Sorption of radionuclides to a cementitious backfill material under near-field conditions

2012 ◽  
Vol 76 (8) ◽  
pp. 3401-3410 ◽  
Author(s):  
M. Felipe-Sotelo ◽  
J. Hinchliff ◽  
N. Evans ◽  
P. Warwick ◽  
D. Read
Keyword(s):  
Organic Compounds ◽  
Degradation Products ◽  
Cellulose Degradation ◽  
Near Field ◽  
Organic Ligand ◽  
Sorption Isotherms ◽  
Field Conditions ◽  
Sorption Behaviour ◽  
Backfill Material ◽  
Order Of Magnitude

AbstractThe sorption behaviour of I−, Cs+, Ni2+, Eu3+, Th4+ and UO2+2on NRVB (Nirex reference vault backfill) a possible vault backfill, at pH 12.8 was studied. Sorption isotherms generated were compared to results obtained in the presence of cellulose degradation products (CDP). Whereas Cs was not affected by the presence of the organic compounds, a notable reduction in the sorption of Th and Eu to cement was observed. The results also indicated limited removal of Ni from solution (with or without an organic ligand) by sorption, the concentration in solution seemingly being determined solely by solubility processes. In the case of uranium, the presence of CDP increased the sorption to cement by almost one order of magnitude. Further studies into the uptake of CDP by cement are being undertaken to identify the mechanism(s) responsible.

The Degradation of Cellulose in the Near Field of a Radioactive Waste Repository

1993 ◽  
Vol 333 ◽  
Author(s):  
B.F. Greenfield ◽  
M.H. Hurdus ◽  
N.J. Pilkington ◽  
M.W. Spindler ◽  
S.J. Williams
Keyword(s):  
Degradation Products ◽  
Cellulose Degradation ◽  
Near Field ◽  
Research Programme ◽  
Water Soluble ◽  
Anaerobic Conditions ◽  
Factors Affecting ◽  
Deep Underground ◽  
The Uk ◽  
Assessment Research

ABSTRACTUK Nirex Ltd is seeking to develop a deep underground repository for the disposal of solid low- and intermediate-level radioactive wastes in the UK. The Nirex Safety Assessment Research Programme (NSARP) comprises scientific research to support the post-closure performance assessment of the repository. One of the investigations carried out by AEA Technology under the NSARP is the investigation of the formation of water-soluble complexants from the degradation of the solid organic polymers and cellulosic materials present in such wastes. The influence of these complexants on the solubility and sorption of a number of radionuclides is also being investigated by a combination of experimental measurements and thermodynamic modelling. Under the alkaline, anaerobic conditions representative of the near field of the repository, cellulose has previously been shown to degrade to yield soluble products which enhance the solubilities and reduce the sorption of several radionuclides. As part of this investigation, cellulose was chemically degraded under conditions similar to those expected in the near field and the leachate analysed. Separation of the products by HPLC gave direct identification of 2-C-(hydroxymethyl)-3-deoxy-D-erythro-pentonic (isosaccharinic) acid as one of the degradation products. More tentative assignments were made for glycolic, formic, lactic and acetic acids. A comparison was made with the degradation products suggested in the literature. The possible mechanisms and extent of cellulose degradation are discussed, as well as the factors affecting its degradation in the near field. The sorption of plutonium on to cement from a leachate produced under alkaline, anaerobic conditions is reported.

Impact of iron(II) and oxygen on degradation of oak – modeling of the Vasa wood

Holzforschung ◽  
2014 ◽  
Vol 68 (6) ◽  
pp. 649-655 ◽  
Author(s):  
Shahin Norbakhsh ◽  
Ingela Bjurhager ◽  
Gunnar Almkvist
Keyword(s):  
Molecular Weight ◽  
Tensile Strength ◽  
Oxalic Acid ◽  
Degradation Products ◽  
Cellulose Degradation ◽  
Chemical Degradation ◽  
Low Molecular Weight ◽  
Wood Degradation ◽  
Model Studies ◽  
Order Of Magnitude

Abstract In the wood of the Swedish 17th century warship Vasa, iron (Fe)-catalyzed chemical degradation has taken place after the salvation in 1961, which is manifested in increased acidity accompanied by cellulose degradation and reduced strength in the oak hull. Model studies on fresh oak impregnated with Fe(II) also led to tensile strength (TS) reduction in the same order of magnitude as observed in the wood of the Vasa. In the present study, further experiments have been performed concerning the Fe-catalyzed wood degradation. Namely, the degree of wood degradation was monitored quantitatively by measurement of the O2 consumption of Fe(II)-impregnated oak, kept in closed vials with different relative humidities (RH), as a function of time. The initial O2 consumption was high and declined with time. After 200 days, the accumulated O2 consumption was 0.3–0.4 mmol g-1 wood. Degradation products with low molecular weight were analyzed. The release of CO2 and oxalic acid (OA) was positively correlated with RH (0.235 and 0.044 mmol g-1, respectively, at RH98% after 200 days). Samples kept for 1500 days at RH54% had accumulated 0.044 mmol OA g-1 wood, which is equal to the average OA content in the interior of Vasa oak (corresponding to 4 mg g-1). Oak samples, from which extractives had been removed prior to Fe(II) impregnation, did not change their O2 consumption or TS reduction compared to the nonextracted samples, indicating that extractives are not essential for cellulose degradation in this context.

The effect of cellulose degradation products on thorium sorption onto hematite: studies of a model ternary system

2012 ◽  
Vol 76 (8) ◽  
pp. 3381-3390 ◽  
Author(s):  
G. M. N. Baston ◽  
M. M. Cowper ◽  
T. G. Heath ◽  
T. A. Marshall ◽  
S. W. Swanton
Keyword(s):  
Degradation Products ◽  
Cellulose Degradation ◽  
Near Field ◽  
Principal Component ◽  
High Concentration ◽  
Sorption System ◽  
Model Predictions ◽  
The Impact ◽  
Isosaccharinic Acid ◽  
Good Agreement

AbstractCellulose degradation products (CDPs) can complex with radioelements causing solubility enhancement and sorption reduction, effects which are detrimental to the containment of radionuclides in the near field of a geological disposal facility and surrounding geosphere. Isosaccharinic acid (ISA) is the principal component of CDPs formed under the alkaline anaerobic conditions of a cement-based near field and appears to be largely responsible for the impact of CDPs on radionuclide solubility and sorption under near-field conditions. However, the situation appears to be more complicated under near-neutral pH geosphere conditions.A combined experimental and modelling study was undertaken to compare the impact of a CDP leachate to ISA in a simple model ternary sorption system consisting of hematite as a single mineral substrate, thorium as the radioelement and ISA or a CDP leachate as the complexant. Thorium sorbs strongly to hematite. A triple layer model for thorium sorption to hematite was refined to fit to the experimental data in the absence of ISA or CDP leachate; the effect of ISA on thorium sorption was then predicted.In the presence of CDP leachate, a significant reduction in thorium sorption was observed from pH 6 to 12 in good agreement with model predictions based on a high concentration of ISA. However, only a limited impact of ISA on thorium sorption was observed at pH 6 to 12, in contrast to predictions. The effects of ISA could be accounted for by assuming the formation of a ternary thorium–ISA–surface complex. The model has yet to be extended to the more complex CDP systems. Differences in the thorium speciation in solution due to the formation of a ternary calcium–thorium–ISA complex in the CDP leachate, which is absent from solutions with ISA only, provides the most likely explanation for the differences observed experimentally.

The Identification and Degradation of Isosaccharinic Acid, a Cellulose Degradation Product

1994 ◽  
Vol 353 ◽  
Author(s):  
B. F. Greenfield ◽  
G. J. Holtom ◽  
M. H. Hurdus ◽  
N. O’Kelly ◽  
N.J. Pilkington ◽  
...  
Keyword(s):  
High Performance ◽  
Degradation Products ◽  
Cellulose Degradation ◽  
Near Field ◽  
Experimental Studies ◽  
Water Soluble ◽  
Chemical Degradation ◽  
Alkaline Conditions ◽  
Isosaccharinic Acid ◽  
Microbial Action

AbstractNirex is seeking to develop a deep underground repository for the disposal of solid intermediate-level and low-level radioactive wastes (ILW and LLW) in the UK. One possible influence on the behaviour of radionuclides is the formation of water-soluble complexants by the degradation of the solid organic polymers that will be present in the wastes. The degradation products of cellulose have been shown to increase the solubility of plutonium and other radionuclides and to reduce sorption onto near-field and far-field materials. Degradation of cellulose under anaerobic alkaline conditions produces a range of organic acids. In this paper 2-C-(hydroxymethyl)-3-deoxy-D-pentonic acid (isosaccharinic acid, ISA) is identified by High Performance Liquid Chromatography as a significant component of cellulose leachates. A combination of fractionation of cellulose leachates and plutonium solubility determinations shows that ISA is responsible for the majority of the enhancement of plutonium solubility observed in such leachates. Further degradation of ISA by chemical or microbial action may lessen the effect of degraded cellulose leachates. Experimental studies on the chemical degradation of this compound under alkaline conditions suggest that the presence of oxygen is required. Microbial degradation studies show that the plutonium solubility in solutions of ISA is reduced by their exposure to microbial action.

Near-field scanning optical microscopy

1986 ◽  
Vol 44 ◽  
pp. 642-643
Author(s):  
E. Betzig ◽  
A. Harootunian ◽  
M. Isaacson ◽  
A. Lewis
Keyword(s):  
Near Field ◽  
Optical Microscope ◽  
Visible Radiation ◽  
Field Methods ◽  
Optical Elements ◽  
Optical Region ◽  
Order Of Magnitude ◽  
Nondestructive Imaging ◽  
Scanning Optical Microscopy ◽  
Near Field Scanning

In general, conventional methods of optical imaging are limited in spatial resolution by either the wavelength of the radiation used or by the aberrations of the optical elements. This is true whether one uses a scanning probe or a fixed beam method. The reason for the wavelength limit of resolution is due to the far field methods of producing or detecting the radiation. If one resorts to restricting our probes to the near field optical region, then the possibility exists of obtaining spatial resolutions more than an order of magnitude smaller than the optical wavelength of the radiation used. In this paper, we will describe the principles underlying such "near field" imaging and present some preliminary results from a near field scanning optical microscope (NS0M) that uses visible radiation and is capable of resolutions comparable to an SEM. The advantage of such a technique is the possibility of completely nondestructive imaging in air at spatial resolutions of about 50nm.

Immobilization of Radionuclides on Iron Canister Material at Simulated Near-field Conditions

2008 ◽  
Author(s):  
Daqing Cui ◽  
Ylva Ranebo ◽  
Jeanett Low ◽  
Vincenzo Rondinella ◽  
Jinshan Pan ◽  
...  
Keyword(s):  
Near Field ◽  
Field Conditions

Heat Transfer Spectroscopy and “Heat Transfer-Distance” Curves

2008 ◽  
Author(s):  
Arvind Narayanaswamy ◽  
Sheng Shen ◽  
Gang Chen
Keyword(s):  
Heat Transfer ◽  
Radiative Transfer ◽  
Atomic Force Microscope ◽  
Near Field ◽  
Surface Force ◽  
Casimir Forces ◽  
Distance Curve ◽  
Transfer Distance ◽  
Atomic Force ◽  
Order Of Magnitude

Thermal radiative transfer between objects as well as near-field forces such as van der Waals or Casimir forces have their origins in the fluctuations of the electrodynamic field. Near-field radiative transfer between two objects can be enhanced by a few order of magnitude compared to the far-field radiative transfer that can be described by Planck’s theory of blackbody radiation and Kirchoff’s laws. Despite this common origin, experimental techniques of measuring near-field forces (using the surface force apparatus and the atomic force microscope) are more sophisticated than techniques of measuring near-field radiative transfer. In this work, we present an ultra-sensitive experimental technique of measuring near-field using a bi-material atomic force microscope cantilever as the thermal sensor. Just as measurements of near-field forces results in a “force distance curve”, measurement of near-field radiative transfer results in a “heat transfer-distance” curve. Results from the measurement of near-field radiative transfer will be presented.

P. vortex-mediated strategies for polysaccharides decomposition

TECHNOLOGY ◽  
2015 ◽  
Vol 03 (02n03) ◽  
pp. 80-83
Author(s):  
Mark Polikovsky ◽  
Eshel Ben-Jacob ◽  
Alin Finkelshtein
Keyword(s):  
Degradation Products ◽  
Cellulose Degradation ◽  
Cellulose Hydrolysis ◽  
Industrial Applications ◽  
Biofuel Production ◽  
E Coli ◽  
Novel Approach ◽  
Textile Manufacture ◽  
Hydrolysis Of Cellulose ◽  
The Relationship

Cellulose hydrolysis has many industrial applications such as biofuel production, food, paper and textile manufacture. Here, we present a novel approach to cellulose hydrolysis using a consortium of motile bacteria, Paenibacillus vortex, that can swarm on solid medium carrying a non-motile recombinant E. coli cargo strain expressing the β-glucosidase and cellulase genes that facilitate the hydrolysis of cellulose. These two species cooperate; the relationship is mutually beneficial: the E. coli is dispersed over long distances, while the P. vortex bacteria gain from the supply of cellulose degradation products. This enables the use of such consortia in this area of biotechnology.

Uranium(VI) Uptake by Synthetic Calcium Silicate Hydrates

2008 ◽  
Vol 1107 ◽  
Author(s):  
J. Tits ◽  
T. Fujita ◽  
M. Tsukamoto ◽  
E. Wieland
Keyword(s):  
Solid Phase ◽  
Near Field ◽  
Sorption Isotherms ◽  
Alkaline Solutions ◽  
Precipitation Process ◽  
Direct Reaction ◽  
Reaction Method ◽  
Calcium Silicate Hydrates ◽  
Chemical Conditions ◽  
Co Precipitation

AbstractThe immobilization of U(VI) by C-S-H phases under conditions relevant for the cementitious near field of a repository for radioactive waste has been investigated. C-S-H phases have been synthesized using two different procedures: the “direct reaction” method and the “solution reaction” method.The stabilities of alkaline solutions of U(VI) (presence of precipitates or colloidal material) were studied prior to sorption and co-precipitation tests in order to determine the experimental U(VI) solubility limits. These U(VI) solubility limits were compared with the U(VI) solubilities obtained from thermodynamic speciation calculations assuming the presence of combinations of different solid U(VI) phases. The solid phase controlling U(VI) solubility in the present experiments was found to be CaUO4(s).The U(VI) uptake kinetics and sorption isotherms on C-S-H phases with different C:S ratios were determined under various chemical conditions; e.g., sorption and co-precipitation experiments and different pH’s. U(VI) was found to sorb fast and very strongly on C-S-H phases with distribution ratios (Rd values) ranging in value between 103 L kg-1 and 106 L kg-1. Both sorption and co-precipitation experiments resulted in Rd values which were very similar, thus indicating that no additional sorption sites for U(VI) were generated in the co-precipitation process. Furthermore, C-S-H synthesis procedures did not have a significant influence on U(VI) uptake. The U(VI) sorption isotherms were found to be non-linear, and further, increasing Ca concentrations resulted in increasing U(VI) uptake. The latter observation suggests that U(VI) uptake is controlled by a solubility-limiting process, while the former observation further indicates that pure Ca-uranate is not the solubility-limiting phase. It is proposed that a solid solution containing Ca and could control U(VI) uptake by C-S-H phases.

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