectrometry thin sources were prepared by microprecipitation techniques. Additionally these fractions separated from the soil samples were measured by Accelerator Mass Spectrometry (AMS) to get information on the isotopic ratios 236U/238U, 240Pu/239Pu and 236U/239Pu, respectively. The 236U concentrations [atoms/g] in each surface layer (∼2 cm) were surprisingly high compared to deeper layers where values around two orders of magnitude smaller were found. Since the isotopic ratio 240Pu/239Pu indicated a global fallout signature we assume the same origin as the probable source for 236U. Our measured 236U/239Pu value of around 0.2 is within the expected range for this contamination source. PMID:21481502

Measurement of the 242Pu neutron capture cross section

NASA Astrophysics Data System (ADS)

Buckner, M. Q.; Wu, C. Y.; Henderson, R. A.; Bucher, B.; Bredeweg, T. A.; Baramsai, B.; Couture, A.; Jandel, M.; Mosby, S.; O'Donnell, J. M.; Ullmann, J. L.; Chyzh, A.; Dance Collaboration

2015-10-01

Precision (n,f) and (n, γ) cross sections are important for the network calculations of the radiochemical diagnostic chain for the U.S. DOE's Stockpile Stewardship Program. 242Pu(n, γ) cross section is relevant to the network calculations of Pu and Am. Additionally, new reactor concepts have catalyzed considerable interest in the measurement of improved cross sections for neutron-induced reactions on key actinides. To date, little or no experimental data has been reported on 242Pu(n, γ) for incident neutron energy below 50 keV. A new measurement of the 242Pu(n, γ) reaction was performed with the DANCE together with an improved PPAC for fission-fragment detection at LANSCE during FY14. The relative scale of the 242Pu(n, γ) cross section spans four orders of magnitude for incident neutron energies from thermal to ~ 30 keV. The absolute scale of the 242Pu(n, γ) cross section is set according to the measured 239Pu(n,f) resonance at 7.8 eV; the target was spiked with 239Pu for this measurement. The absolute 242Pu(n, γ) neutron capture cross section is ~ 30% higher than the cross section reported in ENDF for the 2.7 eV resonance. Latest results to be reported. Funded by U.S. DOE Contract No. DE-AC52-07NA27344 (LLNL) and DE-AC52-06NA25396 (LANL). U.S. DOE/NNSA Office of Defense Nuclear Nonproliferation Research and Development. Isotopes (ORNL).

Effects of humic acid concentration on the microbially-mediated reductive solubilization of Pu(IV) polymers.

PubMed

Xie, Jinchuan; Han, Xiaoyuan; Wang, Weixian; Zhou, Xiaohua; Lin, Jianfeng

2017-10-05

The role of humic acid concentration in the microbially-mediated reductive solubilization of Pu(IV) polymers remains unclear until now. The effects of humic concentration (0-150.5mg/L) on the rate and extent of reduction of polymeric Pu(IV) were studied under anaerobic and pH 7.2 conditions. The results show that Shewanella putrefaciens, secreting flavins as endogenous electron shuttles, cannot notably stimulate the reduction of polymeric Pu(IV). In the presence of humic acids, the reduction rate of polymeric Pu(IV) increased with increasing humic concentrations (0-15.0mg/L): e.g., a 102-fold increase from 4.1×10 -15 (HA=0) to 4.2×10 -13 mol Pu(III) aq /h (HA=15.0mg/L). The bioreduced humic acids by S. putrefaciens facilitated the extracellular electron transfer to Pu(IV) polymers and thus the reduction of polymeric Pu(IV) to Pu(III) aq became thermodynamically favorable. However, the reduction rate did not increase but decrease with increasing humic concentrations from 15.0 to 150.5mg/L. Humic coatings formed on the polymer surfaces at relatively high humic concentrations limited the electron transfer to the polymers and thus decreased the reduction rate. The finding of the dynamic role of humic acids in the bioreductive solubilization may be helpful in evaluating Pu mobility in the geosphere. Copyright © 2017 Elsevier B.V. All rights reserved.

Analysis on fuel breeding capability of FBR core region based on minor actinide recycling doping

DOE Office of Scientific and Technical Information (OSTI.GOV)

Permana, Sidik; Novitrian,; Waris, Abdul

Nuclear fuel breeding based on the capability of fuel conversion capability can be achieved by conversion ratio of some fertile materials into fissile materials during nuclear reaction processes such as main fissile materials of U-233, U-235, Pu-239 and Pu-241 and for fertile materials of Th-232, U-238, and Pu-240 as well as Pu-238. Minor actinide (MA) loading option which consists of neptunium, americium and curium will gives some additional contribution from converted MA into plutonium such as conversion Np-237 into Pu-238 and it's produced Pu-238 converts to Pu-239 via neutron capture. Increasing composition of Pu-238 can be used to produce fissilemore » material of Pu-239 as additional contribution. Trans-uranium (TRU) fuel (Mixed fuel loading of MOX (U-Pu) and MA composition) and mixed oxide (MOX) fuel compositions are analyzed for comparative analysis in order to show the effect of MA to the plutonium productions in core in term of reactor criticality condition and fuel breeding capability. In the present study, neptunium (Np) nuclide is used as a representative of MAin trans-uranium (TRU) fuel composition as Np-MOX fuel type. It was loaded into the core region gives significant contribution to reduce the excess reactivity in comparing to mixed oxide (MOX) fuel and in the same time it contributes to increase nuclear fuel breeding capability of the reactor. Neptunium fuel loading scheme in FBR core region gives significant production of Pu-238 as fertile material to absorp neutrons for reducing excess reactivity and additional contribution for fuel breeding.« less

Identifying Patterns in Implementation of Hospital Pressure Ulcer Prevention Programs: A Multisite Qualitative Study.

PubMed

Soban, Lynn M; Finley, Erin P; Miltner, Rebecca S

2016-01-01

To describe the presence or absence of key components of hospital pressure ulcer (PU) prevention programs in 6 acute care hospitals. Multisite comparative case study. Using purposeful selection based on PU rates (high vs low) and hospital size, 6 hospitals within the Veterans Health Administration health care system were invited to participate. Key informant interviews (n = 48) were conducted in each of the 6 participating hospitals among individuals playing key roles in PU prevention: senior nursing leadership (n = 9), nurse manager (n = 7), wound care specialist (n = 6), frontline RNs (n = 26). Qualitative data were collected during face-to-face, semistructured interviews. Interview protocols were tailored to each interviewee's role with a core set of common questions covering 3 major content areas: (1) practice environment (eg, policies and wound care specialists), (2) current prevention practices (eg, conduct of PU risk assessment and skin inspection), and (3) barriers to PU prevention. We conducted structured coding of 5 key components of PU prevention programs and cross-case analysis to identify patterns in operationalization and implementation of program components across hospitals based on facility size and PU rates (low vs high). All hospitals had implemented all PU prevention program components. Component operationalization varied considerably across hospitals. Wound care specialists were integral to the operationalization of the 4 other program components examined; however, staffing levels and work assignments of wound care specialists varied widely. Patterns emerged among hospitals with low and high PU rates with respect to wound care specialist staffing, data monitoring, and staff education. We found hospital-level variations in PU prevention programs. Wound care specialist staffing may represent a potential point of leverage in achieving other PU program components, particularly performance monitoring and staff education.

PU.1 regulates TCR expression by modulating GATA-3 activity

PubMed Central

Chang, Hua-Chen; Han, Ling; Jabeen, Rukhsana; Carotta, Sebastian; Nutt, Stephen L.; Kaplan, Mark H.

2009-01-01

The Ets transcription factor PU.1 is a master regulator for the development of multiple lineages during hematopoiesis. The expression pattern of PU.1 is dynamically regulated during early T lineage development in the thymus. We previously revealed that PU.1 delineates heterogeneity of effector Th2 populations. In this study, we further define the function of PU.1 on the Th2 phenotype using mice that specifically lack PU.1 in T cells using an lck-Cre transgene with a conditional Sfpi1 allele (Sfpi1lck-/-). While deletion of PU.1 by the lck-Cre transgene does not affect T cell development, Sfpi1lck-/- T cells have a lower activation threshold than wild type T cells. When TCR engagement is limiting, Sfpi1lck-/- T cells cultured in Th2 polarizing conditions secrete higher levels of Th2 cytokines and have greater cytokine homogeneity than wild type cells. We show that PU.1 modulates the levels of TCR expression in CD4+ T cells by regulating the DNA-binding activity of GATA-3 and limiting GATA-3 regulation of TCR gene expression. GATA-3 dependent regulation of TCR expression is also observed in Th1 and Th2 cells. In CD4+ T cells, PU.1 expression segregates into subpopulations of cells that have lower levels of surface TCR, suggesting that PU.1 contributes to the heterogeneity of TCR expression. Thus, we have identified a mechanism whereby increased GATA-3 function in the absence of the antagonizing activity of PU.1 leads to increased TCR expression, a reduced activation threshold and increased homogeneity in Th2 populations. PMID:19801513

New approaches for MOX multi-recycling

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gain, T.; Bouvier, E.; Grosman, R.

Due to its low fissile content after irradiation, Pu from used MOX fuel is considered by some as not recyclable in LWR (Light Water Reactors). The point of this paper is hence to go back to those statements and provide a new analysis based on AREVA extended experience in the fields of fissile and fertile material management and optimized waste management. This is done using the current US fuel inventory as a case study. MOX Multi-recycling in LWRs is a closed cycle scenario where U and Pu management through reprocessing and recycling leads to a significant reduction of the usedmore » assemblies to be stored. The recycling of Pu in MOX fuel is moreover a way to maintain the self-protection of the Pu-bearing assemblies. With this scenario, Pu content is also reduced repetitively via a multi-recycling of MOX in LWRs. Simultaneously, {sup 238}Pu content decreases. All along this scenario, HLW (High-Level Radioactive Waste) vitrified canisters are produced and planned for deep geological disposal. Contrary to used fuel, HLW vitrified canisters do not contain proliferation materials. Moreover, the reprocessing of used fuel limits the space needed on current interim storage. With MOX multi-recycling in LWR, Pu isotopy needs to be managed carefully all along the scenario. The early introduction of a limited number of SFRs (Sodium Fast Reactors) can therefore be a real asset for the overall system. A few SFRs would be enough to improve the Pu isotopy from used LWR MOX fuel and provide a Pu-isotopy that could be mixed back with multi-recycled Pu from LWRs, hence increasing the Pu multi-recycling potential in LWRs.« less

Transfer of aged 239+240Pu, 238Pu, 241Am, and 137Cs to cattle grazing a contaminated arid environment.

PubMed

Gilbert, R O; Engel, D W; Anspaugh, L R

1989-09-01

In this paper, estimates are obtained of the fraction of ingested 239+240Pu, 238Pu, 241Am and 137Cs transferred to blood, muscle, liver, kidney, femur, vertebra, and gonads of a reproducing herd of 17 beef cattle, individuals of which grazed within fenced enclosures for up to 1064 days under natural conditions with no supplemental feeding at an arid site contaminated 16 years previously with transuranic radionuclides. The estimated geometric mean (GM) GI-to-blood fractional transfer of 238Pu (0.0001) was about 20 times larger than the estimated transfer of 239+240Pu (0.000005), while the estimated transfer of 241Am (0.00001) was about 2 times larger than that of 239+240Pu. These GM GI-to-blood transfers were smaller than the GI-to-blood transfer value of 0.001 recommended by the International Commission on Radiological Protection (ICRP) for humans exposed via food chains or occupationally from unknown mixtures or compounds of plutonium and americium. Statistical tests indicated significantly (p less than 0.05) larger GI-to-tissue transfers of (1) 238Pu as compared to 239+240Pu for all tissues examined, (2) of 238Pu as compared to 241Am for muscle, liver, femur, and vertebra, and (3) of 241Am as compared to 239+240Pu for blood serum, femur, and kidney. The estimated GM fractional transfers of 137Cs from GI to muscle and liver were 0.03 (n = 8) and 0.001 (n = 3), respectively, assuming a 50-day biological half-time of 137Cs in cattle tissue.

Chronology of Pu isotopes and 236U in an Arctic ice core.

PubMed

Wendel, C C; Oughton, D H; Lind, O C; Skipperud, L; Fifield, L K; Isaksson, E; Tims, S G; Salbu, B

2013-09-01

In the present work, state of the art isotopic fingerprinting techniques are applied to an Arctic ice core in order to quantify deposition of U and Pu, and to identify possible tropospheric transport of debris from former Soviet Union test sites Semipalatinsk (Central Asia) and Novaya Zemlya (Arctic Ocean). An ice core chronology of (236)U, (239)Pu, and (240)Pu concentrations, and atom ratios, measured by accelerator mass spectrometry in a 28.6m deep ice core from the Austfonna glacier at Nordaustlandet, Svalbard is presented. The ice core chronology corresponds to the period 1949 to 1999. The main sources of Pu and (236)U contamination in the Arctic were the atmospheric nuclear detonations in the period 1945 to 1980, as global fallout, and tropospheric fallout from the former Soviet Union test sites Novaya Zemlya and Semipalatinsk. Activity concentrations of (239+240)Pu ranged from 0.008 to 0.254 mBq cm(-2) and (236)U from 0.0039 to 0.053 μBq cm(-2). Concentrations varied in concordance with (137)Cs concentrations in the same ice core. In contrast to previous published results, the concentrations of Pu and (236)U were found to be higher at depths corresponding to the pre-moratorium period (1949 to 1959) than to the post-moratorium period (1961 and 1962). The (240)Pu/(239)Pu ratio ranged from 0.15 to 0.19, and (236)U/(239)Pu ranged from 0.18 to 1.4. The Pu atom ratios ranged within the limits of global fallout in the most intensive period of nuclear atmospheric testing (1952 to 1962). To the best knowledge of the authors the present work is the first publication on biogeochemical cycles with respect to (236)U concentrations and (236)U/(239)Pu atom ratios in the Arctic and in ice cores. Copyright © 2013 Elsevier B.V. All rights reserved.

Solid state reactions of CeO 2, PuO 2, (U,Ce)O 2 and (U,Pu)O 2 with K 2S 2O 8

NASA Astrophysics Data System (ADS)

Keskar, Meera; Kasar, U. M.; Mudher, K. D. Singh; Venugopal, V.

2004-09-01

Solid state reactions of CeO 2, PuO 2 and mixed oxides (U,Ce)O 2 and (U,Pu)O 2 containing different mol.% of Ce and Pu, were carried out with K 2S 2O 8 at different temperatures to identify the formation of various products and to investigate their dissolution behaviour. X-ray, chemical and thermal analysis methods were used to characterise the products formed at various temperatures. The products obtained by heating two moles of K 2S 2O 8 with one mole each of CeO 2, PuO 2, (U,Ce)O 2 and (U,Pu)O 2 at 400 °C were identified as K 4Ce(SO 4) 4, K 4Pu(SO 4) 4, K 4(U,Ce)(SO 4) 4 and K 4(U,Pu)(SO 4) 4, respectively. K 4Ce(SO 4) 4 further decomposed to form K 4Ce(SO 4) 3.5 at 600 °C and mixture of K 2SO 4 and CeO 2 at 950 °C. Thus the products formed during the reaction of 2K 2S 2O 8 + CeO 2 show that cerium undergoes changes in oxidation state from +4 to +3 and again to +4. XRD data of K 4Ce(SO 4) 4 and K 4Ce(SO 4) 3.5 were indexed on triclinic and monoclinic system, respectively. PuO 2 + 2K 2S 2O 8 reacts at 400 °C to form K 4Pu(SO 4) 4 which was stable upto 750 °C and further decomposes to form K 2SO 4 + PuO 2 at 1000 °C. The products formed at 400 °C during the reactions of the oxides and mixed oxides were found to be readily soluble in 1-2 M HNO 3.

Plutonium concentration and (240)Pu/(239)Pu atom ratio in biota collected from Amchitka Island, Alaska: recent measurements using ICP-SFMS.

PubMed

Bu, Kaixuan; Cizdziel, James V; Dasher, Douglas

2013-10-01

Three underground nuclear tests, including the Unites States' largest, were conducted on Amchitka Island, Alaska. Monitoring of the radiological environment around the island is challenging because of its remote location. In 2008, the Department of Energy (DOE) Office of Legacy Management (LM) became responsible for the long term maintenance and surveillance of the Amchitka site. The first DOE LM environmental survey occurred in 2011 and is part of a cycle of activities that will occur every 5 years. The University of Alaska Fairbanks, a participant in the 2011 study, provided the lichen (Cladonia spp.), freshwater moss (Fontinalis neomexicanus), kelp (Eualaria fistulosa) and horse mussel (Modiolus modiolus) samples from Amchitka Island and Adak Island (a control site). These samples were analyzed for (239)Pu and (240)Pu concentration and (240)Pu/(239)Pu atom ratio using inductively coupled plasma sector field mass spectrometry (ICP-SFMS). Plutonium concentrations and (240)Pu/(239)Pu atom ratios were generally consistent with previous terrestrial and marine studies in the region. The ((239)+)(240)Pu levels (mBq kg(-1), dry weight) ranged from 3.79 to 57.1 for lichen, 167-700 for kelp, 27.9-148 for horse mussel, and 560-573 for moss. Lichen from Adak Island had higher Pu concentrations than Amchitka Island, the difference was likely the result of the higher precipitation at Adak compared to Amchitka. The (240)Pu/(239)Pu atom ratios were significantly higher in marine samples compared to terrestrial and freshwater samples (t-test, p < 0.001); lichen and moss averaged 0.184 ± 0.007, similar to the integrated global fallout ratio, whereas kelp and mussel (soft tissue) averaged 0.226 ± 0.003. These observations provide supporting evidence that a large input of isotopically heavier Pu occurred into the North Pacific Ocean, likely from the Marshall Island high yield nuclear tests, but other potential sources, such as the Kamchatka Peninsula Rybachiy Naval Base and Amchitka Island underground nuclear test site cannot be ruled out. Copyright © 2013 Elsevier Ltd. All rights reserved.

Determination of (236)U and transuranium elements in depleted uranium ammunition by alpha-spectrometry and ICP-MS.

PubMed

Desideri, D; Meli, M A; Roselli, C; Testa, C; Boulyga, S F; Becker, J S

2002-11-01

It is well known that ammunition containing depleted uranium (DU) was used by NATO during the Balkan conflict. To evaluate the origin of DU (the enrichment of natural uranium or the reprocessing of spent nuclear fuel) it is necessary to directly detect the presence of activation products ((236)U, (239)Pu, (240)Pu, (241)Am, and (237)Np) in the ammunition. In this work the analysis of actinides by alpha-spectrometry was compared with that by inductively coupled plasma mass spectrometry (ICP-MS) after selective separation of ultratraces of transuranium elements from the uranium matrix. (242)Pu and (243)Am were added to calculate the chemical yield. Plutonium was separated from uranium by extraction chromatography, using tri- n-octylamine (TNOA), with a decontamination factor higher than 10(6); after elution plutonium was determined by ICP-MS ((239)Pu and (240)Pu) and alpha-spectrometry ((239+240)Pu) after electroplating. The concentration of Pu in two DU penetrator samples was 7 x 10(-12) g g(-1) and 2 x 10(-11) g g(-1). The (240)Pu/(239)Pu isotope ratio in one penetrator sample (0.12+/-0.04) was significantly lower than the (240)Pu/(239)Pu ratios found in two soil samples from Kosovo (0.35+/-0.10 and 0.27+/-0.07). (241)Am was separated by extraction chromatography, using di(2-ethylhexyl)phosphoric acid (HDEHP), with a decontamination factor as high as 10(7). The concentration of (241)Am in the penetrator samples was 2.7 x 10(-14) g g(-1) and <9.4 x 10(-15) g g(-1). In addition (237)Np was detected at ultratrace levels. In general, ICP-MS and alpha-spectrometry results were in good agreement. The presence of anthropogenic radionuclides ((236)U, (239)Pu,(240)Pu, (241)Am, and (237)Np) in the penetrators indicates that at least part of the uranium originated from the reprocessing of nuclear fuel. Because the concentrations of radionuclides are very low, their radiotoxicological effect is negligible.

Equilibrium, kinetic, and reactive transport models for plutonium

NASA Astrophysics Data System (ADS)

Schwantes, Jon Michael

Equilibrium, kinetic, and reactive transport models for plutonium (Pu) have been developed to help meet environmental concerns posed by past war-related and present and future peacetime nuclear technologies. A thorough review of the literature identified several hurdles that needed to be overcome in order to develop capable predictive tools for Pu. These hurdles include: (1) missing or ill-defined chemical equilibrium and kinetic constants for environmentally important Pu species; (2) no adequate conceptual model describing the formation of Pu oxy/hydroxide colloids and solids; and (3) an inability of two-phase reactive transport models to adequately simulate Pu behavior in the presence of colloids. A computer program called INVRS K was developed that integrates the geochemical modeling software of PHREEQC with a nonlinear regression routine. This program provides a tool for estimating equilibrium and kinetic constants from experimental data. INVRS K was used to regress on binding constants for Pu sorbing onto various mineral and humic surfaces. These constants enhance the thermodynamic database for Pu and improve the capability of current predictive tools. Time and temperature studies of the Pu intrinsic colloid were also conducted and results of these studies were presented here. Formation constants for the fresh and aged Pu intrinsic colloid were regressed upon using INVRS K. From these results, it was possible to develop a cohesive diagenetic model that describes the formation of Pu oxy/hydroxide colloids and solids. This model provides for the first time a means of deciphering historically unexplained observations with respect to the Pu intrinsic colloid, as well as a basis for simulating the behavior within systems containing these solids. Discussion of the development and application of reactive transport models is also presented and includes: (1) the general application of a 1-D in flow, three-phase (i.e., dissolved, solid, and colloidal), reactive transport model; (2) a simulation of the effects of dissolution of PuO2 solid and radiolysis on the behavior of Pu diffusing out of a confined pore space; and (3) application of a steady-state three phase reactive transport model to groundwater at the Nevada Test Site.

Association of actinides with microorganisms and clay: Implications for radionuclide migration from waste-repository sites

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ohnuki, T.; Francis, A.; Kozai, N.

2010-04-01

We conducted a series of basic studies on the microbial accumulation of actinides to elucidate their migration behavior around backfill materials used in the geological disposal of radioactive wastes. We explored the interactions of U(VI) and Pu(VI) with Bacillus subtilis, kaolinite clay, and within a mixture of the two, directly analyzing their association with the bacterium in the mixture by transmission electron microscopy (TEM) and scanning electron microscopy (SEM). The accumulation of U by the mixture rose as the numbers of B. subtilis cells increased. Treating the kaolinite with potassium acetate (CH{sub 3}COOK) removed approximately 80% of the associated uraniummore » while only 65% was removed in the presence of B. subtilis. TEM-EDS analysis confirmed that most of the U taken from solution was associated with B. subtilis. XANES analyses revealed that the oxidation state of uranium associated with B. subtilis, kaolinite, and with the mixture containing both was U(VI). The amount of Pu sorbed by B. subtilis increased with time, but did not reach equilibrium in 48 h; in kaolinite alone, equilibrium was attained within 8 h. After 48 h, the oxidation state of Pu in the solutions exposed to B. subtilis and to the mixture had changed to Pu(V), whereas the oxidation state of the Pu associated with both was Pu(IV). In contrast, there was no change in the oxidation state of Pu in the solution nor on kaolinite after exposure to Pu(VI). SEM-EDS analysis indicated that most of the Pu in the mixture was associated with the bacteria. These results suggest that U(VI) and Pu(VI) preferentially are sorbed to bacterial cells in the presence of kaolinite clay, and that the mechanism of accumulation of U and Pu differs. U(VI) is sorbed directly to the bacterial cells, whereas Pu(VI) first is reduced to Pu(V) and then to Pu(IV), and the latter is associated with the cells. These results have important implications on the migrations of radionuclides around the repository sites of geological disposal. Microbial cells compete with clay colloids for radionuclides accumulation, and because of their higher affinity and larger size, the microbes accumulate radionuclides and migrate much slower than do the clay colloids. Additionally, biofilm coatings formed on the fractured rock surfaces also accumulate radionuclides, thereby retarding radionuclide migration.« less

CAPABILITY TO RECOVER PLUTONIUM-238 IN H-CANYON/HB-LINE

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fuller, Kenneth S. Jr.; Smith, Robert H. Jr.; Goergen, Charles R.

2013-01-09

Plutonium-238 is used in Radioisotope Thermoelectric Generators (RTGs) to generate electrical power and in Radioisotope Heater Units (RHUs) to produce heat for electronics and environmental control for deep space missions. The domestic supply of Pu-238 consists of scrap material from previous mission production or material purchased from Russia. Currently, the United States has no significant production scale operational capability to produce and separate new Pu-238 from irradiated neptunium-237 targets. The Department of Energy - Nuclear Energy is currently evaluating and developing plans to reconstitute the United States capability to produce Pu-238 from irradiated Np-237 targets. The Savannah River Site hadmore » previously produced and/or processed all the Pu-238 utilized in Radioisotope Thermoelectric Generators (RTGs) for deep space missions up to and including the majority of the plutonium for the Cassini Mission. The previous full production cycle capabilities included: Np-237 target fabrication, target irradiation, target dissolution and Np-237 and Pu-238 separation and purification, conversion of Np-237 and Pu-238 to oxide, scrap recovery, and Pu-238 encapsulation. The capability and equipment still exist and could be revitalized or put back into service to recover and purify Pu-238/Np-237 or broken General Purpose Heat Source (GPHS) pellets utilizing existing process equipment in HB-Line Scrap Recovery, and H-anyon Frame Waste Recovery processes. The conversion of Np-237 and Pu-238 to oxide can be performed in the existing HB-Line Phase-2 and Phase-3 Processes. Dissolution of irradiated Np-237 target material, and separation and purification of Np-237 and Pu-238 product streams would be possible at production rates of ~ 2 kg/month of Pu-238 if the existing H-Canyon Frames Process spare equipment were re-installed. Previously, the primary H-Canyon Frames equipment was removed to be replaced: however, the replacement project was stopped. The spare equipment is stored and still available for installation. Out of specification Pu-238 scrap material can be purified and recovered by utilizing the HB-Line Phase-1 Scrap Recovery Line and the Phase-3 Pu-238 Oxide Conversion Line along with H-Canyon Frame Waste Recovery process. In addition, it also covers and describes utilizing the Phase-2 Np-237 Oxide Conversion Line, in conjunction with the H-Canyon Frames Process to restore the H-Canyon capability to process and recover Np-237 and Pu-238 from irradiated Np-237 targets and address potential synergies with other programs like recovery of Pu-244 and heavy isotopes of curium from other target material.« less

Deviation between the chemistry of Ce(IV) and Pu(IV) and routes to ordered and disordered heterobimetallic 4f/5f and 5f/5f phosphonates

DOE Office of Scientific and Technical Information (OSTI.GOV)

Diwu, Juan; Wang, Shuao; Good, Justin J.

2011-06-06

The heterobimetallic actinide compound UO₂Ce(H₂O)[C₆H₄(PO₃H)₂]₂·H₂O was prepared via the hydrothermal reaction of U(VI) and Ce(IV) in the presence of 1,2-phenylenediphosphonic acid. We demonstrate that this is a kinetic product that is not stable with respect to decomposition to the monometallic compounds. Similar reactions have been explored with U(VI) and Ce(III), resulting in the oxidation of Ce(III) to Ce(IV) and the formation of the Ce(IV) phosphonate, Ce[C₆H₄(PO₃H)(PO₃H₂)][C₆H₄(PO₃H)(PO₃)]·2H₂O, UO₂Ce(H₂O)[C₆H₄(PO₃H)₂]₂·H₂O, and UO₂[C₆H₄(PO₃H)₂](H₂O)·H₂O. In comparison, the reaction of U(VI) with Np(VI) only yields Np[C₆H₄(PO₃H)₂]₂·2H₂O and aqueous U(VI), whereas the reaction of U(VI) with Pu(VI) yields the disordered U(VI)/Pu(VI) compound, (U 0.9Pu 0.1)O₂[C₆H₄(PO₃H)₂](H₂O)·H₂O, and themore » Pu(IV) phosphonate, Pu[C₆H₄(PO₃H)(PO₃H₂)][C₆H₄(PO₃H)(PO₃)]·2H₂O. The reactions of Ce(IV) with Np(VI) yield disordered heterobimetallic phosphonates with both M[C₆H₄(PO₃H)(PO₃H₂)][C₆H₄(PO₃H)(PO₃)]·2H₂O (M = Ce, Np) and M[C₆H₄(PO₃H)₂]₂·2H₂O (M = Ce, Np) structures, as well as the Ce(IV) phosphonate Ce[C₆H₄(PO₃H)(PO₃H₂)][C₆H₄(PO₃H)(PO₃)]·2H₂O. Ce(IV) reacts with Pu(IV) to yield the Pu(VI) compound, PuO₂[C₆H₄(PO₃H)₂](H₂O)·3H₂O, and a disordered heterobimetallic Pu(IV)/Ce(IV) compound with the M[C₆H₄(PO₃H)(PO₃H₂)][C₆H₄(PO₃H)(PO₃)]·2H₂O (M = Ce, Pu) structure. Mixtures of Np(VI) and Pu(VI) yield disordered heterobimetallic Np(IV)/Pu(IV) phosphonates with both the An[C₆H₄(PO₃H)(PO₃H₂)][C₆H₄(PO₃H)(PO₃)]·2H₂O (M = Np, Pu) and An[C₆H₄(PO₃H)₂]₂·2H₂O (M = Np, Pu) formulas.« less

A unified algorithm for predicting partition coefficients for PBPK modeling of drugs and environmental chemicals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Peyret, Thomas; Poulin, Patrick; Krishnan, Kannan, E-mail: kannan.krishnan@umontreal.ca

The algorithms in the literature focusing to predict tissue:blood PC (P{sub tb}) for environmental chemicals and tissue:plasma PC based on total (K{sub p}) or unbound concentration (K{sub pu}) for drugs differ in their consideration of binding to hemoglobin, plasma proteins and charged phospholipids. The objective of the present study was to develop a unified algorithm such that P{sub tb}, K{sub p} and K{sub pu} for both drugs and environmental chemicals could be predicted. The development of the unified algorithm was accomplished by integrating all mechanistic algorithms previously published to compute the PCs. Furthermore, the algorithm was structured in such amore » way as to facilitate predictions of the distribution of organic compounds at the macro (i.e. whole tissue) and micro (i.e. cells and fluids) levels. The resulting unified algorithm was applied to compute the rat P{sub tb}, K{sub p} or K{sub pu} of muscle (n = 174), liver (n = 139) and adipose tissue (n = 141) for acidic, neutral, zwitterionic and basic drugs as well as ketones, acetate esters, alcohols, aliphatic hydrocarbons, aromatic hydrocarbons and ethers. The unified algorithm reproduced adequately the values predicted previously by the published algorithms for a total of 142 drugs and chemicals. The sensitivity analysis demonstrated the relative importance of the various compound properties reflective of specific mechanistic determinants relevant to prediction of PC values of drugs and environmental chemicals. Overall, the present unified algorithm uniquely facilitates the computation of macro and micro level PCs for developing organ and cellular-level PBPK models for both chemicals and drugs.« less

Emissions of amides (N,N-dimethylformamide and formamide) and other obnoxious volatile organic compounds from different mattress textile products.

PubMed

Kim, Ki-Hyun; Pandey, Sudhir K; Kim, Yong-Hyun; Sohn, Jong Ryeul; Oh, J-M

2015-04-01

The emission rates of N,N-dimethylformamide (DMF), formamide (FAd), and certain hazardous volatile organic compounds (VOCs) were measured from seventeen mattress textile samples with four different raw material types: polyurethane (PU: n=3), polyester/polyethylene (PE: n=7), ethylene vinyl acetate (EV: n=3), and polyvinyl chloride (PC: n=4). To simulate the emissions in a heated room during winter season, measurements were made under temperature-controlled conditions, i.e., 50°C by using a mini-chamber system made of a midget impinger. Comparison of the data indicates that the patterns were greatly distinguished between DMF and FAd. PU products yielded the highest mean emission rates of DMF (2940 μg m(-2)h(-1): n=3) followed by PE (325 μg m(-2)h(-1): n=7), although its emission was not seen from other materials (EV and PC). In contrast, the pattern of FAd emission was moderately reversed from that of DMF: EV>PC>PE>PU. The results of our analysis confirm that most materials used for mattress production have the strong potential to emit either DMF or FAd in relatively large quantities while in use in children׳s care facilities, especially in winter months. Moreover, it was also observed that an increase in temperature (25°C to 50°C) had a significant impact on the emission rate of FAd and other hazardous VOCs. In addition to the aforementioned amides, the study revealed significant emissions of a number of hazardous VOCs, such as aromatic and carbonyl compounds. Copyright © 2014 Elsevier Inc. All rights reserved.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Andrews, Madison Theresa; Bates, Cameron Russell; Mckigney, Edward Allen

Here, this work presents the organic scintillation simulation capabilities of DRiFT, a post-processing Detector Response Function Toolkit for MCNPR output. DRiFT is used to create realistic scintillation detector response functions to incident neutron and gamma mixed- field radiation. As a post-processing tool, DRiFT leverages the extensively validated radiation transport capabilities of MCNPR ®6, which also provides the ability to simulate complex sources and geometries. DRiFT is designed to be flexible, it allows the user to specify scintillator material, PMT type, applied PMT voltage, and quenching data used in simulations. The toolkit's capabilities, which include the generation of pulse shape discriminationmore » plots and full-energy detector spectra, are demonstrated in a comparison of measured and simulated neutron contributions from 252Cf and PuBe, and photon spectra from 22Na and 228Th sources. DRiFT reproduced energy resolution effects observed in EJ-301 measurements through the inclusion of scintillation yield variances, photon transport noise, and PMT photocathode and multiplication noise.« less

Plutonium oxalate precipitation for trace elemental determination in plutonium materials

DOE PAGES

Xu, Ning; Gallimore, David; Lujan, Elmer; ...

2015-05-26

In this study, an analytical chemistry method has been developed that removes the plutonium (Pu) matrix from the dissolved Pu metal or oxide solution prior to the determination of trace impurities that are present in the metal or oxide. In this study, a Pu oxalate approach was employed to separate Pu from trace impurities. After Pu(III) was precipitated with oxalic acid and separated by centrifugation, trace elemental constituents in the supernatant were analyzed by inductively coupled plasma-optical emission spectroscopy with minimized spectral interferences from the sample matrix.

PRODUCTION OF PLUTONIUM FROM PLUTONIUM FLUORIDE

DOEpatents

Baker, R.D.

1959-06-01

Reduction of PuF/sub 4/ to metal is described. In the example given, PuF/sub 4/ is mixed with 0.3 mole I/sub 2/ per mole of Pu and Ca powder 25% in excess of that required for eduction of the Pu salt, and I/sub 2/ is added. The mixture is charged to a magnesia-lined steel bomb which is heated until reacted in a furnace. The Pu is reduced to metal and recovered as a slug after the bomb is cooled and opened. About 90% yield is obtained. (T.R.H.)

Electrochemistry and Spectroelectrochemistry of the Pu (III/IV) and (IV/VI) Couples in Nitric Acid Systems

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lines, Amanda M.; Adami, Susan R.; Casella, Amanda J.

The solution chemistry of Pu in nitric acid is explored via electrochemistry and spectroelectrochemistry. By utilizing and comparing these techniques, an improved understanding of Pu behavior and its dependence on nitric acid concentration can be achieved. Here the Pu (III/IV) couple is characterized using cyclic voltammetry, square wave voltammetry, and a spectroelectrochemical Nernst step. Results indicate the formal reduction potential of the couple shifts negative with increasing acid concentration and reversible electrochemistry is no longer attainable above 6 M HNO3. Spectroelectrochemistry is also used to explore the irreversible oxidation of Pu(IV) to Pu(VI) and shine light on the mechanism andmore » acid dependence of the redox reaction.« less

Facile preparation of high density polyethylene superhydrophobic/superoleophilic coatings on glass, copper and polyurethane sponge for self-cleaning, corrosion resistance and efficient oil/water separation.

PubMed

Cheng, Yuanyuan; Wu, Bei; Ma, Xiaofan; Lu, Shixiang; Xu, Wenguo; Szunerits, Sabine; Boukherroub, Rabah

2018-04-18

Inspired by the lotus effect and water-repellent properties of water striders' legs, superhydrophobic surfaces have been intensively investigated from both fundamental and applied perspectives for daily and industrial applications. Various techniques are available for the fabrication of artificial superoleophilic/superhydrophobic (SS). However, most of these techniques are tedious and often require hazardous or expensive equipment, which hampers their implementation for practical applications. In the present work, we used a versatile and straightforward technique based on polymer drop-casting for the preparation SS materials that can be implemented on any substrate. High density polyethylene (HDPE) SS coatings were prepared on different substrates (glass, copper mesh and polyurethane (PU) sponge) by drop casting the parent polymer xylene-ethanol solution at room temperature. All the substrates exhibited a superhydrophobic behavior with a water contact angle (WCA) greater than 150°. Furthermore, the corrosion resistance, stability, self-cleaning property, and water/oil separation of the developed materials were also assessed. While copper mesh and PU sponge exhibited good ability for oil and organic solvents separation from water, the HDPE-functionalized PU sponge displayed good adsorption capacity, 32-90 times the weight of adsorbed substance vs. the weight of adsorbent. Copyright © 2018 Elsevier Inc. All rights reserved.

Cell–material interactions on biphasic polyurethane matrix

PubMed Central

Dicesare, Patrick; Fox, Wade M.; Hill, Michael J.; Krishnan, G. Rajesh; Yang, Shuying; Sarkar, Debanjan

2013-01-01

Cell–matrix interaction is a key regulator for controlling stem cell fate in regenerative tissue engineering. These interactions are induced and controlled by the nanoscale features of extracellular matrix and are mimicked on synthetic matrices to control cell structure and functions. Recent studies have shown that nanostructured matrices can modulate stem cell behavior and exert specific role in tissue regeneration. In this study, we have demonstrated that nanostructured phase morphology of synthetic matrix can control adhesion, proliferation, organization and migration of human mesenchymal stem cells (MSCs). Nanostructured biodegradable polyurethanes (PU) with segmental composition exhibit biphasic morphology at nanoscale dimensions and can control cellular features of MSCs. Biodegradable PU with polyester soft segment and hard segment composed of aliphatic diisocyanates and dipeptide chain extender were designed to examine the effect polyurethane phase morphology. By altering the polyurethane composition, morphological architecture of PU was modulated and its effect was examined on MSC. Results show that MSCs can sense the nanoscale morphology of biphasic polyurethane matrix to exhibit distinct cellular features and, thus, signifies the relevance of matrix phase morphology. The role of nanostructured phases of a synthetic matrix in controlling cell–matrix interaction provides important insights for regulation of cell behavior on synthetic matrix and, therefore, is an important tool for engineering tissue regeneration. PMID:23255285

A facile method to prepare superparamagnetic iron oxide and hydrophobic drug-encapsulated biodegradable polyurethane nanoparticles

PubMed Central

Cheng, Kuo-Wei; Hsu, Shan-hui

2017-01-01

Superparamagnetic iron oxide nanoparticles (SPIO NPs) have a wide range of biomedical applications such as in magnetic resonance imaging, targeting, and hyperthermia therapy. Aggregation of SPIO NPs can occur because of the hydrophobic surface and high surface energy of SPIO NPs. Here, we developed a facile method to encapsulate SPIO NPs in amphiphilic biodegradable polymer. Anionic biodegradable polyurethane nanoparticles (PU NPs) with ~35 nm size and different chemistry were prepared by waterborne processes. SPIO NPs were synthesized by chemical co-precipitation. SPIO NPs were then added to the aqueous dispersion of PU NPs, followed by application of high-frequency (~20 kHz) ultrasonic vibration for 3 min. This method rendered SPIO-PU hybrid NPs (size ~110 nm) suspended in water. SPIO-PU hybrid NPs contained ~50–60 wt% SPIO and retained the superparamagnetic property (evaluated by a magnetometer) as well as high contrast in magnetic resonance imaging. SPIO-PU NPs also showed the ability to provide cell hyperthermic treatment. Using the same ultrasonic method, hydrophobic drug (Vitamin K3 [VK3]) or (9-(methylaminomethyl) anthracene [MAMA]) could also be encapsulated in PU NPs. The VK3-PU or MAMA-PU hybrid NPs had ~35 nm size and different release profiles for PUs with different chemistry. The encapsulation efficiency for VK3 and MAMA was high (~95%) without burst release. The encapsulation mechanism may be attributed to the low glass transition temperature (Tg) and good mechanical compliance of PU NPs. The new encapsulation method involving waterborne biodegradable PU NPs is simple, rapid, and effective to produce multimodular NP carriers. PMID:28280341

A facile method to prepare superparamagnetic iron oxide and hydrophobic drug-encapsulated biodegradable polyurethane nanoparticles.

PubMed

Cheng, Kuo-Wei; Hsu, Shan-Hui

2017-01-01

Superparamagnetic iron oxide nanoparticles (SPIO NPs) have a wide range of biomedical applications such as in magnetic resonance imaging, targeting, and hyperthermia therapy. Aggregation of SPIO NPs can occur because of the hydrophobic surface and high surface energy of SPIO NPs. Here, we developed a facile method to encapsulate SPIO NPs in amphiphilic biodegradable polymer. Anionic biodegradable polyurethane nanoparticles (PU NPs) with ~35 nm size and different chemistry were prepared by waterborne processes. SPIO NPs were synthesized by chemical co-precipitation. SPIO NPs were then added to the aqueous dispersion of PU NPs, followed by application of high-frequency (~20 kHz) ultrasonic vibration for 3 min. This method rendered SPIO-PU hybrid NPs (size ~110 nm) suspended in water. SPIO-PU hybrid NPs contained ~50-60 wt% SPIO and retained the superparamagnetic property (evaluated by a magnetometer) as well as high contrast in magnetic resonance imaging. SPIO-PU NPs also showed the ability to provide cell hyperthermic treatment. Using the same ultrasonic method, hydrophobic drug (Vitamin K3 [VK3]) or (9-(methylaminomethyl) anthracene [MAMA]) could also be encapsulated in PU NPs. The VK3-PU or MAMA-PU hybrid NPs had ~35 nm size and different release profiles for PUs with different chemistry. The encapsulation efficiency for VK3 and MAMA was high (~95%) without burst release. The encapsulation mechanism may be attributed to the low glass transition temperature (Tg) and good mechanical compliance of PU NPs. The new encapsulation method involving waterborne biodegradable PU NPs is simple, rapid, and effective to produce multimodular NP carriers.

Layer-by-layer assembly of type I collagen and chondroitin sulfate on aminolyzed PU for potential cartilage tissue engineering application

NASA Astrophysics Data System (ADS)

He, Xianyun; Wang, Yingjun; Wu, Gang

2012-10-01

In this paper, a two-step method was used to synthesize a biodegradable polyurethane (PU) composed of L-lysine ethyl ester diisocyanate (LDI), poly(ɛ-caprolactone) diols (PCL-diol) and 1,4:3,6-dianhydro-D-sorbitol (isosorbide). Amino groups were introduced onto the surface of the PU membrane by an amination reacting with 1,3-propanediamine to produce polycationic substratum. And then, type I collagen (Col) and chondroitin sulfate (CS) were deposited alternately on the polycationic substratum through layer-by-layer (LBL) assembly technology. The FTIR and 1H NMR results showed that the polyurethane was successfully synthesized. Rhodamine B isothiocyanate (RBITC) fluorescence spectrum indicated that amino groups were successfully introduced onto the PU surface. The results of quartz-crystal microbalance (QCM) and RBITC-Col fluorescence spectroscopy monitoring the LBL assemble process presented that the Col/CS deposited alternately on the PU surface. X-ray photoelectron spectroscopy (XPS) results displayed that the CS deposited on the PU surface as well. The surface of the assembled PU became even smoother observed from the surface morphology by atomic force microscopy (AFM) imaging. The hydrophilicity of the PU membrane was greatly enhanced though the modification of LBL assembly. The PU modified with the adsorption of Col/CS may be a potential application for cartilage tissue engineering due to its created mimicking chondrogenic environment.

In situ high temperature X-Ray diffraction study of the phase equilibria in the UO2-PuO2-Pu2O3 system

NASA Astrophysics Data System (ADS)

Belin, Renaud C.; Strach, Michal; Truphémus, Thibaut; Guéneau, Christine; Richaud, Jean-Christophe; Rogez, Jacques

2015-10-01

The region of the U-Pu-O phase diagram delimited by the compounds UO2-PuO2-Pu2O3 is known to exhibit a miscibility gap at low temperature. Consequently, MOX fuels with a composition entering this region could decompose into two fluorite phases and thus exhibit chemical heterogeneities. The experimental data on this domain found in the literature are scarce and usually provided using DTA that is not suitable for the investigation of such decomposition phenomena. In the present work, new experimental data, i.e. crystallographic phases, lattice parameters, phase fractions and temperature of phase separation, were measured in the composition range 0.14 < Pu/(U + Pu) < 0.62 and 1.85 < O/(U + Pu) < 2 from 298 to 1750 K using a novel in situ high temperature X-ray diffraction apparatus. A very good agreement is found between the temperature of phase separation determined from our results and using the thermodynamic model of the U-Pu-O system based on the CALPHAD method. Also, the combined use of thermodynamic calculations and XRD results refinement proved helpful in the determination of the O/M ratio of the samples during cooling. The methodology used in the current work might be useful to investigate other oxides systems exhibiting a miscibility gap.

Two Dihydroxo-Bridged Plutonium(IV) Nitrate Dimers and Their Relevance to Trends in Tetravalent Ion Hydrolysis and Condensation

DOE PAGES

Knope, Karah E.; Skanthakumar, S.; Soderholm, L.

2015-10-13

We report the room temperature synthesis and structural characterization of a μ2-hydroxobridged PuIV dimer obtained from an acidic, nitric acid solution. The discrete Pu 2(OH) 2(NO 3) 6(H 2O) 4 moiety crystallized with two distinct crystal structures, (1) [Pu 2(OH) 2(NO 3) 6(H 2O) 4] 2·11H 2O and (2) Pu 2(OH) 2(NO 3) 6(H 2O) 4·2H 2O, which differ primarily in the number of incorporated water molecules. High-energy X-ray scattering (HEXS) data obtained from the mother liquor showed evidence of a correlation at 3.7(10) Å but only after concentration of the stock solution. This distance is consistent with the dihydroxo-bridgedmore » distance of 3.799(1) Å seen in the solid-state structure as well as with the known Pu-Pu distance in PuO 2. The structural characterization of a dihydroxo-bridged Pu moiety is discussed in terms of its relevance to the underlying mechanisms of tetravalent-metal-ion condensation« less

Separation of plutonium from lanthanum by electrolysis in LiCl KCl onto molten bismuth electrode

NASA Astrophysics Data System (ADS)

Serp, J.; Lefebvre, P.; Malmbeck, R.; Rebizant, J.; Vallet, P.; Glatz, J.-P.

2005-04-01

This work presents a study on the electroseparation of plutonium from lanthanum using molten bismuth electrodes in LiCl-KCl eutectic at 733 K. The reduction potentials of Pu3+ and La3+ ions were measured on a Bi thin film electrode using cyclic voltammetry (CV). A difference between the peak potentials for the formation of PuBi2 and LaBi2 of approximately 100 mV was found. Separation tests were then carried out using different current densities and salt phase compositions between a plutonium rod anode and an unstirred molten Bi cathode in order to evaluate the efficiency of an electrolytic separation process. At a current density of 12 mA/cm2/wt% (Pu3+), only Pu3+ ions are reduced into the molten Bi electrode, leaving La3+ ions in the salt melt. Similar results were found at two different Pu/La concentration ratios ([Pu]/[La] = 4 and 10). At a current density of 26 mA/cm2/wt% (Pu3+), co-reduction of Pu and La was observed as expected by the large negative potential of the Bi cathode during the separation test.

Minimal PU.1 reduction induces a preleukemic state and promotes development of acute myeloid leukemia

PubMed Central

Will, Britta; Vogler, Thomas O.; Narayanagari, Swathi; Bartholdy, Boris; Todorova, Tihomira I.; da Silva Ferreira, Mariana; Chen, Jiahao; Yu, Yiting; Mayer, Jillian; Barreyro, Laura; Carvajal, Luis; Ben Neriah, Daniela; Roth, Michael; van Oers, Johanna; Schaetzlein, Sonja; McMahon, Christine; Edelmann, Winfried; Verma, Amit; Steidl, Ulrich

2016-01-01

Modest transcriptional changes caused by genetic or epigenetic mechanisms are frequent in human cancer. Although loss or near-complete loss of the hematopoietic transcription factor PU.1 induces acute myeloid leukemia (AML) in mice, a similar degree of PU.1 impairment is exceedingly rare in human AML; yet moderate PU.1 inhibition is common in AML patients. We assessed functional consequences of modest reduction of PU.1 expression on leukemia development in mice harboring DNA lesions resembling those acquired during human stem cell aging. Heterozygous deletion of an enhancer of PU.1, which resulted in 35% reduction of PU.1 expression, was sufficient to induce myeloid biased preleukemic stem cells and subsequent transformation to AML in a DNA mismatch repair-deficient background. AML progression was mediated by inhibition of expression of a PU.1 cooperating transcription factor, Irf8. Strikingly, we found significant molecular similarities with human myelodysplastic syndrome and AML. This study demonstrates that minimal reduction of a key lineage-specific transcription factor that commonly occurs in human disease is sufficient to initiate cancer development and provides mechanistic insight into the formation and progression of preleukemic stem cells in AML. PMID:26343801

Electrowinning of U-Pu onto inert solid cathode in LiCl-KCl eutectic melts containing UCl3 and PuCl3

NASA Astrophysics Data System (ADS)

Sakamura, Yoshiharu; Murakami, Tsuyoshi; Tada, Kohei; Kitawaki, Shinichi

2018-04-01

Electrowinning process was investigated for extracting actinides from molten salts used for the pyrochemical reprocessing of spent nuclear fuels. The separation of actinides from lanthanides is expected to be enhanced by employing inert solid cathodes due to larger potential differences on these cathodes. In this study, the co-deposition behavior of Pu and U metals onto an inert solid cathode made of tungsten was examined in LiCl-KCl eutectic melts containing UCl3 and PuCl3 at 773 K. The standard potential of U3+/U is 0.31 V more positive than that of Pu3+/Pu. The U3+ concentration was varied in the range of 0.11-0.66 wt%, while the Pu3+ concentration was maintained at approximately 2.9 wt%. When the U3+ concentration was not sufficiently low, the deposited U metal readily grew outward from the electrode surface and the electrode surface area rapidly increased, which facilitated only the deposition of U metal. It was estimated that metallic Pu can be efficiently collected along with U at U3+ concentrations lower than ∼0.2 wt%.

Polyurethane nanocomposites incorporating biobased polyols and reinforced with a low fraction of cellulose nanocrystals.

PubMed

Kong, Xiaohua; Zhao, Liyan; Curtis, Jonathan M

2016-11-05

High solids content polyurethane (PU) nanocomposites with enhanced thermal and mechanical properties were produced by incorporating of low fractions of cellulose nanocrystals (CNC) in a solvent-free process. This involved the use of a simple procedure to produce well dispersed and stable suspensions of CNC in biobased polyols, which were then used to produce PU-CNC nanocomposites. Transmission electron microscopy revealed that individual CNC particles were dispersed homogenously within the PU matrix. FTIR results suggested that CNC particles are covalently bonded to the PU molecular chains during polymerization. The thermal mechanical properties of the nanocomposites are significantly improved over pure PU as indicated by differential scanning calorimetry and dynamic mechanical analysis. Compared to pure PU, the PU nanocomposites made with the addition of only 0.5% of CNC had glass transition temperatures that were 6°C higher, their Young's moduli were about 10% higher and their abrasion resistance was higher by about 25%. The optimal composition contains only 0.5% CNC (w/w) which indicates that there is good potential for utilization of low levels of CNC for reinforcement of PU composites made using biobased polyols. Copyright © 2016 Elsevier Ltd. All rights reserved.

Context and implementation: A concept analysis towards conceptual maturity.

PubMed

Pfadenhauer, Lisa Maria; Mozygemba, Kati; Gerhardus, Ansgar; Hofmann, Bjørn; Booth, Andrew; Lysdahl, Kristin Bakke; Tummers, Marcia; Burns, Jacob; Rehfuess, Eva Annette

2015-01-01

Context and implementation of health interventions have received increasing attention over the past decade, in particular with respect to their influence on the effectiveness and reach of complex interventions. The underlying concepts are both considered partially mature, limiting their operationalization in research and practice. We conducted systematic literature searches and pragmatic utility (PU) concept analyses to provide a state-of-the-art assessment of the concepts of "context" and "implementation" in the health sciences to create a common understanding for their use within systematic reviews and HTA. We performed two separate searches, one for context (EMBASE, MEDLINE) and the other for implementation (Google Scholar) to identify relevant models, theories and frameworks. 17 publications on context and 35 articles on implementation met our inclusion criteria. PU concept analysis comprises three guiding principles: selection of the literature, organization and structuring of the literature, and asking analytic questions of the literature. Both concepts were analyzed according to four features of conceptual maturity, i.e., consensual definitions, clear characteristics, fully described preconditions and outcomes, and delineated boundaries. Context and implementation are highly intertwined, with both concepts influencing and interacting with each other. Context is defined as a set of characteristics and circumstances that surround the implementation effort. Implementation is conceptualized as a planned and deliberately initiated effort with the intention to put an intervention into practice. The concept of implementation presents largely consensual definitions and relatively well-defined boundaries, while distinguishing features, preconditions and outcomes are not yet fully articulated. In contrast, definitions of context vary widely, and boundaries with neighbouring concepts, such as setting and environment, are blurred; characteristics, preconditions and outcomes are ill-defined. Therefore, the maturity of both concepts should be further improved to facilitate operationalization in systematic reviews and HTAs. Copyright © 2015. Published by Elsevier GmbH.

Activity measurements of a suite of radionuclides (241Am, 239,240Pu, 238Pu, 238U, 234U, 235U, 232Th, 230Th, 228Th, 228Ra, 137Cs, 210Pb, 90Sr and 40K) in biota reference material (Ocean Shellfish): CCRI(II)-S3

NASA Astrophysics Data System (ADS)

Nour, S.; Karam, L. R.; Inn, K. G. W.

2012-01-01

In 2005, the CCRI decided that a comparison undertaken from 2002 to 2008 by the NIST (under the auspices of the Inter-America Metrology System [SIM]) in the development of a new biota (Ocean Shellfish) standard reference material (SRM) was sufficiently well constructed that it could be converted into a supplementary comparison under CCRI(II), with comparison identifier CCRI(II)-S3. This would enable the comparison to be used to support calibration and measurement capability (CMC) claims for radionuclide measurements in reference materials (specifically, animal-based organic materials). Previous comparisons of radionuclides have been of single or multiple nuclides in non-complex matrices and results of such could not be extended to support capabilities to measure the same nuclides in reference materials. The results of this comparison have been used to determine the certified reference value of the SRM. The key comparison working group (KCWG) of the CCRI(II) has approved this approach as a mechanism to link all the results to certified 'reference values' in lieu of the key comparison reference value (KCRV) of these specified radionuclides in this type of matrix (shellfish) so as to support CMCs of similar materials submitted by the present participants. Main text. To reach the main text of this paper, click on Final Report. Note that this text is that which appears in Appendix B of the BIPM key comparison database kcdb.bipm.org/. The final report has been peer-reviewed and approved for publication by the CCRI, according to the provisions of the CIPM Mutual Recognition Arrangement (CIPM MRA).

137Cs and plutonium isotopes accumulation/retention in bottom sediments and soil in Lithuania: A case study of the activity concentration of anthropogenic radionuclides and their provenance before the start of operation of the Belarusian Nuclear Power Plant (NPP).

PubMed

Marčiulionienė, D; Lukšienė, B; Montvydienė, D; Jefanova, O; Mažeika, J; Taraškevičius, R; Stakėnienė, R; Petrošius, R; Maceika, E; Tarasiuk, N; Žukauskaitė, Z; Kazakevičiūtė, L; Volkova, M

2017-11-01

Knowledge of the background activity concentrations of anthropogenic radionuclides before the start of operations of the new nuclear facilities in Belarus is of great value worldwide. Inland water bodies in Lithuania (specifically the Neris River, the Nemunas River and the Curonian Lagoon) are near the site of the Belarusian NPP under construction and, for this reason, sediments and flooded soils from these sensitive areas were analysed for radiocesium and plutonium isotopes (macrophytes were analysed only for 137 Cs) in 2011-2012. The 137 Cs and 239+240 Pu activity concentrations in bottom sediments from the Nemunas River, sampled in 1995-1996 and re-calculated to the year 2016, were compared with those of 2011-2012. The obtained activity of 137 Cs in bottom sediments of the Nemunas River and Curonian Lagoon varied from 1 Bq/kg to 47.0 Bq/kg. The activity of 137 Cs in the tested soils ranged from 5.3 B g/kg to 32.9 Bq/kg. The 239+240 Pu activity in bottom sediments of the studied sampling sites varied between 0.016 and 0.34 Bq/kg and in flooded soils from 0.064 to 0.55 Bq/kg. The 238 Pu activity values were very low or lower than the detection limit. The activity of 137 Cs in macrophytes varied from values lower than the detection limit to 6 Bq/kg. A strong positive linear correlation for bottom sediments was calculated between: 239+240 Pu and total organic carbon (TOC), r = 0.86, p-value 0.01; 239+240 Pu and silt, r = 0.80, p-value 0.029; 137 Cs and silt, r = 0.78, p-value 0.04; and 137 Cs and TOC, r = 0.85, p-value 0.015. The similar peculiarities of 137 Cs and 239+240 Pu accumulation in bottom sediments and flooded soil allow us to assume that 137 Cs can be used as a tracer for 239+240 Pu in the initial stage of searching for radionuclide accumulation zones. A remaining impact of the Chernobyl fallout in average comprised: in the Lower Nemunas River and Curonian Lagoon sediments - 51%, in the Middle Nemunas River -90% and in the floodplains of the Nemunas River - 59%, while the provenance of plutonium in studied bottom sediments and flooded soil was the global fallout. Copyright © 2017 Elsevier Ltd. All rights reserved.

Solution speciation of plutonium and Americium at an Australian legacy radioactive waste disposal site.

PubMed

Ikeda-Ohno, Atsushi; Harrison, Jennifer J; Thiruvoth, Sangeeth; Wilsher, Kerry; Wong, Henri K Y; Johansen, Mathew P; Waite, T David; Payne, Timothy E

2014-09-02

During the 1960s, radioactive waste containing small amounts of plutonium (Pu) and americium (Am) was disposed in shallow trenches at the Little Forest Burial Ground (LFBG), located near the southern suburbs of Sydney, Australia. Because of periodic saturation and overflowing of the former disposal trenches, Pu and Am have been transferred from the buried wastes into the surrounding surface soils. The presence of readily detected amounts of Pu and Am in the trench waters provides a unique opportunity to study their aqueous speciation under environmentally relevant conditions. This study aims to comprehensively investigate the chemical speciation of Pu and Am in the trench water by combining fluoride coprecipitation, solvent extraction, particle size fractionation, and thermochemical modeling. The predominant oxidation states of dissolved Pu and Am species were found to be Pu(IV) and Am(III), and large proportions of both actinides (Pu, 97.7%; Am, 86.8%) were associated with mobile colloids in the submicron size range. On the basis of this information, possible management options are assessed.

The incorporation of plutonium in lanthanum zirconate pyrochlore

NASA Astrophysics Data System (ADS)

Gregg, Daniel J.; Zhang, Yingjie; Middleburgh, Simon C.; Conradson, Steven D.; Triani, Gerry; Lumpkin, Gregory R.; Vance, Eric R.

2013-11-01

The incorporation of plutonium (Pu) within lanthanum zirconate pyrochlore was investigated using air, argon, and N2-3.5%H2 sintering atmospheres together with Ca2+ and Sr2+ incorporation for charge compensation. The samples have been characterised in the first instance by X-ray diffraction (XRD), scanning electron microscopy (SEM) and diffuse reflectance spectroscopy (DRS). The results show Pu can be exchanged for La3+ on the A-site with and without charge compensation and for Zr4+ on the B-site. DRS measurements were made over the wavenumber range of 4000-19,000 cm-1 and the Pu in all air- and argon-sintered samples was found to be present as Pu4+ while that in samples sintered in N2-3.5%H2 was present as Pu3+. The Pu valence was confirmed for three of the samples using X-ray near-edge absorption spectroscopy (XANES). Pu valences >4+ were not observed in any of the samples.

Investigation of the interfacial properties of polyurethane/carbon nanotube hybrid composites: A molecular dynamics study

NASA Astrophysics Data System (ADS)

Goclon, Jakub; Panczyk, Tomasz; Winkler, Krzysztof

2018-03-01

Considering the varied applications of hybrid polymer/carbon nanotube composites and the constant progress in the synthesis methods of such materials, we report a theoretical study of interfacial layer formation between pristine single-wall carbon nanotubes (SWCNTs) and polyurethane (PU) using molecular dynamic simulations. We vary the SWCNT diameter and the number of PU chains to examine various PU-SWCNT interaction patterns. Our simulations indicate the important role of intra-chain forces in PU. No regular polymeric structures could be identified on the carbon nanotube surface during the simulations. We find that increasing the SWCNT diameter results in stronger polymer binding. However, higher surface loadings of PU lead to stronger interpenetration by the polymeric segments; this effect is more apparent for SWCNTs with small diameters. Our core finding is that the attached PU binds most strongly to the carbon nanotubes with the largest diameters. Polymer dynamics reveal the loose distribution of PU chains in these systems.

Determination of 241Pu in low-level radioactive wastes from reactors.

PubMed

Martin, J E

1986-11-01

Plutonium-241 is unique in low-level radioactive wastes (LLW) from nuclear power plants because it is the only significant beta-emitting transuranic nuclide in LLW, has a relatively short half-life of 14.4 y, and has a fairly high allowable concentration for shallow land burial. Radiochemical separation of Pu followed by liquid scintillation analysis was used to quantitate 241Pu in a wide range of solid, semi-solid, and liquid LLW samples from two nuclear plants in Michigan. The 241Pu concentrations varied considerably by sample type and reactor operational period as did their correlation with 137Cs, 144Ce, 239Pu and 240Pu concentrations in the same sample. These patterns were also found in reported data for 241Pu in LLW from other reactors, raising the difficulty of accurately determining the inventory (or source term) in a LLW shallow land burial site and its implications for predicting and controlling the future environmental and public health impacts of such disposal.

Determination of the 240Pu/ 239Pu atomic ratio in soils from Palomares (Spain) by low-energy accelerator mass spectrometry

NASA Astrophysics Data System (ADS)

Chamizo, E.; García-León, M.; Synal, H.-A.; Suter, M.; Wacker, L.

2006-08-01

In 1966, the nuclear fuel of two thermonuclear bombs was released over the Spanish region of Palomares, due to a B52 bomber accident during a refuelling operation. Since then, much effort has been made to assess its impact to the different environmental compartments of this area in South-East Spain, mostly by measuring the 239+240Pu activity concentration and the 238Pu/239+240Pu activity ratio. Nevertheless, these measurements do not give enough information on the problem. In order to recognize unambiguously small traces of the weapon-grade plutonium released in the accident, the ratio of the two major isotopes of plutonium, 240Pu/239Pu, has to be determined. In this work, this ratio has been measured in low- and high-activity samples from Palomares by means of low-energy accelerator mass spectrometry (AMS). That way, we will show the potential of the new generation of compact AMS facilities in terms of plutonium characterization at ultra-trace levels.

Toxicity of inhaled plutonium dioxide in beagle dogs

DOE Office of Scientific and Technical Information (OSTI.GOV)

Muggenburg, M.A.; Guilmette, R.A.; Mewhinney, J.A.

This study was conducted to determine the biological effects of inhaled {sup 238}PuO{sub 2} over the life spans of 144 beagle dogs. The dogs inhaled one of two sizes of monodisperse aerosols of {sup 238}PuO{sub 2} to achieve graded levels of initial lung burden (ILB). The aerosols also contained {sup 169}Yb to provide a {gamma}-ray-emitting label for the {sup 238}Pu inhaled by each dog. Excreta were collected periodically over each dog`s life span to estimate plutonium excretion; at death, the tissues were analyzed radiochemically for plutonium activity. The tissue content and the amount of plutonium excreted were used to estimatemore » the ILB. These data for each dog were used in a dosimetry model to estimate the ILB. These data for each dog were used in a dosimetry model to estimate tissue doses. The lung, skeleton and liver received the highest {alpha}-particle doses, ranging from 0.16-68 Gy for the liver. At death, all dogs were necropsied, and all organs and lesions were sampled and examined by histopathology. Findings of non-neoplastic changes included neutropenia and lymphopenia that developed in a dose-related fashion soon after inhalation exposure. These effects persisted for up to 5 years in some animals, but no other health effects could be related to the blood changes observed. Radiation pneumonitis was observed among the dogs with the highest ILBs. Deaths from radiation pneumonitis occurred from 1.5 to 5.4 years after exposure. Tumors of the lung, skeleton and liver occurred beginning at about 3 years after exposure. These findings in dogs suggest that similar dose-related biological effects could be expected in humans accidentally exposed to {sup 238}PuO{sub 2}. 89 refs., 10 figs., 11 tab.« less

High resolution gamma-ray spectrometry of culverts containing transuranic waste at the Savannah River Site

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hofstetter, K.J.; Sigg, R.

1990-12-31

A number of concrete culverts used to retrievably store drummed, dry, radioactive waste at the Savannah River Site (SRS), were suspected of containing ambiguous quantities of transuranic (TRU) nuclides. These culverts were assayed in place for Pu-239 content using thermal and fast neutron counting techniques. High resolution gamma-ray spectroscopy on 17 culverts, having neutron emission rates several times higher than expected, showed characteristic gamma-ray signatures of neutron emitters other than Pu-239 (e.g., Pu-238, Pu/Be, or Am/Be neutron sources). This study confirmed the Pu-239 content of the culverts with anomalous neutron rates and established limits on the Pu-239 mass in eachmore » of the 17 suspect culverts by in-field, non-intrusive gamma-ray measurements.« less

High resolution gamma-ray spectrometry of culverts containing transuranic waste at the Savannah River Site

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hofstetter, K.J.; Sigg, R.

1990-01-01

A number of concrete culverts used to retrievably store drummed, dry, radioactive waste at the Savannah River Site (SRS), were suspected of containing ambiguous quantities of transuranic (TRU) nuclides. These culverts were assayed in place for Pu-239 content using thermal and fast neutron counting techniques. High resolution gamma-ray spectroscopy on 17 culverts, having neutron emission rates several times higher than expected, showed characteristic gamma-ray signatures of neutron emitters other than Pu-239 (e.g., Pu-238, Pu/Be, or Am/Be neutron sources). This study confirmed the Pu-239 content of the culverts with anomalous neutron rates and established limits on the Pu-239 mass in eachmore » of the 17 suspect culverts by in-field, non-intrusive gamma-ray measurements.« less

Improved precision and accuracy in quantifying plutonium isotope ratios by RIMS

DOE PAGES

Isselhardt, B. H.; Savina, M. R.; Kucher, A.; ...

2015-09-01

Resonance ionization mass spectrometry (RIMS) holds the promise of rapid, isobar-free quantification of actinide isotope ratios in as-received materials (i.e. not chemically purified). Recent progress in achieving this potential using two Pu test materials is presented. RIMS measurements were conducted multiple times over a period of two months on two different Pu solutions deposited on metal surfaces. Measurements were bracketed with a Pu isotopic standard, and yielded absolute accuracies of the measured 240Pu/ 239Pu ratios of 0.7% and 0.58%, with precisions (95% confidence intervals) of 1.49% and 0.91%. In conclusion, the minor isotope 238Pu was also quantified despite the presencemore » of a significant quantity of 238U in the samples.« less

Extinct 244Pu in ancient zircons.

PubMed

Turner, Grenville; Harrison, T Mark; Holland, Greg; Mojzsis, Stephen J; Gilmour, Jamie

2004-10-01

We have found evidence, in the form of fissiogenic xenon isotopes, for in situ decay of 244Pu in individual 4.1- to 4.2-billion-year-old zircons from the Jack Hills region of Western Australia. Because of its short half-life, 82 million years, 244Pu was extinct within 600 million years of Earth's formation. Detrital zircons are the only known relics to have survived from this period, and a study of their Pu geochemistry will allow us to date ancient metamorphic events and determine the terrestrial Pu/U ratio for comparison with the solar ratio.

Ferro- and antiferro-magnetism in (Np, Pu)BC

NASA Astrophysics Data System (ADS)

Klimczuk, T.; Shick, A. B.; Kozub, A. L.; Griveau, J.-C.; Colineau, E.; Falmbigl, M.; Wastin, F.; Rogl, P.

2015-04-01

Two new transuranium metal boron carbides, NpBC and PuBC, have been synthesized. Rietveld refinements of powder XRD patterns of {Np,Pu}BC confirmed in both cases isotypism with the structure type of UBC. Temperature dependent magnetic susceptibility data reveal antiferromagnetic ordering for PuBC below TN = 44 K, whereas ferromagnetic ordering was found for NpBC below TC = 61 K. Heat capacity measurements prove the bulk character of the observed magnetic transition for both compounds. The total energy electronic band structure calculations support formation of the ferromagnetic ground state for NpBC and the antiferromagnetic ground state for PuBC.

Capability to Recover Plutonium-238 in H-Canyon/HB-Line - 13248

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fuller, Kenneth S. Jr.; Smith, Robert H. Jr.; Goergen, Charles R.

2013-07-01

Plutonium-238 is used in Radioisotope Thermoelectric Generators (RTGs) to generate electrical power and in Radioisotope Heater Units (RHUs) to produce heat for electronics and environmental control for deep space missions. The domestic supply of Pu-238 consists of scrap material from previous mission production or material purchased from Russia. Currently, the United States has no significant production scale operational capability to produce and separate new Pu-238 from irradiated neptunium-237 targets. The Department of Energy - Nuclear Energy is currently evaluating and developing plans to reconstitute the United States capability to produce Pu-238 from irradiated Np-237 targets. The Savannah River Site hadmore » previously produced and/or processed all the Pu-238 utilized in Radioisotope Thermoelectric Generators (RTGs) for deep space missions up to and including the majority of the plutonium for the Cassini Mission. The previous full production cycle capabilities included: Np- 237 target fabrication, target irradiation, target dissolution and Np-237 and Pu-238 separation and purification, conversion of Np-237 and Pu-238 to oxide, scrap recovery, and Pu-238 encapsulation. The capability and equipment still exist and could be revitalized or put back into service to recover and purify Pu-238/Np-237 or broken General Purpose Heat Source (GPHS) pellets utilizing existing process equipment in HB-Line Scrap Recovery, and H-Canyon Frame Waste Recovery processes. The conversion of Np-237 and Pu-238 to oxide can be performed in the existing HB-Line Phase-2 and Phase- 3 Processes. Dissolution of irradiated Np-237 target material, and separation and purification of Np-237 and Pu-238 product streams would be possible at production rates of ∼2 kg/month of Pu-238 if the existing H-Canyon Frames Process spare equipment were re-installed. Previously, the primary H-Canyon Frames equipment was removed to be replaced: however, the replacement project was stopped. The spare equipment is stored and still available for installation. Out of specification Pu-238 scrap material can be purified and recovered by utilizing the HB-Line Phase- 1 Scrap Recovery Line and the Phase-3 Pu-238 Oxide Conversion Line along with H-Canyon Frame Waste Recovery process. In addition, it also covers and describes utilizing the Phase-2 Np-237 Oxide Conversion Line, in conjunction with the H-Canyon Frames Process to restore the H-Canyon capability to process and recover Np-237 and Pu-238 from irradiated Np-237 targets and address potential synergies with other programs like recovery of Pu-244 and heavy isotopes of curium from other target material. (authors)« less

Chemistry of Non-Equilibrium Film Deposition.

DTIC Science & Technology

1985-12-01

titanium isopropoxide mixed with water solutions of lanthanum and lead nitrate. The gels were dehydrated, then fired to 600C to remove all organics...OW- ’so IRO $Va. ame Thin films; titanium dioxide; -PuZT,- ion beam deposition; annealing,’ trnmiso electron microscopy. 4 - . - S \\AISST 0A ZT *Can...Deposition....... . ... *.... .. ... .. ..... .. . .... 2 C. Nonequilibrium Physical Deposition.................... 3 1. Titanium Oxide Films

Hydrologic Resources Management Program and Underground Test Area Project FY 2006 Progress Report

DOE Office of Scientific and Technical Information (OSTI.GOV)

Culham, H W; Eaton, G F; Genetti, V

2008-04-08

This report describes FY 2006 technical studies conducted by the Chemical Biology and Nuclear Science Division (CBND) at Lawrence Livermore National Laboratory (LLNL) in support of the Hydrologic Resources Management Program (HRMP) and the Underground Test Area Project (UGTA). These programs are administered by the U.S. Department of Energy, National Nuclear Security Administration, Nevada Site Office (NNSA/NSO) through the Defense Programs and Environmental Restoration Divisions, respectively. HRMP-sponsored work is directed toward the responsible management of the natural resources at the Nevada Test Site (NTS), enabling its continued use as a staging area for strategic operations in support of national security.more » UGTA-funded work emphasizes the development of an integrated set of groundwater flow and contaminant transport models to predict the extent of radionuclide migration from underground nuclear testing areas at the NTS. The report is organized on a topical basis and contains four chapters that highlight technical work products produced by CBND. However, it is important to recognize that most of this work involves collaborative partnerships with the other HRMP and UGTA contract organizations. These groups include the Energy and Environment Directorate at LLNL (LLNL-E&E), Los Alamos National Laboratory (LANL), the Desert Research Institute (DRI), the U.S. Geological Survey (USGS), Stoller-Navarro Joint Venture (SNJV), and National Security Technologies (NSTec). Chapter 1 is a summary of FY 2006 sampling efforts at near-field 'hot' wells at the NTS, and presents new chemical and isotopic data for groundwater samples from four near-field wells. These include PM-2 and U-20n PS 1DDh (CHESHIRE), UE-7ns (BOURBON), and U-19v PS No.1ds (ALMENDRO). Chapter 2 is a summary of the results of chemical and isotopic measurements of groundwater samples from three UGTA environmental monitoring wells. These wells are: ER-12-4 and U12S located in Area 12 on Rainier Mesa and USGS HGH No.2 WW2 located in Yucca Flat. In addition, three springs were sampled White Rock Spring and Captain Jack Spring in Area 12 on Rainier Mesa and Topopah Spring in Area 29. Chapter 3 is a compilation of existing noble gas data that has been reviewed and edited to remove inconsistencies in presentation of total vs. single isotope noble gas values reported in the previous HRMP and UGTA progress reports. Chapter 4 is a summary of the results of batch sorption and desorption experiments performed to determine the distribution coefficients (Kd) of Pu(IV), Np(V), U(VI), Cs and Sr to zeolitized tuff (tuff confining unit, TCU) and carbonate (lower carbonate aquifer, LCA) rocks in synthetic NTS groundwater Chapter 5 is a summary of the results of a series of flow-cell experiments performed to examine Np(V) and Pu(V) sorption to and desorption from goethite. Np and Pu desorption occur at a faster rate and to a greater extent than previously reported. In addition, oxidation changes occurred with the Pu whereby the surface-sorbed Pu(IV) was reoxidized to aqueous Pu(V) during desorption.« less

Preserving Plutonium-244 as a National Asset

DOE Office of Scientific and Technical Information (OSTI.GOV)

Patton, Bradley D; Alexander, Charles W; Benker, Dennis

Plutonium-244 (244 Pu) is an extremely rare and long-lived isotope of plutonium with a half-life of 80 million years. Measureable amounts of 244 Pu are found in neither reactor-grade nor weapons-grade plutonium. Production of this isotope requires a very high thermal flux to permit the two successive neutron captures that convert 242 Pu to 243 Pu to 244 Pu, particularly given the short (about 5 hour) half-life of 243 Pu. Such conditions simply do not exist in plutonium production processes. Therefore, 244 Pu is ideal for precise radiochemical analyses measuring plutonium material properties and isotopic concentrations in items containing plutonium.more » Isotope dilution mass spectrometry is about ten times more sensitive when using 244 Pu rather than 242 Pu for determining plutonium isotopic content. The isotope can also be irradiated in small quantities to produce superheavy elements. The majority of the existing global inventory of 244 Pu is contained in the outer housing of Mark-18A targets at the Savannah River Site (SRS). The total inventory is about 20 grams of 244 Pu in about 400 grams of plutonium distributed among the 65 targets. Currently, there are no specific plans to preserve these targets. Although the cost of separating and preserving this material would be considerable, it is trivial in comparison to new production costs. For all practical purposes, the material is irreplaceable, because new production would cost billions of dollars and require a series of irradiation and chemical separation cycles spanning up to 50 years. This paper will discuss a set of options for overcoming the significant challenges to preserve the 244 Pu as a National Asset: (1) the need to relocate the material from SRS in a timely manner, (2) the need to reduce the volume of material to the extent possible for storage, and (3) the need to establish an operational capability to enrich the 244 Pu in significant quantities. This paper suggests that if all the Mark-18A plutonium is separated, it would occupy a small volume and would be inexpensive to store while an enrichment capability is developed. Very small quantities could be enriched in existing mass separators to support critical needs.« less

Aerosol Physics Considerations for Using Cerium Oxide CeO 2 as a Surrogate for Plutonium Oxide PuO 2 in Airborne Release Fraction Measurements for Storage Container Investigations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Moore, Murray E.; Tao, Yong

Cerium oxide (CeO2) dust is recommended as a surrogate for plutonium oxide (PuO2) in airborne release fraction experiments. The total range of applicable particle sizes for PuO2 extends from 0.0032 μm (the diameter of a single PuO2 molecule) to 10 μm (the defined upper boundary for respirable particles). For particulates with a physical particle diameter of 1.0 μm, the corresponding aerodynamic diameters for CeO2 and PuO2 are 2.7 μm and 3.4 μm, respectively. Cascade impactor air samplers are capable of measuring the size distributions of CeO2 or PuO2 particulates. In this document, the aerodynamic diameters for CeO2 and PuO2 weremore » calculated for seven different physical diameters (0.0032, 0.02, 0.11, 0.27, 1.0, 3.2, and 10 μm). For cascade impactor measurements, CeO2 and PuO2 particulates with the same physical diameter would be collected onto the same or adjacent collection substrates. The difference between the aerodynamic diameter of CeO2 and PuO2 particles (that have the same physical diameter) is 39% of the resolution of a twelve-stage MSP Inc. 125 cascade impactor, and 34% for an eight-stage Andersen impactor. An approach is given to calculate the committed effective dose (CED) coefficient for PuO2 aerosol particles, compared to a corresponding aerodynamic diameter of CeO2 particles. With this approach, use of CeO2 as a surrogate for PuO2 material would follow a direct conversion based on a molar equivalent. In addition to the analytical information developed for this document, several US national labs have published articles about the use of CeO2 as a PuO2 surrogate. Different physical and chemical aspects were considered by these investigators, including thermal properties, ceramic formulations, cold pressing, sintering, molecular reactions, and mass loss in high temperature gas flows. All of those US national lab studies recommended the use of CeO2 as a surrogate material for PuO2.« less

First measurements of (236)U concentrations and (236)U/(239)Pu isotopic ratios in a Southern Hemisphere soil far from nuclear test or reactor sites.

PubMed

Srncik, M; Tims, S G; De Cesare, M; Fifield, L K

2014-06-01

The variation of the (236)U and (239)Pu concentrations as a function of depth has been studied in a soil profile at a site in the Southern Hemisphere well removed from nuclear weapon test sites. Total inventories of (236)U and (239)Pu as well as the (236)U/(239)Pu isotopic ratio were derived. For this investigation a soil core from an undisturbed forest area in the Herbert River catchment (17°30' - 19°S) which is located in north-eastern Queensland (Australia) was chosen. The chemical separation of U and Pu was carried out with a double column which has the advantage of the extraction of both elements from a relatively large soil sample (∼20 g) within a day. The samples were measured by Accelerator Mass Spectrometry using the 14UD pelletron accelerator at the Australian National University. The highest atom concentrations of both (236)U and (239)Pu were found at a depth of 2-3 cm. The (236)U/(239)Pu isotopic ratio in fallout at this site, as deduced from the ratio of the (236)U and (239)Pu inventories, is 0.085 ± 0.003 which is clearly lower than the Northern Hemisphere value of ∼0.2. The (236)U inventory of (8.4 ± 0.3) × 10(11) at/m(2) was more than an order of magnitude lower than values reported for the Northern Hemisphere. The (239)Pu activity concentrations are in excellent agreement with a previous study and the (239+240)Pu inventory was (13.85 ± 0.29) Bq/m(2). The weighted mean (240)Pu/(239)Pu isotopic ratio of 0.142 ± 0.005 is slightly lower than the value for global fallout, but our results are consistent with the average ratio of 0.173 ± 0.027 for the southern equatorial region (0-30°S). Copyright © 2014 Elsevier Ltd. All rights reserved.

Density functional theory study of defects in unalloyed δ-Pu

DOE PAGES

Hernandez, S. C.; Freibert, F. J.; Wills, J. M.

2017-03-19

Using density functional theory, we explore in this paper various classical point and complex defects within the face-centered cubic unalloyed δ-plutonium matrix that are potentially induced from self-irradiation. For plutonium only defects, the most energetically stable defect is a distorted split-interstitial. Gallium, the δ-phase stabilizer, is thermodynamically stable as a substitutional defect, but becomes unstable when participating in a complex defect configuration. Finally, complex uranium defects may thermodynamically exist as uranium substitutional with neighboring plutonium interstitial and stabilization of uranium within the lattice is shown via partial density of states and charge density difference plots to be 5f hybridization betweenmore » uranium and plutonium.« less

Complex chromatid-isochromatid exchanges following irradiation with heavy ions?

PubMed

Loucas, B D; Eberle, R L; Durante, M; Cornforth, M N

2004-01-01

We describe a peculiar and relatively rare type of chromosomal rearrangement induced in human peripheral lymphocytes that were ostensibly irradiated in G(0) phase of the cell cycle by accelerated heavy ions, and which, to the best of our knowledge, have not been previously described. The novel rearrangements which were detected using mFISH following exposure to 500 MeV/nucleon and 5 GeV/n 56Fe particles, but were not induced by either 137Cs gamma rays or 238Pu alpha particles, can alternatively be described as either complex chromatid-isochromatid or complex chromatid-chromosome exchanges. Different mechanisms potentially responsible for their formation are discussed. Copyright 2003 S. Karger AG, Basel

Density functional theory study of defects in unalloyed δ-Pu

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hernandez, S. C.; Freibert, F. J.; Wills, J. M.

Using density functional theory, we explore in this paper various classical point and complex defects within the face-centered cubic unalloyed δ-plutonium matrix that are potentially induced from self-irradiation. For plutonium only defects, the most energetically stable defect is a distorted split-interstitial. Gallium, the δ-phase stabilizer, is thermodynamically stable as a substitutional defect, but becomes unstable when participating in a complex defect configuration. Finally, complex uranium defects may thermodynamically exist as uranium substitutional with neighboring plutonium interstitial and stabilization of uranium within the lattice is shown via partial density of states and charge density difference plots to be 5f hybridization betweenmore » uranium and plutonium.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Begg, James D.; Zavarin, Mavrik; Kersting, Annie B.

Desorption of plutonium (Pu) will likely control the extent to which it is transported by mineral colloids. In this article, we evaluated the adsorption/desorption behavior of Pu on SWy-1 montmorillonite colloids at pH 4, pH 6, and pH 8 using batch adsorption and flow cell desorption experiments. After 21 days adsorption, Pu(IV) affinity for montmorillonite displayed a pH dependency, with K d values highest at pH 4 and lowest at pH 8. The pH 8 experiment was further allowed to equilibrate for 6 months and showed an increase in K d, indicating that true sorption equilibrium was not achieved withinmore » the first 21 days. For the desorption experiments, aliquots of the sorption suspensions were placed in a flow cell, and Pu-free solutions were then pumped through the cell for a period of 12 days. Changes in influent solution flow rate were used to investigate the kinetics of Pu desorption and demonstrated that it was rate-limited over the experimental timescales. At the end of the 12-day flow cell experiments, the extent of desorption was again pH dependent, with pH 8 > pH 6 > pH 4. Further, at pH 8, less Pu was desorbed after an adsorption contact time of 6 months than after a contact time of 21 days, consistent with an aging of Pu on the clay surface. In addition, a conceptual model for Pu adsorption/desorption that incorporated known surface-mediated Pu redox reactions was used to fit the experimental data. The resulting rate constants indicated processes occurring on timescales of months and even years which may, in part, explain observations of clay colloid-facilitated Pu transport on decadal timescales. Importantly, however, our results also imply that migration of Pu adsorbed to montmorillonite colloids at long (50–100 year) timescales under oxic conditions may not be possible without considering additional phenomena, such as co-precipitation.« less

Desorption of plutonium from montmorillonite: An experimental and modeling study

DOE PAGES

Begg, James D.; Zavarin, Mavrik; Kersting, Annie B.

2017-01-15

Desorption of plutonium (Pu) will likely control the extent to which it is transported by mineral colloids. In this article, we evaluated the adsorption/desorption behavior of Pu on SWy-1 montmorillonite colloids at pH 4, pH 6, and pH 8 using batch adsorption and flow cell desorption experiments. After 21 days adsorption, Pu(IV) affinity for montmorillonite displayed a pH dependency, with K d values highest at pH 4 and lowest at pH 8. The pH 8 experiment was further allowed to equilibrate for 6 months and showed an increase in K d, indicating that true sorption equilibrium was not achieved withinmore » the first 21 days. For the desorption experiments, aliquots of the sorption suspensions were placed in a flow cell, and Pu-free solutions were then pumped through the cell for a period of 12 days. Changes in influent solution flow rate were used to investigate the kinetics of Pu desorption and demonstrated that it was rate-limited over the experimental timescales. At the end of the 12-day flow cell experiments, the extent of desorption was again pH dependent, with pH 8 > pH 6 > pH 4. Further, at pH 8, less Pu was desorbed after an adsorption contact time of 6 months than after a contact time of 21 days, consistent with an aging of Pu on the clay surface. In addition, a conceptual model for Pu adsorption/desorption that incorporated known surface-mediated Pu redox reactions was used to fit the experimental data. The resulting rate constants indicated processes occurring on timescales of months and even years which may, in part, explain observations of clay colloid-facilitated Pu transport on decadal timescales. Importantly, however, our results also imply that migration of Pu adsorbed to montmorillonite colloids at long (50–100 year) timescales under oxic conditions may not be possible without considering additional phenomena, such as co-precipitation.« less

The hematopoietic cell-specific transcription factor PU.1 is critical for expression of CD11c.

PubMed

Yashiro, Takuya; Kasakura, Kazumi; Oda, Yoshihito; Kitamura, Nao; Inoue, Akihito; Nakamura, Shusuke; Yokoyama, Hokuto; Fukuyama, Kanako; Hara, Mutsuko; Ogawa, Hideoki; Okumura, Ko; Nishiyama, Makoto; Nishiyama, Chiharu

2017-02-01

PU.1 is a hematopoietic cell-specific transcription factor belonging to the Ets family, which plays an important role in the development of dendritic cells (DCs). CD11c (encoded by Itgax) is well established as a characteristic marker of hematopoietic lineages including DCs. In the present study, we analyzed the role of PU.1 (encoded by Spi-1) in the expression of CD11c. When small interfering RNA (siRNA) for Spi-1 was introduced into bone marrow-derived DCs (BMDCs), the mRNA level and cell surface expression of CD11c were dramatically reduced. Using reporter assays, the TTCC sequence at -56/-53 was identified to be critical for PU.1-mediated activation of the promoter. An EMSA showed that PU.1 directly bound to this region. ChIP assays demonstrated that a significant amount of PU.1 bound to this region on chromosomal DNA in BMDCs, which was decreased in LPS-stimulated BMDCs in accordance with the reduced levels of mRNAs of Itgax and Spi-1, and the histone acetylation degree. Enforced expression of exogenous PU.1 induced the expression of the CD11c protein on the cell surface of mast cells, whereas control transfectants rarely expressed CD11c. Quantitative RT-PCR also showed that the expression of a transcription factor Irf4, which is a partner molecule of PU.1, was reduced in PU.1-knocked down BMDCs. IRF4 transactivated the Itgax gene in a synergistic manner with PU.1. Taken together, these results indicate that PU.1 functions as a positive regulator of CD11c gene expression by directly binding to the Itgax promoter and through transactivation of the Irf4 gene. © The Japanese Society for Immunology. 2017. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

Desorption of plutonium from montmorillonite: An experimental and modeling study

NASA Astrophysics Data System (ADS)

Begg, James D.; Zavarin, Mavrik; Kersting, Annie B.

2017-01-01

Desorption of plutonium (Pu) will likely control the extent to which it is transported by mineral colloids. We evaluated the adsorption/desorption behavior of Pu on SWy-1 montmorillonite colloids at pH 4, pH 6, and pH 8 using batch adsorption and flow cell desorption experiments. After 21 days adsorption, Pu(IV) affinity for montmorillonite displayed a pH dependency, with Kd values highest at pH 4 and lowest at pH 8. The pH 8 experiment was further allowed to equilibrate for 6 months and showed an increase in Kd, indicating that true sorption equilibrium was not achieved within the first 21 days. For the desorption experiments, aliquots of the sorption suspensions were placed in a flow cell, and Pu-free solutions were then pumped through the cell for a period of 12 days. Changes in influent solution flow rate were used to investigate the kinetics of Pu desorption and demonstrated that it was rate-limited over the experimental timescales. At the end of the 12-day flow cell experiments, the extent of desorption was again pH dependent, with pH 8 > pH 6 > pH 4. Further, at pH 8, less Pu was desorbed after an adsorption contact time of 6 months than after a contact time of 21 days, consistent with an aging of Pu on the clay surface. A conceptual model for Pu adsorption/desorption that incorporated known surface-mediated Pu redox reactions was used to fit the experimental data. The resulting rate constants indicated processes occurring on timescales of months and even years which may, in part, explain observations of clay colloid-facilitated Pu transport on decadal timescales. Importantly, however, our results also imply that migration of Pu adsorbed to montmorillonite colloids at long (50-100 year) timescales under oxic conditions may not be possible without considering additional phenomena, such as co-precipitation.

Biodegradable polyurethane micelles with pH and reduction responsive properties for intracellular drug delivery.

PubMed

Guan, Yayuan; Su, Yuling; Zhao, Lili; Meng, Fancui; Wang, Quanxin; Yao, Yongchao; Luo, Jianbin

2017-06-01

Polyurethane micelles with disulfide linkage located at the interface of hydrophilic shell and hydrophobic core (PU-SS-I) have been shown enhanced drug release profiles. However, the payloads could not be released completely. The occurrence of aggregation of hydrophobic cores upon shedding hydrophilic PEG coronas was considered as the reason for the incomplete release. To verify the above hypothesis and to develop a new polyurethane based micelles with dual stimuli respond properties and controllable location of pH and reduction responsive groups in the PU main chains, a tertiary amine was incorporated into the hydrophobic core PU-SS-I, which resulted polyurethane with both reduction and pH sensitive properties (PU-SS-N). Biodegradable polyurethane with only disulfide linkages located between the hydrophilic PEG segment and the hydrophobic PCL segments (PU-SS-I) and polyurethane with only pH sensitive tertiary amine at the hydrophobic core (PU-N-C) were used as comparisons. Paclitaxel (PTX) was chosen as mode hydrophobic drug to evaluate the loading and redox triggered release profiles of the PU micelles. It was demonstrated that PU-SS-N micelles disassembled instantly at the presence of 10mM GSH and at an acidic environment (pH=5.5), which resulted the nearly complete release (~90%) of the payloads within 48h, while about ~70% PTX was released from PU-SS-I and PU-SS-N micelles at neutral environment (pH=7.4) with the presence of 10mM GSH. The rapid and complete redox and pH stimuli release properties of the PU-SS-N nanocarrier will be a promising anticancer drug delivery system to ensure sufficient drug concentration to kill the cancer cells and to prevent the emergency of MDR. The in vitro cytotoxicity and cell uptake of the PTX-loaded micelles was also assessed in H460 and HepG2 cells. Copyright © 2017 Elsevier B.V. All rights reserved.

Progress Report on FY15 Crystalline Experiments M4FT-15LL0807052

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zavarin, M.; Zhao, P.; Joseph, C.

2015-08-13

Colloid-facilitated plutonium transport is expected to be the dominant mechanism in its migration through the environment. The forms of Pu colloids (intrinsic versus pseudo-colloid) and their stabilities control temporal and spatial scales of Pu transport in the environment. In the present study, we examine the stability of Pu intrinsic colloids freshly prepared in alkaline solution relative to Pu-montmorillonite pseudo-colloids using a dialysis device and modeling approaches. Intrinsic colloids prepared under alkaline conditions were found to be unstable over a timescale of months. The kinetics of multiple processes, including hydrolysis/precipitation of Pu(IV), dissolution of intrinsic colloids in the absence and presencemore » of the clay colloids, transport of dissolved Pu species across the dialysis membrane, and formation of pseudo-colloids were examined. The dissolution of intrinsic colloids was the rate-limiting process in most cases. The apparent intrinsic colloid dissolution rate constants range from 6×10 -7 to 1×10 - 6 mol·m -2·day -1 and 4×10 -6 to 8×10 -6 mol·m -2·day -1 at 25 and 80°C, respectively, while the apparent diffusion rate constants for Pu ions crossing the dialysis membrane are >200 times higher. Elevated temperatures enhance dissolution of Pu colloids and the activation energy for the process is estimated to be 28 kJ mol -1. The sorption of Pu to montmorillonite appears to be endothermic as the affinity of Pu for the clay increases with increasing temperature. Our results provide an in-depth understanding of how intrinsic and pseudo-colloids interact with each other kinetically. Although the fact that intrinsic colloids tend to dissolve in the presence of montmorillonite and transform into pseudo-colloids may limit the migration of intrinsic colloids, the thermodynamically more stable pseudo-colloids may play an important role in Pu transport in the environment over significant temporal and spatial scales.« less

Environmental aspects of the transuranics: a selected, annotated bibliography. [Pu-238, Pu-239

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ensminger, J.T.; Martin, F.M.; Fore, C.S.

This eighth published bibliography of 427 references is compiled from the Nevada Applied Ecology Information Center's Data Base on the Environmental Aspects of the Transuranics. The data base was built to provide information support to the Nevada Applied Ecology Group (NAEG) of ERDA's Nevada Operations Office. The general scope covers environmental aspects of uranium and the transuranic elements, with emphasis on plutonium. This bibliography highlights literature on plutonium 238 and 239 and americium in the critical organs of man and animals. Supporting information on ecology of the Nevada Test Site and reviews and summarizing literature on other radionuclides have beenmore » included at the request of the NAEG. The references are arranged by subject category with leading authors appearing alphabetically in each category. Indexes are provided for author(s), geographic location, keyword(s), taxon, title, and publication description.« less

Understanding oxygen adsorption on 9.375 at. % Ga-stabilized δ-Pu (111) surface: A DFT study

DOE PAGES

Hernandez, Sarah C.; Wilkerson, Marianne P.; Huda, Muhammad N.

2015-08-30

Plutonium (Pu) metal reacts rapidly in the presence of oxygen (O), resulting in an oxide layer that will eventually have an olive green rust appearance over time. Recent experimental work suggested that the incorporation of gallium (Ga) as an alloying impurity to stabilize the highly symmetric high temperature δ-phase lattice may also provide resistance against corrosion/oxidation of plutonium. In this paper, we modeled a 9.375 at. % Ga stabilized δ-Pu (111) surface and investigated adsorption of atomic O using all-electron density functional theory. Key findings revealed that the O bonded strongly to a Pu-rich threefold hollow fcc site with amore » chemisorption energy of –5.06 eV. Migration of the O atom to a Pu-rich environment was also highly sensitive to the surface chemistry of the Pu–Ga surface; when the initial on-surface O adsorption site included a bond to a nearest neighboring Ga atom, the O atom relaxed to a Ga deficient environment, thus affirming the O preference for Pu. Only one calculated final on-surface O adsorption site included a Ga-O bond, but this chemisorption energy was energetically unfavorable. Chemisorption energies for interstitial adsorption sites that included a Pu or Pu-Ga environment suggested that over-coordination of the O atom was energetically unfavorable as well. Electronic structure properties of the on-surface sites, illustrated by the partial density of states, implied that the Ga 4p states indirectly but strongly influenced the Pu 6d states strongly to hybridize with the O 2p states, while also weakly influenced the Pu 5f states to hybridize with the O 2p states, even though Ga was not participating in bonding with O.« less

Characterization of U/Pu Particles Originating From the Nuclear Weapon Accidents at Palomares, Spain, 1966 And Thule, Greenland, 1968

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lind, O.C.; Salbu, B.; Janssens, K.

2007-07-10

Following the USAF B-52 bomber accidents at Palomares, Spain in 1966 and at Thule, Greenland in 1968, radioactive particles containing uranium (U) and plutonium (Pu) were dispersed into the environment. To improve long-term environmental impact assessments for the contaminated ecosystems, particles from the two sites have been isolated and characterized with respect to properties influencing particle weathering rates. Low [239]Pu/[235]U (0.62-0.78) and [240]Pu/[239]Pu (0.055-0.061) atom ratios in individual particles from both sites obtained by Inductively Coupled Plasma Mass Spectrometry (ICP-MS) show that the particles contain highly enriched U and weapon-grade Pu. Furthermore, results from electron microscopy with Energy Dispersive X-raymore » analysis (EDX) and synchrotron radiation (SR) based micrometer-scale X-ray fluorescence ({micro}-XRF) 2D mapping demonstrated that U and Pu coexist throughout the 1-50 {micro}m sized particles, while surface heterogeneities were observed in EDX line scans. SR-based micrometer-scale X-ray Absorption Near Edge Structure Spectroscopy ({micro}-XANES) showed that the particles consisted of an oxide mixture of U (predominately UO[2] with the presence ofU[3][8]) and Pu ((III)/(IV), (V)/(V) or (III), (IV) and (V)). Neither metallic U or Pu nor uranyl or Pu(VI) could be observed. Characteristics such as elemental distributions, morphology and oxidation states are remarkably similar for the Palomares and Thule particles, reflecting that they originate from similar source and release scenarios. Thus, these particle characteristics are more dependent on the original material from which the particles are derived (source) and the formation of particles (release scenario) than the environmental conditions to which the particles have been exposed since the late 1960s.« less

Biodegradation of polyester polyurethane by Aspergillus tubingensis.

PubMed

Khan, Sehroon; Nadir, Sadia; Shah, Zia Ullah; Shah, Aamer Ali; Karunarathna, Samantha C; Xu, Jianchu; Khan, Afsar; Munir, Shahzad; Hasan, Fariha

2017-06-01

The xenobiotic nature and lack of degradability of polymeric materials has resulted in vast levels of environmental pollution and numerous health hazards. Different strategies have been developed and still more research is being in progress to reduce the impact of these polymeric materials. This work aimed to isolate and characterize polyester polyurethane (PU) degrading fungi from the soil of a general city waste disposal site in Islamabad, Pakistan. A novel PU degrading fungus was isolated from soil and identified as Aspergillus tubingensis on the basis of colony morphology, macro- and micro-morphology, molecular and phylogenetic analyses. The PU degrading ability of the fungus was tested in three different ways in the presence of 2% glucose: (a) on SDA agar plate, (b) in liquid MSM, and (c) after burial in soil. Our results indicated that this strain of A. tubingensis was capable of degrading PU. Using scanning electron microscopy (SEM), we were able to visually confirm that the mycelium of A. tubingensis colonized the PU material, causing surface degradation and scarring. The formation or breakage of chemical bonds during the biodegradation process of PU was confirmed using Attenuated Total Reflectance Fourier Transform Infrared (ATR-FTIR) spectroscopy. The biodegradation of PU was higher when plate culture method was employed, followed by the liquid culture method and soil burial technique. Notably, after two months in liquid medium, the PU film was totally degraded into smaller pieces. Based on a comprehensive literature search, it can be stated that this is the first report showing A. tubingensis capable of degrading PU. This work provides insight into the role of A. tubingensis towards solving the dilemma of PU wastes through biodegradation. Copyright © 2017 Elsevier Ltd. All rights reserved.

Understanding oxygen adsorption on 9.375 at. % Ga-stabilized δ-Pu (111) surface: A DFT study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hernandez, Sarah C.; Wilkerson, Marianne P.; Huda, Muhammad N.

Plutonium (Pu) metal reacts rapidly in the presence of oxygen (O), resulting in an oxide layer that will eventually have an olive green rust appearance over time. Recent experimental work suggested that the incorporation of gallium (Ga) as an alloying impurity to stabilize the highly symmetric high temperature δ-phase lattice may also provide resistance against corrosion/oxidation of plutonium. In this paper, we modeled a 9.375 at. % Ga stabilized δ-Pu (111) surface and investigated adsorption of atomic O using all-electron density functional theory. Key findings revealed that the O bonded strongly to a Pu-rich threefold hollow fcc site with amore » chemisorption energy of –5.06 eV. Migration of the O atom to a Pu-rich environment was also highly sensitive to the surface chemistry of the Pu–Ga surface; when the initial on-surface O adsorption site included a bond to a nearest neighboring Ga atom, the O atom relaxed to a Ga deficient environment, thus affirming the O preference for Pu. Only one calculated final on-surface O adsorption site included a Ga-O bond, but this chemisorption energy was energetically unfavorable. Chemisorption energies for interstitial adsorption sites that included a Pu or Pu-Ga environment suggested that over-coordination of the O atom was energetically unfavorable as well. Electronic structure properties of the on-surface sites, illustrated by the partial density of states, implied that the Ga 4p states indirectly but strongly influenced the Pu 6d states strongly to hybridize with the O 2p states, while also weakly influenced the Pu 5f states to hybridize with the O 2p states, even though Ga was not participating in bonding with O.« less

Radionuclide Basics: Plutonium

EPA Pesticide Factsheets

Plutonium (chemical symbol Pu) is a radioactive metal. Plutonium is considered a man-made element. Plutonium-239 is used to make nuclear weapons. Pu-239 and Pu-240 are byproducts of nuclear reactor operations and nuclear bomb explosions.

Coordination of Myeloid Differentiation with Reduced Cell Cycle Progression by PU.1 Induction of MicroRNAs Targeting Cell Cycle Regulators and Lipid Anabolism.

PubMed

Solomon, Lauren A; Podder, Shreya; He, Jessica; Jackson-Chornenki, Nicholas L; Gibson, Kristen; Ziliotto, Rachel G; Rhee, Jess; DeKoter, Rodney P

2017-05-15

During macrophage development, myeloid progenitor cells undergo terminal differentiation coordinated with reduced cell cycle progression. Differentiation of macrophages from myeloid progenitors is accompanied by increased expression of the E26 transformation-specific transcription factor PU.1. Reduced PU.1 expression leads to increased proliferation and impaired differentiation of myeloid progenitor cells. It is not understood how PU.1 coordinates macrophage differentiation with reduced cell cycle progression. In this study, we utilized cultured PU.1-inducible myeloid cells to perform genome-wide chromatin immunoprecipitation sequencing (ChIP-seq) analysis coupled with gene expression analysis to determine targets of PU.1 that may be involved in regulating cell cycle progression. We found that genes encoding cell cycle regulators and enzymes involved in lipid anabolism were directly and inducibly bound by PU.1 although their steady-state mRNA transcript levels were reduced. Inhibition of lipid anabolism was sufficient to reduce cell cycle progression in these cells. Induction of PU.1 reduced expression of E2f1 , an important activator of genes involved in cell cycle and lipid anabolism, indirectly through microRNA 223. Next-generation sequencing identified microRNAs validated as targeting cell cycle and lipid anabolism for downregulation. These results suggest that PU.1 coordinates cell cycle progression with differentiation through induction of microRNAs targeting cell cycle regulators and lipid anabolism. Copyright © 2017 American Society for Microbiology.

Nuclear weapons produced 236U, 239Pu and 240Pu archived in a Porites Lutea coral from Enewetak Atoll.

PubMed

Froehlich, M B; Tims, S G; Fallon, S J; Wallner, A; Fifield, L K

2017-11-01

A slice from a Porites Lutea coral core collected inside the Enewetak Atoll lagoon, within 15 km of all major nuclear tests conducted at the atoll, was analysed for 236 U, 239 Pu and 240 Pu over the time interval 1952-1964 using a higher time resolution than previously reported for a parallel slice from the same core. In addition two sediment samples from the Koa and Oak craters were analysed. The strong peaks in the concentrations of 236 U and 239 Pu in the testing years are confirmed to be considerably wider than the flushing time of the lagoon. This is likely due to the growth mechanism of the coral. Following the last test in 1958 atom concentrations of both 236 U and 239 Pu decreased from their peak values by more than 95% and showed a seasonal signal thereafter. Between 1959 and 1964 the weighted average of the 240 Pu/ 239 Pu atom ratio is 0.124 ± 0.008 which is similar to that in the lagoon sediments (0.129 ± 0.006) but quite distinct from the global fallout value of ∼0.18. This, and the high 239,240 Pu and 236 U concentrations in the sediments, provides clear evidence that the post-testing signal in the coral is dominated by remobilisation of the isotopes from the lagoon sediments rather than from global fallout. Copyright © 2017 Elsevier Ltd. All rights reserved.

Pu-erh Tea Protects the Nervous System by Inhibiting the Expression of Metabotropic Glutamate Receptor 5.

PubMed

Li, Chunjie; Chai, Shaomeng; Ju, Yongzhi; Hou, Lu; Zhao, Hang; Ma, Wei; Li, Tian; Sheng, Jun; Shi, Wei

2017-09-01

Glutamate is one of the major excitatory neurotransmitters of the CNS and is essential for numerous key neuronal functions. However, excess glutamate causes massive neuronal death and brain damage owing to excitotoxicity via the glutamate receptors. Metabotropic glutamate receptor 5 (mGluR5) is one of the glutamate receptors and represents a promising target for studying neuroprotective agents of potential application in neurodegenerative diseases. Pu-erh tea, a fermented tea, mainly produced in Yunnan province, China, has beneficial effects, including the accommodation of the CNS. In this study, pu-erh tea markedly decreased the transcription and translation of mGluR5 compared to those by black and green teas. Pu-erh tea also inhibited the expression of Homer, one of the synaptic scaffolding proteins binding to mGluR5. Pu-erh tea protected neural cells from necrosis via blocked Ca 2+ influx and inhibited protein kinase C (PKC) activation induced by excess glutamate. Pu-erh tea relieved rat epilepsy induced by LiCl-pilocarpine in behavioural and physiological assays. Pu-erh tea also decreased the expression of mGluR5 in the hippocampus. These results show that the inhibition of mGluR5 plays a role in protecting neural cells from glutamate. The results also indicate that pu-erh tea contains biological compounds binding transcription factors and inhibiting the expression of mGluR5 and identify pu-erh tea as a novel natural neuroprotective agent.

The purine scaffold Hsp90 inhibitor PU-H71 sensitizes cancer cells to heavy ion radiation by inhibiting DNA repair by homologous recombination and non-homologous end joining.

PubMed

Lee, Younghyun; Li, Huizi Keiko; Masaoka, Aya; Sunada, Shigeaki; Hirakawa, Hirokazu; Fujimori, Akira; Nickoloff, Jac A; Okayasu, Ryuichi

2016-10-01

PU-H71 is a purine-scaffold Hsp90 inhibitor developed to overcome limitations of conventional Hsp90 inhibitors. This study was designed to investigate the combined effect of PU-H71 and heavy ion irradiation on human tumor and normal cells. The effects of PU-H71 were determined by monitoring cell survival by colony formation, and DNA double-strand break (DSB) repair by γ-H2AX foci and immuno-blotting DSB repair proteins. The mode of cell death was evaluated by sub-G1 DNA content (as an indicator for apoptosis), and mitotic catastrophe. PU-H71 enhanced heavy ion irradiation-induced cell death in three human cancer cell lines, but the drug did not radiosensitize normal human fibroblasts. In irradiated tumor cells, PU-H71 increased the persistence of γ-H2AX foci, and it reduced RAD51 foci and phosphorylated DNA-PKcs, key DSB repair proteins involved in homologous recombination (HR) and non-homologous end joining (NHEJ). In some tumor cell lines, PU-H71 altered the sub-G1 cell fraction and mitotic catastrophe following carbon ion irradiation. Our results demonstrate that PU-H71 sensitizes human cancer cells to heavy ion irradiation by inhibiting both HR and NHEJ DSB repair pathways. PU-H71 holds promise as a radiosensitizer for enhancing the efficacy of heavy ion radiotherapy. Copyright © 2016 Elsevier Ireland Ltd. All rights reserved.

Quantitative non-destructive assay of PuBe neutron sources

NASA Astrophysics Data System (ADS)

Lakosi, László; Bagi, János; Nguyen, Cong Tam

2006-02-01

PuBe neutron sources were assayed, using a combination of high resolution γ-spectrometry (HRGS) and neutron correlation technique. In a previous publication [J. Bagi, C. Tam Nguyen, L. Lakosi, Nucl. Instr. and Meth. B 222 (2004) 242] a passive neutron well-counter was reported with 3He tubes embedded in a polyamide (TERRAMID) moderator (lined inside with Cd) surrounding the sources to be measured. Gross and coincidence neutron counting was performed, and the Pu content of the sources was found out from isotope analysis and by adopting specific (α, n) reaction yields of the Pu isotopes and 241Am in Be, based on supplier's information and literature data. The method was further developed and refined. Evaluation algorithm was more precisely worked out. The contribution of secondary (correlated) neutrons to the total neutron output was derived from the coincidence (doubles) count rate and taken into account in assessing the Pu content. A new evaluation of former results was performed. Assay was extended to other PuBe sources, and new results were added. In order to attain higher detection efficiency, a more efficient moderator was also applied, with and without Cd shielding around the assay chamber. Calibration seems possible using neutron measurements only (without γ-spectrometry), based on a correlation between the Pu amount and the coincidence-to-total ratio. It is expected that the method could be used for Pu accountancy and safeguards verification as well as identification and assay of seized, found, or not documented PuBe neutron sources.

Charge distribution and local structure and speciation in the UO 2+x and PuO 2+x binary oxides for x⩽0.25

NASA Astrophysics Data System (ADS)

Conradson, Steven D.; Begg, Bruce D.; Clark, David L.; den Auwer, Christophe; Ding, Mei; Dorhout, Peter K.; Espinosa-Faller, Francisco J.; Gordon, Pamela L.; Haire, Richard G.; Hess, Nancy J.; Hess, Ryan F.; Webster Keogh, D.; Lander, Gerard H.; Manara, Dario; Morales, Luis A.; Neu, Mary P.; Paviet-Hartmann, Patricia; Rebizant, Jean; Rondinella, Vincenzo V.; Runde, Wolfgang; Drew Tait, C.; Kirk Veirs, D.; Villella, Phillip M.; Wastin, Franck

2005-02-01

The local structure and chemical speciation of the mixed valence, fluorite-based oxides UO 2+x (0.00⩽ x⩽0.20) and PuO 2+x/PuO 2+x-y(OH) 2y· zH 2O have been determined by U/Pu L III XAFS spectroscopy. The U spectra indicate (1) that the O atoms are incorporated as oxo groups at short (1.75 Å) U-O distances consistent with U(VI) concomitant with a large range of U displacements that reduce the apparent number of U neighbors and (2) that the UO 2 fraction remains intact implying that these O defects interact to form clusters and give the heterogeneous structure consistent with the diffraction patterns. The PuO 2+x system, which does not show a separate phase at its x=0.25 endpoint, also displays (1) oxo groups at longer 1.9 Å distances consistent with Pu(V+ δ), (2) a multisite Pu-O distribution even when x is close to zero indicative of the formation of stable species with H 2O and its hydrolysis products with O 2-, and (3) a highly disordered, spectroscopically invisible Pu-Pu component. The structure and bonding in AnO 2+x are therefore more complicated than have previously been assumed and show both similarities but also distinct differences among the different elements.

A study on the ability of quaternary ammonium groups attached to a polyurethane foam wound dressing to inhibit bacterial attachment and biofilm formation.

PubMed

Tran, Phat L; Hamood, Abdul N; de Souza, Anselm; Schultz, Gregory; Liesenfeld, Bernd; Mehta, Dilip; Reid, Ted W

2015-01-01

Bacterial infection of acute and chronic wounds impedes wound healing significantly. Part of this impediment is the ability of bacterial pathogens to grow in wound dressings. In this study, we examined the effectiveness of a polyurethane (PU) foam wound dressings coated with poly diallyl-dimethylammonium chloride (pDADMAC-PU) to inhibit the growth and biofilm development by three main wound pathogens, Staphylococcus aureus, Pseudomonas aeruginosa, and Acinetobacter baumannii, within the wound dressing. pDADMAC-PU inhibited the growth of all three pathogens. Time-kill curves were conducted both with and without serum to determine the killing kinetic of pDADMAC-PU. pDADMAC-PU killed S. aureus, A. baumannii, and P. aeruginosa. The effect of pDADMAC-PU on biofilm development was analyzed quantitatively and qualitatively. Quantitative analysis, colony-forming unit assay, revealed that pDADMAC-PU dressing produced more than eight log reduction in biofilm formation by each pathogen. Visualization of the biofilms by either confocal laser scanning microscopy or scanning electron microscopy confirmed these findings. In addition, it was found that the pDADMAC-PU-treated foam totally inhibited migration of bacteria through the foam for all three bacterial strains. These results suggest that pDADMAC-PU is an effective wound dressing that inhibits the growth of wound pathogens both within the wound and in the wound dressing. © 2014 by the Wound Healing Society.

Criticality Safety Controls for 55-Gallon Drums with a Mass Limit of 200 grams Pu-239

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chou, P

The following 200-gram Pu drum criticality safety controls are applicable to RHWM drum storage operations: (1) Mass (Fissile/Pu) - each 55-gallon drum or its equivalent shall be limited to 200 gram Pu or Pu equivalent; (2) Moderation - Hydrogen materials with a hydrogen density greater than that (0.133 g H/cc) of polyethylene and paraffin are not allowed and hydrogen materials with a hydrogen density no greater than that of polyethylene and paraffin are allowed with unlimited amounts; (3) Interaction - a spacing of 30-inches (76 cm) is required between arrays and 200-gram Pu drums shall be placed in arrays formore » 200-gram Pu drums only (no mingling of 200-gram Pu drums with other drums not meeting the drum controls associated with the 200-gram limit); (4) Reflection - no beryllium and carbon/graphite (other than the 50-gram waiver amount) is allowed, (note that Nat-U exceeding the waiver amount is allowed when its U-235 content is included in the fissile mass limit of 200 grams); and (5) Geometry - drum geometry, only 55-gallon drum or its equivalent shall be used and array geometry, 55-gallon drums are allowed for 2-high stacking. Steel waste boxes may be stacked 3-high if constraint.« less

Multirecycling of Plutonium from LMFBR Blanket in Standard PWRs Loaded with MOX Fuel

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sonat Sen; Gilles Youinou

2013-02-01

It is now well-known that, from a physics standpoint, Pu, or even TRU (i.e. Pu+M.A.), originating from LEU fuel irradiated in PWRs can be multirecycled also in PWRs using MOX fuel. However, the degradation of the isotopic composition during irradiation necessitates using enriched U in conjunction with the MOX fuel either homogeneously or heterogeneously to maintain the Pu (or TRU) content at a level allowing safe operation of the reactor, i.e. below about 10%. The study is related to another possible utilization of the excess Pu produced in the blanket of a LMFBR, namely in a PWR(MOX). In this casemore » the more Pu is bred in the LMFBR, the more PWR(MOX) it can sustain. The important difference between the Pu coming from the blanket of a LMFBR and that coming from a PWR(LEU) is its isotopic composition. The first one contains about 95% of fissile isotopes whereas the second one contains only about 65% of fissile isotopes. As it will be shown later, this difference allows the PWR fed by Pu from the LMFBR blanket to operate with natural U instead of enriched U when it is fed by Pu from PWR(LEU)« less

Bioactivity and biotechnological production of punicic acid.

PubMed

Holic, Roman; Xu, Yang; Caldo, Kristian Mark P; Singer, Stacy D; Field, Catherine J; Weselake, Randall J; Chen, Guanqun

2018-04-01

Punicic acid (PuA; 18: 3Δ 9cis,11trans,13cis ) is an unusual 18-carbon fatty acid bearing three conjugated double bonds. It has been shown to exhibit a myriad of beneficial bioactivities including anti-cancer, anti-diabetes, anti-obesity, antioxidant, and anti-inflammatory properties. Pomegranate (Punica granatum) seed oil contains approximately 80% PuA and is currently the major natural source of this remarkable fatty acid. While both PuA and pomegranate seed oil have been used as functional ingredients in foods and cosmetics for some time, their value in pharmaceutical/medical and industrial applications are presently under further exploration. Unfortunately, the availability of PuA is severely limited by the low yield and unstable supply of pomegranate seeds. In addition, efforts to produce PuA in transgenic crops have been limited by a relatively low content of PuA in the resulting seed oil. The production of PuA in engineered microorganisms with modern fermentation technology is therefore a promising and emerging method with the potential to resolve this predicament. In this paper, we provide a comprehensive review of this unusual fatty acid, covering topics ranging from its natural sources, biosynthesis, extraction and analysis, bioactivity, health benefits, and industrial applications, to recent efforts and future perspectives on the production of PuA in engineered plants and microorganisms.

Trench 'bathtubbing' and surface plutonium contamination at a legacy radioactive waste site.

PubMed

Payne, Timothy E; Harrison, Jennifer J; Hughes, Catherine E; Johansen, Mathew P; Thiruvoth, Sangeeth; Wilsher, Kerry L; Cendón, Dioni I; Hankin, Stuart I; Rowling, Brett; Zawadzki, Atun

2013-01-01

Radioactive waste containing a few grams of plutonium (Pu) was disposed between 1960 and 1968 in trenches at the Little Forest Burial Ground (LFBG), near Sydney, Australia. A water sampling point installed in a former trench has enabled the radionuclide content of trench water and the response of the water level to rainfall to be studied. The trench water contains readily measurable Pu activity (~12 Bq/L of (239+240)Pu in 0.45 μm-filtered water), and there is an associated contamination of Pu in surface soils. The highest (239+240)Pu soil activity was 829 Bq/kg in a shallow sample (0-1 cm depth) near the trench sampling point. Away from the trenches, the elevated concentrations of Pu in surface soils extend for tens of meters down-slope. The broader contamination may be partly attributable to dispersion events in the first decade after disposal, after which a layer of soil was added above the trenched area. Since this time, further Pu contamination has occurred near the trench-sampler within this added layer. The water level in the trench-sampler responds quickly to rainfall and intermittently reaches the surface, hence the Pu dispersion is attributed to saturation and overflow of the trenches during extreme rainfall events, referred to as the 'bathtub' effect.

A generalized method for characterization of 235U and 239Pu content using short-lived fission product gamma spectroscopy

DOE PAGES

Knowles, Justin R.; Skutnik, Steven E.; Glasgow, David C.; ...

2016-06-23

Rapid non-destructive assay methods for trace fissile material analysis are needed in both nuclear forensics and safeguards communities. To address these needs, research at the High Flux Isotope Reactor Neutron Activation Analysis laboratory has developed a generalized non-destructive assay method to characterize materials containing fissile isotopes. This method relies on gamma-ray emissions from short-lived fission products and capitalizes off of differences in fission product yields to identify fissile compositions of trace material samples. Although prior work has explored the use of short-lived fission product gamma-ray measurements, the proposed method is the first to provide a holistic characterization of isotopic identification,more » mass ratios, and absolute mass determination. Successful single fissile isotope mass recoveries of less than 6% error have been conducted on standards of 235U and 239Pu as low as 12 nanograms in less than 10 minutes. Additionally, mixtures of fissile isotope standards containing 235U and 239Pu have been characterized as low as 229 nanograms of fissile mass with less than 12% error. The generalizability of this method is illustrated by evaluating different fissile isotopes, mixtures of fissile isotopes, and two different irradiation positions in the reactor. Furthermore, it is anticipated that this method will be expanded to characterize additional fissile nuclides, utilize various irradiation sources, and account for increasingly complex sample matrices.« less

A generalized method for characterization of 235U and 239Pu content using short-lived fission product gamma spectroscopy

NASA Astrophysics Data System (ADS)

Knowles, Justin; Skutnik, Steven; Glasgow, David; Kapsimalis, Roger

2016-10-01

Rapid nondestructive assay methods for trace fissile material analysis are needed in both nuclear forensics and safeguards communities. To address these needs, research at the Oak Ridge National Laboratory High Flux Isotope Reactor Neutron Activation Analysis facility has developed a generalized nondestructive assay method to characterize materials containing fissile isotopes. This method relies on gamma-ray emissions from short-lived fission products and makes use of differences in fission product yields to identify fissile compositions of trace material samples. Although prior work has explored the use of short-lived fission product gamma-ray measurements, the proposed method is the first to provide a complete characterization of isotopic identification, mass ratios, and absolute mass determination. Successful single fissile isotope mass recoveries of less than 6% recovery bias have been conducted on standards of 235U and 239Pu as low as 12 ng in less than 10 minutes. Additionally, mixtures of fissile isotope standards containing 235U and 239Pu have been characterized as low as 198 ng of fissile mass with less than 7% recovery bias. The generalizability of this method is illustrated by evaluating different fissile isotopes, mixtures of fissile isotopes, and two different irradiation positions in the reactor. It is anticipated that this method will be expanded to characterize additional fissile nuclides, utilize various irradiation facilities, and account for increasingly complex sample matrices.

A generalized method for characterization of 235U and 239Pu content using short-lived fission product gamma spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Knowles, Justin R.; Skutnik, Steven E.; Glasgow, David C.

Rapid non-destructive assay methods for trace fissile material analysis are needed in both nuclear forensics and safeguards communities. To address these needs, research at the High Flux Isotope Reactor Neutron Activation Analysis laboratory has developed a generalized non-destructive assay method to characterize materials containing fissile isotopes. This method relies on gamma-ray emissions from short-lived fission products and capitalizes off of differences in fission product yields to identify fissile compositions of trace material samples. Although prior work has explored the use of short-lived fission product gamma-ray measurements, the proposed method is the first to provide a holistic characterization of isotopic identification,more » mass ratios, and absolute mass determination. Successful single fissile isotope mass recoveries of less than 6% error have been conducted on standards of 235U and 239Pu as low as 12 nanograms in less than 10 minutes. Additionally, mixtures of fissile isotope standards containing 235U and 239Pu have been characterized as low as 229 nanograms of fissile mass with less than 12% error. The generalizability of this method is illustrated by evaluating different fissile isotopes, mixtures of fissile isotopes, and two different irradiation positions in the reactor. Furthermore, it is anticipated that this method will be expanded to characterize additional fissile nuclides, utilize various irradiation sources, and account for increasingly complex sample matrices.« less

Electronic structures of Plutonium compounds with the NaCl-type monochalcogenides structure

NASA Astrophysics Data System (ADS)

Maehira, Takahiro; Tatetsu, Yasutomi

2012-12-01

We calculate the energy band structure and the Fermi surface of PuS, PuSe and PuTe by using a self-consistent relativistic linear augmented-plane-wave method with the exchange and correlation potential in a local density approximation. It is found in common that the energy bands in the vicinity of the Fermi level are mainly due to the hybridization between Pu 5/ and monochalcogenide p electrons. The obtained main Fermi surfaces are composed of two hole sheets and one electron sheet, all of which are constructed from the band having the Pu 5/ state and the monochalcogenide p state.

Seaborg's plutonium? A case study in nuclear forensics

DOE PAGES

Norman, Eric B.; Thomas, Keenan J.; Telhami, Kristina E.

2015-10-01

Passive X-ray and gamma-ray analysis was performed on a curious sample from UC Berkeley's Hazardous Material Facility inventory, and the object was found to contain 239Pu. No other radioactive isotopes were observed. The mass of 239Pu contained in this object was determined to be 2.0 ± 0.3 μg. These observations are consistent with the identification of this object as containing the 2.77-μg PuO2 (2.44 μg 239Pu) sample produced in 1942 and described by Seaborg and his collaborators as the first sample of 239Pu that was large enough to be weighed.

Plutonium hexaboride is a correlated topological insulator.

PubMed

Deng, Xiaoyu; Haule, Kristjan; Kotliar, Gabriel

2013-10-25

We predict that plutonium hexaboride (PuB(6)) is a strongly correlated topological insulator, with Pu in an intermediate valence state of Pu(2.7+). Within the combination of dynamical mean field theory and density functional theory, we show that PuB(6) is an insulator in the bulk, with nontrivial Z(2) topological invariants. Its metallic surface states have a large Fermi pocket at the X[over ¯] point and the Dirac cones inside the bulk derived electronic states, causing a large surface thermal conductivity. PuB(6) has also a very high melting temperature; therefore, it has ideal solid state properties for a nuclear fuel material.

A new Pu(iii) coordination geometry in (C5H5NBr)2[PuCl3(H2O)5]·2Cl·2H2O as obtained via supramolecular assembly in aqueous, high chloride media.

PubMed

Surbella, Robert G; Ducati, Lucas C; Pellegrini, Kristi L; McNamara, Bruce K; Autschbach, Jochen; Schwantes, Jon M; Cahill, Christopher L

2017-09-28

Crystals of a hydrated Pu(iii) chloride, (C 5 H 5 NBr) 2 [PuCl 3 (H 2 O) 5 ]·2Cl·2H 2 O, were grown via slow evaporation from acidic aqueous, high chloride media. X-ray diffraction data reveals the neutral [PuCl 3 (H 2 O) 5 ] tecton is assembled via charge assisted hydrogen and halogen bonds donated by 4-bromopyridinium cations and a series of inter-tecton hydrogen bonds.

Oxygen potentials, oxygen diffusion coefficients and defect equilibria of nonstoichiometric (U,Pu)O2±x

NASA Astrophysics Data System (ADS)

Kato, Masato; Watanabe, Masashi; Matsumoto, Taku; Hirooka, Shun; Akashi, Masatoshi

2017-04-01

Oxygen potential of (U,Pu)O2±x was evaluated based on defect chemistry using an updated experimental data set. The relationship between oxygen partial pressure and deviation x in (U,Pu)O2±x was analyzed, and equilibrium constants of defect formation were determined as functions of Pu content and temperature. Brouwer's diagrams were constructed using the determined equilibrium constants, and a relational equation to determine O/M ratio was derived as functions of O/M ratio, Pu content and temperature. In addition, relationship between oxygen potential and oxygen diffusion coefficients were described.

ZPR-6 assembly 7 high {sup 240}Pu core experiments : a fast reactor core with mixed (Pu,U)-oxide fuel and a centeral high{sup 240}Pu zone.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lell, R. M.; Morman, J. A.; Schaefer, R.W.

ZPR-6 Assembly 7 (ZPR-6/7) encompasses a series of experiments performed at the ZPR-6 facility at Argonne National Laboratory in 1970 and 1971 as part of the Demonstration Reactor Benchmark Program (Reference 1). Assembly 7 simulated a large sodium-cooled LMFBR with mixed oxide fuel, depleted uranium radial and axial blankets, and a core H/D near unity. ZPR-6/7 was designed to test fast reactor physics data and methods, so configurations in the Assembly 7 program were as simple as possible in terms of geometry and composition. ZPR-6/7 had a very uniform core assembled from small plates of depleted uranium, sodium, iron oxide,more » U{sub 3}O{sub 8} and Pu-U-Mo alloy loaded into stainless steel drawers. The steel drawers were placed in square stainless steel tubes in the two halves of a split table machine. ZPR-6/7 had a simple, symmetric core unit cell whose neutronic characteristics were dominated by plutonium and {sup 238}U. The core was surrounded by thick radial and axial regions of depleted uranium to simulate radial and axial blankets and to isolate the core from the surrounding room. The ZPR-6/7 program encompassed 139 separate core loadings which include the initial approach to critical and all subsequent core loading changes required to perform specific experiments and measurements. In this context a loading refers to a particular configuration of fueled drawers, radial blanket drawers and experimental equipment (if present) in the matrix of steel tubes. Two principal core configurations were established. The uniform core (Loadings 1-84) had a relatively uniform core composition. The high {sup 240}Pu core (Loadings 85-139) was a variant on the uniform core. The plutonium in the Pu-U-Mo fuel plates in the uniform core contains 11% {sup 240}Pu. In the high {sup 240}Pu core, all Pu-U-Mo plates in the inner core region (central 61 matrix locations per half of the split table machine) were replaced by Pu-U-Mo plates containing 27% {sup 240}Pu in the plutonium component to construct a central core zone with a composition closer to that in an LMFBR core with high burnup. The high {sup 240}Pu configuration was constructed for two reasons. First, the composition of the high {sup 240}Pu zone more closely matched the composition of LMFBR cores anticipated in design work in 1970. Second, comparison of measurements in the ZPR-6/7 uniform core with corresponding measurements in the high {sup 240}Pu zone provided an assessment of some of the effects of long-term {sup 240}Pu buildup in LMFBR cores. The uniform core version of ZPR-6/7 is evaluated in ZPR-LMFR-EXP-001. This document only addresses measurements in the high {sup 240}Pu core version of ZPR-6/7. Many types of measurements were performed as part of the ZPR-6/7 program. Measurements of criticality, sodium void worth, control rod worth and reaction rate distributions in the high {sup 240}Pu core configuration are evaluated here. For each category of measurements, the uncertainties are evaluated, and benchmark model data are provided.« less

Polymer/reduced graphene oxide functionalized sponges as superabsorbents for oil removal and recovery.

PubMed

Periasamy, Arun Prakash; Wu, Wen-Ping; Ravindranath, Rini; Roy, Prathik; Lin, Guan-Lin; Chang, Huan-Tsung

2017-01-30

Polyurethane dish-washing (PU-DW) sponges are functionalized sequentially with polyethylenimine (PEI) and graphene oxide (GO) to form PEI/reduced graphene oxide (RGO) PU-DW sponges. The PEI/RGO PU-DW sponge consists of PEI/RGO sheets having numerous pores, with diameters ranging from 236 to 254nm. To further enhance hydrophobicity and absorption capacity of oil, PEI/RGO PU-DW sponge is further coated with 20% phenyltrimethoxysilane (PTMOS). The PTMOS/PEI/RGO PU-DW sponge absorbs various oils within 20s, with maximum absorption capacity values of 880% and 840% for bicycle chain oil and motorcycle engine oil, respectively. The absorbed oils were released completely by squeezing or immersed in hexane. The PTMOS/PEI/RGO PU-DW sponge efficiently separates oil/water mixtures through a flowing system. Having the advantages of faster absorption rate, reusability, and low cost, the PTMOS/PEI/RGO PU-DW sponge holds great potential as a superabsorbent for efficient removal and recovery of oil spills as well as for the separation of oil/water mixtures. Copyright © 2016 Elsevier Ltd. All rights reserved.

Ground-state wave function of plutonium in PuSb as determined via x-ray magnetic circular dichroism

DOE PAGES

Janoschek, M.; Haskel, D.; Fernandez-Rodriguez, J.; ...

2015-01-14

Measurements of x-ray magnetic circular dichroism (XMCD) and x-ray absorption near-edge structure (XANES) spectroscopy at the Pu M₄,₅ edges of the ferromagnet PuSb are reported. Using bulk magnetization measurements and a sum rule analysis of the XMCD spectra, we determine the individual orbital [μ L = 2.8(1)μ B/Pu] and spin moments [μ S = –2.0(1)μ B/Pu] of the Pu 5f electrons for the first time. Atomic multiplet calculations of the XMCD and XANES spectra reproduce well the experimental data and are consistent with the experimental value of the spin moment. These measurements of L z and S z are inmore » excellent agreement with the values that have been extracted from neutron magnetic form factor measurements, and confirm the local character of the 5f electrons in PuSb. We demonstrate that a split M₅ as well as a narrow M₄ XMCD signal may serve as a signature of 5f electron localization in actinide compounds.« less

Some Thermodynamic Features of Uranium-Plutonium Nitride Fuel in the Course of Burnup

NASA Astrophysics Data System (ADS)

Rusinkevich, A. A.; Ivanov, A. S.; Belov, G. V.; Skupov, M. V.

2017-12-01

Calculation studies on the effect of carbon and oxygen impurities on the chemical and phase compositions of nitride uranium-plutonium fuel in the course of burnup are performed using the IVTANTHERMO code. It is shown that the number of moles of UN decreases with increasing burnup level, whereas UN1.466, UN1.54, and UN1.73 exhibit a considerable increase. The presence of oxygen and carbon impurities causes an increase in the content of the UN1.466, UN1.54 and UN1.73 phases in the initial fuel by several orders of magnitude, in particular, at a relatively low temperature. At the same time, the presence of impurities abruptly reduces the content of free uranium in unburned fuel. Plutonium in the considered system is contained in form of Pu, PuC, PuC2, Pu2C3, and PuN. Plutonium carbides, as well as uranium carbides, are formed in small amounts. Most of the plutonium remains in the form of nitride PuN, whereas unbound Pu is present only in the areas with a low burnup level and high temperatures.

Plutonium isotopes in the Hungarian environment.

PubMed

Varga, Beata; Tarján, Sandor; Vajda, Nora

2008-04-01

More than 50 soil samples were analysed from different parts of the country, the activity concentration of 239+240Pu was in the range of 0.01-0.84 Bq/kg dry soil with the average of 0.10 Bq/kg. 238Pu could be detected only in few moss samples and 238Pu/239+240Pu ratio determines the origin of plutonium. 241Pu was determined by liquid scintillation spectrometry. The activity concentration of this isotope in the soil is between 0.04 and 3.74 Bq/kg with the average of 0.82 Bq/kg, while in the moss is also similar 0.01-2.07 Bq/kg fresh mass with the average of 0.43 Bq/kg. Significant difference could not be observed between the different types of soils occurring in the country, but the results could be sorted according to the sampling carried out on undisturbed or cultivated area. The isotope ratios 241Pu/239+240Pu prove that the origin of the plutonium in Hungary is the global fallout determined by the atmospheric nuclear weapon tests.

Development of Instrumentation for Boundary Layer Transition Detection

DTIC Science & Technology

1991-01-01

assistance of Maj. Aaron Byerley were largely responsible for my decision to stay on. 4t Contents Abstract Acknowledgements Nomenclature Chapter 1...The use of shr sensitive liquid crystals in aerodynamic measurements has been a mor wPu imovation. Two different prcesses can be employed to...transition location. The steady-state heat transfer technique is unsuited for use on complex geometries, may be time consuming , and has an element of

A hardware-oriented concurrent TZ search algorithm for High-Efficiency Video Coding

NASA Astrophysics Data System (ADS)

Doan, Nghia; Kim, Tae Sung; Rhee, Chae Eun; Lee, Hyuk-Jae

2017-12-01

High-Efficiency Video Coding (HEVC) is the latest video coding standard, in which the compression performance is double that of its predecessor, the H.264/AVC standard, while the video quality remains unchanged. In HEVC, the test zone (TZ) search algorithm is widely used for integer motion estimation because it effectively searches the good-quality motion vector with a relatively small amount of computation. However, the complex computation structure of the TZ search algorithm makes it difficult to implement it in the hardware. This paper proposes a new integer motion estimation algorithm which is designed for hardware execution by modifying the conventional TZ search to allow parallel motion estimations of all prediction unit (PU) partitions. The algorithm consists of the three phases of zonal, raster, and refinement searches. At the beginning of each phase, the algorithm obtains the search points required by the original TZ search for all PU partitions in a coding unit (CU). Then, all redundant search points are removed prior to the estimation of the motion costs, and the best search points are then selected for all PUs. Compared to the conventional TZ search algorithm, experimental results show that the proposed algorithm significantly decreases the Bjøntegaard Delta bitrate (BD-BR) by 0.84%, and it also reduces the computational complexity by 54.54%.

Preparation of nanosize polyaniline and its utilization for microwave absorber.

PubMed

Abbas, S M; Dixit, A K; Chatterjee, R; Goel, T C

2007-06-01

Polyaniline powder in nanosize has been synthesized by chemical oxidative route. XRD, FTIR, and TEM were used to characterize the polyaniline powder. Crytallite size was estimated from XRD profile and also ascertained by TEM in the range of 15 to 20 nm. The composite absorbers have been prepared by mixing different ratios of polyaniline into procured polyurethane (PU) binder. The complex permittivity (epsilon' - jepsilon") and complex permeability (mu' - jmu") were measured in X-band (8.2-12.4 GHz) using Agilent network analyzer (model PNA E8364B) and its software module 85071 (version 'E'). Measured values of these parameters were used to determine the reflection loss at different frequencies and sample thicknesses, based on a model of a single layered plane wave absorber backed by a perfect conductor. An optimized polyaniline/PU ratio of 3:1 has given a minimum reflection loss of -30 dB (99.9% power absorption) at the central frequency 10 GHz and the bandwidth (full width at half minimum) of 4.2 GHz over whole X-band (8.2 to 12.4 GHz) in a sample thickness of 3.0 mm. The prepared composites can be fruitfully utilized for suppression of electromagnetic interference (EMI) and reduction of radar signatures (stealth technology).

Iron Corrosion Observations: Pu(VI)-Fe Reduction Studies

DOE Office of Scientific and Technical Information (OSTI.GOV)

Reed, Donald T.; Swanson, Juliet S.; Richmann, Michael K.

Iron and Pu Reduction: (1) Very different appearances in iron reaction products were noted depending on pH, brine and initial iron phase; (2) Plutonium was associated with the Fe phases; (3) Green rust was often noted at the higher pH; (4) XANES established the green rust to be an Fe2/3 phase with a bromide center; and (5) This green rust phase was linked to Pu as Pu(IV).

Statistical properties of Pu 243 , and Pu 242 ( n , γ ) cross section calculation

DOE PAGES

Laplace, T. A.; Zeiser, F.; Guttormsen, M.; ...

2016-01-29

The level density and γ-ray strength function (γSF) of 243Pu have been measured in the quasicontinuum using the Oslo method. Excited states in 243Pu were populated using the 242Pu(d,p) reaction. The level density closely follows the constant-temperature level density formula for excitation energies above the pairing gap. The γSF displays a double-humped resonance at low energy as also seen in previous investigations of actinide isotopes. The structure is interpreted as the scissors resonance and has a centroid of ω SR = 2.42(5) MeV and a total strength of B SR = 10.1(15) μ 2 N, which is in excellent agreementmore » with sum-rule estimates. Lastly, the measured level density and γSF were used to calculate the 242Pu(n,γ) cross section in a neutron energy range for which there were previously no measured data.« less

PU.1 is a major transcriptional activator of the tumour suppressor gene LIMD1

PubMed Central

Foxler, Daniel E.; James, Victoria; Shelton, Samuel J.; Vallim, Thomas Q. de A.; Shaw, Peter E.; Sharp, Tyson V.

2011-01-01

LIMD1 is a tumour suppressor gene (TSG) down regulated in ∼80% of lung cancers with loss also demonstrated in breast and head and neck squamous cell carcinomas. LIMD1 is also a candidate TSG in childhood acute lymphoblastic leukaemia. Mechanistically, LIMD1 interacts with pRB, repressing E2F-driven transcription as well as being a critical component of microRNA-mediated gene silencing. In this study we show a CpG island within the LIMD1 promoter contains a conserved binding motif for the transcription factor PU.1. Mutation of the PU.1 consensus reduced promoter driven transcription by 90%. ChIP and EMSA analysis demonstrated that PU.1 specifically binds to the LIMD1 promoter. siRNA depletion of PU.1 significantly reduced endogenous LIMD1 expression, demonstrating that PU.1 is a major transcriptional activator of LIMD1. PMID:21402070

Chemical potential of oxygen in (U, Pu) mixed oxide with Pu/(U+Pu) = 0.46

NASA Astrophysics Data System (ADS)

Dawar, Rimpi; Chandramouli, V.; Anthonysamy, S.

2016-05-01

Chemical potential of oxygen in (U,Pu) mixed oxide with Pu/(U + Pu) = 0.46 was measured for the first time using H2/H2O gas equilibration combined with solid electrolyte EMF technique at 1073, 1273 and 1473 K covering an oxygen potential range of -525 to -325 kJ mol-1. The effect of oxygen potential on the oxygen to metal ratio was determined. Increase in oxygen potential increases the O/M. In this study the minimum O/M obtained was 1.985 below which reduction was not possible. Partial molar enthalpy ΔHbar O2 and entropy ΔSbar O2 of oxygen were calculated from the oxygen potential data. The values of -752.36 kJ mol-1 and 0.25 kJ mol-1 were obtained for ΔHbar O2 and ΔSbar O2 respectively.

A comparative, descriptive study of systemic factors and survival in elderly patients with sacral pressure ulcers.

PubMed

Jaul, Efraim; Menczel, Jacob

2015-03-01

Sacral pressure ulcers (PUs) are a serious complication in frail elderly patients. Thin tissue in the sacral area, low body mass index, and anatomical location contribute to the development of sacral PUs. A comparative, descriptive study was conducted to identify patient systemic factors associated with sacral PUs and to compare survival time in patients with and without PU. All consecutive patients with PUs (n = 77) and without sacral PUs (n = 53) admitted to the skilled nursing department of a geriatric hospital in Jerusalem, Israel between July 1, 2008 and December 31, 2011 were eligible to participate. Charts of previously admitted patients were abstracted and patients were prospectively followed until discharge, death, or the end of the study. Patient demographics, comorbidities, nutritional status, physical and cognitive function (measured using the Reisberg's Functional Assessment Staging Tool [FAST], Stages of Dementia of Alzheimer Scale, and the Glasgow Coma Scale), PU status, number of courses of antibiotic treatment during admission, length of hospitalization, and mortality were compared between patients admitted with and without a sacral PU using descriptive and univariate statistics. Logistic regression models were used to estimate the odds ratio (OR) and 95% confidence intervals (CI) for sacral PU versus without PU by study covariate. The association between sacral PU and survival time was assessed using Kaplan-Meier models. Patients with a sacral PU were significantly older (average age 81.60 ±10.78 versus 77.06±11.19 years old, P = 0.02) and had a higher prevalence of dementia (70% versus 30%, P = 0.007), Parkinson's disease (92.3% versus 7.7%, P = 0.03), and anemia (67.7% versus 32.3%, P = 0.06) than patients admitted without a PU. Patients with a sacral PU also had a lower body mass index (23.1 versus 25.4, P = 0.04), and lower hemoglobin (10.54 versus 11.11, P = 0.03), albumin (26.2 versus 29.7, P = 0.002), and total protein levels (61.3 versus 65.7, P = 0.04). In addition, antibiotic treatment was significantly higher in the patients with PU (50.6% versus 28.3%, P = 0.01). Patients with a sacral PU also had significantly lower physical and cognitive functioning scores and their median survival time was 70 days compared to 401 days in the non-PU group (P <0.001). These findings are generally consistent with the literature regarding risk factors for PU development and confirm the need for preventive measures. In addition, clinicians need to address the overall goal of patient care and patient quality of life when considering PU management interventions in this patient population.

Biomedical aspects of natural and manufactured environmental radioactivity

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hodge, V.

1996-12-31

While weapons testing has altered natural radioactivity background, manufactured radioactivity in most parts of the world constitutes but a very small fraction of the total alpha, beta, and gamma radioactivity in soil, air, water, and the biota. For example, in the early 1970s, we found what appeared to be the highest natural concentration of radioactivity ever reported in fish while attempting to measure the manufactured plutonium ({sup 239}Pu and {sup 240}Pu) in organs of oceanic tuna. The natural alpha emitter polonium ({sup 210}Po) was discovered in the same organs at orders of magnitude higher concentrations. In particular, the caecum, whichmore » is a digestive organ composed of many small closed-ended sacs, contained concentrations of polonium as high as 79 pCi/g of wet tissue and lesser amounts of two manufactured isotopes: 0.0001 pCi/g of plutonium and 0.01 pCi/g of radiocesium ({sup 137}Cs). This equates to {approximately}80 rem/yr of radiation dose to this organ, overwhelmingly from the natural polonium, or {approximately}5000 times higher than is found in the human liver, the highest polonium concentration in man. The average background radiation for humans, for comparison, is {approximately}0.2 rem/yr, but the dose for Japanese, whose diet is high in seafood, is {approximately}15 rem/yr. The question arose: {open_quotes}Are these high concentrations of natural polonium limited to oceanic fish?{close_quotes} To answer this question, polonium was determined in the organs of striped bass and catfish from Lake Mead. In a related study, the plutonium and radiocesium ({sup 137}Cs) distributions in soils were determined to ascertain the impact of weapons testing on the natural background radioactivity of soils.« less

Isotopic compositions of (236)U and Pu isotopes in "black substances" collected from roadsides in Fukushima prefecture: fallout from the Fukushima Dai-ichi nuclear power plant accident.

PubMed

Sakaguchi, Aya; Steier, Peter; Takahashi, Yoshio; Yamamoto, Masayoshi

2014-04-01

Black-colored road dusts were collected in high-radiation areas in Fukushima Prefecture. Measurement of (236)U and Pu isotopes and (134,137)Cs in samples was performed to confirm whether refractory elements, such as U and Pu, from the fuel core were discharged and to ascertain the extent of fractionation between volatile and refractory elements. The concentrations of (134,137)Cs in all samples were exceptionally high, ranging from 0.43 to 17.7 MBq/kg, respectively. (239+240)Pu was detected at low levels, ranging from 0.15 to 1.14 Bq/kg, and with high (238)Pu/(239+240)Pu activity ratios of 1.64-2.64. (236)U was successfully determined in the range of (0.28 to 6.74) × 10(-4) Bq/kg. The observed activity ratios for (236)U/(239+240)Pu were in reasonable agreement with those calculated for the fuel core inventories, indicating that trace amounts of U from the fuel cores were released together with Pu isotopes but without large fractionation. The quantities of U and (239+240)Pu emitted to the atmosphere were estimated as 3.9 × 10(6) Bq (150 g) and 2.3 × 10(9) Bq (580 mg), respectively. With regard to U, this is the first report to give a quantitative estimation of the amount discharged. Appreciable fractionation between volatile and refractory radionuclides associated with the dispersal/deposition processes with distance from the Fukushima Dai-ichi Nuclear Power Plant was found.

Effect of Starch Loading on the Thermo-Mechanical and Morphological Properties of Polyurethane Composites

PubMed Central

Gaaz, Tayser Sumer; Sulong, Abu Bakar; Ansari, M. N. M.; Kadhum, Abdul Amir H.; Nassir, Mohamed H.

2017-01-01

The advancements in material science and technology have made polyurethane (PU) one of the most important renewable polymers. Enhancing the physio-chemical and mechanical properties of PU has become the theme of this and many other studies. One of these enhancements was carried out by adding starch to PU to form new renewable materials called polyurethane-starch composites (PUS). In this study, PUS composites are prepared by adding starch at 0.5, 1.0, 1.5, and 2.0 wt.% to a PU matrix. The mechanical, thermal, and morphological properties of PU and PUS composites were investigated. Scanning electron microscope (SEM) images of PU and PUS fractured surfaces show cracks and agglomeration in PUS at 1.5 wt.% starch. The thermo-mechanical properties of the PUS composites were improved as starch content increased to 1.5 wt.% and declined by more starch loading. Despite this reduction, the mechanical properties were still better than that of neat PU. The mechanical strength increased as starch content increased to 1.5 wt.%. The tensile, flexural, and impact strengths of the PUS composites were found to be 9.62 MPa, 126.04 MPa, and 12.87 × 10−3 J/mm2, respectively, at 1.5 wt.% starch. Thermal studies showed that the thermal stability and crystallization temperature of the PUS composites increased compared to that of PU. The loss modulus curves showed that neat PU crystallizes at 124 °C and at 127 °C for PUS-0.5 wt.% and rises with increasing loading from 0.5 to 2 wt.%. PMID:28773134

Time-resolved record of 236U and 239,240Pu isotopes from a coral growing during the nuclear testing program at Enewetak Atoll (Marshall Islands).

PubMed

Froehlich, M B; Chan, W Y; Tims, S G; Fallon, S J; Fifield, L K

2016-12-01

A comprehensive series of nuclear tests were carried out by the United States at Enewetak Atoll in the Marshall Islands, especially between 1952 and 1958. A Porites Lutea coral that was growing in the Enewetak lagoon within a few km of all of the high-yield tests contains a continuous record of isotopes, which are of interest (e.g. 14 C, 236 U, 239,240 Pu) through the testing period. Prior to the present work, 14 C measurements at ∼2-month resolution had shown pronounced peaks in the Δ 14 C data that coincided with the times at which tests were conducted. Here we report measurements of 236 U and 239,240 Pu on the same coral using accelerator mass spectrometry, and again find prominent peaks in the concentrations of these isotopes that closely follow those in 14 C. Consistent with the 14 C data, the magnitudes of these peaks do not, however, correlate well with the explosive yields of the corresponding tests, indicating that smaller tests probably contributed disproportionately to the debris that fell in the lagoon. Additional information about the different tests can also be obtained from the 236 U/ 239 Pu and 240 Pu/ 239 Pu ratios, which are found to vary dramatically over the testing period. In particular, the first thermonuclear test, Ivy-Mike, has characteristic 236 U/ 239 Pu and 240 Pu/ 239 Pu signatures which are diagnostic of the first arrival of nuclear test material in various archives. Copyright © 2016 Elsevier Ltd. All rights reserved.

Effect of Starch Loading on the Thermo-Mechanical and Morphological Properties of Polyurethane Composites.

PubMed

Gaaz, Tayser Sumer; Sulong, Abu Bakar; Ansari, M N M; Kadhum, Abdul Amir H; Al-Amiery, Ahmed A; Nassir, Mohamed H

2017-07-10

The advancements in material science and technology have made polyurethane (PU) one of the most important renewable polymers. Enhancing the physio-chemical and mechanical properties of PU has become the theme of this and many other studies. One of these enhancements was carried out by adding starch to PU to form new renewable materials called polyurethane-starch composites (PUS). In this study, PUS composites are prepared by adding starch at 0.5, 1.0, 1.5, and 2.0 wt.% to a PU matrix. The mechanical, thermal, and morphological properties of PU and PUS composites were investigated. Scanning electron microscope (SEM) images of PU and PUS fractured surfaces show cracks and agglomeration in PUS at 1.5 wt.% starch. The thermo-mechanical properties of the PUS composites were improved as starch content increased to 1.5 wt.% and declined by more starch loading. Despite this reduction, the mechanical properties were still better than that of neat PU. The mechanical strength increased as starch content increased to 1.5 wt.%. The tensile, flexural, and impact strengths of the PUS composites were found to be 9.62 MPa, 126.04 MPa, and 12.87 × 10 -3 J/mm², respectively, at 1.5 wt.% starch. Thermal studies showed that the thermal stability and crystallization temperature of the PUS composites increased compared to that of PU. The loss modulus curves showed that neat PU crystallizes at 124 °C and at 127 °C for PUS-0.5 wt.% and rises with increasing loading from 0.5 to 2 wt.%.

Radiation leukemogenesis in mice: loss of PU.1 on chromosome 2 in CBA and C57BL/6 mice after irradiation with 1 GeV/nucleon 56Fe ions, X rays or gamma rays. Part I. Experimental observations.

PubMed

Peng, Yuanlin; Brown, Natalie; Finnon, Rosemary; Warner, Christy L; Liu, Xianan; Genik, Paula C; Callan, Matthew A; Ray, F Andrew; Borak, Thomas B; Badie, Christophe; Bouffler, Simon D; Ullrich, Robert L; Bedford, Joel S; Weil, Michael M

2009-04-01

Since deletion of the PU.1 gene on chromosome 2 is a crucial acute myeloid leukemia (AML) initiating step in the mouse model, we quantified PU.1 deleted cells in the bone marrow of gamma-, X- and 56Fe-ion-irradiated mice at various times postirradiation. Although 56Fe ions were initially some two to three times more effective than X or gamma rays in inducing PU.1 deletions, by 1 month postirradiation, the proportions of cells with PU.1 deletions were similar for the HZE particles and the sparsely ionizing radiations. These results indicate that while 56Fe ions are more effective in inducing PU.1 deletions, they are also more effective in causing collateral damage that removes hit cells from the bone marrow. After X, gamma or 56Fe-ion irradiation, AML-resistant C57BL/6 mice have fewer cells with PU.1 deletions than CBA mice, and those cells do not persist in the bone marrow of the C57B6/6 mice. Our findings suggest that quantification of PU.1 deleted bone marrow cells 1 month postirradiation can be used as surrogate for the incidence of radiation-induced AML measured in large-scale mouse studies. If so, PU.1 loss could be used to systematically assess the potential leukemogenic effects of other ions and energies in the space radiation environment.

Distribution of neptunium and plutonium in New Mexico lichen samples ( Usnea arizonica) contaminated by atmospheric fallout

DOE PAGES

Oldham, Jr., Warren J.; Hanson, Susan K.; Lavelle, Kevin B.; ...

2015-08-30

In this study, the concentrations of 237Np, 239Pu and 240Pu were determined in lichen samples ( Usnea arizonica) that were collected from ten locations in New Mexico between 2011 and 2013 using isotope dilution inductively-coupled plasma mass spectrometry (ID-ICP-MS). The observed isotopic ratios for 237Np/ 239Pu and 240Pu/ 239Pu indicate trace contamination from global and regional fallout (e.g. Trinity test and atmospheric testing at the Nevada Test Site). The fact that actinide contamination is detected in recent lichen collections suggests continuous re-suspension of fallout radionuclides even 50 years after ratification of the Limited Test Ban Treaty.

No Fukushima Dai-ichi derived plutonium signal in marine sediments collected 1.5-57km from the reactors.

PubMed

Wendel, C C S; Lind, O C; Fifield, L K; Tims, S G; Salbu, B; Oughton, D H

2017-11-01

Based on AMS analysis, it is shown that no Pu signals from the Fukushima accident could be discerned in marine sediments collected 1.5-57km away from the Fukushima Da-ichi power plant (FDNPP), which were clearly influenced by accident-derived radiocesium. The 240 Pu/ 239 Pu atom ratios (0.21-0.28) were significantly higher than terrestrial global fallout (0.182 ± 0.005), but still in agreement with pre-FDNPP accident baseline data for Pu in near coastal seawaters influenced by global fallout and long-range transport of Pu from the Pacific Proving Grounds. Copyright © 2017 Elsevier Ltd. All rights reserved.

Trench ‘Bathtubbing’ and Surface Plutonium Contamination at a Legacy Radioactive Waste Site

PubMed Central

2013-01-01

Radioactive waste containing a few grams of plutonium (Pu) was disposed between 1960 and 1968 in trenches at the Little Forest Burial Ground (LFBG), near Sydney, Australia. A water sampling point installed in a former trench has enabled the radionuclide content of trench water and the response of the water level to rainfall to be studied. The trench water contains readily measurable Pu activity (∼12 Bq/L of 239+240Pu in 0.45 μm-filtered water), and there is an associated contamination of Pu in surface soils. The highest 239+240Pu soil activity was 829 Bq/kg in a shallow sample (0–1 cm depth) near the trench sampling point. Away from the trenches, the elevated concentrations of Pu in surface soils extend for tens of meters down-slope. The broader contamination may be partly attributable to dispersion events in the first decade after disposal, after which a layer of soil was added above the trenched area. Since this time, further Pu contamination has occurred near the trench-sampler within this added layer. The water level in the trench-sampler responds quickly to rainfall and intermittently reaches the surface, hence the Pu dispersion is attributed to saturation and overflow of the trenches during extreme rainfall events, referred to as the ‘bathtub’ effect. PMID:24256473

Caustic Precipitation of Plutonium and Uranium with Gadolinium as a Neutron Poison

DOE Office of Scientific and Technical Information (OSTI.GOV)

VISSER, ANN E.; BRONIKOWSKI, MICHAEL G.; RUDISILL, TRACY S.

2005-10-18

The caustic precipitation of plutonium (Pu) and uranium (U) from Pu and U-containing waste solutions has been investigated to determine whether gadolinium (Gd) could be used as a neutron poison for precipitation with greater than a fissile mass containing both Pu and enriched U. Precipitation experiments were performed using both process solution samples and simulant solutions with a range of 2.6-5.16 g/L U and 0-4.3:1 U:Pu. Analyses were performed on solutions at intermediate pH to determine the partitioning of elements for accident scenarios. When both Pu and U were present in the solution, precipitation began at pH 4.5 and bymore » pH 7, 99% of Pu and U had precipitated. When complete neutralization was achieved at pH > 14 with 1.2 M excess OH{sup -}, greater than 99% of Pu, U, and Gd had precipitated. At pH > 14, the particles sizes were larger and the distribution was a single mode. The ratio of hydrogen:fissile atoms in the precipitate was determined after both settling and centrifuging and indicates that sufficient water was associated with the precipitates to provide the needed neutron moderation for Gd to prevent a criticality in solutions containing up to 4.3:1 U:Pu and up to 5.16 g/L U.« less

Caustic Precipitation of Plutonium and Uranium with Gadolinium as a Neutron Poison

DOE Office of Scientific and Technical Information (OSTI.GOV)

ANN, VISSER

2005-04-14

The caustic precipitation of plutonium (Pu) and uranium (U) from Pu and U containing waste solutions has been investigated to determine whether gadolinium (Gd) could be used as a neutron poison for precipitation with greater than a fissile mass containing both Pu and enriched U. Precipitation experiments were performed using both actual samples and simulant solutions with a range of 2.6-5.16 g/L U and 0-4.3 to 1 U to Pu. Analyses were performed on solutions at intermediate pH to determine the partitioning of elements for accident scenarios. When both Pu and U were present in the solution, precipitation began atmore » pH 4.5 and by pH 7, 99 percent of Pu and U had precipitated. When complete neutralization was achieved at pH greater than 14 with 1.2 M excess OH-, greater than 99 percent of Pu, U, and Gd had precipitated. At pH greater than 14, the particles sizes were larger and the distribution was a single mode. The ratio of hydrogen to fissile atoms in the precipitate was determined after both settling and centrifuging and indicates that sufficient water was associated with the precipitates to provide the needed neutron moderation for Gd to prevent a criticality in solutions containing up to 4.3 to 1 U to Pu and up to 5.16 g/L U.« less

The coprecipitation of Pu and other radionuclides with CaCO[sub 3

DOE Office of Scientific and Technical Information (OSTI.GOV)

Meece, D.E.; Benninger, L.K.

1993-04-01

The record of fallout plutonium concentrations in annual bands of corals is strikingly similar to the record of atmospheric deposition of [sup 90]Sr. This similarity implies that corals may incorporate Pu from seawater with a constant partition coefficient (constant discrimination). To investigate physicochemical aspects of Pu incorporation, the following have been coprecipitated with CaCO[sub 3] (calcite and aragonite): oxidized and reduced Pu; americium, thorium, and uranium as analogs to Pu oxidation states (III, IV, VI), respectively; and [sup 210]Pb as a particle-reactive nuclide which may be incorporated by corals with constant discrimination. Americium, thorium, and lead adsorb onto both calcitemore » and aragonite, with more than 99% of the recovered activity found associated with the solids. Uranium exhibits a behavior consistent with lattice substitution. Partition coefficients for U in aragonite range from 1.8 to 9.8 and vary inversely with pH and/or rate of precipitation. The partition coefficient for U in calcite is less than 0.2 and may be as low as 0.046. Reduced Pu sorbs with 3 to 4% remaining in solution. Oxidized Pu may both sorb and coprecipitate. The coral record for Pb and U results primarily from biological, rather than physicochemical, effects; it is likely that the PU coral record also reflects biological discrimination. 50 refs., 4 figs., 5 tabs.« less

The solubility of hydrogen in plutonium in the temperature range 475 to 825 degrees centigrade

DOE Office of Scientific and Technical Information (OSTI.GOV)

Allen, T.H.

1991-01-01

The solubility of hydrogen (H) in plutonium metal (Pu) was measured in the temperature range of 475 to 825{degree}C for unalloyed Pu (UA) and in the temperature range of 475 to 625{degree}C for Pu containing two-weight-percent gallium (TWP). For TWP metal, in the temperature range 475 to 600{degree}C, the saturated solution has a maximum hydrogen to plutonium ration (H/Pu) of 0.00998 and the standard enthalpy of formation ({Delta}H{degree}{sub f(s)}) is (-0.128 {plus minus} 0.0123) kcal/mol. The phase boundary of the solid solution in equilibrium with plutonium dihydride (PuH{sub 2}) is temperature independent. In the temperature range 475 to 625{degree}C, UAmore » metal has a maximum solubility at H/Pu = 0.011. The phase boundary between the solid solution region and the metal+PuH{sub 2} two-phase region is temperature dependent. The solubility of hydrogen in UA metal was also measured in the temperature range 650 to 825{degree}C with {Delta}H{degree}{sub f(s)} = (-0.104 {plus minus} 0.0143) kcal/mol and {Delta}S{degree}{sub f(s)} = 0. The phase boundary is temperature dependent and the maximum hydrogen solubility has H/Pu = 0.0674 at 825{degree}C. 52 refs., 28 figs., 9 tabs.« less

Effects of pressure ulcer classification system education programme on knowledge and visual differential diagnostic ability of pressure ulcer classification and incontinence-associated dermatitis for clinical nurses in Korea.

PubMed

Lee, Yun Jin; Kim, Jung Yoon

2016-03-01

The objective of this study was to evaluate the effect of pressure ulcer classification system education on clinical nurses' knowledge and visual differential diagnostic ability of pressure ulcer (PU) classification and incontinence-associated dermatitis (IAD). One group pre and post-test was used. A convenience sample of 407 nurses, participating in PU classification education programme of continuing education, were enrolled. The education programme was composed of a 50-minute lecture on PU classification and case-studies. The PU Classification system and IAD knowledge test (PUCS-KT) and visual differential diagnostic ability tool (VDDAT), consisting of 21 photographs including clinical information were used. Paired t-test was performed using SPSS/WIN 20.0. The overall mean difference of PUCS-KT (t = -11·437, P<0·001) and VDDAT (t = -21·113, P<0·001) was significantly increased after PU classification education. Overall understanding of six PU classification and IAD after education programme was increased, but lacked visual differential diagnostic ability regarding Stage III PU, suspected deep tissue injury (SDTI), and Unstageable. Continuous differentiated education based on clinical practice is needed to improve knowledge and visual differential diagnostic ability for PU classification, and comparison experiment study is required to examine effects of education programmes. © 2016 Medicalhelplines.com Inc and John Wiley & Sons Ltd.

Vaporization chemistry of hypo-stoichiometric (U,Pu)O 2

NASA Astrophysics Data System (ADS)

Viswanathan, R.; Krishnaiah, M. V.

2001-04-01

Calculations were performed on hypo-stoichiometric uranium plutonium di-oxide to examine its vaporization behavior as a function of O/ M ( M= U+ Pu) ratio and plutonium content. The phase U (1- y) Pu yO z was treated as an ideal solid solution of (1- y)UO 2+ yPuO (2- x) such that x=(2- z)/ y. Oxygen potentials for different desired values of y, z, and temperature were used as the primary input to calculate the corresponding partial pressures of various O-, U-, and Pu-bearing gaseous species. Relevant thermodynamic data for the solid phases UO 2 and PuO (2- x) , and the gaseous species were taken from the literature. Total vapor pressure varies with O/M and goes through a minimum. This minimum does not indicate a congruently vaporizing composition. Vaporization behavior of this system can at best be quasi-congruent. Two quasi-congruently vaporizing compositions (QCVCs) exist, representing the equalities (O/M) vapor=(O/M) mixed-oxide and (U/Pu) vapor=(U/Pu) mixed-oxide, respectively. The (O/M) corresponding to QCVC1 is lower than that corresponding to QCVC2, but very close to the value where vapor pressure minimum occurs. The O/M values of both QCVCs increase with decrease in plutonium content. The vaporization chemistry of this system, on continuous vaporization under dynamic condition, is discussed.

Analysis of oxygen potential of (U 0.7Pu 0.3)O 2±x and (U 0.8Pu 0.2)O 2±x based on point defect chemistry

NASA Astrophysics Data System (ADS)

Kato, Masato; Konashi, Kenji; Nakae, Nobuo

2009-06-01

Stoichiometries in (U 0.7Pu 0.3)O 2±x and (U 0.8Pu 0.2)O 2±x were analyzed with the experimental data of oxygen potential based on point defect chemistry. The relationship between the deviation x of stoichiometric composition and the oxygen partial pressure P was evaluated using a Kröger-Vink diagram. The concentrations of the point defects in uranium and plutonium mixed oxide (MOX) were estimated from the measurement data of oxygen potentials as functions of temperature and P. The analysis results showed that x was proportional to PO2±1/2 near the stoichiometric region of both (U 0.7Pu 0.3)O 2±x and (U 0.8Pu 0.2)O 2±x, which suggested that intrinsic ionization was the dominant defect. A model to calculate oxygen potential was derived and it represented the experimental data accurately. Further, the model estimated the thermodynamic data, ΔH and ΔS, of stoichiometric (U 0.7Pu 0.3)O 2.00 and (U 0.8Pu 0.2)O 2.00 as -552.5 kJ·mol -1 and -149.7 J·mol -1, and -674.0 kJ · mol -1 and -219.4 J · mol -1, respectively.

Long-range tropospheric transport of uranium and plutonium weapons fallout from Semipalatinsk nuclear test site to Norway.

PubMed

Wendel, Cato Christian; Fifield, L Keith; Oughton, Deborah H; Lind, Ole Christian; Skipperud, Lindis; Bartnicki, Jerzy; Tims, Stephen G; Høibråten, Steinar; Salbu, Brit

2013-09-01

A combination of state-of-the-art isotopic fingerprinting techniques and atmospheric transport modelling using real-time historical meteorological data has been used to demonstrate direct tropospheric transport of radioactive debris from specific nuclear detonations at the Semipalatinsk test site in Kazakhstan to Norway via large areas of Europe. A selection of archived air filters collected at ground level at 9 stations in Norway during the most intensive atmospheric nuclear weapon testing periods (1957-1958 and 1961-1962) has been screened for radioactive particles and analysed with respect to the concentrations and atom ratios of plutonium (Pu) and uranium (U) using accelerator mass spectrometry (AMS). Digital autoradiography screening demonstrated the presence of radioactive particles in the filters. Concentrations of (236)U (0.17-23nBqm(-3)) and (239+240)Pu (1.3-782μBqm(-3)) as well as the atom ratios (240)Pu/(239)Pu (0.0517-0.237) and (236)U/(239)Pu (0.0188-0.7) varied widely indicating several different sources. Filter samples from autumn and winter tended to have lower atom ratios than those sampled in spring and summer, and this likely reflects a tropospheric influence in months with little stratospheric fallout. Very high (236)U, (239+240)Pu and gross beta activity concentrations as well as low (240)Pu/(239)Pu (0.0517-0.077), (241)Pu/(239)Pu (0.00025-0.00062) and (236)U/(239)Pu (0.0188-0.046) atom ratios, characteristic of close-in and tropospheric fallout, were observed in filters collected at all stations in Nov 1962, 7-12days after three low-yield detonations at Semipalatinsk (Kazakhstan). Atmospheric transport modelling (NOAA HYSPLIT_4) using real-time meteorological data confirmed that long range transport of radionuclides, and possibly radioactive particles, from Semipalatinsk to Norway during this period was plausible. The present work shows that direct tropospheric transport of fallout from atmospheric nuclear detonations periodically may have had much larger influence on radionuclide air concentrations and deposition than previously anticipated. Copyright © 2013 Elsevier Ltd. All rights reserved.

A xenograft model reveals that PU.1 functions as a tumor suppressor for multiple myeloma in vivo

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nishimura, Nao; Endo, Shinya; Ueno, Shikiko

We previously demonstrated that PU.1 expression is down-regulated in the majority of myeloma cell lines and primary myeloma cells from patients. We introduced the tet-off system into the human myeloma cell lines U266 and KMS12PE that conditionally express PU.1 and demonstrated that PU.1 induces cell cycle arrest and apoptosis in myeloma cells in vitro. Here, we established a mouse xenograft model of myeloma using these cell lines to analyze the effects of PU.1 on the phenotype of myeloma cells in vivo. When doxycycline was added to the drinking water of mice engrafted with these myeloma cells, all mice had continuous growth ofmore » subcutaneous tumors and could not survived more than 65 days. In contrast, mice that were not exposed to doxycycline did not develop subcutaneous tumors and survived for at least 100 days. We next generated mice engrafted with subcutaneous tumors 5–10 mm in diameter that were induced by exposure to doxycycline. Half of the mice stopped taking doxycycline-containing water, whereas the other half kept taking the water. Although the tumors in the mice taking doxycycline continued to grow, tumor growth in the mice not taking doxycycline was significantly suppressed. The myeloma cells in the tumors of the mice not taking doxycycline expressed PU.1 and TRAIL and many of such cells were apoptotic. Moreover, the expression of a cell proliferation marker Ki67 was significantly decreased in tumors from the mice not taking doxycycline, compared with that of tumors from the mice continuously taking doxycycline. The present data strongly suggest that PU.1 functions as a tumor suppressor of myeloma cells in vivo. - Highlights: • PU.1 suppresses xenograft myeloma cell growth and prolongs survival periods of mice. • PU.1 induces TRAIL expression and apoptosis in myeloma cells in vivo. • PU.1 suppresses Ki67 expression in myeloma cells in vivo. • Up-regulation of PU.1 is a promising strategy for generating anti-myeloma agents.« less

THERMODYNAMICS AND KINETICS OF PHASE TRANSFORMATIONS IN PLUTONIUM ALLOYS - PART I

DOE Office of Scientific and Technical Information (OSTI.GOV)

Turchi, P A; Kaufman, L; Liu, Z

2004-08-18

In this report we investigate order, stability, and phase transformations for a series of actinide-based alloys. The statics and kinetics of precipitation and ordering in this class of alloys are modeled with a scheme that couples fundamental information on the alloy energetics obtained from experimental and assessed thermo-chemical data to the CALPHAD approach commonly used in industry for designing alloys with engineering specificity with the help of the Thermo-Calc software application. The CALPHAD approach is applied to the study of the equilibrium thermodynamic properties of Pu-based alloys, Pu-X, where X=Al, Fe, Ga. The assessment of the equilibrium phase diagrams inmore » the whole range of alloy composition has been performed with the PARROT module of the Thermo-Calc application software. Predictions are made on the low temperature and Pu-rich side of the phase diagrams of Pu-Ga and Pu-Al for which controversy has been noted in the past. The validity of the assessed thermo-chemical database will be discussed by comparing predicted heats of transformation for pure Pu with measured values from differential scanning calorimetry analysis. An overall picture for the stability properties of Pu-Ga and Pu-Al that reconciles the results of past studies carried out on these alloys is proposed. Results on phase stability in the ternary Fe-Ga-Pu and Al-Fe-Pu alloys are discussed. The information collected in this study is then used to model metastability, long-term stability and aging for this class of alloys by coupling Thermo-Calc with DICTRA, a series of modules that allow the analysis of DIffusion Controlled TRAnsformations. Kinetics information is then summarized in so-called TTT (temperature-time-transformations) diagrams for the most relevant phases of actinide alloys. Specifically, results are presented on kinetics of phase transformations associated with the eutectoid-phase decomposition reaction occurring at low temperature, and with the martensitic transformation that takes place at low Ga content in Pu-Ga alloys. Finally, after a summary of the most salient results, suggestions are made for further studies at the micro- and mesoscales.« less

High-Resolution Inductively Coupled Plasma Optical Emission Spectrometry for (234)U/(238)Pu Age Dating of Plutonium Materials and Comparison to Sector Field Inductively Coupled Plasma Mass Spectrometry.

PubMed

Krachler, Michael; Alvarez-Sarandes, Rafael; Rasmussen, Gert

2016-09-06

Employing a commercial high-resolution inductively coupled plasma optical emission spectrometry (HR-ICP-OES) instrument, an innovative analytical procedure for the accurate determination of the production age of various Pu materials (Pu powder, cardiac pacemaker battery, (242)Cm heat source, etc.) was developed and validated. This undertaking was based on the fact that the α decay of (238)Pu present in the investigated samples produced (234)U and both mother and daughter could be identified unequivocally using HR-ICP-OES. Benefiting from the high spectral resolution of the instrument (<5 pm) and the isotope shift of the emission lines of both nuclides, (234)U and (238)Pu were selectively and directly determined in the dissolved samples, i.e., without a chemical separation of the two analytes from each other. Exact emission wavelengths as well as emission spectra of (234)U centered around λ = 411.590 nm and λ = 424.408 nm are reported here for the first time. Emission spectra of the isotopic standard reference material IRMM-199, comprising about one-third each of (233)U, (235)U, and (238)U, confirmed the presence of (234)U in the investigated samples. For the assessment of the (234)U/(238)Pu amount ratio, the emission signals of (234)U and (238)Pu were quantified at λ = 424.408 nm and λ = 402.148 nm, respectively. The age of the investigated samples (range: 26.7-44.4 years) was subsequently calculated using the (234)U/(238)Pu chronometer. HR-ICP-OES results were crossed-validated through sector field inductively coupled plasma mass spectrometry (SF-ICPMS) analysis of the (234)U/(238)Pu amount ratio of all samples applying isotope dilution combined with chromatographic separation of U and Pu. Available information on the assumed ages of the analyzed samples was consistent with the ages obtained via the HR-ICP-OES approach. Being based on a different physical detection principle, HR-ICP-OES provides an alternative strategy to the well-established mass spectrometric approach and thus effectively adds to the quality assurance of (234)U/(238)Pu age dates.

Trends in intrusive and eruptive activity during Kilauea's long-lived east rift zone eruption

NASA Astrophysics Data System (ADS)

Orr, T. R.; Patrick, M. R.; Heliker, C.

2011-12-01

Kilauea Volcano's Pu`u `O`o eruption, continuing for nearly three decades, offers a unique opportunity to study trends in eruptive behavior. One such trend, that of uprift intrusion ± eruption, accompanied by crater floor collapse and eruptive hiatus, has been repeated several times at Pu`u `O`o. This includes the February 7, 1993, intrusion; the January 29, 1997, intrusion and eruption; the September 12, 1999, intrusion; and the June 17, 2007, intrusion and eruption. Activity resumed within Pu`u `O`o following each of these events, and crater refilling culminated eventually in the outbreak of lava from new vents on the flank of the Pu`u `O`o cone. The pattern was repeated again in 2011, when a brief fissure eruption uprift from Pu`u `O`o started on March 5. The Pu`u `O`o crater floor dropped about 115 m in response to the eruption, which ceased on March 9. After a short hiatus, lava reappeared in Pu`u `O`o on March 26, and the crater began to fill slowly thereafter by overflow from a central lava lake. Starting in late June 2011, however, the crater floor began to uplift in a wholesale fashion, suggesting an increase in the pressure beneath the Pu`u `O`o edifice. By late July, the lava within the crater had reached its highest level since early 2004, and lava had begun to overflow from the southwestern side of the crater. On August 3, the west side of the Pu`u `O`o cone was abruptly thrust upward as a sill was injected beneath that portion of the cone. Within minutes, lava began to erupt from a crack on the west flank of Pu`u `O`o, completing the pattern of intrusion, crater collapse, refilling, and breakout. During a long-lived eruption, maintaining a detailed observational and geophysical record is essential for recognizing patterns that may emerge. Recognizing such a pattern allowed Hawaiian Volcano Observatory scientists to prepare a response well in advance of the August 3, 2011 event, and provides guidance for responding to future eruption crises at Pu`u `O`o that evolve similarly.

Mechanical environmental transport of actinides and ¹³⁷Cs from an arid radioactive waste disposal site

DOE PAGES

Snow, Mathew S.; Clark, Sue B.; Morrison, Samuel S.; ...

2015-10-01

Particulate transport represents an important mechanism for actinides and fission products at the Earth's surface; soil samples taken in the early 1970's near the Subsurface Disposal Area (SDA) at Idaho National Laboratory (INL) provide a case study for examining the mechanisms and characteristics of actinide transport under arid conditions. Transuranic waste was disposed via shallow land burial at the SDA until shortly after a flooding event that occurred in 1969. In this study we analyze soils collected in the early 1970's for ¹³⁷Cs, ²⁴¹Am, and Pu using a combination of radiometric and mass spectrometric techniques. Two distinct ²⁴⁰Pu/²³⁹Pu isotopic ratiosmore » are observed for contamination from the SDA, with values ranging from at least 0.059 to 0.069. ²⁴¹Am concentrations are observed to increase only slightly in 0-4 cm soils over the ~40 year period since soil sampling, contrary to Markham's previous hypothesis that ²⁴¹Pu is principally associated with the 0-4 cm soil fractions (Markham 1978). The lack of statistical difference in ²⁴¹Am/²³⁹⁺²⁴⁰Pu ratios with depth suggests mechanical transport and mixing discrete contaminated particles under arid conditions. Occasional samples beyond the northeastern corner are observed to contain anomalously high Pu concentrations with corresponding low ²⁴⁰Pu/²³⁹Pu atoms ratios, suggesting the occurrence of "hot particles;" application of a background Pu subtraction results in calculated Pu atom ratios for the "hot particles" which are statistically similar to those observed in the northeastern corner. Taken together, our data suggests that flooding resulted in mechanical transport of contaminated particles into the area between the SDA and the flood containment dike in the northeastern corner, following which subsequent contamination spreading resulted from wind transport of discrete particles.« less

Temporal evolution of 137Cs, 237Np, and 239+240Pu and estimated vertical 239+240Pu export in the northwestern Mediterranean Sea.

PubMed

Bressac, M; Levy, I; Chamizo, E; La Rosa, J J; Povinec, P P; Gastaud, J; Oregioni, B

2017-10-01

The evolution of 137 Cs, 237 Np and 239+240 Pu at the DYFAMED station (NW Mediterranean) is discussed in relation to physical processes, downward fluxes of particles, and changes in the main input sources. The data set presented in this study represents the first complete 237 Np vertical profiles (0.12-0.27μBqL -1 ), and constitutes a baseline measurement to assess future changes. A similar behavior of Cs and Np has been evidenced, confirming that Np behaves conservatively. While the 137 Cs decrease has been driven by its radioactive decay, the vertical distribution of 237 Np has not substantially changed over the last decade. In the absence of recent major inputs, a homogenization of their vertical distribution occurred, partly due to deep convection events that became more intense during the last decade. In contrast, 239+240 Pu surface levels in the NW Mediterranean waters have fallen in the past four decades by a factor of 5. This decrease in surface has been balanced by higher concentrations in the deep-water layers. A first estimate of the downward 239+240 Pu fluxes in the NW Mediterranean Sea is proposed over more than two decades. This estimation, based on the DYFAMED sediment trap time-series data and published 239+240 Pu flux measurements, suggests that sinking particles have accounted for 60-90% of the upper layer (0-200m) Pu inventory loss over the period 1989-2013. The upper layer residence time of Pu is estimated to be ~28years, twice as long as the residence time estimated for the whole western Mediterranean (~15years). This difference highlights the slow removal of Pu in the open waters of the NW Mediterranean and confirms that most of the Pu removal occurs along the coastal margin where sedimentation rates are high. Copyright © 2017 Elsevier B.V. All rights reserved.

In vivo modulation of foreign body response on polyurethane by surface entrapment technique.

PubMed

Khandwekar, Anand P; Patil, Deepak P; Hardikar, Anand A; Shouche, Yogesh S; Doble, Mukesh

2010-11-01

Implanted polymeric materials, such as medical devices, provoke the body to initiate an inflammatory reaction, known as the foreign body response (FBR), which causes several complications. In this study, polyurethane (Tecoflex®, PU) surface modified with the nonionic surfactant Tween80® (PU/T80) and the cell adhesive PLL-RGD peptide (PU/PLL-RGD) by a previously described entrapment technique were implanted in the peritoneal cavity of Wistar rats for 30 days. Implants were retrieved and examined for tissue reactivity and cellular adherence by various microscopic and analytical techniques. Surface-induced inflammatory response was assessed by real-time PCR based quantification of proinflammatory cytokine transcripts, namely, TNF-α and IL-1β, normalized to housekeeping gene GAPDH. Cellular adherence and their distribution profile were assessed by microscopic examination of H&E stained implant sections. It was observed that PU/PLL-RGD followed by the bare PU surface exhibited severe inflammatory and fibrotic response with an average mean thickness of 19 and 12 μm, respectively, in 30 days. In contrast, PU/T80 surface showed only a cellular monolayer of 2-3 μm in thickness, with a mild inflammatory response and no fibrotic encapsulation. The PU/PLL-RGD peptide-modified substrate promoted an enhanced rate of macrophage cell fusion to form foreign body giant cell (FBGCs), whereas FBGCs were rarely observed on Tween80®-modified substrate. The expression levels of proinflammatory cytokines (TNF-α and IL-1β) were upregulated on PU/PLL-RGD surface followed by bare PU, whereas the cytokine expressions were significantly suppressed on PU/T80 surface. Thus, our study highlights modulation of foreign body response on polyurethane surfaces through surface entrapment technique in the form of differential responses observed on PLL-RGD and Tween80® modified surfaces with the former effective in triggering tissue cell adhesion thereby fibrous encapsulation, while the later being mostly resistant to this phenomenon.

Investigating Pu and U isotopic compositions in sediments: a case study in Lake Obuchi, Rokkasho Village, Japan using sector-field ICP-MS and ICP-QMS.

PubMed

Zheng, Jian; Yamada, Masatoshi

2005-08-01

The objectives of the present work were to study isotope ratios and the inventory of plutonium and uranium isotope compositions in sediments from Lake Obuchi, which is in the vicinity of several nuclear fuel facilities in Rokkasho, Japan. Pu and its isotopes were determined using sector-field ICP-MS and U and its isotopes were determined with ICP-QMS after separation and purification with a combination of ion-exchange and extraction chromatography. The observed (240)Pu/(239)Pu atom ratio (0.186 +/- 0.016) was similar to that of global fallout, indicating that the possible early tropospheric fallout Pu did not deliver Pu from the Pacific Proving Ground to areas above 40 degrees N. The previously reported higher Pu inventory in the deep water area of Lake Obuchi could be attributed to the lateral transportation of Pu deposited in the shallow area which resulted from the migration of deposited global fallout Pu from the land into the lake by river runoff and from the Pacific Ocean by tide movement and sea water scavenging, as well as from direct soil input by winds. The (235)U/(238)U atom ratios ranged from 0.00723 to 0.00732, indicating the natural origin of U in the sediments. The average (234)U/(238)U activity ratio of 1.11 in a sediment core indicated a significant sea water U contribution. No evidence was found for the release of U containing wastes from the nearby nuclear facilities. These results will serve as a reference baseline on the levels of Pu and U in the studied site so that any further contamination from the spent nuclear fuel reprocessing plants, the radioactive waste disposal and storage facilities, and the uranium enrichment plant can be identified, and the impact of future release can be rapidly assessed.

Mechanical environmental transport of actinides and ¹³⁷Cs from an arid radioactive waste disposal site

DOE Office of Scientific and Technical Information (OSTI.GOV)

Snow, Mathew S.; Clark, Sue B.; Morrison, Samuel S.

Particulate transport represents an important mechanism for actinides and fission products at the Earth's surface; soil samples taken in the early 1970's near the Subsurface Disposal Area (SDA) at Idaho National Laboratory (INL) provide a case study for examining the mechanisms and characteristics of actinide transport under arid conditions. Transuranic waste was disposed via shallow land burial at the SDA until shortly after a flooding event that occurred in 1969. In this study we analyze soils collected in the early 1970's for ¹³⁷Cs, ²⁴¹Am, and Pu using a combination of radiometric and mass spectrometric techniques. Two distinct ²⁴⁰Pu/²³⁹Pu isotopic ratiosmore » are observed for contamination from the SDA, with values ranging from at least 0.059 to 0.069. ²⁴¹Am concentrations are observed to increase only slightly in 0-4 cm soils over the ~40 year period since soil sampling, contrary to Markham's previous hypothesis that ²⁴¹Pu is principally associated with the 0-4 cm soil fractions (Markham 1978). The lack of statistical difference in ²⁴¹Am/²³⁹⁺²⁴⁰Pu ratios with depth suggests mechanical transport and mixing discrete contaminated particles under arid conditions. Occasional samples beyond the northeastern corner are observed to contain anomalously high Pu concentrations with corresponding low ²⁴⁰Pu/²³⁹Pu atoms ratios, suggesting the occurrence of "hot particles;" application of a background Pu subtraction results in calculated Pu atom ratios for the "hot particles" which are statistically similar to those observed in the northeastern corner. Taken together, our data suggests that flooding resulted in mechanical transport of contaminated particles into the area between the SDA and the flood containment dike in the northeastern corner, following which subsequent contamination spreading resulted from wind transport of discrete particles.« less

Influence of therapeutic radiation on polycaprolactone and polyurethane biomaterials.

PubMed

Cooke, Shelley L; Whittington, Abby R

2016-03-01

Biomedical polymers are exposed in vivo to ionizing radiation as implants, coatings and bystander materials. High levels of ionizing radiation (e.g. X-ray and gamma) have been reported to cause degradation and/or cross-linking in many polymers. This pilot study sought to determine causes of failure, by investigating how therapeutic radiation affects two different porous polymeric scaffolds: polycaprolactone (PCL) and polyurethane (PU). PCL is a bioresorbable material used in biomedical devices (e.g., dentistry, internal fixation devices and targeted drug delivery capsules). PU is commonly used in medical applications (e.g., coatings for pacemakers, tissue expanders, catheter tubing and wound dressings). PU was specifically fabricated to be a non-degradable polymer in this study. Porous scaffolds, fabricated using solvent casting and/or salt leeching techniques, were placed in phosphate buffered saline (PBS, pH=7.4) and exposed to typical cancer radiotherapy. A total dose of 50 Gy was broken into 25 doses over an eleven-week period. Collected PBS was tested for polymer leachants and degradation products using Gas Chromatography Mass Spectroscopy (GC-MS), results revealed no analyzable leachants from either polymer. Scaffolds were characterized using Environmental Scanning Electron Microscopy, Size-exclusion chromatography (SEC), Differential Scanning Calorimetry (DSC) and Fourier Transform Infrared Spectroscopy (FTIR). No gross visual changes were observed in either polymer, however PU exhibited microstructure changes after irradiation. Increased number average molecular weight and weight average molecular weight in PCL and PU were observed after irradiation, indicating crosslinking. PU displayed an increase in intrinsic viscosity that further confirms increased crosslinking. PCL and PU showed decreases in crystallinity after irradiation, and PU crystallinity shifted from long-range-order hard segments to short-range-order hard segments after irradiation. Results from both PCL and PU suggest changes in polymer backbones. This preliminary study suggests that therapeutic radiation doses cause both degradation and crosslinking in PCL and PU. Copyright © 2015 Elsevier B.V. All rights reserved.

Electrically responsive microstructured polypyrrole-polyurethane composites for stimulated osteogenesis

NASA Astrophysics Data System (ADS)

Luculescu, Catalin Romeo; Acasandrei, Adriana Maria; Mustaciosu, Cosmin Catalin; Zamfirescu, Marian; Dinescu, Maria; Calin, Bogdan Stefanita; Popescu, Andrei; Chioibasu, Diana; Cristian, Dan; Paun, Irina Alexandra

2018-03-01

In this work, we demonstrate the efficiency of substrate-mediated electrical stimulation of micropatterned polypyrrole/polyurethane (PPy/PU) composites for enhancing the osteogenesis in osteoblast-like cells. The PPy/PU substrates were obtained by dispersing electrically conductive PPy nanograins within a mechanically resistant PU matrix. Spin-coated PPy/PU layers were micropatterned with predefined 3D geometries by ultrashort laser ablation. Then they were conformally coated by Matrix Assisted Pulsed Laser Evaporation, in order to restore their chemical and electrical integrity. The chemical structure of the laser-processed PPy/PU substrates was investigated by 2D and 3D mapping of the laser-processed areas, via Raman microspectroscopy. In vitro studies revealed that the micropatterned PPy/PU substrates facilitated the topological and electrical communication of the seeded osteoblasts. Specifically, we demonstrated the cells attachment on the predefined 3D micropatterns. More importantly, we found evidence about the cells mineralization inside the 3D micropatterns by investigating the calcium deposits by Energy-Dispersive X-Ray Spectroscopy (EDS) and Alizarin Red staining. We found that the substrate-mediated electrical stimulation of the PPy/PU substrates induced a twofold increase of the Ca deposits in the cultured cells.

Plutonium and cesium baseline concentrations in seawater from northern Arabian Gulf.

PubMed

Uddin, S; Aba, A; Behbehani, M; Al-Ghadban, A N; Al-Zekri, W; Al-Shammari, H

2017-07-15

The Arabian Gulf is a semi-enclosed water body that has witnessed accelerated anthropogenic activity, in terms of commissioning of nuclear power plants, desalination facilities, oil refineries and extensive coastal development. Furthermore, three wars during the past three decades is a potential worry. This study presents the first plutonium baseline in seawater from the Northern Arabian Gulf. The 239+240 Pu concentrations in seawater vary, between 2.9 and 4.9mBqm -3 , a range that is comparable to other water masses at this latitude. The 238 Pu ranged between 0.04 and 0.05mBqm -3 and the 137 Cs concentration between 1.04 and 1.18Bqm -3 . The ratio of 238 Pu/ 239+240 Pu at all eight sampling stations was 0.01, while the ratio of 239+240 Pu/ 137 Cs varied between 0.01 and 0.02. The presence of 137 Cs and 239+240 Pu in seawater from this region can mainly be attributed to the global atmospheric deposition and fluvial transport. The seawater concentration of 239+240 Pu is five order of magnitude lower than bottom sediments in the area. Copyright © 2017 Elsevier Ltd. All rights reserved.

Results of the Excreta Bioassay Quality Control Program for April 1, 2009 through March 31, 2010

DOE Office of Scientific and Technical Information (OSTI.GOV)

Antonio, Cheryl L.

2012-07-19

A total of 58 urine samples and 10 fecal samples were submitted during the report period (April 1, 2009 through March 31, 2010) to General Engineering Laboratories, South Carolina by the Hanford Internal Dosimetry Program (IDP) to check the accuracy, precision, and detection levels of their analyses. Urine analyses for Sr, 238Pu, 239Pu, 241Am, 243Am 235U, 238U, elemental uranium and fecal analyses for 241Am, 238Pu and 239Pu were tested this year as well as four tissue samples for 238Pu, 239Pu, 241Am and 241Pu. The number of QC urine samples submitted during the report period represented 1.3% of the total samplesmore » submitted. In addition to the samples provided by IDP, GEL was also required to conduct their own QC program, and submit the results of analyses to IDP. About 33% of the analyses processed by GEL during the third year of this contract were quality control samples. GEL tested the performance of 21 radioisotopes, all of which met or exceeded the specifications in the Statement of Work within statistical uncertainty (Table 4).« less

Conversion electron spectrometry of Pu isotopes with a silicon drift detector.

PubMed

Pommé, S; Paepen, J; Peräjärvi, K; Turunen, J; Pöllänen, R

2016-03-01

An electron spectrometry set-up was built at IRMM consisting of a vacuum chamber with a moveable source holder and windowless Peltier-cooled silicon drift detector (SDD). The SDD is well suited for measuring low-energy x rays and electrons emitted from thin radioactive sources with low self-absorption. The attainable energy resolution is better than 0.5keV for electrons of 30keV. It has been used to measure the conversion electron spectra of three plutonium isotopes, i.e. (238)Pu, (239)Pu, (240)Pu, as well as (241)Am (being a decay product of (241)Pu). The obtained mixed x-ray and electron spectra are compared with spectra obtained with a close-geometry set-up using another SDD in STUK and spectra measured with a Si(Li) detector at IRMM. The potential of conversion electron spectrometry for isotopic analysis of mixed plutonium samples is investigated. With respect to the (240)Pu/(239)Pu isotopic ratio, the conversion electron peaks of both isotopes are more clearly separated than their largely overlapping peaks in alpha spectra. Copyright © 2015 The Authors. Published by Elsevier Ltd.. All rights reserved.

Unusual behaviour of (Np,Pu)B2C

NASA Astrophysics Data System (ADS)

Klimczuk, Tomasz; Boulet, Pascal; Griveau, Jean-Christophe; Colineau, Eric; Bauer, Ernst; Falmbigl, Matthias; Rogl, Peter; Wastin, Franck

2015-02-01

Two transuranium metal boron carbides, NpB2C and PuB2C have been synthesized by argon arc melting. The crystal structures of the {Np,Pu}B2C compounds were determined from single-crystal X-ray data to be isotypic with the ThB2C-type (space group ?, a = 0.6532(2) nm; c = 1.0769(3) nm for NpB2C and a = 0.6509(2) nm; c = 1.0818(3) nm for PuB2C; Z = 9). Physical properties have been derived from polycrystalline bulk material in the temperature range from 2 to 300 K and in magnetic fields up to 9 T. Magnetic susceptibility and heat capacity data indicate the occurrence of antiferromagnetic ordering for NpB2C with a Neel temperature TN = 68 K. PuB2C is a Pauli paramagnet most likely due to a strong hybridization of s(p,d) electrons with the Pu-5f states. A pseudo-gap, as concluded from the Sommerfeld value and the electronic transport, is thought to be a consequence of the hybridization. The magnetic behaviour of {Np,Pu}B2C is consistent with the criterion of Hill.

The effect of x rays, DTPA, and aspirin on the absorption of plutonium from the gastrointestinal tract of rats

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sullivan, M.F.; Gorham, L.S.; Miller, B.M.

To measure the effect of radiation on plutonium transport, rats that were exposed to 250-kVp X rays were given /sup 238/Pu 3 days afterwards by either gavage or injection into a ligated segment of the duodenum. In a second group of experiments, rats were either injected intraduodenally with /sup 238/Pu-DTPA or administered the chelate intravenously and the /sup 238/Pu by gavage. In a third experiment, rats that had been gavaged with 200 or 400 mg/kg/day of aspirin for 2 days were injected intragastrically with /sup 238/Pu nitrate. Results of the first experiment showed a dose-dependent increase in /sup 238/Pu absorptionmore » between 800 and 1500 rad of lower-body X irradiation. Intravenous or intraduodenal injections of DTPA caused a marked increase in /sup 238/Pu absorption but resulted in decreased plutonium deposition in the skeleton and liver. Retention of /sup 238/Pu in the skeleton of rats given aspirin was double that of controls, but the effect on plutonium absorption was less marked than that of DTPA.« less

An Episode 56 Perspective on Post-2001 Comagmatic Mixing Along Kilauea's East Rift Zone

NASA Astrophysics Data System (ADS)

Thornber, C.; Orr, T.; Lowers, H.; Heliker, C.; Hoblitt, R.

2007-12-01

A significant change in the petrology of Pu`u `O`o -Kupaianaha lava occurred in April 2001 (3 years after the onset of the decade-long episode 55). Prior to that time all steady-state eruption products were olivine phryic. After that time and until the Kane Nui o Hamo eruption of June 19, 2007 (episode 56), all magma erupted from vents in and around Pu`u `O`o was olivine and pyroxene-phyric containing <1mm, isolated or clustered clinopyroxene (±olivine, ±plagioclase), usually with resorbed edges. Textures, phase chemistry and low-pressure phase relations define a pre-eruptive mixing environment that is driven by continuous recharge of a stagnant, near-cotectic shallow magma body. The comagmatic nature of the cooler component in the post-2001 hybrid magma is verified by low concentrations of incompatible elements relative to MgO. Since the eruption began in 1983, the olivine-saturated liquid-line-of-descent has progressively shifted toward the present-day low concentrations of incompatible elements. Superimposed on this long-term trend are shorter chemical cycles (months to years) which track fractionation and recharge between comagmatic endmembers of ~10 and ~7 wt% MgO. These shorter cycles correspond to heating and cooling events and imply magmatic recharge of a sustained shallow magma reservoir within the eruptive plumbing system. The longest cooling cycle of the entire eruption began in April 1998 after effusion of the hottest and most- primitive lava erupted since 1985 (episodes 30 and 31). Glass temperatures up to 1168°C and bulk MgO of 9.5 wt% steadily declined for 6 years until late 2004 when they bottomed-out at 1140°C and 6.8 wt%. This signaled a stable near-cotectic magma condition. MgO contents and glass temperatures stailized at ~7.1 wt% and 1146°C for the remainder of episode 55, as the hybrid magmas were stirred by a steady influx of summit-derived magma beneath a complex of intermittently active Pu`u O`o vents. During the June 19, 2007 Kane Nui O Hamo eruption (episode 56), as with the January 1997 Napua Crater event (episode 54), the summit deflated and Pu`u O`o collapsed as magma was drawn from either end of the active rift conduit toward a zone of extension. In both cases, magma returned to the Pu`u `O`o vent area after the conduit repressurized. However, in contrast to cool and porphyritic hybrid magma erupted through isolated and chemically evolved rift magma reservoirs at Napau Crater, the episode 56 lava is relatively primitive (8.7 wt% MgO) and 30 to 50°C hotter at 1160°C. This is likely to be summit-derived magma from within the active rift conduit beneath Kane Nui o Hamo. The episode 56 lava is ~15°C hotter than the late episode 55 hybrid magmas with consistently low incompatible elements and likely represents the recharge component that maintained a shallow reservoir at near-cotectic conditions beneath the vicinity of the Pu`u `O`o vents for the last several years. Both lava erupted from Pu`u `O`o in early June, 2007(episode 57), and lava the from the July 21-24 sequence of fissure eruptions down-rift of Pu`u `O`o (early episode 58) contain a distinctly hybrid phenocryst and glomerocryst assemblage, suggesting a flushing of cooler crystal-laden magma from the conduit.

Deviation between the chemistry of Ce(IV) and Pu(IV) and routes to ordered and disordered heterobimetallic 4f/5f and 5f/5f phosphonates.

PubMed

Diwu, Juan; Wang, Shuao; Good, Justin J; DiStefano, Victoria H; Albrecht-Schmitt, Thomas E

2011-06-06

The heterobimetallic actinide compound UO(2)Ce(H(2)O)[C(6)H(4)(PO(3)H)(2)](2)·H(2)O was prepared via the hydrothermal reaction of U(VI) and Ce(IV) in the presence of 1,2-phenylenediphosphonic acid. We demonstrate that this is a kinetic product that is not stable with respect to decomposition to the monometallic compounds. Similar reactions have been explored with U(VI) and Ce(III), resulting in the oxidation of Ce(III) to Ce(IV) and the formation of the Ce(IV) phosphonate, Ce[C(6)H(4)(PO(3)H)(PO(3)H(2))][C(6)H(4)(PO(3)H)(PO(3))]·2H(2)O, UO(2)Ce(H(2)O)[C(6)H(4)(PO(3)H)(2)](2)·H(2)O, and UO(2)[C(6)H(4)(PO(3)H)(2)](H(2)O)·H(2)O. In comparison, the reaction of U(VI) with Np(VI) only yields Np[C(6)H(4)(PO(3)H)(2)](2)·2H(2)O and aqueous U(VI), whereas the reaction of U(VI) with Pu(VI) yields the disordered U(VI)/Pu(VI) compound, (U(0.9)Pu(0.1))O(2)[C(6)H(4)(PO(3)H)(2)](H(2)O)·H(2)O, and the Pu(IV) phosphonate, Pu[C(6)H(4)(PO(3)H)(PO(3)H(2))][C(6)H(4)(PO(3)H)(PO(3))]·2H(2)O. The reactions of Ce(IV) with Np(VI) yield disordered heterobimetallic phosphonates with both M[C(6)H(4)(PO(3)H)(PO(3)H(2))][C(6)H(4)(PO(3)H)(PO(3))]·2H(2)O (M = Ce, Np) and M[C(6)H(4)(PO(3)H)(2)](2)·2H(2)O (M = Ce, Np) structures, as well as the Ce(IV) phosphonate Ce[C(6)H(4)(PO(3)H)(PO(3)H(2))][C(6)H(4)(PO(3)H)(PO(3))]·2H(2)O. Ce(IV) reacts with Pu(IV) to yield the Pu(VI) compound, PuO(2)[C(6)H(4)(PO(3)H)(2)](H(2)O)·3H(2)O, and a disordered heterobimetallic Pu(IV)/Ce(IV) compound with the M[C(6)H(4)(PO(3)H)(PO(3)H(2))][C(6)H(4)(PO(3)H)(PO(3))]·2H(2)O (M = Ce, Pu) structure. Mixtures of Np(VI) and Pu(VI) yield disordered heterobimetallic Np(IV)/Pu(IV) phosphonates with both the An[C(6)H(4)(PO(3)H)(PO(3)H(2))][C(6)H(4)(PO(3)H)(PO(3))]·2H(2)O (M = Np, Pu) and An[C(6)H(4)(PO(3)H)(2)](2)·2H(2)O (M = Np, Pu) formulas. © 2011 American Chemical Society

Laser Doppler imager (LDI) scanner and intradermal injection for in vivo pharmacology in human skin microcirculation: responses to acetylcholine, endothelin-1 and their repeatability

PubMed Central

Saez, Anabelle M Opazo; Mosel, Frank; Nürnberger, Jens; Rushentsova, U; Gössl, Mario; Mitchell, Anna; Schäfers, Rafael F; Philipp, Thomas; Wenzel, René R

2005-01-01

Aims The purpose of this study was to evaluate the repeatability of forearm skin blood flow responses to intradermal injections of acetylcholine (ACh) and endothelin-1 (ET-1) using a double injection technique (DIT) and a laser Doppler imager (LDI) scanner in the human skin microcirculation. Methods We used a laser Doppler imager (Moor LDI V3.01) to continuously monitor the change in skin blood flow during intradermal administration of physiological saline (0.9% NaCl), acetylcholine (ACh 10−7, 10−8, 10−9 M) and endothelin-1 (ET-1 10−14, 10−16, 10−18 M) in 10 healthy male subjects. Subjects were examined on 3 different days for assessment of interday and interobserver repeatability. Injections of either drug were randomly placed on different sites of the forearm. Laser Doppler images were collected before and after injection at 2.5 min intervals for 30 min. Data were analysed after the completion of each experiment using Moor Software V.3.01. Results are expressed as changes from baseline in arbitrary perfusion units (PU). Results ACh caused a significant vasodilation (P< 0.0001 anova, mean ± SE: 766 ± 152 PU, ACh 10−9 M; 1868 ± 360 PU, ACh 10−8 M; 4188 ± 848 PU, ACh 10−7 M; mean of days 1 and 2, n = 10), and ET-1 induced a significant vasoconstrictive response (P< 0.0001 anova, −421 ± 83 PU, ET-1 10−18 M; −553 ± 66 PU, ET-1 10−16 M; −936 ± 90 PU, ET-1 10−14 M; mean of days 1 and 2, n = 10). There was no difference on the response to either drug on repeated days. Bland-Altman analyses showed a close agreement of responses between days with repeatability coefficients of 1625.4 PU for ACh, and 386.0 PU for ET-1 (95% CI: ACh, −1438 to 1747 PU, ET-1, −399 to 358 PU) and between observers with repeatability coefficients of 1057.2 PU for ACh and 255.8 PU for ET-1 (95% CI: ACh, −1024 to 1048 PU, ET-1, −252 to 249 PU). The variability between these responses was independent of average flux values for both ACh and ET-1. There was a significant correlation between responses measured in the same site, in the same individual on two different days by the same observer (ACh, r = 0.94, P < 0.0001; ET-1, r = 0.90, P < 0.0006), and between responses measured by two different observers (ACh, r = 0.94, P < 0.0001; ET-1, r = 0.91, P < 0.0003). Conclusion We have shown that interday and intraobserver responses to intradermal injections of ET-1 and ACh, assessed using the DIT in combination with an LDI scanner, exhibited good reproducibility and may be a useful tool for studying the skin microcirculation in vivo. PMID:15842548

Method for dissolving plutonium oxide with HI and separating plutonium

DOEpatents

Vondra, Benedict L.; Tallent, Othar K.; Mailen, James C.

1979-01-01

PuO.sub.2 -containing solids, particularly residues from incomplete HNO.sub.3 dissolution of irradiated nuclear fuels, are dissolved in aqueous HI. The resulting solution is evaporated to dryness and the solids are dissolved in HNO.sub.3 for further chemical reprocessing. Alternatively, the HI solution containing dissolved Pu values, can be contacted with a cation exchange resin causing the Pu values to load the resin. The Pu values are selectively eluted from the resin with more concentrated HI.

The Influence of Oil Contamination on the Nucleate Pool-Boiling Behavior of R-114 from a Structured Surface.

DTIC Science & Technology

1985-03-01

1 7015 IF Pu-a THEN PRINT "PA" Y,"PO" 70Ze IF Pu-) THEN PRINT "PA" .,Y. "PU" 702S NEXT Xa 7038 PRINT "PU" 783S Ian.-Ion+ I 7848 COTO 6540 7845 END IF...Heat Transfer over the wide Range of Pressure," Proceedinqs of the Seventh International Heat Transfer CencYne-,Mun- ch -vI-, �, pp. 19. Webb, R. L

Surrogate 239Pu(n, fxn) and 241Pu(n, fxn) average fission-neutron-multiplicity measurements

DOE Office of Scientific and Technical Information (OSTI.GOV)

Burke, J. T.; Alan, B. S.; Akindele, O. A.

2017-09-26

We have constructed a new neutron-charged-particle detector array called NeutronSTARS. It has been described extensively in LLNL-TR-703909 [1] and Akindele et al [2]. We have used this new neutron-charged-particle array to measure the 241Pu and 239Pu fissionneutron multiplicity as a function of equivalent incident-neutron energy from 100 keV to 20 MeV. The experimental approach, detector array, data analysis, and results are summarized in the following sections.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vorobev, A.M.; Kuzmina, V.P.

A method is described for determining Pu in the presence of large quantities of U. Pu is extracted using thenoyltrifluoroacetone (TTA) and precipitated using bismuth phosphate. In contrast to U (VI), plutonium (IV) is easily separated by TTA from 1M nitric acid and lends itself to quantitative precipitation. The yield of Pu amounted to 90%. The presence of U/sup 235/ in quantities exceeding 200-fold the Pu content did not influence the determination in 10-mg specimens. The order of error was plus or minus 20%. (R.V.J.)

REDUCTION OF PLUTONIUM VALUES IN AN ACIDIC AQUEOUS SOLUTION WITH FORMALDEHYDE

DOEpatents

Olson, C.M.

1959-06-01

A method is given for reducing Pu to the tetravalent state and lowering the high acidity of dissolver solutions containing U and Pu. Formaldehyde is added to the HNO/sub 3/ solution of U and Pu to effect a formaldehyde to HNO/sub 3/ molar ratio of 0.375:1 to 1.5:1. The Pu can then be removed from the solution by carrier precipitation using BiPO/sub 4/ or by ion exchange. (T.R.H.)

The impact of culture medium on the development and physiology of biofilms of Pseudomonas fluorescens formed on polyurethane paint.

PubMed

Crookes-Goodson, Wendy J; Bojanowski, Caitlin L; Kay, Michelle L; Lloyd, Pamela F; Blankemeier, Andrew; Hurtubise, Jennifer M; Singh, Kristi M; Barlow, Daniel E; Ladouceur, Harold D; Matt Eby, D; Johnson, Glenn R; Mirau, Peter A; Pehrsson, Pehr E; Fraser, Hamish L; Russell, John N

2013-01-01

Microbial biofilms cause the deterioration of polymeric coatings such as polyurethanes (PUs). In many cases, microbes have been shown to use the PU as a nutrient source. The interaction between biofilms and nutritive substrata is complex, since both the medium and the substratum can provide nutrients that affect biofilm formation and biodeterioration. Historically, studies of PU biodeterioration have monitored the planktonic cells in the medium surrounding the material, not the biofilm. This study monitored planktonic and biofilm cell counts, and biofilm morphology, in long-term growth experiments conducted with Pseudomonas fluorescens under different nutrient conditions. Nutrients affected planktonic and biofilm cell numbers differently, and neither was representative of the system as a whole. Microscopic examination of the biofilm revealed the presence of intracellular storage granules in biofilms grown in M9 but not yeast extract salts medium. These granules are indicative of nutrient limitation and/or entry into stationary phase, which may impact the biodegradative capability of the biofilm.

Developing a physiologically based approach for modeling plutonium decorporation therapy with DTPA.

PubMed

Kastl, Manuel; Giussani, Augusto; Blanchardon, Eric; Breustedt, Bastian; Fritsch, Paul; Hoeschen, Christoph; Lopez, Maria Antonia

2014-11-01

To develop a physiologically based compartmental approach for modeling plutonium decorporation therapy with the chelating agent Diethylenetriaminepentaacetic acid (Ca-DTPA/Zn-DTPA). Model calculations were performed using the software package SAAM II (©The Epsilon Group, Charlottesville, Virginia, USA). The Luciani/Polig compartmental model with age-dependent description of the bone recycling processes was used for the biokinetics of plutonium. The Luciani/Polig model was slightly modified in order to account for the speciation of plutonium in blood and for the different affinities for DTPA of the present chemical species. The introduction of two separate blood compartments, describing low-molecular-weight complexes of plutonium (Pu-LW) and transferrin-bound plutonium (Pu-Tf), respectively, and one additional compartment describing plutonium in the interstitial fluids was performed successfully. The next step of the work is the modeling of the chelation process, coupling the physiologically modified structure with the biokinetic model for DTPA. RESULTS of animal studies performed under controlled conditions will enable to better understand the principles of the involved mechanisms.

Comparative Photoemission Study of Actinide (Am, Pu, Np and U) Metals, Nitrides, and Hydrides

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gouder, Thomas; Seibert, Alice; Rebizant, Jean

2007-07-01

Core-level and valence-band spectra of Pu and the other early actinide compounds show remarkable systematics, which can be understood in the framework of final state screening. We compare the early actinide (U, Np, Pu and Am) metals, nitrides and hydrides and a few other specific compounds (PuSe, PuS, PuCx, PuSix) prepared as thin films by sputter deposition. In choosing these systems, we combine inherent 5f band narrowing, due to 5f orbital contraction throughout the actinide series, with variations of the chemical environment in the compounds. Goal of this work was to learn more on the electronic structure of the earlymore » actinide systems and to achieve the correct interpretation of their photoemission spectra. The highly correlated nature of the 5f states in systems, which are on the verge to localization, makes this a challenging task, because of the peculiar interplay between ground state DOS and final-state effects. Their influence can be estimated by doing systematic studies on systems with different (5f) bandwidths. We conclude on the basis of such systematic experiments that final-state effects due to strong e-e correlations in narrow 5f-band systems lead to multiplet like structures, analogous to those observed in the case of systems with localized electron states. Such observations in essentially band-like 5f-systems was first surprising, but the astonishing similarity of photoemission spectra of very different chemical systems (e.g. PuSe, Pu{sub 2}C{sub 3}..) points to a common origin, relating them to atomic features rather than material dependent density of states (DOS) features. (authors)« less

A simple and efficient feeder-free culture system to up-scale iPSCs on polymeric material surface for use in 3D bioprinting.

PubMed

Wong, Chui-Wei; Chen, You-Tzung; Chien, Chung-Liang; Yu, Tien-Yu; Rwei, Syang-Peng; Hsu, Shan-Hui

2018-01-01

The 3D bioprinting and cell/tissue printing techniques open new possibilities for future applications. To facilitate the 3D bioprinting process, a large amount of living cells are required. Induced pluripotent stem cells (iPSCs) represent a promising cell source for bioprinting. However, the maintenance and expansion of undifferentiated iPSCs are expensive and time consuming. Therefore, in this study a culture method to obtain a sufficient amount of healthy and undifferentiated iPSCs in a short-term period was established. The iPSCs could be passaged for twice on tissue culture polystyrene (TCPS) dish with the conditional medium and could adapt to the feeder-free environment. Feeder-free dishes were further prepared from chitosan, chitosan-hyaluronan, silk fibroin, and polyurethane (PU1 and PU2) two-dimensional substrates. The iPSCs cultured on the chitosan substrates showed a higher proliferation rate without losing the stemness feature. Among the different materials, PU2 could be prepared as a thermoresponsive hydrogel, which was a potential ink for 3D bioprinting. The iPSCs cultured on PU2 substrates well survived when further embedded in PU2 hydrogel. Moreover, PU2 hydrogel printed with iPSCs remained structural integrity. The use of PU2 hydrogel to embed iPSCs reduced the injury to iPSCs by shear stress. These results indicate that iPSCs could be expanded on chitosan or PU2 membranes without the feeder layer and then printed in PU2 hydrogel. The combination of these steps could offer a new possibility for future applications of iPSC-based 3D bioprinting in tissue engineering. Copyright © 2017 Elsevier B.V. All rights reserved.

Synthesis and characterization of novel fluoroalkyl-terminated hyperbranched polyurethane latex

NASA Astrophysics Data System (ADS)

Xu, Wei; Zhao, Weijia; Hao, Lifen; Wang, Sha; Pei, Mengmeng; Wang, Xuechuan

2018-04-01

Waterborne polyurethane (PU) emulsions are widely used in various fields and the demand for them is ever-increasing over the years. However, the hydrophilic chain extender inevitably bonded into the PU backbone can affect the water tolerance of PU. Thus, it is of great importance to improve PU water resistance effectively. Herein, novel fluoroalkyl-terminated hyperbranched polyurethane (HBPUF) latex was accordingly synthesized by graft reaction of perfluorohexyl ethyl alcohol and hyperbranched polyurethane (HBPU), which was previously obtained from interaction between hydroxyl-terminated hyperbranched polymer and PU prepolymer manufactured via the acetone process, as well as using neutralization, adding water, and high-speed stirring operations. We characterized the resultants and investigated its surface properties by IR, NMR, TEM, XRD, TGA, DSC, FE-SEM, AFM, XPS, and contact angle measurements, etc. IR and NMR tests confirmed that the fluorinated fragments had been grafted onto the tail end of HBPU. TEM, XRD, DSC, and FE-SEM results all accounted for the fact that there were multi-crystals in PU, HBPU and HBPUF. TGA results showed that thermal stabilities of the PU, HBPU, and HBPUF latex films were enhanced in turn. XPS and AFM analyses demonstrated that the fluorine-containing segments from the HBPUF terminals were prone to migrate and enrich on the film-air surface of the HBPUF latex film, which made water contact angle and water absorption of the HBPUF film be as 113.9° and 11.1%, respectively, compared to those of the PU film (77.8° and 136.2%). This research indicates that water resistance of the PU film can be efficiently enhanced by fluorinated polyurethane with novel fluoroalkyl-terminated hyperbranched structure.

Ecological studies of small vertebrates in Pu-contaminated study areas of NTS and TTR

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bradley, W.G.; Moor, K.S.; White, M.G.

Ecological studies of vertebrates in plutonium-contaminated areas of the Nevada Test Site (NTS) were initiated in March 1972, and have continued to date. In September 1973, standard census methods were also employed to derive a qualitative and quantitative inventory of vertebrate biota of four Nevada Applied Ecology Group (NAEG) study areas of the Tonopah Test Range (TTR). A checklist of vertebrates of NAEG study areas of NTS and TTR is presented. Data are presented on vertebrate composition, relative abundance, and seasonal status in the study areas. Concentrations of $sup 239$Pu and $sup 241$Am were determined in pelt or skin, GImore » tract, and carcass of 13 lizards and 16 mammals resident on Clean Slate 2, TTR, and Area 11, NTS. A total of 71 animals were collected for radioanalysis. However, the data were not available at the time this report was written. Pu tissue burdens were highest in lizards from Area 11 GZ. Maximum values obtained in nCi/g ash were 30.9, 42.2, and 0.43 for the pelt, GI tract, and carcass, respectively. Maximum $sup 239$Pu values in tissues of small rodents from Area 11 (not from GZ) were 11.4, 6.49, and 0.20 nCi/g ash for pelt, GI tract, and carcass, respectively. Pu/Am ratios were relatively consistent in tissue samples of lizards and small mammals from Area 11 (approximately 6:1, Pu/Am). Pu/Am ratios were not consistent in vertebrates of Clean Slate 2, TTR, and appeared to be lower in carcass (28:1, Pu/Am in mammals) than GI tract (9:1, Pu/Am in mammals). Although this trend was more conspicuous in mammals, it was also evident in reptiles. (auth)« less

Determination and comparison of γ-aminobutyric acid (GABA) content in pu-erh and other types of Chinese tea.

PubMed

Zhao, Ming; Ma, Yan; Wei, Zhen-zhen; Yuan, Wen-xia; Li, Ya-li; Zhang, Chun-hua; Xue, Xiao-ting; Zhou, Hong-jie

2011-04-27

Two previous studies have reported that pu-erh tea contains a high level of γ-aminobutyric acid (GABA), which is the major inhibitory neurotransmitter in the central nervous system and has several physiological functions. However, two other researchers have demonstrated that the GABA content of several pu-erh teas was low. Due to the high value and health benefits of GABA, analysis of mass-produced pu-erh tea is necessary to determine whether it is actually enriched with GABA. A high-performance liquid chromatography (HPLC) method was developed for the determination of GABA in tea, the results of which were verified by amino acid analysis using an Amino Acid Analyzer (AAA). A total of 114 samples of various types of Chinese tea, including 62 pu-erh teas, 13 green teas, 8 oolong teas, 8 black teas, 3 white teas, 4 GABA teas, and 16 process samples from two industrial fermentations of pu-erh tea (including the raw material and the first to seventh turnings), were analyzed using HPLC. Statistical analysis demonstrated that the GABA content in pu-erh tea was significantly lower than that in other types of tea (p < 0.05) and that the GABA content decreased during industrial fermentation of pu-erh tea (p < 0.05). This mass analysis and comparison suggested GABA was not a major bioactive constituent and resolved the disagreement GABA content in pu-erh tea. In addition, the GABA content in white tea was found to be significantly higher than that in the other types of tea (p < 0.05), leading to the possibility of producing GABA-enriched white tea.

HOW OLD IS IT? - 241PU/241AM NUCLEAR FORENSIC CHRONOLOGY REFERENCE MATERIALS

PubMed Central

Fitzgerald, Ryan; Inn, Kenneth G.W.; Horgan, Christopher

2018-01-01

One material attribute for nuclear forensics is material age. 241Pu is almost always present in uranium- and plutonium-based nuclear weapons, which pose the greatest threat to our security. The in-growth of 241Am due to the decay of 241Pu provides an excellent chronometer of the material. A well-characterized 241Pu/241Am standard is needed to validate measurement capability, as a basis for between-laboratory comparability, and as material for verifying laboratory performance. This effort verifies the certification of a 38 year old 241Pu Standard Reference Material (SRM4340) through alpha-gamma anticoincidence counting, and also establishes the separation date to two weeks of the documented date. PMID:29720779

Investigation on Thermal Properties of Kenaf Fibre Reinforced Polyurethane Bio-Composites

NASA Astrophysics Data System (ADS)

Athmalingam, Mathan; Vicki, W. V.

2018-01-01

This research focuses on the effect of Kenaf fibre on thermal properties of Polyurethane (PU) reinforced kenaf bio-composites. The samples were prepared using the polymer casting method with different percentages of kenaf fibre content (5 wt%, 10 wt%, 15 wt%). The thermal properties of Kenaf/PU bio-composite are determined through the Thermogravimetric Analysis and Differential Scanning Calorimeter test. The TGA results revealed that 10 wt% Kenaf/PU bio-composite appeared to be more stable. DSC results show that the glass transition temperature (Tg) value of 10 wt% Kenaf/PU composite is significant to pure polyurethane. It can be said that the thermal stability of 10 wt% Kenaf/PU bio-composite exhibits higher thermal stability compared to other samples.

Plutonium release from Fukushima Daiichi fosters the need for more detailed investigations

NASA Astrophysics Data System (ADS)

Schneider, Stephanie; Walther, Clemens; Bister, Stefan; Schauer, Viktoria; Christl, Marcus; Synal, Hans-Arno; Shozugawa, Katsumi; Steinhauser, Georg

2013-10-01

The contamination of Japan after the Fukushima accident has been investigated mainly for volatile fission products, but only sparsely for actinides such as plutonium. Only small releases of actinides were estimated in Fukushima. Plutonium is still omnipresent in the environment from previous atmospheric nuclear weapons tests. We investigated soil and plants sampled at different hot spots in Japan, searching for reactor-borne plutonium using its isotopic ratio 240Pu/239Pu. By using accelerator mass spectrometry, we clearly demonstrated the release of Pu from the Fukushima Daiichi power plant: While most samples contained only the radionuclide signature of fallout plutonium, there is at least one vegetation sample whose isotope ratio (0.381 +/- 0.046) evidences that the Pu originates from a nuclear reactor (239+240Pu activity concentration 0.49 Bq/kg). Plutonium content and isotope ratios differ considerably even for very close sampling locations, e.g. the soil and the plants growing on it. This strong localization indicates a particulate Pu release, which is of high radiological risk if incorporated.

Impact fragmentation of polyurethane and polypropylene cylinder

NASA Astrophysics Data System (ADS)

Kishimura, Hiroaki; Noguchi, Daisuke; Preechasupanya, Worrayut; Matsumoto, Hitoshi

2013-11-01

The impact fragmentation of a bulk polyurethane elastomer (PU) and polypropylene (PP) cylinder have been investigated using a Cu plate projectile launched by a propellant gun at a velocity of 0.53-1.4 km/s. A projectile drills into a PU sample and forms a cavity in the sample. A small number of tiny fragments are formed. When the projectile smashes in at 1.4 km/s, the PU cylinder bursts and PU fragments form. On the other hand, a brittle fracture occurs on the PP cylinder. The mass of fragments from the PU sample generated at a lower impact velocity is distributed in the lognormal form, whereas the mass of fragments from the PU sample generated by a 1.4 km/s impact follows a power-law distribution. The fragment mass distribution of the PP sample generated at a lower impact velocity obeys the power-law form, whereas that generated at a higher impact velocity follows the lognormal form.

Effects of ZnO Nanoparticle on the Gas Separation Performance of Polyurethane Mixed Matrix Membrane

PubMed Central

Soltani, Banafsheh

2017-01-01

Polyurethane (PU)-ZnO mixed matrix membranes (MMM) were fabricated and characterized for gas separation. A thermogravimetric analysis (TGA), a scanning electron microscope (SEM) test and an atomic-force microscopy (AFM) revealed that the physical properties and thermal stability of the membranes were improved through filler loading. Hydrogen Bonding Index, obtained from the Fourier transform infrared spectroscopy (FTIR), demonstrate that the degree of phase separation in PU-ZnO 0.5 wt % MMM was more than the neat PU, while in PU-ZnO 1.0 wt % MMM, the phase mixing had increased. Compared to the neat membrane, the CO2 permeability of the MMMs increased by 31% for PU-ZnO 0.5 wt % MMM and decreased by 34% for 1.0 wt % ZnO MMM. The CO2/CH4 and CO2/N2 selectivities of PU-ZnO 0.5 wt % were 18.75 and 64.75, respectively. PMID:28800109

Predictions of Actinide Solubilities under Near-Field Conditions Expected in the WIPP

NASA Astrophysics Data System (ADS)

Brush, L. H.; Xiong, Y.

2009-12-01

The Waste Isolation Pilot Plant (WIPP) is a U.S. Department of Energy (DOE) repository in southeast New Mexico for defense-related transuranic (TRU) waste. The repository, which opened in March 1999, is located at a subsurface depth of 655 m (2150 ft) in the Salado Fm., a Permian bedded-salt formation. The repository will eventually contain the equivalent of 844,000 208 L (55 gal) drums of TRU waste. After filling the rooms and access drifts and installing panel closures, creep closure of the salt will crush the steel waste containers in most cases and encapsulate the waste. The WIPP actinide source term model used for long-term performance assessment (PA) of the repository comprises dissolved and suspended submodels (solubilities and colloids). This presentation will describe the solubilities. From the standpoint of long-term PA, the order of importance of the radioelements in the TRU waste to be emplaced in the WIPP is Pu ~ Am >> U > Th >> Np ~ Cm and fission products. The DOE has included all of these actinides, but not fission products, in the WIPP Actinide Source Term Program (ASTP). Anoxic corrosion of Fe- and Al-base metals and microbial consumption of cellulosic, plastic, and rubber materials will produce gas and create strongly reducing conditions in the WIPP after closure. The use of MgO as an engineered barrier to consume microbially produced CO2 will result in low fCO2 and basic pH. Under these conditions, Th, U, Np, Pu, and Am will speciate essentially entirely as Th(IV), U(IV), Np(IV), Pu(III), and Am(III); or Th(IV), U(VI), Np(V), Pu(IV), and Am(III). The DOE has developed thermodynamic speciation-and-solubility models for +III, +IV, and +V actinides in brines. Experimental data for Nd, Am, and Cm species were used to parameterize the +III Pitzer activity-coefficient model; data for Th species were used for the +IV model; and data for Np(V) species were used for the +V model. These models include the effects of the organic ligands acetate, citrate, EDTA, and oxalate in TRU waste. The oxidation-state analogy was then used to extend the +III model to Pu(III), and the +IV model to Pu(IV), U(IV), and Np(IV). The solubility of U(VI) was estimated. For the recent WIPP Compliance Recertification Application PA Baseline Calculations, we calculated actinide solubilities with fCO2 buffered at 3.14 × 10-6 atm by the brucite-hydromagnesite carbonation reaction, with pH maintained at ~9 by the brucite dissolution-precipitation reaction, and with estimated concentrations of the organic ligands in brines from the Salado and the Castile Fm., which underlies the Salado. The calculated +III, +IV, and +V solubilities are 1.56 × 10-6, 5.64 × 10-8, and 4.07 × 10-7 M, respectively, in Salado brine; and 1.51 × 10-6, 6.98 × 10-8, and 8.75 × 10-7 M in Castile brine. The U(VI) solubility estimated for both brines is 1 × 10-3 M. This research is funded by WIPP programs administered by the U.S. Department of Energy. Sandia is a multiprogram laboratory operated by Sandia Corporation, a Lockheed Martin Company, for the United States Department of Energy’s National Nuclear Security Administration under contract DE-AC04-94AL85000.

Pressure ulcers in ICU patients: Incidence and clinical and epidemiological features: A multicenter study in southern Brazil.

PubMed

Becker, Delmiro; Tozo, Tatiane Cristiana; Batista, Saionara Savaris; Mattos, Andréa Luciana; Silva, Mirian Carla Bortolamedi; Rigon, Sabrina; Laynes, Rosane Lucia; Salomão, Edilaine C; Hubner, Karina Drielli Gonçalves; Sorbara, Silvia Garcia Barros; Duarte, Péricles A D

2017-10-01

To evaluate the incidence and risk factors of pressure ulcers (PU) in adult patients admitted to intensive care units (ICUs), as well as the outcome (including ICU and hospital mortality) of these patients. Epidemiological cohort multicenter prospective study, evaluating patients admitted for a period of 31days (June 01 to July 01, 2015) until hospital discharge. Epidemiological and clinical data were collected daily until ICU discharge, as was the incidence of PU, either new or present on admission. 10 general adult ICUs. We evaluated 332 patients, 52.1% male, mean age 63.1 years. The most common cause of admission was medical diseases (50.3%), and the mean APACHE II score was 14.9. A total of 45 patients (13.6%) had PU; the most common sites were sacral, calcaneal, ears, and trochanter. The incidence of PU was related to predictive factors, such as the Braden Scale and length of lack of nutrition. The presence of PU was strongly related to unfavorable outcomes, such as Mechanical Ventilation (MV) duration and ICU and hospital mortality. PU incidence is related to severity of the patient's condition and predicted by Braden Scale score. The presence of PU is also related to adverse outcomes, such as MV duration and ICU and hospital mortality. It was also shown that patients with PU have a higher incidence of medical complications, such as acute renal failure, pneumonia, and the need for vasoactive drugs. Copyright © 2017 Elsevier Ltd. All rights reserved.